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Critical Reviews in Solid State and Materials Sciences


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Carbon Nanostructures
O. A. Shenderova ab; V. V. Zhirnov ac; D. W. Brenner a
a
North Carolina State University, Raleigh, North Carolina b International Technology Center, North
Carolina c Semiconductor Research Corporation, North Carolina

To cite this Article Shenderova, O. A., Zhirnov, V. V. and Brenner, D. W.(2002) 'Carbon Nanostructures', Critical Reviews
in Solid State and Materials Sciences, 27: 3, 227 — 356
To link to this Article: DOI: 10.1080/10408430208500497
URL: http://dx.doi.org/10.1080/10408430208500497

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Critical Reviews in Solid State and Materials Sciences, 27(3/4):227–356 (2002)

Carbon Nanostructures
O.A. Shenderova,1,2 V.V. Zhirnov,1,3 and D.W. Brenner1
1North Carolina State University, Raleigh, North Carolina; 2International Technology Center, Research Triangle

Park, North Carolina; 3Semiconductor Research Corporation, North Carolina

ABSTRACT: An overview of the various carbon structures with characteristic sizes in the nanoscale region is
presented, with special attention devoted to the structures and properties of ‘nanodiamond’ and carbon nanotubes.
The term ‘nanodiamond’ is used broadly for a variety of diamond-based materials at the nanoscale ranging from
single diamond clusters to bulk nanocrystalline films. Only selected properties of carbon nanotubes are discussed,
with an aim to summarize the most recent discoveries. Current and potential applications of carbon nanostructures
are critically analyzed.
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Table of Contents
I. Introduction ............................................................................................................................. 228
A. Historical Overview ........................................................................................................... 228
B. Carbon Family at the Nanoscale ....................................................................................... 230
II. Stability of Carbon Phases at the Nanoscale ....................................................................... 233
A. Phase Diagram of Carbon at the Nanoscale ..................................................................... 236
B. Theoretical Studies on the Relative Stability of Different Forms of Carbon at
the Nanoscale ..................................................................................................................... 240
III. Selected Carbon Nanostructures, Their Synthesis, and Properties .................................. 249
A. Diamond at the Nanoscale (‘Nanodiamond’) ................................................................... 249
1. Types of ‘Nanodiamond’ ........................................................................................... 249
2. Ultradispersed Diamond ............................................................................................ 266
a. Synthesis and Post-Synthesis Treatment ............................................................. 266
b. Experimental Characterization of Ultradispersed Diamond ............................... 270
3. Atomistic Simulation on Diamond Nanostructures................................................... 283
a. Diamond Clusters: Structural Properties ............................................................. 283
b. Diamond Clusters: Electronic Properties ............................................................ 290
c. Diamond Nanorods .............................................................................................. 294
B. Carbon Nanotubes ............................................................................................................. 298
1. Synthesis and Properties ............................................................................................ 298
2. Mechanical Properties ................................................................................................ 302
3. Assemblies of Nanotubes and Nanodiamond ............................................................ 313
IV. Applications of Carbon Nanostructures ............................................................................... 319
A. Diamond-Based Nanostructured Materials for Macroscopic Applications ...................... 320
1. Applications of Ultradispersed Diamond .................................................................. 322
2. Applications of Ultrananocrystalline Diamond Films............................................... 326
3. Applications of Carbide-Derived Diamond-Structured Carbon ................................ 327
B. Carbon Nanotubes in Advanced Electron Sources ........................................................... 329
C. Carbon Nanotubes as Nanoelectronics Components ........................................................ 338
D. Medical Applications of Fullerene-Based Materials ........................................................ 343
E. Atomic Modeling of Carbon Nanostructures as a Tool for Developing New
Materials and Technologies ............................................................................................... 343
V. Conclusions and Future Outlook ........................................................................................... 347
1040-8436/02/$.50
© 2002 by CRC Press, Inc.

227
I. INTRODUCTION particularly, in more detail, ultradispersed dia-
mond obtained by detonation synthesis, the topic
Much of the discussion of nanotechnology of research that is popular in Russia and eastern
perspectives is currently centered around carbon- countries and less known in the U.S. research
based nanostructures. While the popularity of community. Some properties of nanotubes, se-
carbon nanostructures to a large extent is due to lected according to the authors’ interests, are also
fullerenes and nanotubes, other members of the discussed in Section III. In Section IV a critical
nanocarbon family are also attracting steadily analysis of current and perspective applications
increasing attention. For confirmation we refer to of selected nanocarbon structures is provided.
recent reviews1,2 and a book3 on nanodiamond
materials. Accordingly, structures, properties, and
numerous applications of nanostructured graph- A. Historical Overview
ite, which belongs to a broad group of so called
new carbon materials, has been summarized re- While the history of synthetic graphite begins
cently in a book by Inagaki.4 In parallel, new in the 19th century,11 artificial diamonds were not
carbon allotropes are being discovered such synthesized until the middle of the 20th century.
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as, for example, carbolite, an esoteric chain-like Since then, both graphite- and diamond-related
crystalline form of carbon.5 Clearly, carbon groups of carbon materials have experienced sev-
nanoscience, a discipline studying properties of eral waves of renewed interest in scientific com-
all groups of carbon entities at the nanoscale within munities when new types of materials or synthe-
a unified framework, including interrelationships sis techniques had been discovered. Within the
between the various forms of nanocarbon, condi- graphite-based group, new materials (“new car-
tions under which one form transforms to an- bon”4), such as carbon fibers, glass-like carbons,
other, and the possibility of combining nanocarbon pyrolitic carbons, etc., were developed in the early
entities to hierarchical structures, is becoming a 1960s, and found broad industrial applications.4
field onto itself. There is also a new tendency to The most significant relatively recent application
bring together at scientific forums researchers from of this class of carbon material is probably lithium
different carbon communities, graphite fibers, ion rechargeable batteries that use nanostructured
fullerenes, and diamond, which were developing carbon anodes, which have made possible por-
before rather independently.6 While there are ex- table electronic devices.4 Within this group of
cellent reviews7–10 that discuss several classes of ‘new carbon’ materials, texture on a nanometer
carbon nanostructures in one general scheme, in scale based on preferred orientation of anistropic
particular graphite-related and fullerene materi- hexagonal layers play an important role in their
als, nanodiamond has remained out of the scope properties. Some of the ‘new’ graphitic materi-
of most recent discussions. This is despite a num- als contain nanostructural units within a com-
ber of recent discoveries demonstrating that lay- plex hierarchical structure such as, for example,
ered graphite nanoparticles can transform to carbon fibers consisting of carbon nanotubes in
nanodiamond and vice versa, in other words, in- their cores.
timate interrelations between different forms of A new era in carbon materials began when in
nanocarbon exist. Moreover, a variety of interest- the mid-1980s the family of buckminsterfullerenes
ing research on the thermodynamics and kinetics (“buckyballs”) were discovered12 followed by the
of carbon at the nanoscale have been published discovery of fullerene nanotubules (“buckytubes”).13
recently. We review this topic in Section II. The discovery of these structures set in motion a
In the present work we try to generalize re- new world-wide research boom that seems still to
sults on the currently known nanocarbon materi- be growing. As mentioned above, fullerene
als. After a short historical overview on carbon nanotubules and graphite-based materials are in-
nanostructures, we complete Section I by classi- herently connected, and researchers who produced
fying the carbon family at the nanoscale. In Sec- carbon filaments had been unknowingly growing
tion III we discuss classes of nanodiamond and nanotubes decades before Iijima’s publication.13

228
Some of the related topics, predictions, and discov- been developed at the beginning of 1960s. The
eries of the carbon cage structures are summarized area of the CVD of diamond films experienced
in Table 1 in chronological order. several shifts of scientific and funding activity,
Diamond was synthesized from graphite by with the last peak taking place in the United States
high-pressure/high-temperature methods in the in the mid-1990s. The interest in diamond thin
1950s, and low-pressure chemical vapor deposi- films has increased in the last few years as re-
tion (CVD) of diamond polycrystalline films had search activities related to nanotechnology have
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229
grown world-wide, and new synthesis methods of carats per year.3 At the present time the produc-
nanocrystalline diamond films have been discov- tion of detonation diamond by “ALTAI” is lim-
ered.2,14 ited. Currently, there are several commercial cen-
Diamond powder was synthesized by shock ters in the world producing UDD, particularly
waves in the beginning of the 1960s by Du Pont in Russia (e.g., the ‘Diamond Center’ in
de Nemour & Co, a leader in explosive technol- S.Petersburg), Ukraine (e.g., “Alit”), Belorussia,
ogy previously applied to other materials. Du Germany, Japan, and China. A center for the pro-
Pont produced diamond using shock wave com- duction of UDD is being organized in India.
pression induced by solid explosive detonation of
carbon materials (graphite, carbon black) mixed
with metal powder (Ni, Cu, Al, Co) placed in a B. Carbon Family at the Nanoscale
capsule (which was destroyed after the process).
Produced polycrystalline diamond particles of In principle, different approaches can be used
micron size (1 to 60 µm) (tradename MypolexTM) to classify carbon nanostructures. The appropriate
consist of nanometer-sized diamond grains (1 to classification scheme depends on the field of appli-
50 nm). This material has been used for high- cation of the nanostructures. For example, a classi-
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precision polishing applications for a long time. fication can be based on an analysis of the
In 1999, the DuPont Corporation was acquired by dimensionalities of the structures,4,19 which in turn
Spring Holding, a Swiss holding company and are connected with the dimensionality of quantum
parent company of Mypodiamond Inc. The pro- confinement and thus is related to nanoelectronic
duction volume of the company is about 2 million applications. The entire range of dimensionalities
carats per year (less than half a ton).15 is represented in the nanocarbon world, beginning
Another approach for producing diamond with zero dimension structures (fullerenes, dia-
powder by a more effective means with a reusable mond clusters) and includes one-dimensional struc-
detonation capsule is the conversion of carbon- tures (nanotubes), two-dimensional structures
containing compounds into diamond during fir- (graphene), and three-dimensional structures
ing of explosives in hermetic tanks.17 The history (nanocrystalline diamond, fullerite). In a different
of the discovery of this type of nanodiamond, also approach, the scale of characteristic sizes can be
known as ultradispersed diamond (UDD) or deto- introduced as the major criterion for classification.
nation diamond, is much less known and has been This scheme more naturally allows the consider-
described in a recently published book by ation of complicated hierarchical structures of car-
Vereschagin.3 This method was initiated in Rus- bon materials (carbon fibers, carbon polyhedral
sia in the earlier 1960s soon after Du Pont’s work particles). A summary based on different shapes
on shock wave synthesis and was a very active and spatial arrangements of elemental structural
area of research in the 1980s, where it was studied units of carbon caged structures also provides a
independently by different groups of researchers very useful picture of the numerous forms of car-
(Table 2). Publications in this area at that time bon structures at the nanoscale.20 Regarding the
were very scarce, with some reports appearing last approach, the spatial distribution of penta- and
decades after the actual discoveries had been hexa-rings within structures also can provide a
made.17 The first work on nanodiamond produced basis for classification.21
by detonation in the United States was published In terms of a more fundamental basis for the
in 1987, where the method of synthesis was de- classification of carbon nanostructures, it would
scribed.18 In 1983 the NPO “ALTAI” was founded be logical to develop a classification scheme based
in Russia, the first industrial company to com- on existing carbon allotropes that is inherently
mercialize the process of detonation diamond connected with the nature of bonding in carbon
production in bulk quantities (tons of the product materials. Ironically, there is no consensus on
per year).3 According to a USSR government re- how many carbon allotropes/forms are defined at
port (1989) on UDD production, it was planned to present. From time to time publications appear
increase UDD production by up to 250 million proposing new crystalline forms or allotropic

230
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modifications of carbon. Whether fullerenes or measure its physical properties. Similarly, the
carbynes are considered as new carbon allotropes ‘carbyne community’ does not classify fullerenes
depends to a large extent on the corresponding as an allotrope.25 Until the 1960s when ‘new car-
scientific community.5,22,24–26 Sometimes the bon’ materials were synthesized, only two allot-
‘fullerene community’ appears to ignore the ropic forms of carbon were known, graphite and
carbynes,24 which were discovered in the 1960s.5 diamond, including their polymorphous modifi-
However, because it can be produced only in cations. Until recently, ‘amorphous carbon’ had
nanoscopic quantities, it was very difficult to been considered as a third carbon allotrope. Pres-

231
ently, however, the structure of amorphous and lem of what constitutes an allotrope is also be-
quasiamorphous carbons (such as carbon blacks, yond the purpose of our discussion and definitely
soot, cokes, glassy carbon, etc.) is known to ap- will be debated in the future, as there is no con-
proach that of graphite to various degrees.4,5 In sensus on the subject.5
this context, it should be noted that within the For the purposes of the present discussion we
diamond community the same term ‘amorphous consider diamond, graphite, fullerenes, and
carbon’ is used for diamond like carbon thin carbyne as four basic carbon forms. The inor-
films.27 ganic carbon family consisting of these four mem-
An interesting discussion of carbon allotropy bers has been classified by Inogaki.4 The scheme
and a scheme for classifying existing carbon forms suggested by Inogaki4 demonstrates interrelations
is provided in Ref. 22. The classification scheme between organic/inorganic carbon substances at
is based on the types of chemical bonds in carbon, the scale of molecules. Such a scheme is also
with each valence state corresponding to a certain useful to illustrate the interdisciplinary nature of
form of a simple substance. Elemental carbon carbon nanotechnology, which is based on both
exists in three bonding states corresponding to materials science and chemistry. We combined
sp3, sp2, and sp hybridization of the atomic orbit- both classification schemes outlined above to clas-
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als, and the corresponding three carbon allotropes sify carbon nanostructures (Figure 2). The modi-
with an integer degree of carbon bond hybridiza- fied scheme is based on two major characteris-
tion are diamond, graphite, and carbyne.22 All tics: the type of carbon atom hybridization and
other carbon forms constitute so-called transi- the characteristic sizes of nanostructures. Starting
tional forms that can be divided to two big groups. with a description of the bonding nature of carbon
The first group comprises mixed short-range or- atoms, the idea is to analyze how different classes
der carbon forms of more or less arranged carbon of carbon networks are formed with increasing
atoms of different hybridization states, for ex- characteristic size of a carbon structure. Starting
ample, diamond-like carbon, vitreous carbon, soot, with small organic molecules, the hierarchy of
carbon blacks, etc., as well as numerous carbon materials can be described as an extension
hypothetical structures like graphynes and of organic molecular species to bulk inorganic
‘superdiamond’. The second group includes in- all-carbon materials through a wide variety of
termediate carbon forms with a non-integer de- carbon entities in the nanoscopic size range. If we
gree of carbon bond hybridization, spn. The sub- consider fullerenes, nanotubes, graphene of finite
group with 1<n<2 includes various monocyclic size and nanodiamond clusters as basic structural
carbon structures. For 2<n<3, the intermediate units in the carbon nanoworld, prototype mol-
carbon forms comprise closed-shell carbon struc- ecules can be assigned to these at the scale of
tures such as fullerenes (the degree of hybridiza- molecules (inner circle). It should be noted, how-
tion in C60 according to Ref. 28 is ~ 2.28), carbon ever, that this scheme does not mean that these
onions and nanotubes, hypothetical tori, etc. The molecules are involved in the synthesis of the
fractional degree of hybridization in this group of units, rather we would emphasize topological simi-
carbon structures is due to the curvature of the larities between organic species and inorganic
framework. A tentative ternary carbon allotropy materials. It should be mentioned, however, that
diagram based on carbon valence bond hybridiza- an elegant model for the formation of different
tion is shown in Figure 1. The value of the sug- diamond polytypes during CVD growth from cor-
gested scheme is that any form of carbon sub- responding molecular precursors (such as ada-
stance is included in the classification. We do not mantine) has been suggested by Matsumoto.29
speculate here on the existence of carbyne, but However, it was discovered that the molecules
rather refer interested readers to a recently pub- are unstable above 700oC.30 Typical sizes of basic
lished book.5 For completeness of the classifica- structural units for nanocarbon are summarized in
tion of carbon based on the degree of carbon bond Table 3. The next structural level, with a corre-
hybridization, it is a necessary to define elemental sponding increase of the characteristic sizes (Fig-
substances for the sp type of bonding. The prob- ure 2), can be considered as consisting of assem-

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FIGURE 1. Ternary “phase” diagram of carbon allotropes. P/H corresponds to the ratio of pentago-
nal/hexagonal rings. (Reprinted from Ref. 22, Copyright (1997), with permission from Elsevier
Science.)

blies of the structural units, ranging from simple nanopatterning techniques such as, for example,
forms, such as multiwall nanotubes (MWNT) or fabrication of diamond nanorods of 40 nm diam-
carbon onions (Table 3) to more complicated eter by plasma etching of diamond films.33 Obvi-
carbon architectures such as carbon black, ously, structural units from different families can
schwarzites, and agglomerates of nanodiamond be combined to form hybrid nanostructures.
particles with fractal structure. An example of a From this section, it should be obvious that
carbon structure with a complex architecture com- one of the approaches to classification of carbon
bining two structural units are recently discov- nanostructures is based on combinations of the
ered graphite polyhedral nano- and microcrystals type of hybridization of carbon bonds within the
with axial carbon structures having nanotube cores, structure and characteristic size of the structure.
nanotube-structured tips, and graphitic faces.31
Finally, at the upper micro/macroscopic scale there
is diamond, graphite, carbolite, fullerite and re- II. STABILITY OF CARBON PHASES AT
cently discovered single wall nanotube (SWNT) THE NANOSCALE
strands of macroscopic sizes.32 While the described
scheme corresponds to the bottom-up approach of It is well known that the most stable carbon
molecular synthesis, it is also necessary to add to phase on the macroscale is graphite and that dia-
the scheme for completeness the nanostructures mond is metastable. The energy difference be-
obtained by top down approaches using different tween the two phases is only 0.02 eV/atom. How-

233
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FIGURE 2. Classification of carbon nanostructures. The mark ‘spn ‘ indicates intermediate carbon forms with a non-
integer degree of carbon bond hybridization.

ever, because of the high activation barrier for a ing detonation that correspond to the equilibrium
phase transition (~0.4 eV/atom), very high tem- diamond region, the idea that nanoscale diamond
peratures and pressures and/or the use of a cata- can be more stable than graphite was put for-
lyst are required to realize the phase transforma- ward.72,73 Several researchers have since addressed
tion. Several factors, however, prompted a number this question by atomistic modeling at various
of researchers to reconsider the issue of carbon levels of sophistication.76–81 Other research areas
phase stability at the nanoscale at the end of the related to the stability of carbon forms at the
1980s.72,73 It was necessary to explain the homo- nanoscale are simulations, performed back in the
geneous nucleation of diamond at low pressures early 1980s, of very small carbon clusters (less
from the gas phase,74 the formation of nanometer- than 20 to 30 atoms) to understand interstellar
sized diamond particles during detonation of ex- carbon as well as studies of the energetics of
plosives,18 and the observation of nanometer-sized fullerene and nanotube formation after these spe-
interstellar diamond in meteorites, which was cies had been discovered.
hypothesized to form from metastable carbon Very interesting transformations between car-
condensates.58 While there can be alternative ex- bon forms at the nanoscale had been discovered
planations for these observations, such as kineti- in the mid-1990s. After annealing at around 1300
cally hindered formation of graphite from the gas to 1800 K, nanodiamond particles transform to
phase,75 or nucleation of diamond at the high carbon onions with a transformation temperature
pressure-temperature conditions that occur dur- that depends on the particle size.60 Moreover, it

234
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235
was discovered that carbon-onions transform to Below we discuss a recent analysis of the
nanocrystalline diamond under electron irradia- phase diagram for nanocarbon, including the
tion.61 Several groups performed atomistic simu- nonequilibrium phase diagram of carbon under
lations to understand both these phenomena.82–84 irradiation as well as recent atomistic simulations
Recently, considering the nanodiamond-onion of the stability of carbon forms at the nanoscale.
transformation, Barnard and colleagues included A very important related topic for a general
fullerenes in the ‘traditional’ analysis of the rela- understanding of carbon behavior at the nanoscale
tive stability of diamond and graphite at the is diamond nucleation from the gas phase,75 which
nanoscale and defined a size region of diamond is not considered in the present review, however.
stability.81 As the system size is increased the
most stable carbon form at the nanoscale changes
from fullerene — to nanodiamond — to graphite. A. Phase Diagram of Carbon at the
The crossover from fullerenes to closed nanotubes Nanoscale
has also been analyzed recently.85 In principle, a
relatively large amount of accurate simulation The phase diagram of carbon has been recon-
results have been generated that create a general sidered several times; a recent version91 is in-
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concept of the stability of carbon forms at the cluded. It includes, for example, an indication of
nanoscale. It is desirable, however, that the simu- regions of rapid solid phase graphite to diamond
lations be done using the same computational conversion, fast transformation of diamond to
approach (of ab initio level) so that a quantitative graphite, hexagonal graphite to hexagonal dia-
comparison of energetics reported by different mond synthesis, shock compression of graphite to
groups is possible. hexagonal or cubic diamond synthesis, and other
Another important area to achieving an un- phase transitions recently observed experimen-
derstanding of carbon behavior at the nanoscale is tally. Low pressure–high–temperature regions of
a reexamination of the carbon phase diagram by the diagram have also been tentatively assigned
introducing in addition to pressure and tempera- for carbyne formation (another example includ-
ture a third parameter — cluster size.86–88 ing carbyne in the phase diagram is Ref. 5).
Although very important, phase diagrams Fullerenes and carbon onions were also consid-
and analysis of relative stabilities of different ered in one of the schematic versions of the dia-
carbon forms at zero temperature are not enough gram.92
for a general understanding of the complex re- Estimates for the displacement of the phase
lationship: initial carbon material – application equilibrium lines for small carbon particles con-
of certain external conditions – final nanocarbon taining from several hundred to several tens of
structure. At finite temperature, the stability thousands of atoms had been made recently.80,86,87
depends on the transition probabilities among In the expressions for the Gibbs free energy per
the possible configurational states of the sys- atom of a cluster of n atoms in a given phase, the
tem and is directly related to the height of the surface energy contribution is added to the bulk
energy barrier separating the particular states.89 free energy:
Recently, the potential energy surface control-
ling the dynamics of the graphite-diamond phase Gi(T,P,n)=dEi n–1/3 + Gi (T,P), (1)
transformation has been investigated along a
model reaction path using first principles and where dEi is the n-atom cluster surface energy of
semiempirical total energy calculations on fi- the i-th phase (it is assumed 70, 40, and 1 kcal/
nite carbon clusters.80,82,90 In general, the acti- mol for diamond, graphite, and liquid carbon,
vation barrier is size dependent and increases respectively80). Then the phase equilibrium lines
as the size of the cluster is increased, achieving for an n-atom cluster is defined by equating the
a value of the order of several tens of eV for the Gibbs energies of the corresponding phases (Fig-
largest clusters (~3 nm) as found in bulk dia- ure 3). The authors report better agreement with
mond.80,90 calculations for experimental shock pressure-vol-

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FIGURE 3. Approximate phase diagram for 1000 atom carbon clusters. Shad-
owed region corresponds to estimated uncertainties in location of equilibrium
lines derived from available experimental data. (Reprinted from Ref. 87, Copy-
right 2001, with permission from the American Institute of Physics.)

ume and temperature data than those obtained drawn based on the fact that spherical diamond
with a bulk carbon equation of state. The results particles with an average size 4 nm are produced
also suggest that carbon particles, of the order of from the liquid state at a temperature of 3000 K.55
103 to 104 atoms, can exist in the liquid state at Therefore the triple point has been shifted to this
lower temperatures than bulk carbon. point accordingly. Unfortunately, the positions of
Figure 4a illustrates a three-dimensional phase the critical points for construction of the diagram
diagram where particle size is an additional pa- along the pressure axis were not discussed in Ref.
rameter.88 It was derived based on the published 88. In addition, the position of the triple point in
data on properties of detonation diamond. The Figure 3 and Figure 4a is different for small par-
lower horizontal plane corresponds to the phase ticle sizes. The triple point displaces toward higher
diagram for bulk phases. The vertical axis corre- pressures in Figure 3 and toward lower pressures
sponds to the particle size. The diamond phase in Figure 4a as the particle size is decreased.
diminishes at a particle size 1.8 nm or below (the While calculations to derive Figure 3 are quite
point T1a at the figure) that corresponds to the accurate, they do not explain the higher stability
experimentally observed minimum particle size. of diamond particles over graphite at the nanom-
At particle sizes below 3 nm the diamond phase eter size scale. Thus, we suggest one more variant
is considered the most stable phase, so at the of the 3-D phase diagram based on the results
upper part of the state diagram only the diamond reported in Ref. 80, but, in addition, tentatively
phase is present. The striped vertical plane is introduce a change of the slope of the diamond/

237
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FIGURE 4. Three-dimensional phase diagrams for carbon. Phase diagram constructed


according to published data on detonation diamond properties (a).88 Schematic 3-D
phase diagram, including fullerenes (b).92 (Reprinted from Ref. 88 and Ref. 92 with
permission.)

238
graphite equilibrium line as particle size is de- As mentioned above, under the nonequilib-
creased (Figure 5). This change results in a higher rium conditions of intense irradiation, the phase
stability of nanodiamond over nanographite at equilibrium between graphite and diamond can
ambient conditions. be reversed so that graphite can be transformed
According to the fact that at sizes below 1.8 into diamond even if no external pressure is ap-
nm other carbon forms are abundant, such as plied.61 A detailed quantitative study of the
fullerenes and onions, it was suggested to assign nonequilibrium phase diagram of carbon under
the corresponding region of the state diagram to irradiation was presented in Ref. 93. The theoreti-
fullerenes and onions as shown schematically in cal treatment is based on the master equation
Figure 4b. approach for incoherent phase transformation in-
Although the diagrams illustrated in Figures volving motion of the interface between two
3 to 5 are rather tentative, it is a good starting phases. In addition to the thermally activated ex-
point for constructing the nano-phase carbon dia- change of atoms across the interface, under irra-
grams using more accurate methods. One of the diation conditions atoms are ‘ballistically’ dis-
critical points is accurate surface energies of the placed from the lattice positions (with different
corresponding particles as well as realism of the threshold energies for different phases) to inter-
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related structural models (mostly surface struc- stitial positions within the interface. Then, de-
ture). Fortunately, rapidly increasing the number pending on the temperature conditions, interstitial
of the ab initio-based works addressing these is- atoms will relax toward particular bulk lattice
sues for relatively big systems will provide a sites. A nonequilibrium effective free energy is
deeper understanding of the phase equilibrium of defined93 that governs the phase stability under
nanocarbon. irradiation and yields quantitative predictions of

FIGURE 5. Schematic 3-D phase diagram for carbon illustrating the change in
the position of the triple point as a function of particle size drawn according to Ref.
87. As shown, the nanodiamond phase is the most stable phase at ambient
conditions.

239
the interface velocity that can be directly com- the enthalpies of hydrocarbon molecules to larger
pared to the experimental observations obtained scales, Badziag et al.73 suggested that diamond-
by TEM. As a result of this work, the nonequilib- like clusters with sizes up to 3 nm are more stable
rium phase diagram (irradiation intensity vs tem- than aromatic structures with comparable hydro-
perature) is illustrated in Figure 6. The kinetics of gen to carbon ratios (the transitions are predicted
a reverse transition, from nanodiamond to onions to occur at about H/C=0.24). A similar result was
during annealing, was described in Ref. 94. obtained for relaxed hydrogenated graphitic and
diamond-like structures using bond-order inter-
atomic potential functions for which the transi-
B. Theoretical Studies on the Relative tion in stability for diamond/graphite occures at
Stability of Different Forms of Carbon at H/C ratios of ~0.3.95 Gamarnik78 compared the
the Nanoscale cohesive energies of bare surface diamond clus-
ters and 3-D graphite clusters using an empirical
There is a relatively large number of the theo- description of interatomic interactions. He also
retical studies devoted to the relative stability of calculated the temperature dependence of the criti-
diamond/graphite at the nanoscale. Within the cal size of stable diamond clusters, including the
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earliest studies, the energy advantage of entropy contribution to free energy: dF=T(Sg-
londsdaleite over graphite for very small particles Sd). The difference in entropy of graphite and
elongated along the c axis was reported based on diamond was chosen as Sg-Sd=3.37 kJ/mol at
the comparison of the number of dangling bonds lower temperatures and 4.59 kJ/mol at 800 to
of graphite and londsdaleite.76 To explain the ob- 1100oC. A more extended discussion of these
servation of a 5 nm-diamond found in meteorites, values can be found in Ref. 96. According to the
Nuth compared the surface energies of graphite prediction,78 diamond nanocrystals formed, for
and diamond, but the uncertainty was too large to example, at 1100oC should be less than 5 nm in
make a reasonable conclusion. Based on scaling size and the maximum size of stable diamond

FIGURE 6. Experimentally and theoretically (solid line) determined


nonequilibrium phase diagram (irradiation intensity vs temperature) for irra-
diation with 1250 keV electrons. Open circles: diamond growth, black squares:
graphite growth. (Reprinted from Ref. 93, Copyright 2000, with permission
from American Physical Society.)

240
crystals should not exceed 10 nm at room tem- N is number of carbon atoms along one edge.
perature. This can be also estimated from the formula for
There are also several studies based on the symmetric polycyclic aromatics C6m2H6m, where
‘classic’ thermodynamic functions modified to m is the number of rings along a single edge.79 For
account for the size of the cluster.96,97,98 Hwang et a diamond octahedral with edges of n atoms, the
al. in their study of homogeneous diamond vs. cluster contains NC =N(4N2-1)/3 and Ndb=4N2.73
graphite nucleation outlined a chemical potential The parameters Edb and EC are the energy per
model98 and a charged cluster model, where the dangling bond and per carbon atom, respectively.
critical size for charged particles was evaluated as Atomistic simulations provide a set of values of
350 atoms.97 The additional pressure contribution Etot for a particular system size and configuration
due to the curvature of the nanometer-sized par- such that the parameters EC and Edb can be ex-
ticles was considered.96,97 It was assumed that due tracted from a least squares fit of Etot as a function
to the additional pressure, the external pressure of Ndb/NC for the graphite and carbon clusters. The
necessary for the transition of nanographite to cohesive energy of a cluster is defined as the
nanodiamond decreases.96 After introducing this difference between the total energy per atom in a
contribution to the pressure-temperature analyti- cluster and the carbon free energy (e.g., it is Etot/
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cal expression for the diamond/graphite equilib- NC). The surface energy contribution becomes
rium line in the bulk phase diagram, the authors less and less important as cluster size increases,
obtained a size-dependent phase diagram. The so that for an infinite cluster extrapolation of the
reported critical cluster size at room temperature cluster cohesive energy should be close to the
was ~6 nm. A general theory of dynamic and bulk carbon cohesive energy, EC,, according to the
static nanodiamond formation from different solid expression:
carbon forms was suggested by Lin.109 The sug-
gested cluster transformation mechanism is based Etot /NC = EC + Ndb/NC Edb . (3)
on the concept of vibrational interactions between
objects with an anomalously high Debye tem- With such tests, the accuracy of the method
perature. describing interatomic interactions can be evalu-
Results from the first ab initio restricted ated for both diamond and graphite systems.
Hartree-Fock calculations on the phase stability Equally, instead of dangling bonds, hydrogen ter-
of a graphene sheet and cubic diamond clusters mination of a cluster surface can be considered
were reported in Ref. 77. Both bare and hydroge- within the above scheme. Such an evaluation was
nated surfaces were considered. The cohesive done by Winter and Ree for the density functional
energies obtained by extrapolation to bulk values approach, using ab initio restricted Hartree Fock
of diamond and graphite were rather different and semiempirical AM1 and PM3 methods79 for
from experimental values, indicating the low ac- both bare and hydrogenated clusters. It was con-
curacy of the method. cluded that the best accuracy was obtained utiliz-
The general scheme for calculation of the ing semiempirical methods (which is not surpris-
heats of formation for graphene sheets and dia- ing because the enthalpies of formation of organic
mond clusters was outlined in Refs. 73, 77, 79. compounds are within the fitted data set).
Below we follow the outline of Ref. 79. Analysis of the heat of formation in terms of
The dependence of the total energy of a bond energies provides more physical meaning to
nanocarbon system on the number of carbon at- the parameters rather than the empirical expres-
oms can be expressed as: sions above. Each carbon atom in graphite forms
three intralayer sp2 bonds and experiences a weak
Etot = NCEC + NdbEdb , (2) interlayer interaction. In the diamond lattice each
carbon atom forms identical sp3 bonds. The heats
where NC is the number of carbon atoms and Ndb of formation for sp2 and sp3 carbon clusters can be
is the number of dangling bonds. For two-dimen- expressed in terms of the CC and CH bond ener-
sional graphite sheets NC =6N2 and Ndb=6N, where gies and the atomic heats of formation as follows:

241
graphite and diamond (left part of the equation at
∆H 0f ( sp 2 ) 3 sp 2 N H  sp 2 1 sp 2 big NC), bond energies can be estimated. Thus, an
= ECC + ECH − ECC + ∆H Of ( H ) outcome of the scheme is an analytical expression
NC 2 NC  2 
for atomic heats of formation of hydrogenated
1 disp
+ ∆H Of (C ) + ECC (2.4a) nanodiamond and hydrogenated nanographite as
2 functions of the number of carbon atoms. Figure
7 illustrates an example of such dependences
obtained by Winter and Ree using a semiempirical
∆H 0f ( sp 3 ) N H  sp3 1 sp3
ECH − ECC + ∆H Of ( H )
3
= 2 ECC
sp
+ approach (PM3 cluster calculations). The curve
NC NC  2 
crossing corresponds approximately to 33,000
+ ∆H Of (C ) (2.4b) atoms (~7 nm particle size).
Analysis of the stability of hydrogenated
nanodiamond and nanographite is relatively
where NH is the number of hydrogen atoms, ECC
straightforward. What is also important is that the
and EHC are the energies of a C-C and H-C bond,
relaxation of hydrogenated nanodiamond surfaces
respectively, and Edisp is the C-C pair energy due
is in general comparable to bulk diamond,99,100 so
to the interlayer dispersion (1.66 kcal/mol79).
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that bond energies of bulk diamond can be used


∆H 0f ( H ) =171.29 kcal/mol and ∆H 0f (C ) =52 kcal/ for rough estimations.
mol are the experimental values of the standard However, analysis of the optimized geometries
heat of formation of carbon and hydrogen, re- of the bare nanodiamond surfaces showed that the
spectively, at room temperature. Equating the picture is quite complicated. The first analysis of
intercepts to experimental cohesive energies of nonhydrogenated octahedral nanodiamond clusters

FIGURE 7. Comparison of the cluster size dependence of the heat of formation


∆Hf(sp3) and ∆Hf(sp2) determined by the PM3 HF method.80 The fits to the sp3
(open circles) and sp2 (crosses) data are given by the dashed and solid lines,
correspondingly. (Reprinted from Ref. 80, Copyright 1999, with permission from
Elsevier Science.)

242
and graphene sheets using a semiempirical ap- for the smallest octahedral molecule C10 is also
proach was done by Winter and Ree.79 If the sur- reduced (Figure 8). Optimized structures of all
face orbitals are left uncapped, a finite graphene other octahedral molecules with larger sizes re-
sheet distorts due to bond formation between adja- semble onion-like carbon with a diamond core and
cent pairs of adjacent planar dangling bonds (Fig- flattened outer layers of the octahedral cluster to
ure 8). For the example in Figure 8, 12 out of 18 form π bonds from the unbonded orbitals (Figure 8).
dangling bonds form 6 in-plane π bonds. In the The bonds between core and surface atoms are
case of nanodiamond, the number of dangling bonds elongated by up to 1.7 to 3.0 Å, followed by round-
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FIGURE 8. Configurations of a bare graphene sheet (a) and diamond octahedral clusters (b-d) after geometry
optimization.79 In the case of the graphene sheet (a) six additional in-plane p bonds (1.31 Å long) formed from 12
of the original 18 dangling bonds and the locations of the remaining six open-shell orbitals. The number of dangling
bonds reduces from 16 to 8 for C10 (adamante-related) diamond cluster (b). The “buckification” – formation of the
sp2 shell over a diamond core begins with a C35 cluster (1sp3 atom in the core) (c) and persist as a crystal size is
increased (d). The atoms in the core of C165 cluster are highlited by dashed lines. (Reprinted from Ref. 79, Copyright
1998, with permission from Kluwer Academic Publishers.)

243
ing of the cluster surface; this bond elongation is from sp3 to sp2 bonding only on the (111) planes.
more pronounced for larger clusters. No cohesive The (100) surfaces initially reconstructed (thereby
energies had been reported for the reconstructed increasing the (111) surface area), followed by a
diamond clusters in Ref. 79. reorientation of the surface dimers to form curved
The preferential exfoliation of the diamond graphite-like (111) cages (Figure 9).99 The results
(111) surface over other low-index faces was of relaxation of the C29 nanodiamond showed a
considered by Kuznetsov et al.82 using standard transformation to the C@C28 endofullerene
semiempirical method (MNDO) calculations of a (Figure 9). The ‘buckification” of spherical
two-layer cluster model for the (111) and (110) nanodiamond clusters (which mostly consist of
surfaces and physical arguments to excluding the (111) and (100) surfaces) was also observed in ab
(100) surface. It was shown that the activation initio DFT as well as Quantum Monte Carlo simu-
barrier for (111) plane exfoliation is much lower. lations90 that is discussed in Section III.A.3. Three
A comprehensive analysis of the stability of cubic (100) structures that were considered con-
nanodiamond clusters of three specific morpholo- tained 28, 54, and 259 atoms. In the case of the 28
gies was done by Barnard et al. using ab initio atoms cluster, the final structure was a metastable
Density Functional Theory with the Generalized- amorphous structure and not a C28 fullerene, as
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Gradient Approximation.99–101 The cohesive ener- had been expected. Additional analysis did not
gies of the diamond clusters calculated by Barnard reveal the transformation path of this structure to
et al. are summarized in Table 4. The results on the fullerene. Preliminary conclusion might be
octahedral clusters are similar to those by Winter that the lack of a (111) surface may influence the
and Ree.79 Cuboctahedral clusters, the surface area onset of graphitization and thus the transforma-
of which is comprised of 40% of (111) and 60% tion into fullerene-like structures. The two larger
of (100)-oriented surfaces, exhibited transitions cubic nanodiamonds were found to have surface

244
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(a)

(b)

FIGURE 9. Cubic (a) and cuboctahedral (b) nanodiamond crystals before


and after relaxation. Note surface reconstruction of the (100) surface and
‘buckification’ of the (111) surfaces. As an extreme case of ‘buckification’
a C28 fullerene with an endohedral C atom is formed for the C29 cluster.
(Reprinted from Ref. 99 with permission.)

245
reconstructions and relaxations comparable to bulk sponding size of the cubic diamond cluster ~1.9
diamond (Figure 9).99 nm). At a system size 1127 < NC < 24,389 atoms,
Thus, ab initio simulations demonstrate that diamond is the most stable form (‘bucky’ dia-
within the size range 1 nm99–101 up to 3 nm for monds were excluded from the analysis). The size
spherical clusters in Ref. 90, the crystal morphol- of a diamond cubic cluster corresponding to 24389
ogy plays a very important role in cluster stabil- atoms is ~5.2 nm. Finally, at a system size larger
ity. While the surfaces of the cubic crystals ex- than ~24,000 atoms, graphite is the most stable
hibit structures similar to bulk diamond, the phase. In principle, it would be interesting also to
surfaces of the octahedral and cuboctahedral clus- include in the analysis nonhydrogenated graphite
ters showed transition from sp3 to sp2 bonding. clusters, which have not yet been thoroughly in-
The preferential exfoliation of the (111) surfaces vestigated. Results obtained in Ref. 81 are also
begins for clusters in the subnanometer size range important for the construction of the 3-D phase
and promotes the cluster transition to endo- diagrams discussed above.
fullerences for small clusters (~ tens of atoms) Recently, a comparison of the stability of
and onion-like shells with diamond cores for larger members of two other carbon families, fullerenes
clusters.99 and closed nanotubes, was made85 using first prin-
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In principle, a analysis similar to that outlined ciples pseudopotential calculations for carbon clus-
above for hydrogenated carbon clusters can be ters of CN (60 ≤ n ≤ 540). The analytical expres-
done for bare reconstructed surfaces if one re- sions obtained for stabilities are based on strain
places parameters for hydrogen with those for energy contributions due to the curvature effects
dangling bonds. This was done by Barnard et al.81 as well as a contribution due to the presence of
Plotting the total energy per atom as a function of pentagons, which introduces nonplanarity of the
the fractional ratio of dangling bonds for non- graphitic sheet incurring incompleteness of the π
bucky clusters from Table 4, and extrapolation of bonding, as had been shown earlier by Adams and
Ndb/Ntot → 0 gave a linear fit of cohesive energy co-workers. 102 The model 85 predicts that a
for the atoms within the inner region of the dia- nanotube of ~13 Å in diameter (e.g., a (9,9) or
mond cluster of 7.71 eV/atom. As can be seen (10,10)) is the energetically most stable form
from Table 4, the cohesive energies of diamond among various single-walled nanotubes and
clusters are below 7 eV/atom due to the highly fullerenes (Figure 10), consistent with many ex-
defective surface atoms. However, due to bond perimental observations. The curve of stability of
shortening and the high freedom for relaxation fullerenes in Ref. 85 is different from the previous
inner atoms can gain an additional energy so that predictions102 for cluster sizes above ~200 atoms.
cohesive energy becomes 7.71 eV/atom. At the There are several studies that investigated the
same time, extrapolation using this procedure for stability of nanotubes relative to graphene. For
unrelaxed clusters with dangling bonds gives a example, graphene is the least stable structure
cohesive energy of 7.39 eV for bulk diamond. In until about 6000 atoms, where it becomes more
principle, as the crystal size is increased, the ‘in- stable than the (10,0) and (5,5) nanotubes.108 En-
ner’ cohesive energy of diamond crystals should ergy gain due to the arrangement of SWNT into
asymptotically decrease toward the bulk diamond arrays caused by van der Waals interactions, as
value. With more data points for larger clusters, it well as faceting (flattening) of nanotube walls at
might be possible that three (or more) groups of a larger nanotube diameter, has been addressed in
diamond clusters with specific morphologies and Refs. 380–383 (see also Table 3). Similarly, the
corresponding specific energetics (cohesive en- stability of nanotubes arranged in multi-shell struc-
ergy of the inner core) can be defined. tures, as well as their faceting with increasing
Barnard et al.81 also predicted the relative nanotube size were studied in Refs. 377–379
stability of nonhydrogenated diamond clusters, (Table 3). The authors107,373–376 discussed the en-
fullerenes and hydrogenated graphite within the ergy characteristics of carbon onions and related
same study. At a system size of up to 1127 atoms, faceting issues. In addition, the molecular dynam-
fullerenes are the most stable structures (corre- ics method was used to estimate the barriers to

246
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FIGURE 10. Dependence of excess energy (relatively to an infinite


graphene sheet) on the system size for (n,n) capped nanotubes and
fullerenes (Reprinted from Ref. 85, Copyright 2002, with permission
from American Physical Society.)

relative shell rotation as well as the temperature recent work.106 It was shown that charge influ-
dependence of the mutual arrangement of the ences both geometry and stability of flat clusters,
shells.107 promoting folding to curved structures as well as
Regarding “small” carbon clusters, it was dissociation. The hierarchy of the stabilities of
known long ago from mass spectra data of mo- carbon forms at the nanoscale are summarized in
lecular beams39 that the 11, 15, 19, and 23 atoms Figure 12.
clusters are abundant, while between 28 and 36 A number of atomistic studies dealt with
atoms the abundance of clusters is very low. Above carbon onions. In particular, concentric-
36 atoms and up to hundreds of atoms, only even- shell fullerenes were generated from diamond
numbered clusters are produced. An extensive nanoparticles of 1.2 nm to 1.4 nm diameters by
study of the stability of “small” carbon clusters means of molecular dynamics simulations based
for a wide size range and several types of configu- on approximate Kohn-Sham equations.83 The dia-
rations were carried out by Tomanek and Schluter mond-to-concentric-shell fullerene transformation
within a tight binding method.103 A recent study were observed at temperatures from 1400 K to
using a density function formalism showed simi- 2800 K and started at the surface of the diamond
lar tendencies and some differences in detailed particle. The final structure consisted of two con-
behavior.104 In general, the current studies104,105 centric graphitic shells with the intershell spacing
show three regions for the stability of small car- distinctly below the interlayer distance of graph-
bon clusters; below 20 atoms the most stable ite with sp3-like cross links between the shells.
geometries are one-dimensional ring clusters; Simulated irradiation accelerated the transforma-
between 20 and 28 atoms clusters with quite dif- tion and reduced the number of cross links. In a
ferent types of geometry have similar energetics; subsequent study,84 structural transformations of
for larger clusters fullerenes should be more stable carbon nanoparticles were studied by means of
(Figure 11). Thermodynamic estimates for the molecular dynamics using a density-functional-
efficiency of formation of spheroidal, flat clus- based tight-binding method. The starting particles
ters, and linear carbon chains depending on the consisted of 64 to 275 atoms arranged on a gra-
charge of the reacting particles was analyzed in a phitic or diamond lattice. At elevated tempera-

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FIGURE 11. The calculated binding energy of carbon clusters as a function of the
number of atoms in a cluster. For the smallest sizes, the rings are the most stable
structures. For the largest size, the fullerene structure is the most stable. For 20 and 24
atoms, ring, bowl, and fullerene clusters have similar energies. (Reprinted from Ref.
104, Copyright 2001, with permission from Kluwer Academic Publishers.)

FIGURE 12. Schematic representation of the most stable carbon phase, depending on the size of
the carbon structure.

248
tures (1400 to 2800 K), the particles transformed perature graphite transformation within a shock
into spherical or elongated closed cages, concen- wave. Nanodiamond materials possess different
tric shell fullerenes, carbon nanotips, and degrees of diamond purity, with a wide variety of
spiraloidal and irregularly shaped clusters. The functional groups/elements at the surface of dia-
type of the final cluster depended essentially on mond particles or within grain boundaries in
the size and the atomic order of the starting par- nanocrystalline diamond films. The structures can
ticles, and on the temperature applied. An atomic be as-grown or compacted from previously syn-
mechanism of transformation of nanodiamond to thesized diamond particles.
carbon onions was considered in Ref. 82. In par- There are two major groups of nanodiamond
ticular, the observed the transformation of three structures observed experimentally. The first group
diamond plains to two graphite planes was ex- includes nanodiamond, which is the final product
plained by a “zipper”-like migration mechanism, of one of the methods of synthesis (such as
with the carbon atoms of the middle diamond ultradispersed diamond, diamond obtained by
layer being distributed equally between the two transformation of carbon onions under electron
growing graphitic sheets. beam irradiation, ultrananocrystalline diamond
Besides pure thermodynamic considerations films). Another group includes nanodiamond nu-
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of the carbon phase stability outlined above ki- clei that have been observed when conventional
netic considerations play an equally important processes of micro- and macro-diamond growth
role,110 which are, however, not discussed here. had been interrupted at early stages to study a
In summary, it had been demonstrated by the diamond nucleation process. A summary of the
highest level of sophistication computational ap- representative experimental observations of
proaches that nanodiamond is thermodynamically nanosized diamond is provided in Table 5.
stable over graphite when the particle size is less The information on nanodiamond observa-
than 5 to 10 nm, in contrast to the macroscale where tions is arranged according to the dimensionality
diamond is metastable. At the same time, the com- of the diamond constituents. We discuss systems
putational methods indicate that nanodiamond sta- of increasing complexity beginning with the zero-
bility is restricted by the smallest sizes of ~1.9 nm, dimensional structures in the form of isolated
below which fullerene structures are more stable. particles, particles on a surface, and particles em-
bedded in a matrix of another material. Some of
the nanodiamond particles from this group had
III. SELECTED CARBON been observed during fundamental studies of dia-
NANOSTRUCTURES, THEIR SYNTHESIS mond nucleation or transformation of carbon
AND PROPERTIES phases in specially designed experiments. Other
types of nanodiamond such as ultradispersed dia-
A. Diamond at the Nanoscale mond obtained by the shock wave process are
(“Nanodiamond”) produced in bulk quantities. The least represented
group is one-dimensional diamond structures at
1. Types of Nanodiamond the nanoscale, for which we discuss only three
examples. Finally, three-dimensional assemblies
Below is briefly summarized experimental of diamond nanocrystals grown as thin films or
evidence for diamond structures with critical compacted from UDD powder to preformed bulk
sizes at a nanoscale as well as related methods of shapes are reviewed in more detail due to their
synthesis. The term ‘nanodiamond’ is used to importance in current technological applications.
identify a variety of structures that include dia-
mond crystals present in interstellar dust and
meteorites, isolated diamond particles nucleated a. Zero-Dimensional Nano-Diamond
in the gas phase or on a surface, and nanocrystalline Structures
diamond films. Methods of nanodiamond synthe-
sis are diverse, ranging from gas phase nucleation Representative observations of isolated dia-
at ambient pressure to high-pressure high-tem- mond particles are summarized in Table 5a, with

249
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250
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selected high-resolution transmission electron on ND surface states during ND extraction and


microscopy (HRTEM) images illustrated in Fig- purification for sample preparation is difficult to
ures 13 to 19. Most of the HRTEM images of address. Examples of observations of ND unal-
single particles are obtained from particles etched tered by sample preparation are in situ experi-
out from a matrix of foreign materials or isolated ments on the phase transformation during anneal-
from particle agglomerates, which are typical, for ing60 and electron irradiation in a high-voltage
example, of UDD particles during storage. In electron microscope.61
general, these observations provide valuable in-
formation on diamond stability, morphology, poly-
morphic modifications, and lattice defects at the i. Nanodiamond Nucleated in a Gas
nanoscale, which, in turn, can be related to the Phase
nucleation mechanism and growth conditions. A rather limited number of experiments have
However, the influence of treatment conditions been conducted to examine homogeneous nucle-

251
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FIGURE 13. HRTEM images of nonlinear multiply-twinned nano-diamond exhibiting Σ=3{111} coherent
twin boundaries are present in (a-b) Murchison X, (c-d) vapor grown particles using substrate-free MPCVD
flow reactor, and (e-f) detonation soot residues. (Reprinted from Ref. 117, Copyright 1996, with permission
from Elsevier Science.)

252
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FIGURE 14. High-resolution TEM image of the cluster with the diamond lattice
observed among the clusters captured on the silica membrane for 60 s with a gas
ratio of C2H2:O2=1.04 during the flame deposition of diamond. (Reprinted from
Ref. 116, Copyright 2002, with permission from Elsevier Science.)

FIGURE 15. HRTEM images of ultradispersed diamond particles obtained by explosive deto-
nation synthesis. (After Ref. 183.)

253
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FIGURE 16. Multiple twin particles of a presolar diamond. (Courtesy of T.


L. Daulton, Naval Research Laboratory.)

FIGURE 17. Using particle beams, a “carbon onion,” a structure consisting of


nested fullerene-like balls, can be converted into a diamond. A growing diamond
is seen inside concentric graphitic layers. The diamonds can grow up to 100
nanometers in diameter. (Reprinted from Ref. 61, with permission from Nature,
copyright 1996. Macmillan Magazines, Inc.)

254
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FIGURE 18. HRTEM images of nanodiamond particles extracted from a graphite matrix where they had been formed
by ion irradiation at room temperature.122 (Courtesy T. L. Daulton, Naval Research Laboratory, after Ref. 122,
Copyright 2001, with permission from Elsevier Science.)

FIGURE 19. HRTEM image of a diamond crystallite (diameter ~6 nm) grown directly
on Si with a random alignment. (After Ref. 140.)

255
ation of diamond in the gas phase at atmospheric ure 13c-d). It was found that nanodiamonds in the
and subatmospheric pressures.43,74,111,112 Theoreti- CVD residue have an abundance of linear twins
cal arguments based on classic nucleation theory and star-twin microstructures consistent with ra-
that homogeneous nucleation of diamond is pos- dial (isotropic) gas phase growth conditions. Stud-
sible have been presented by Fedoseev and co- ies of diamond nucleation directly from an acti-
workers.43 They also reported the formation of vated gas phase have important implications in
diamond particles in the gas phase using a wide revealing mechanisms of interstellar dust forma-
variety of methods that are summarized in Ref. tion, which is discussed below.
74. The experimental procedures included (1) an Another example of homogeneous diamond
electric discharge between graphite or nickel elec- nucleation in the gas phase is laser-induced de-
trodes immersed in a liquid hydrocarbon, (2) a composition of C2H4 at low pressures and tem-
drop of an organic liquid exposed to a focused peratures113,114 that results in diamond powder
high intensity IR laser beam, and (3) quenching formation with grain diameters 6 nm to 18 um.
acetylene pyrolysis by either injection of water or According to the authors,113,114 high-purity homo-
expansion of the gas in a nozzle. In the first two geneously nucleated diamond nanoparticles had
cases diamond/lonsdaleite (a hexagonal diamond spherical and faceted morphologies. Homogeneous
phase) powder with average grain size 0.1 µm
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nucleation of diamond particles at low pressure


was obtained, and in the last method the particle by a DC plasma jet115 has also been reported.
size was about 20 nm. The decomposition of A drastically different nucleation and growth
methane in a radio-frequency electric field is an- mechanism, the so-called charged cluster model,
other approach used112 in the synthesis of submi- was suggested by Hwang et al.98 The model pre-
cron size diamond/lonsdaleite particles. dicts that stabilization of diamond originates from
Frenklach and co-workers74 studied nucleation charge rather than hydrogen. The authors suggest
and growth of diamond powder directly from the that charged carbon clusters of a few nanometers
vapor phase in a substrate-free low-pressure mi- are generated in the CVD diamond and are sus-
crowave-plasma CVD reactor. The particles were pended like colloidal particles in the gas phase
collected downstream of the reaction zone on a and then subsequently deposited as diamond films.
filter within the tubular flow reactor and sub- In an extended series of studies to confirm the
jected to wet oxidation to remove nondiamond model, the authors thoroughly analyzed the de-
carbon. The homogeneous diamond nucleation pendence of the nanodiamond nucleus formation
took place when a dichloromethane- and trichlo- on the deposition environment. In the most recent
roethylene-oxygen mixture was used as a source experiments they observed carbon clusters by TEM
material. The particles formed had crystalline after capturing them on a grid membrane during
shapes with an average particle size around 50 oxyacetylene flame synthesis (Figure 14).116 It
nm. A mixture of diamond polytypes was ob- was found that the captured clusters of ~1.5 nm in
served in the powder. a gas mixture with an acetylene-to-oxygen ratio
Frenklach et al.111 also studied the effects of of 1.04 were mostly amorphous with a few having
heteroatom addition on the nucleation of solid car- a diamond lattice. Clusters larger than 5 nm cap-
bon in a low-pressure plasma reactor. The addition tured at a gas ratio of 1.09 were mostly graphite
of diborane (B2H6) resulted in substantial produc- with a minor fraction of diamond.116 The authors
tion of diamond particles, 5 to 450 nm in diameter, also emphasize, following the observation of sev-
under the same conditions that show no diamond eral hundreds atoms clusters by HRTEM that, in
formation without diborane present. The observed principle, the crystallinity can be altered by inter-
yield of the oxidation-resistant powder produced in action with the substrate. So far, these are the
boron-containing mixtures reached 1.3 mg/h. smallest sizes of observed diamond clusters. Re-
Atomic resolution lattice images of CVD garding the charged cluster model, first principles
nanodiamond with ~5-nm particles sizes obtained atomistic simulations of charged diamond cluster
the technique developed by Frenklach et al. had stability can provide deeper insight on the reli-
been thoroughly analyzed by Daulton et al.117 (Fig- ability of the model.

256
2. Ultradispersed Diamond, or Detona- tion and shock-induced metamorphism) is assumed
tion Diamond in the ND synthesis by explosion of a mix of
A technologically important class of nanocarbon species and explosives.3 Another in-
nanodiamond materials is ultradispersed dia- dication of the possible coexistence of the mecha-
mond. UDD synthesis is performed by the deto- nisms is the presence of a bimodal distribution in
nation of solid explosives in an inert atmosphere. the sizes of ND particles produced by shock wave
The product obtained in detonation synthesis, compression, where particles within the 1 to 4 nm
called detonation soot, contains the diamond phase, range are assumed to be condensed from the va-
which is separated by chemical treatment based por phase.3
on moderate temperature oxidation of the impuri- To discriminate among the most likely for-
ties by nitric acid under pressure.1 Therefore, the mation mechanisms, high-pressure shock-induced
final morphology of the particles is influenced by metamorphism or low-pressure vapor condensa-
the treatment conditions. Images of UDD par- tion, the microstructures of presolar diamond crys-
ticles are shown in Figure 13 and Figure 15. A tallites were compared to those of (terrestrially)
very well-developed facet on a particle can be synthesized nano-diamonds by Daulton et al.117
seen in Figure 15. Daulton et al.117 performed Nano-diamonds isolated from acid dissolution
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extensive studies on the morphology of UDD residues of primitive carbonaceous meteorites


particles that is described in the next subsection. (Allende and Murchison) were studied using
HRTEM. The synthesized diamonds used for
comparison in this study were produced by explo-
iii. Interstellar Diamond sive detonation (e.g., UDD particles, because it
Astronomical observations suggest that as was assumed that their morphology should be
much as 10 to 20% of the interstellar carbon is in close to that produced by shock wave transforma-
the form of nanodiamonds.125 Diamond nanograins tion of carbon species) and by direct nucleation
are the most abundant but less understood inter- and homoepitaxial growth from the vapor phase
stellar matter found in metorites, where it com- in CVD processes (obtained from Frenklach’s
prises up to 0.15%, equivalent to about 3% of the group). Microstructural features were identified
total carbon.126 The conclusion about the presolar that appear unique to both explosive detonation
nature of meteoritic nanodiamonds is based mainly synthesis (shock metamorphism) and to nucle-
on isotope composition measurements of trace ation from the vapor phase. Diamonds produced
elements, including noble gases.127 There are by CVD have abundant twin forms with star-like
uncertainties in the fraction of the presolar morphologies (similar to Figure 16) indicative of
nanodiamond population in meteorites because isotropic formation conditions. Shock-produced
the amount of trace elements is very small.118 In diamonds have mostly planar twin forms, pres-
general, questions on the places and times of the ence of dislocations, and other features consistent
origin of nanodiamond particles remain open. with transformation behind a planar shock front117
The first presolar grains discovered were na- (Table 6). A comparison of these features to the
nometer-sized diamonds isolated from meteorite microstructures found in presolar diamonds indi-
Allende58 (Figure 16). The diameter of presolar cates that the predominant mechanism for presolar
diamond particles in Allende ranged between 0.2 diamond formation is a vapor deposition process,
to 10 nm, with an average size near 2.7 nm. suggesting a circumstellar condensation origin.117
The two main theories for presolar diamond It is also possible that a subpopulation of presolar
formation are vapor condensation, similar to CVD diamonds were shock formed, because presolar
processes, in the outer envelopes of carbon and diamonds are also linked to anomalous trapped
red-giant stars58 and shock-induced metamorphism specific Xe isotope (on average one presolar dia-
in a supernovae.121 It has been also suggested that mond out of a million contain a Xe atom). This
vapor condensation of diamond could also occur isotope can only be produced in a supernovae
in a supernovae.119 The coexistence of the two where shock metamorphism conditions would
mechanisms of ND formation (vapor condensa- prevail.117,118

257
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Another theory of presolar diamond forma- importance of an interdisciplinary approach in


tion suggests that graphite grains irradiated by nanoscience from unexpected, from a first sight,
energetic particles could be transformed into dia- perspectives.
mond, for instance, around supernovae.120 So far,
there has been experimental confirmation of graph-
ite transformation to diamond by MeV electron iv. Direct Transformation of Carbon
and ion irradiation at elevated123 and even at Solids to Nanodiamond
ambient 122 temperatures. The observation of Recent experiments have shown that heavy
nanodiamonds in fine-grained uranium-rich car- ion or electron irradiation induces the nucleation
bonaceous materials from the Precambrian pe- of diamond crystallites inside concentric nested
riod124 also supports the theory of diamond nucle- carbon fullerenes.61,93 Other carbon materials can
ation by irradiation of carbonaceous materials by also be transformed to nanodiamond by using
energetic particles. laser pulses, MeV electrons or ion beams.
The comprehensive studies of nanodiamond Nanodiamond particles had been synthesized
morphology by the astrophysical community that from fine particles of carbon black exposed to
reveal its relevance to the mechanism of interstel- intense laser irradiation.128,129 Similarly, the trans-
lar diamond formation demonstrates again the formation from carbon nanotube to carbon onion

258
and then to nanodiamond as a result of laser irra- conditions of a bias-enhanced CVD process132 or
diation has been reported recently in Ref. 130. diamond film growth using direct ion beam bom-
High-energy electron irradiation (1.2 MeV, bardment133 have been also studied extensively.
>1024 e/cm2; ~100 dpa) was used successfully to The biased enhanced nucleation method, in which
convert the cores of concentric-shell graphitic the substrate is negatively biased and ions are
onions into nanometer-size diamonds at irradia- extracted from the CVD plasma,132 provides the
tion temperatures above 900 K (Figure 17 ). These most versatile tool for the control of the density of
experiments were performed in situ in an electron the nucleus. These synthesis conditions create a
microscope, which allowed continuous observa- rather harsh environment that decreases the prob-
tion of the formation process. A strong compres- ability of any nucleus that is formed of surviving
sion in the interior of the onion was inferred by in a gas phase or on a surface; therefore, a new
the observed reduction in the spacing between explanation of the nucleation mechanism was
adjacent concentric shells during irradiation. required.129 Diamond nuclei 5 to 10 nm in diam-
Ion beam irradiation of carbon solids also eter have been observed recently in amorphous
resulted in formation of nanodiamond. Irradiation carbon films grown using bias-enhanced CVD139
with Ne+ (3 MeV, 4 × 1019 cm–2; ~600 dpa) and or exposed to an ion beam.130 A proposed model139
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temperatures between 700˚C and 1100˚C con- for diamond nucleation by energetic species cor-
verted graphitic carbon soot into nanometer-size responding to these two conditions involves the
diamonds.123 Again the diamonds were found to spontaneous bulk nucleation of a diamond em-
nucleate in the cores of graphitic onions that de- bryo cluster (several tens of atoms) in a dense,
veloped under irradiation. The increased diamond amorphous hydrogenated carbon matrix; stabili-
yield when compared with electron beam irradia- zation of the cluster by favorable interface condi-
tion is explained by the higher displacement cross tions of nucleation sites and hydrogen termina-
section, the higher energy transfer, and the higher tion; and, as a final step, ion bombardment induced
total beam current on the specimen. growth through a preferential displacement mecha-
ND nucleation occurs inside graphite under ion nism.134 The preferential displacement mechanism
irradiation at ambient temperature when implanted has been used also by Banhart135 to explain the
by Kr+ ions (350 MeV, 6 × 1012 cm–2).122 The residue transformation of graphite to diamond by MeV
of the ion-irradiated graphite was found to contain electron impact. The displacement energy of sp2
nanodiamonds with an average diameter of 7.5 nm. bonded atoms is considerably lower than that of
Nanodiamond particles extracted from graphite irra- sp3 bonded atoms, so that electron bombardment
diated by ions are illustrated in Figure 18. leaves the diamond atoms intact but displaces the
Another example of nanodiamond formation graphitic atoms to sp3 or diamond-like positions.
is the irradiation of highly oriented pyrolytic graph- On the basis of this mechanism, the explanation
ite surfaces using a highly charged ion (HCI).131 In of the diamond embryo growth under continuous
contrast to the above work, the transformation of bombardment during bias enhanced CVD is due
spherical carbon onions to diamond by low-tem- to preferential displacement and transformation
perature heat treatment at 500oC in air without of amorphous carbon to diamond. The described
electron and ion irradiation was reported.136 mechanism has wide implications in understand-
HRTEM images showed that diamond particles ing diamond nucleation and growth in/from other
several tens of nanometers in diameter as well as carbon-containing phases when sufficient activa-
the carbon onions coexist after the heat treatment tion energy is provided by means of highly acti-
in air. From detailed HRTEM and electron energy- vated species/radiation.
loss spectroscopy studies, the authors136 suggest
that sp3 sites in the onions and the presence of
oxygen during the heat treatment play important v. Diamond Nucleation on a Substrate
roles in the transformation without irradiation. In the development of diamond films by CVD,
Diamond nucleation resulting from the im- studies of the nucleation and early growth mecha-
pact of energetic species corresponding to the nisms on a wide variety of substrates had been

259
quite intensive (see, for example, review Ref. num deposited as an etch-resistant mask33 (Figure
137). This is due to the fact that the nucleation 20). As for the as-grown diamond films,
process is critical in determining the films prop- nanowhiskers were found to form preferentially
erties, morphology, homogeneity, defect forma- at grain boundaries of diamond crystals. Dry etch-
tion, and adhesion. ing of diamond films with Mo deposits created
Because diamond heterogeneous nucleation well-aligned whiskers 60 nm in diameter that were
has been a topic of numerous papers,137,138 we uniformly dispersed over the entire film surface
include one representative study here. HRTEM with a density of 50/µm2.
images of the nucleation sites responsible for Micron-diameter filaments formed by colloi-
epitaxial growth of diamond by CVD on silicon140 dal assemblies of UDD particles have been ob-
revealed 2 to 6 nm diamond clusters at steps on served in Ref. 64 (Figure 21). After extracting
the Si substrate (Figure 19). and drying, the filaments were similar to glass
fibers, but no measurements of mechanical prop-
erties had been performed. Koscheev et al. also
b. 1D Nanodiamond Structures succeeded in the synthesis of submicron-diameter
filaments consisting of UDD particles obtained
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The least represented group is one-dimen- by laser ablation of pressed nanodiamond pel-
sional diamond structures at the nanoscale. Aligned lets64 (Figure 21). In contrast to the dense fila-
diamond whiskers have so far been formed only ments in colloids every laser-ablated fiber is a
by a ‘top down’ approach by air plasma etching of network of nanoparticle chains. Studies of el-
polycrystalline diamond films, particularly of as- emental composition, IR, and Raman spectra of
grown diamond films and films with molybde- filaments confirmed that they consisted of origi-

FIGURE 20. Magnified SEM micrograph of diamond nanowhiskers


(2.5 µm across the picture). (Reprinted from Ref. 33, Copyright
2000, with permission from Elsevier Science.)

260
FIGURE 21. Diamond filaments grown by self-assembly of UDD particles in a colloidal suspension (a) and filaments
obtained by laser oblation of pressed UDD pellets (b).63 (Images courtesy of A. Koscheev.)
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nal nanoparticles that retained a diamond struc- is the result of a new growth and nucleation mecha-
ture. After extraction from the vacuum chamber, nism that involves the insertion of C2 into the
the whole assembly behaved like an aerogel. In π-bonds of the nonhydrogenated reconstructed (100)
both examples of UDD-based filaments, the fila- surface of diamond. Unattached carbon atoms then
ment networks were rather tangled. react with other C2 molecules from the gas phase to
nucleate new diamond crystallites.2 This results in
an extremely high heterogeneous nucleation rate
c. 3D Nanodiamond Structures (1010 cm–2s–1, which is 106 times higher than from
conventional CH4/H2 plasmas). UNCD grown from
i. Ultra-Nanocrystalline Diamond (UNCD) C2 precursors consists of ultrasmall (2 to 5 nm)
Films grains and atomically sharp grain boundaries.
A novel diamond-based material, called More subtle control of the properties of UNCD
ultrananocrystalline diamond, with 2 to 5 nm films can be accomplished via the addition of
grains (both H-containing and H-free) has been supplementary gasses to the plasma (N2, H2, B2H6,
synthesized recently at the Argonne National PH3) and growth conditions (biasing, power). For
Laboratory by Gruen and colleagues2,62,141–143 us- instance, the addition of hydrogen leads to highly
ing a microwave plasma assisted chemical vapor insulating films with large columnar grains. The
deposition (MPCVD) process. addition of nitrogen, however, yields films that
UNCD thin films were synthesized using ar- are much more electrically conductive than UNCD
gon-rich plasmas instead of the hydrogen-rich made with pure CH4/Ar plasmas. The added ni-
plasmas normally used to deposit microcrystal- trogen leads to the formation of CN in addition to
line diamond. By adjusting the noble gas/hydro- C2 in the plasma. The presence of CN results in
gen ratio in the gas mixture, a continuous transi- decreased renucleation rates during growth, which
tion from micro- to nanocrystallinity was achieved. leads to larger grains and grain boundary widths.
The controlled continuous transition from the Up to 10% of the total carbon in the
micro- to nanoscale is a unique capability of the nanocrystalline films is located within 2 to 4 atom-
method.2 wide grain boundaries. Because the grain bound-
The use of small amounts of carbon-containing ary carbon is π-bonded, the mechanical, electri-
source gases (C60, CH4, C2H2) with argon leads to cal, and optical properties of nanocrystalline
the formation of C2-dimers, which is the growth diamond are profoundly altered compared with
species for all UNCD thin films. The nanocrystallinity more conventional grain structures.

261
UNCD films are superior in many ways to ambient pressure and temperatures not exceeding
traditional microcrystalline diamond films. They 1000oC. Nanocrystalline diamond with an aver-
are smooth, dense, pinhole free, phase-pure and age crystallite size of 5 nm is formed after the
can be conformally coated on a wide variety of extraction of silicon from the carbide. Figure 22
materials and high-aspect-ratio structures.2 shows diamond nanocrystals surrounded by amor-
Here it should be emphasized that, although phous carbon regions formed near the SiC/carbon
the term ‘ultra-nanocrystalline diamond’ and phase interface. However, if no hydrogen was
‘ultradispersed diamond’ have the same prefix added to the gas, nanocrystalline diamond slowly
‘ultra-’, these two materials are completely dif- transformed to the graphite phase during the long-
ferent. The latter are single diamond clusters that term treatment at 1000°C, and only amorphous
form agglomerates with loose bonds between and graphitic carbon at a distance of more than
particles within a powder or in solution where 3 µm from the SiC/carbon interface was observed.
they are stored, and the former is a bulk material Following continued heat treatment at low hydro-
with strong chemical bonds and atomically sharp gen content, a typical film microstructure consist-
grain boundaries between nanodiamond crystals. ing of a nanocrystalline diamond layer (Figure
22b) several microns wide near the SiC/carbon
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interface, followed by a region of diamond


ii. Crystalline Diamond-Structured Car- nanocrystals surrounded by carbon onions and
bon Films disordered carbon was observed. The third re-
Recently, a completely different method from gion, closest to the surface layer, consists of car-
what had been discussed so far for the synthesis bon onions as well as curved graphite sheets,
of diamond-structured carbon in bulk quantities some planar graphite, and porous and disordered
has been developed by Gogotsi et al.14 The method amorphous carbon.145
is based on extracting silicon from silicon carbide The specific feature of diamond-structured
or metal carbide in chlorine-containing gases at carbon is multiple diamond structures including

FIGURE 22. High resolution TEM micrographs showing the structure of the carbon coating within a micrometer of
the SiC/carbon interface (a), where nanocrystals of diamond are surrounded by graphitic carbon, including onion-
like structures. The sample was treated in Ar/3.5% Cl2. Typical TEM micrograph of nanocrystalline layer of diamond-
structured carbon produced with hydrogen present in the gas (b): Ar / 2.77% Cl2 / 1.04% H2. (Reprinted from Ref.
14, with permission from Nature, copyright 1996. Macmillan Magazines, Inc.)

262
cubic, hexagonal (londsdalite) structures as well diamond occurred mainly from highly disordered
as a variety of other diamond polytypes.145 For a sp3 carbon produced by selective etching of SiC. In
stable conversion of silicon carbide to the dia- most cases, SiC was first converted to amorphous
mond phase, the presence of hydrogen in the gas sp3 carbon, and then the formation of diamond
mixture to saturate dangling bonds on the surface occurred within nanometers of the SiC/carbon in-
of diamond particles is key. Nanocrystalline dia- terface. The role of hydrogen is primarily to stabi-
mond films grown up to 50 µm thick at high lize the dangling bonds of carbon on the surface of
hydrogen content have been demonstrated.146 Once diamond nanocrystals. Correspondingly, if the start-
the process is optimized, the linear reaction kinet- ing material is SiC powder, a powder of diamond
ics allows transformation to any depth, so that the structured carbon can be synthesized.
entire silicon carbide sample can be converted to Figure 23 shows diamond particles with an
nanocrystalline diamond. A specific feature of average size of 5 nm embedded in an amorphous
the carbide-derived coating is the possibility of matrix formed during chlorination of TiC.144 It is
varying the pores size from angstrom to a few worth noting the absolutely round particle that are
nanometers, depending on the carbide precursor formed as illustrated in Figure 23.
type leading to the growth of nanoporous carbon
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or nanoporous diamond. Thus, the morphological


difference between carbide-derived and CVD-pro- iii. Nanocomposite Material from UDD
duced nanodiamond is a wide range of diamond Bonded by Pyrocarbon
poly types and the nanoporosity of the former. Another interesting bulk form of nanodiamond
Because random orientation of diamond particles is the so-called nanodiamond composite
nanocrystals is typical for carbide-derived carbon, (NDC),146 which consists of UDD particles con-
it was assumed that the growth of nanocrystalline nected by a pyrocarbon (PyC) matrix. Nanodiamond

FIGURE 23. High-resolution TEM image of diamond nanocrystals embedded in amorphous


carbon in a carbide derived carbon produced by chlorination of TiC.144 (Reprinted from Ref. 144
with permission from Y. Gogotsy.)

263
powder is placed in a container of a predetermined parallel to the basal plane of the graphite.147 Dia-
shape, which is then bonded together by pyrocarbon mond particles consisting of crystallites with grain
formed by means of methane decomposition sizes of several tens of nanometres were observed
through the entire volume of the diamond pow- in the upper and middle regions of the post-shock
der.146 This material is characterized by a high sample by HREM.
porosity (50 to 70%). The reported pores size is not An interesting set of experiments was done
greater than 20 to 30 nm with average radius of 4.5 by applying dynamic shock wave pressures (50
nm. The Young’s modulus is 30 GPa. GPa) on samples containing carbon nanotubes
Due to the high density of nanopores, the and polyhedral nanoparticles.148 HRTEM stud-
material posses a high sorption activity, particu- ies of the samples recovered from the soot re-
larly for large biomolecules (such as tripsin).146 vealed that layers of the outer shells of the
The production of the material is realized at Skel- nanotubes break and transform into curled gra-
eton Technologies, Inc. phitic structures, and the inner nanotube walls
and bulk material display structural defects.
Therefore, no one-dimensional nanodiamond is
iv. ND by Shock-Wave Process produced by this method. The shock-wave com-
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Polycrystalline diamond powder can be pro- pression of polyhedral particles, present in the
duced by shock synthesis.16 Under suitable condi- starting material, resulted in nanodiamond pro-
tions, explosively produced shock waves can cre- duction (Figure 24). In this context, it should be
ate high pressure (~140 GPa) high-temperature mentioned that the book by Vereschagin3 con-
conditions in confined volumes for a sufficient tains a reference to work where aggregates of
duration to achieve partial conversion of graphite needle-like diamond crystals and particles with
into nanometer-sized diamond grains that com- sharp edges of about 10 nm in size were pro-
pact into micron-sized, polycrystalline particles. duced by a modified shock wave process. There-
There are two characteristic ranges within the size fore, in principle, the production of diamond
distribution of the primary diamond nano-crys- nanowhiskers by explosive detonation might be
tals: 1…4 nm and 10…160 nm.3 possible.
An essential component that is mixed with Interesting results on diamond production by
graphite utilized in shock wave synthesis is cop- shock-wave compression of carbyne materials
per, which provides fast heat dissipation in order have been discussed by Heimann.149 Linear car-
to avoid the transformation of the diamond back bon allotropes were found to transform readily
to graphite at the high temperatures that are reached into diamond at comparatively weak dynamic
during the explosion. pressures below 5 GPa (when compared with pres-
There are several modifications of the shock- sures above 100 GPa for graphite conversion)
wave process. Particularly, graphite (or other car- without external thermal activation. Because the
bonaceous materials such as carbon black, coal, diamond particle sizes were not reported, we do
etc.) can be loaded into explosives57 vs. loading in not discuss this method in more detail, but in
a fixture vessel external to the explosives. analogy with other carbon precursors we presume
The shock-wave process was commercialized that their characteristic sizes should be within the
by Du Pont de Nemour & Co to produce poly- nanometer scale range. These data emphasize the
crystalline diamond particles of micron size (1 to importance of the carbon precursor material for
60 µm) that is more friable than monocrystalline diamond production.
diamond microparticles (natural or produced by
HPHT) and is widely used in fine polishing appli-
cations. v. High-Pressure High-Temperature
Recently, low dynamic pressures up to 15 Process
GPa have been reported to be enough to produce We are not aware of publications reporting
diamond from ordered pyrolytic graphite (with the production of nanosize diamond by traditional
voids between particles) using planar shock waves HPHT methods, because the method was tradi-

264
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FIGURE 24. An HRTEM image showing nanocrystals of diamond in the post-shock


sample that are the results of carbon polyhedral particles transformation under shock
compression. The inset is a higher magnification of the region marked by the solid arrow.
(Reprinted from Ref. 148, Copyright 1998, with permission from Elsevier Science.)

tionally aimed at the growth of high-quality mac- ambient pressure has also been reported.153 An-
roscopic diamonds and the identification of other group of authors reported the conversion of
nanodiamonds would require special equipment. fullerenes to diamond under ‘moderate’ condi-
There are no obvious obstacles to the production tions 5.0 to 5.5 GPa and 1400˚C.150
of nanodiamonds by this method if the volume of Carbon nanotubes have been converted to
the carbon precursor material was small enough diamond at 4.5 GPa and 1300˚C using NiMnCo
and these small volumes are well separated in catalyst.152 According to their HRTEM observa-
space to prevent growth to microscopic sizes. tions, the authors suggest that under HPHT con-
Another issue is the practicality of the method — ditions the tubular structures collapse and broken
there are many other more economical ways to graphitic shells curl up and close into spheroidal
produce nanodiamonds. networks to eliminate the dangling bonds at the
As there is no special emphasis on the size of edges. The high curvature of the formed nested
diamond produced by HPHT methods, here we graphitic shells and cross-links between the lay-
only refer to recent reports on HPHT production ers in the onion-like structures that are formed
of diamond from exotic precursor materials such lead to an increased fraction of sp3 bonds that
as fullerenes (Refs. 150, 154, and recent review facilitate the formation of diamond.
151) as well as carbon nanotubes152 that allow In Ref. 155 multiwalled carbon nanotubes
much lower temperatures and externally applied were heated in a diamond anvil cell by a laser
pressures when compared with graphite. For ex- above 17 GPa and 2500 K. The recovered product
ample, the transformation of buckyballs to dia- consisted of nano-sized octahedral crystals (dia-
mond at high static pressure can be done at room mond) of less than 50 nm. The tubular structure
temperature and does not require a catalyst.154 completely changed to granular and grain sizes
Alternatively, the production of diamond from a corresponded to the diameter of nanotubes. The
metallofullerite matrix at high temperature and grain size of the diamond suggests that the trans-

265
formation took place by direct conversion of chemically inert coating, a single particle of UDD
nanotubes that might provide a control over dia- consists of a chemically inert diamond core and
mond size by the choice of the MWNT size. chemically active surface, with controllable prop-
The aim of the present section was to summa- erties. In the macro-world they exist in the form
rize reports on the synthesis/observation of of powders (where UDD form agglomerates) and
nanodiamond. In general, it is formed under a suspensions (aggregated or isolated particles).
wide variety of nonequilibrium conditions. The Below we provide more details on the synthesis
methods of diamond synthesis reported in this and properties of UDD.
section are summarized in a tentative scheme
(Figure 25).
a. Synthesis and Post-Synthesis Treatment

2. Ultradispersed Diamond At the beginning we would like to emphasize


the differences between the major methods for
As has already been mentioned above, diamond synthesis using explosives, because the
ultradispersed diamond — a material consisting materials that are produced are very different, and
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of isolated diamond particles — is not well known it is necessary to be aware of this difference when
in the U.S., while it has been on the market and making a choice of the material for particular
used widely in different technologies in the Former applications. There are three major methods that
Soviet Union for more than a decade. The areas of had been commercialized.3 The first is the trans-
application of UDD are completely different from formation of carbon precursors (e.g., graphite,
those, for example, for UNCD films, the material coal, and carbon black) to diamond in a capsule
being actively developed now in the U.S. While compressed by a shockwave (~ 140 GPa) gener-
UNCD as grown is a very hard, very smooth, and ated outside the capsule (the ‘Du Pont method’).

FIGURE 25. Tentative scheme summarizing the methods of synthesis of diamond nanostructures.

266
To prevent diamond regraphitization, a mixture londsdalite and the particle size is smaller —
of graphite (6 to 10%) with metallic powder (Cu, about 8 nm. The diamond yield constitutes up to
Al, Ni) is used. The diamond yield is about 60 17% of the mass of the initial carbon material or
mass percent of the carbon phase or about 5% of about 3.4% of the mass of the explosives.
the initial mixed material loaded into a capsule. The characteristic feature of the diamond
The synthesized nanodiamond had a bimodal size obtained by these two methods based on the shock
distribution; the first maximum was within the wave compression of the initial graphite phase is
1 to 4 nm size range and the second was within formation of polycrystalline material with par-
the 10 to 150 nm range. The product of the syn- ticle sizes comparable to the particle sizes of the
thesis always contained the londsdalite phase due precursor carbon material. The particles consist
to the martensitic type of transformation graphite- of nanocrystalline diamond grains. After purifica-
rombohedral graphite-londsdelite–diamond. 3 tion the particles produced by detonation are clas-
There are several modifications of this method,3 sified by fractions (from 1 to 60 µm ) for use in
however. polishing applications.3
The second method of ND production is based In the third method of using explosion energy
on the detonation of a mixture of carbon-contain- for diamond production, diamond clusters are
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ing material with explosives. In this case diamond formed from carbon atoms contained within ex-
formation takes place both within the carbon- plosive molecules themselves, so only the explo-
containing particles as well by condensation of sive material is used as a precursor material (Fig-
carbon atoms contained in the explosives. The ure 26). A wide variety of explosive materials can
explosion can be done in air or in an inert atmo- be used, including products for military applica-
sphere relative to the product of synthesis.3 In the tions (so that UDD synthesis is a good way of
latter case, a diamond cubic phase not more than utilizing of the stock pile materials). A typical
20 nm in size is formed. When the formation is in explosive is a mixture of TNT (2-methyl-1,3,5-
an atmosphere of air, the samples always contain trinitrobenzene) and hexogen (in proportion 60/

FIGURE 26. Schematic illustration of the steps in the controlled detonation synthesis of nanodiamond from carbon-
containing explosives (1). During explosion (2) the highly dispersed carbon medium condenses from free explosive
carbon in a fraction of a microsecond. Depending on the detonation conditions, the resulting detonation soot (3)
contains 40 to 80 wt.% of ultradispersed diamond. After disposal, the product has to undergo several stages of
purification. Big industrial detonation reactors are able to deliver tons of detonation diamond per month. The
composition of detonation soot is provided based on163 (pictures of the detonation process courtesy of PlasmaChem
GmbH, Mainz/Germany).

267
40) composed of C, N, O, and H with a negative carbon coagulates into small clusters, which grow
oxygen balance (i.e., with the oxygen content larger by diffusion.80,86,87 The product of detona-
lower than the stoichiometric value), so that ‘ex- tion synthesis, called detonation soot or diamond
cess’ carbon is present in the system. A negative blend, contains 40 to 80 wt.% of the diamond
oxygen balance in the system is an important phase depending on the detonation conditions.
condition for UDD formation. The explosion takes The carbon yield is 4 to 10% of the explosive
place in a nonoxidizing medium (Figure 26) of weight for the most effective of the three indus-
either gas (N2, CO2, Ar, or other medium — that trial methods of diamond production using explo-
can be under pressure) or water (ice) — ‘dry’ or sives.
‘wet’ synthesis, correspondingly, that plays the In summary, there are two major technical
role of a coolant. To prevent the UDD formed in requirements for UDD synthesis using explosives.
the detonation wave from transforming into graph- First, the composition of the explosives must pro-
ite at the high temperature generated by the deto- vide the thermodynamic conditions for diamond
nation, the cooling rate of the reaction products formation, and second the composition of the gas
should be no less than 3000 K/min.3 The initial atmosphere must provide the necessary quench-
shock from a detonator compresses the high-ex- ing rate (by appropriate thermal capacity) to pre-
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plosive material, heating it and causing chemical vent diamond oxidation. The diamond yield de-
decomposition that releases enormous amounts pends to a large extent on the explosive mixture
of energy in a fraction of a microsecond (Figure (Figure 27).86 The shape of the explosive also
26). As the detonation wave propagates through influences the yield; the ideal shape is spherical,
the material it generates high temperatures (3000 but for convenience a cylindrical shape is used
to 4000K) and high pressures (20 to 30 GPa) that regularly. The relationship between the mass of
correspond to conditions of thermodynamic sta- the explosives and the mass of the surrounding
bility for diamond. During detonation, the free media influences also yield (e.g., 5 kg of explo-

FIGURE 27. Diamond weight fraction recovered from soot as a function of the
composition of the explosive mixture. The abbreviation for explosives is as
follow: TNT — 2-methyl-1,3,5-trinitrobenzene; HMX — octahydro-1,3,5,7-
tetranitro-1,3,5,7-tetrazocine; TATB — 2,4,6-trinitro-1,3,5-benzenetriamine;
RDX — hexahydro-1,3,5-trinitro-1,3,5-triazine. (Reprinted from Ref. 86, Copy-
right 2000, with permission from American Institute of Physics.)

268
sive requires ~11 m3 of detonation camera with temperature path-dependent value for the
gas media at ambient pressure to provide the nec- nonequilibrium diamond fraction of the soot mix-
essary quenching rate).3 The mechanisms of dia- ture.86
mond formation as well as factors influencing
yield during explosive detonation have been dis-
cussed in numerous publications by different i. Purification
Russian research groups (summarized in Ref. 3). The diamond blend in addition to UDD con-
In the U.S., fundamental studies of carbon par- tains graphite-like structures (35 to 45 wt.%), and
ticle phase transformation in detonation waves incombustible impurities (metals and their oxides
have been performed at Laurence Livermore — 1 to 5wt.%).1 Using X-ray diffraction and
National Laboratory, primarily by Francis Ree small angle X-ray scattering, it was shown that an
and colleagues80,86,87 and Los Alamos National UDD cluster in detonation soot has a complex
Laboratory primarily by Sam Shaw and col- structure consisting of a diamond core of about
leagues.158 Both the thermodynamics of chemi- 4.3 nm in size and a shell made up of sp2 coordi-
cally reactive mixtures and the kinetics of carbon nated carbon atoms (Figure 27).164 The shell struc-
coagulation have been modeled.86,87,158 The kinet- ture and thickness vary with the cooling kinetics
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ics of the formation and growth of finite carbon of the detonation products (dry vs. wet synthesis)
particles contribute significantly to the detonation and conditions of chemical purification of theUDD
properties of carbon-rich CHNO explosives. As clusters from the detonation soot.164 According to
detonation proceeds, the most important products the X-ray diffraction spectra and the results of
behind the reaction zone are carbon dioxide, wa- electron microscopy, UDD of the highest degree
ter, nitrogen, and carbon residues that undergo of purification contain no intermediate amorphous
phase changes. The relatively slow growth rate of phase, graphite, or londsdalite.161,162
carbon particles gives rise to an extended reaction UDD purification is performed by mechani-
zone. As a consequence, the detonation is more cal and chemical methods. After mechanical re-
sensitive to the system configuration, with the moval of process admixtures, the diamond-car-
observed Chapman-Jouguet pressure reflecting the bonic powder is subjected to thermal oxidation
condition of a partially reacted state rather than with nitric acid under pressure to separate the
that of the final detonation product. Carbon clus- diamond phase.1 The method of acid purification
tering is a slow reaction in the detonation regime at elevated temperatures is the most efficient pu-
as demonstrated by Shaw and Johnson at the end rification method at the present time because it
of 1980s158 using a diffusion-limited model. Car- comprehensively influences all admixtures: met-
bon particles build up from random collisions, als are dissolved and non-diamond carbon is oxi-
while the hot dense background fluid maintains dized simultaneously. The diamond should be
the equilibrium temperature, allowing the clusters flushed with water after separation from the acidic
to anneal to compact spherical objects. The final media. After a typical purification step, powders
particle size was estimated to be 104 to 105 atoms of UDD can be considered as a composite con-
(50 Å), which explained the experimental par- sisting of different forms of carbon (80 to 89%),
ticle sizes. The model did not distinguish between nitrogen (2 to 3%), hydrogen (0.5 to 1.5%), oxy-
the various forms of carbon present during the gen (up to 10%), and an incombustible residue
detonation process. The model has been reconsid- (0.5 to 8%).1 The carbon consists of a mix of
ered taking into account the diamond/graphite diamond (90 to 97%) and non-diamond carbon
transitions within the carbon particles.80,86,87 Esti- (3 to 10%).
mates of the displacement of the phase equilib- In detonation synthesis of nanodiamonds, the
rium lines for small carbon particles containing impurity content is higher when compared with
from several hundred to several tens of thousands other artificial diamonds (i.e., HPHT diamonds
of atoms87 was also included in the analysis of the contain no less than 96% carbon). Therefore, the
kinetics of carbon coagulation. A simplified hy- effect of impurities is more pronounced for UDD
drodynamics model yielded a time and pressure- compared with other diamonds.1 Impurities in

269
UDD, in principle, can be divided into the follow- are on the surface, and thus are unavoidably bound
ing groups:1 (1) water-soluble ionized species (free to adsorbed atoms, molecules, and functional
electrolytes); (2) chemically bonded to diamond groups. These adsorbed atoms, which can exceed
surfaces and prone to hydrolysis and ionization the number of atoms in the diamond particle, can
(salt forms of functional surface groups); (3) water strongly affect the physical and chemical proper-
insoluble; and (4) incorporated into the diamond ties of the particles.
lattice and encapsulated. The impurities of the To minimize surface energy, the primary UDD
first and second groups are formed in the chemi- particles with diameters of ~4 nm form larger
cal purification of UDD by acid stage.1 The major clusters 20 to 30 nm in size that, in turn, form
water-soluble admixtures (first group) are removed larger weakly bound aggregates (of an order of
by washing the UDD with water. The surface magnitude of hundreds of nanometers). The UDD
functional groups (second group) can be efficiently aggregates have a fractal nature.1 This hierarchy
removed by ion-exchange resins that involve dem- of nanodiamond blocks needs to be taken into
ineralization of surface groups. The water-in- account in the interpretation of all experimental
soluble impurities represent both individual results.
microparticles of metals, oxides, carbides, salts, The smallest amount of diamond matter, which
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and metal oxides that do not dissociate. For their can be prepared and studied in isolation are pri-
removal, UDD particles are treated with acids. By mary particles of UDD. In addition, the particles
using different methods of UDD purification, one of UDD are thermodynamically stable at ambient
can remove 40 to 95% of the impurities of these conditions, due to their very small size (<10 nm),
three groups. It is practically not possible to re- different from other forms of diamond (Section II).
move the impurities of the fourth group by chemi- At present, the properties of individual nanom-
cal methods. The UDD of the highest purity avail- eter-sized particles of UDD still need to be char-
able at ‘Diamond Center’, Inc. contains 98.5% of acterized. Table 7 contains selected properties of
diamond. UDD. Note that these are collective properties of
Commercial products of purification have UDD powders. The extraction of properties of
the following grades: a water suspension of dia- individual primary nanoparticles is a challenging
mond and powder obtained from suspensions by task.
drying and grinding of UDD are a gray powder
containing up to 99.5 wt.% of a pure diamond
(without counting adsorbed gases).1 To remove X-Ray Diffraction
non-carbon impurities, the chemically purified X-ray diffraction is a standard method for
product is subjected in some cases to additional characterization crystalline materials. A typical
purification using ion-exchange and membrane X-ray diffraction spectrum of UDD is shown in
technologies. Figure 29. This spectrum is typical for cubic dia-
In general, the UDD production consists of mond. The authors167 calculated from the (111)
detonation synthesis, chemical purification and diffraction peak line width that the average crys-
acid washing of UDD, product conditioning, and tallite size of UDD is 4.3 nm. According to
modifying of diamond. Vereshchagin and Sakovich,168 the X-ray powder
diffraction pattern of UDD exhibits only five re-
flections with a relative intensity distribution that
b. Experimental Characterization of is different from bulk diamond: (111) 85.0% {44},
Ultradispersed Diamond (220) 14.0% {22}, (113) 0.5% {18}, (400) 0.3% {4},
(331) 0.2% {12} (the relative values of reflec-
The properties of UDD particles are mainly tions for a standard diamond sample on ASTM
defined by their nanometer-scale sizes (4 to 6 nm Index 6–675 are given in the braces). The UDD
in diameter) that are within a transitional size crystal lattice parameter is 0.3562 ± 0.0004 nm,
range between macromolucules and crystalline slightly smaller than in bulk natural diamond
solids. About half of all atoms in such particles (0.3567 nm).

270
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While by traditional dynamic synthesis from the diamond crystallites using two different sets
graphite diamond particles of both cubic and hex- of constants in the phonon confinement model:
agonal (a=0.252 nm) structures are produced, UDD 3.6 and 4.3 nm. The authors165 noted that the
obtained from explosives has only the cubic struc- estimates of crystalline size based on the photon
ture without any traces of the hexagonal phase.1 confinement model are very sensitive to the choice
of the dispersion relation for the photon modes.165

Raman Spectroscopy
All experimental Raman studies of ultradisperse Annealing Effects and Diamond-Graph-
diamond quote practically the same frequency po- ite Phase Transition
sition of the peak within 1321–1322 cm–1.167 Typi- The narrow size range of UDD nanoparticles
cal Raman spectra of UDD and bulk diamond are of 4 to 5 nm was quoted in a number of studies.165
shown in Figure 30.167 The observed spectrum can The usual explanation is that nanodiamond is more
be explained by the phonon confinement model stable than graphite (see Section II). However, the
(see references in Ref. 167). The authors of Ref. thermodynamic stability reasoning, while explain-
167 calculated from this spectrum based on the ing the upper bound does not give the lower bound
phonon confinement model that the size of the for the size, thus the narrow size distribution still
diamond nanoparticles is 5.5 nm (the X-ray size needs to be clarified.
obtained by the same authors was 4.3 nm). Aleksenskii et al.165 used Raman spectros-
Aleksenskii et al.,165 using the same Raman copy to study the annealing effects on the
technique, obtained two numbers for the size of nanodiamond structure. Starting from an anneal-

271
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FIGURE 28. Model structures of detonation-produced carbon. Depending on purification


conditions, different layers of the UDD shell can be ‘stripped-off’. (Reprinted from Ref. 164,
with permission from American Institute of Physics.)

ing temperature of T=720 K, remarkable changes yielded about 1.5 nm for the size of amorphous
in the Raman spectra were observed. The peak particles.
due to diamond nanoparticles decreased signifi- The diamond-graphite phase transition tem-
cantly in intensity while not exhibiting any shift perature observed in UDD (Tpt>1200 K) is con-
in frequency. With further increases of Tann siderably lower than the phase transition tempera-
a monotonic decrease of intensity of the ture of bulk single-crystal diamond (Tpt>1900 K).
nanocrystalline diamond line at 1322 cm–1 was An interesting result was reported by
observed, without any change in position. At Obraztsova et al.169 The authors developed a spe-
Tann=1200 K this line was no longer observed. cial annealing procedure that provided an effec-
The constancy of the position of the 1322 cm–1 tive means of reducing the size of diamond
Raman line up to Tann=1000 K indicates that no nanoparticles while preserving the diamond crys-
changes occur in the structure of the diamond tal structure. The procedure allowed them to re-
nuclei at such annealing temperatures. X-ray dif- duce the size of diamond particles step by step
fraction data indicated the formation of a gra- from the initial 4.5 nm down to 2 nm by changing
phitic phase for T>1200 K.165 The authors165 the annealing temperature. Obraztsova et al. found
pointed out that because UDD exists in aggre- that for the smaller size the complete particle
gated form, the amorphous phase is apparently transformation into the onion-like carbon struc-
distributed inside the aggregates on the surface of ture takes place. The size and phase transforma-
diamond nuclei. The presence of an amorphous tions were characterized by Raman spectroscopy.
phase was supported by X-ray diffraction, which The authors also observed a strong photolumines-

272
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FIGURE 29. X-ray diffraction from UDD. (Reprinted from Ref. 167,
Copyright 1995, with permission from the American Institute of Phys-
ics.)

cence (PL) simultaneously with the Raman signal ranged from 3.5 nm to 5 µm. Figure 31 shows the
of diamond. The maximum of the PL shifted from exciton state and conduction band edge of the
2.14 to 2.3 eV, while the annealing temperature nanodiamonds as a function of the crystallite
was increased over the range from 1100 to 1600 K, size.170 According to this plot, the conduction
and correspondingly the particle size changed from band edge shifts to higher energy with a decrease
4.5 to 2 nm. The PL signal disappeared simulta- in the crystallite size. A strong change in energy
neously with the disappearance of the Raman structure, which is believed to be due to quantum
signal of diamond. These authors estimated the confinement, takes place for sizes smaller than 10
size of diamond crystals from the phonon con- nm. The authors applied a standard analytical
finement model to be 4.5 nm. approximation for quantum confinement shift of
energy levels in a one-dimensional quantum box
π 2h2
of size a ∆E ≈ and derived the value of
X-ray Spectroscopy 2m*a 2
Quantum confinement effects are expected in effective mass for nanodiamond of about 0.1m0.
nanocrystalline semiconductors when the size of The above results and their interpretation raise
the particle is smaller than some critical value. several questions. First, the objects of this study
However, details of the electronic structure of were not isolated diamond crystallites but a com-
nanodiamonds are still unknown. Chang et al. plex composite material consisting of diamond
studied CVD diamond films with various crystal- crystallites of different sizes, grain boundaries,
lite sizes by X-ray absorption spectroscopy.170 amorphous and possibly graphitic inclusions, etc.
The size of the diamond crystallites in the films Second, Ley et al.171 questioned the validity of the

273
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FIGURE 30. Raman spectra from UDD and bulk diamond. (Reprinted from Ref. 167,
Copyright 1995, with permission from the American Institute of Physics.)

method the authors used for the extraction of the tion tools. HRTEM allows for direct measurements
values of energy shifts. Third, the calculated ef- of the size of the crystallites from lattice images.
fective mass of nanodiamond of 0.1m0 is consid- Usually only {111} planes can be resolved in TEM,
erably smaller than the bulk value. Note that in because of their large (compared with other planes)
the limiting case of a→0, when the particle ap- lattice spacing, d111 =0.206 nm. A HRTEM image of
proaches one atom, m*→m0, that is, the effective UDD is shown in Figure 15. The sharp lattice fringes
mass increases. Fourth, the reported widening allow for measurements of particle size with high
energy gap, remarkable already at a diamond accuracy. It should be mentioned that if eparticles
particle size of about 10 nm, is in contradiction are not isolated (as, e.g., in CVD films or UDD
with theoretical results predicting the critical size clusters), and if the amorphous phase is present on
for the band structure size-effect onset to be 2 to the surface the accuracy of the measurement is lim-
2.5 nm.172 In 2002, Raty et al. presented theoreti- ited by the histogram of the crystallite size in a CVD
cal results suggesting that the widening of the nanodiamond film as shown in Figure 32.2 Note that
energy gap is remarkable only for the size of the the 2.5 to 4 nm crystallites occur most frequently,
diamond particle <1 nm.90 resulting in an average crystallite size about 3 nm.

Transmission Electron Microscopy Electron Energy Loss Spectroscopy


Lattice imaging mode—High-resolution trans- Electron Energy Loss Spectroscopy is a very
mission electron microscopy and associated tech- powerful tool for the analysis of material compo-
niques are among the most important characteriza- sition and composition in TEM. It is widely used

274
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FIGURE 31. The exciton state and conduction band edge of the
nanodiamonds as a function of the crystallite size. (Reprinted from Ref.
170, Copyright 1998, with permission from the American Physical Soci-
ety.)

to obtain bonding information. For example, it It should be noted that the assumption of a
clearly shows sp3 or sp2 bonding of carbon atoms. spherical shape for the diamond nanoparticles led
In principle, the EELS sensitivity in composi- to a considerable difference between the direct
tional analysis can be extended to the single-atom TEM measurements and EELS adjusted values.
limit, as was shown by Suenaga et al.173 Because After more detailed investigations of TEM im-
EELS is usually associated with high-resolution ages, it was found that the particles were not
TEM, it is possible to collect information about really spherical. Taking into account the
bonding with very high spatial resolution within nonspherical shape resulted in better agreement
a nanoparticle. EELS in a TEM can in principle between the EELS predicted and TEM measured
improve the accuracy of size measurements. In diameters. Also, from their analysis the authors
Ref. 174 the approximate diameters measured in conclude that theoretical predictions for the case
a TEM were later adjusted by fitting theoretical of crystalline diamond surrounded by a surface
and experimental EELS spectra. The fitting pro- layer of sp2 (e.g., graphitic) material were defi-
cedure was based on the spherical model shown nitely not capable of reproducing the experimen-
in Figure 33, and both the amorphous layer thick- tal results.174
ness and crystalline diamond core diameter were
varied to obtain the best fit. Table 8 shows mea-
sured diameters of diamond particles of three dif- Shape of Diamond Nanoparticles
ferent sizes compared with calculated values de- The shape of UDD particles 3 to 5 nm in size
rived by matching experimental EELS data. is often assumed to be spherical. As a model, a

275
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FIGURE 32. Histogram of diamond crystallites of various sizes directly measured in a HREM lattice image
of a CVD nanodiamond film. (After Ref. 2.)

spherical shape is easier for calculations. At the droplets.175 One should mention that the state-
same time, there are experimental reports that ments about the spherical shape of diamond
most of the diamond particles have very spherical nanoparticles are usually based on TEM pictures
shape.174,175,176 This led to speculation that the without considerable magnification, where the
diamond nanoparticles are formed from liquid particles appears so small (as for example, in
drops. Chen and Yun175 argued that from the point Ref. 175) that it is impossible to make any as-
of view of the carbon phase diagram, thermody- sessments about shape. Sometimes particles are
namic conditions created by explosive detonation shown in TEM with larger magnification, but
(temperature range 3000 to 3500 K, pressure 30 without isolation from each other and from the
to 35 GPa do not correspond to the liquid state amorphous matrix so again it is difficult to as-
region of diamond crystal). The authors175 sug- sess the shape.
gested that this contradiction could be resolved Vereschagin and Sakovich also argued in fa-
by assuming that while bulk diamond cannot melt vor of a spherical shape for UDD nanocrystals
under the detonation conditions, for the nanom- and the liquid carbon drop formation mecha-
eter-sized diamond particles the effective melting nism.168 Also, they compared the density of
point might decrease. Thus, Chen and Yun con- nanodiamonds calculated from the lattice param-
cluded that the formation mechanism of nano- eters (3.527 g/cm3) with the experimental values
sized diamond is through coagulation of liquid of the helium pycnometric density of UDD, which

276
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FIGURE 33. A model for a diamond nanoparticle consisting of a


sphere of crystalline diamond with diameter dc, surrounded by a
layer of amorphous carbon with thickness ta. The resulting diameter
of the particle is d=dc+ta.

277
is 3.05 to 3.10 g/cm3. Their conclusion was that films were found to be almost free from oxygen
the difference between calculated (X-ray) and contamination, as can be seen in Figure 34.
pycnometric densities supports the liquid phase HeI (hν=21. 2 eV) and HeII (hν=40.8 eV)
model of nanodiamond formation. Moreover, the UV photoelectron spectroscopy measurements
authors168 suggested that diamond nanoparticles have been performed on the as-deposited and
formed by rapid crystallization are hollow spheres! hydrogen plasma-treated nanodiamond films.
They estimated from the density difference that Based on the UPS spectra (Figure 35), the energy
the cavity inside 4 nm particle should be 1.77 nm band diagram of nanodiamond has been proposed
in diameter. (Figure 36). The electron affinity χ of UDD films
was calculated using the emission width W and
the low kinetic energy cut-off in the experimental
Surface Properties UPS spectra (Figure 35): χ=hν-Eg-W.
Maillard-Schaller et al. investigated the sur- The emission width of the as-deposited sample
face and electronic properties of nanometer-sized was 15.0 eV with a low-energy cut-off at 3.1 eV,
diamond particles (UDD Ndp2) by X-ray photo- which results in a positive value of electron affin-
electron spectroscopy (XPS) and UV photoelec- ity of +0.7 eV, assuming that the band gap Eg=5.5
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tron spectroscopy (UPS).177 In these experiments, eV. After H2 plasma treatment, the samples showed
nanodiamonds were deposited on flat Si(100) an emission width of 15.9 eV with a very sharp
substrates by electrophoresis. Figure 34 shows low-energy cut-off at 2.1 eV, indicating a nega-
the XPS spectra of a nanodiamond powder film tive electron affinity of –0.2 eV (Figure 36).
on Si(100). According to the XPS analysis, the
UDD powder did not contain any detectable im-
purities except nitrogen. The N content was esti- Electrical Characterization
mated to be 1 to 2 at. %. The as-deposited UDD There are only a very few experimental re-
films showed a strong oxygen peak. After treat- ports on electrical and electronic properties of
ment in a hydrogen microwave plasma and trans- UDD. Some measured collective electrical char-
fer in air to the XPS system, the nanodiamond acteristics of powders and suspensions are given

FIGURE 34. Survey XPS spectra of the UDD film (a) before and (b) after the H2
plasma treatment. (Reprinted from Ref. 177, with permission from Elsevier Science.)

278
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FIGURE 35. HeI and HeII UPS spectra of as deposited and H2 plasma-treated
UDD surfaces. (Reprinted from Ref. 177, with permission from Elsevier Science.)

FIGURE 36. Energy band diagram of the hydrogenated nanodiamond powder film. (Re-
printed from Ref. 177, with permission from Elsevier Science.)

279
in Table 7. Gordeev et al. reported a resistivity for narrow line with δ=35.1 ppm as relating to
bulk nanodiamond composites obtained by press- diamond carbon, while the wide line with δ=34.2
ing UDD powders.178 Such materials have very ppm is caused by distortion of the tetrahedral
high porosity typically in the range 60 to 70 vol.%.178 coordination. The authors179 concluded that only
The room temperature resistivity of such UDD 30% of bonds in nanodiamond are nondistorted
composites was 1.2 × 109 W-m, consistent with the sp3 bonds, while the remaining 70% of carbon
resistivity reported by Dolmatov (Table 7). bonds are distorted but still with sp3 hybridiza-
Belobrov et al. reported results of studies of tion. For comparison, natural jewel-quality dia-
UDD powders with different surface modifica- monds have a characteristic chemical shift δ=50
tions by electron parmagnetic resonance and ppm.
nuclear magnetic resonance (NMR) spec- Zhirnov et al. characterized UDD particles
troscopies.179 An example of a nanodiamond EPR using electron field emission measurements by
spectrum is shown in Figure 37. The authors179 putting small a amount (0.2 µm in thickness) of
found that the nanodiamond EPR signal is inde- UDD on metal or silicon tips by electrophore-
pendent from the chemical modification of the sis.180,181 In these experiments, the field emission
nanodiamond surface. The g-factor for UDD was characteristics of tips with UDD coatings were
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found to be 2.0027(5).179 Belobrov et al. con- compared to characteristics of bare tips. The
cluded that the paramagnetic properties of the emission experiments showed that the emission
nanodiamond are determined only by the sp3 core characteristics differ significantly for different
of the diamond particle. UDD coating conditions. The different UDD
A 13C NMR spectrum for nanodiamond is coating conditions were obtained from one origi-
shown in Figure 38. According to the authors,179 nal UDD powder (marked as Nd) using different
the resonance line is assymetric and well de- physical and chemical treatments. The modifi-
composed into two Gaussian components, cations differed in concentration of impurities,
whose numerical values are presented in the pH of water suspension, and density as shown in
table in Figure 38. The authors interpreted the Table 9.180

FIGURE 37. Central part of the EPR spectrum of nanodiamond with the Li standard (g=2.0023).
The scan and the modulation are 50 and 0.01 mT (After Ref. 179, with permission from P.
Belobrov.)

280
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FIGURE 38. 13C spectrum for nanodiamond. The numerical values of chemical shifts, intensities, and line widths after
decomposition into Gaussian components are given in the table. (After Ref. 179, with permission of P. Belobrov.)

281
A summary of the emission characteristics characterize in isolation, due to their natural trend
for different UDD coatings is given in Table 10. to form agglomerates.
The emission characteristics of UDD are discussed Tyler et al. recently reported a new technique
in more detail in Ref. 180. An interesting result is for isolating individual nanodiamond particles by
the difference in the emission characteristics of depositing them on sharp (radius 10 to 50 nm)
UDD with modifications NdP and NdP1 (Figure metal tips by pulsed electrophoresis from alcohol
39). NdP1 was prepared using the heavier (bot- suspensions of UDD. Apparently, the very high
tom) fraction of the original NdP modification, electric fields near the sharp tips breaks the ag-
and the main difference between the two was the glomerates, and thus it is possible to manipulate
average crystallite size (larger for NdP1). This individual nanodiamond particles.182 Examples of
result indicates critical role of diamond crystal metal tips with nanometer-size diamonds are
size in the nanoscale regime on the emission prop- shown in Figures 15 and 40. The typical size of
erties of UDD-coated tips. diamond nanoparticle as measured in TEM was
about 3 nm (Figure 40). It should be noted that in
all cases only particles with faceted shapes were
Characterization of Isolated Nanodiamond observed.
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Particles More detailed information about the prepara-


At this point, most of reported results on char- tion procedure and results of characterization can
acterization of nanodiamond describe collective be found elsewhere.183,184 Preliminary results of
properties of multiparticle systems such as CVD field emission characterization of UDD reveal a
nanodiamond films, agglomerates of UDD, etc. considerable difference in emission behavior of
Such systems are composite materials, consisting single isolated diamond nanoparticle and multi-
of sp3-bonded diamonds often surrounded by particle nanodiamond thin film.184
amorphous carbon, sp2-bonded graphitic inclu-
sions, etc. Correspondingly, it is often difficult to
extract specific information about 3 to 6 nm pri- Nonclassical Fluorescence from
mary nanodiamond crystallites. Moreover, in some Diamond Nanoparticle
cases the properties of nanodiamonds can be A new area for physical experimentation with
modified due to the presence of surrounding ma- possible applications in advanced information pro-
terials. For example, the surface energy, and cor- cessing is the generation of light sources that are
respondingly shape of particles, is very sensitive able to emit individual photons on demand.
to their surroundings. The characterization of iso- Beveratos et al. investigated the quantum proper-
lated nanodiamond particles is an important but ties of the light emitted by diamond nanocrystals
challenging task. There are few reports of charac- containing a single nitrogen-vacancy color cen-
terization of isolated diamond particles 40 to 100 ter.185 The typical size of diamond particles used in
nm in size (see, for example, the next section). these experiments was 40 nm. According to the
However, the smallest nanodiamond crystallites authors, there are several very important optical
with a size of 3 to 6 nm are very difficult to properties of diamond nanocrystals that are impor-

282
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FIGURE 39. Current-voltage characteristics of Si tips with UDD coatings of the same
modification with different size of diamond crystallites: NdP and NdP1. (Reprinted from
Ref. 180, Copyright 1999, with permission from the American Institute of Physics.)

tant for their use as individual photon light sources. a diamond particle of a particular size, and possible
First, the subwavelength size of these nanocrystals shapes of a single nanodiamond particles. Although
renders refraction irrelevant. A nanocrystal can be in reality diamond nanoparticles contain functional
regarded as a point light source. Second, the very groups at the surface (Section III.B.2), the present
small volume of diamond excited by the pump analysis is restricted to hydrocarbon systems.
light yields very small background light. This is
very important for single photon sources.
By exciting nanodiamond crystals using a How Many Atoms Are in a Single ND
YAG laser (l=532 nm), the authors were able to Particle?
observe fluorescence with almost background- Plotted in Figure 41a is the number of atoms
free photon antibunching from single nitrogen- in a spherical diamond particle as a function of
vacancy centers in diamond nanocrystals at room particle size estimated from the formula:
temperature. The excited state lifetime in the bulk
is tb=11.6 ns. The measured lifetime in the 4
Ntot = πR3 , (5)
nanocrystals was 25 ns. The authors argue that 3V0
this lifetime modification is a quantum electrody-
namic effect.
where V0 = 5.667 Å3 is atomic volume in bulk
diamond. For example, a particle with a diameter
of 4.3 nm the equation yields about 7200 atoms,
3. Atomistic Simulations on Diamond
while a particle with diameter 10 nm is predicted
Clusters
to contain about 92,000 atoms.
Another important characteristic that influ-
a. Simulations of Diamond Clusters:
ences particle properties is the number of surface
Structural Properties
atoms. Assuming
Below we discuss two questions related to the
nS = ( n Bulk ) 2 /3 (6),
number of atoms, the fraction of surface atoms in

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FIGURE 40. Isolated nanodiamond particle on molybdenum tip.184

where ns and nbulk are surface and bulk atomic surface atoms that are not accounted for in Eq. 6,
densities, respectively, the following analytical which assumes a density of surface atoms equal
expression is often used to estimate the number of to that for a (001) facet. The number of surface
surface atoms in a spherical particle: atoms for a spherical cluster as a function of
cluster diameter taking into account surface
3 faceting is plotted in Figure 41.
N S / Ntot = (7)
4 Rn1Bulk
/3

What is the Shape of a Nanodiamond


It is possible to cut out a sphere of a given radius Cluster?
and count the number of atoms with a coordina- Until recently, most of the experimental work
tion number less than four at the surface of the dealing with nanodiamond produced by means of
sphere. The difference between the fraction of the detonation described the shape of clusters as be-
surface atoms evaluated this way and from Eq. 6 ing spherical (Section III.A.2.b). Indeed, HRTEM
can be as big as 2 to 2.5 times. This difference pictures of nanodiamond agglomerates resemble
arises from the presence of various surface facets spherical forms (Figure 42a) as well, as, for ex-
in the second method for counting the number of ample, nanodiamond clusters embedded in metal-

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FIGURE 41. Total number of atoms and the number of surface atoms in a spherical nanodiamond
particle as a function of particle size. Bottom image provides more details for smaller particles.

lic matrices after chlorination of metal carbide (111) facets and often possess chamfered edges
(Figure 23). However, recent HRTEM images of along certain directions (such as <110>) (Figure
a single nanodiamond cluster on the surface of a 42b). Multiply twinned nanodiamond particles
Mo tip clearly indicate the presence of facets at have had been observed in meteorites (Figure 16).
the particle surface, with the cluster resembling a The shape of a diamond cluster is inherently
polyhedral shape (Figure 15). This shape is simi- connected to its stability, which in turn depends
lar to that of microscopically sized diamond par- on the state of the surface atoms. Important fac-
ticles formed in the gas phase during a CVD tors that impact cluster stability include the pres-
process as first was reported by Matsumoto and ence of active groups on the surface of UDD
Matsui29 (Figure 42b). The typical habit of these particles after different types of purification treat-
clusters was regularly shaped cubo-octahedron ments, hydrogenation of the surface, and possible
and twinned crystals, that is, twinned cubo-octa- surface reconstructions on a bare surface that elimi-
hedron, an icosahedron and a decahedral-Wulff- nates (or at least reduces) the number of dangling
polyhedron. The particles have exposed (100) and bonds. As discussed in Section II based on ab

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FIGURE 42. TEM images of diamond clusters revealing different


shapes: spherical (a) shapes of nanodiamond particles (After Ref.
90, courtesy of G. Galli) and well-faceted diamond particles of
micron and submicron sizes (b). (After Ref. 29.)

initio simulations, bare diamond surfaces, con- Figure 43. Binding energies have been calculated
taining (111) planes undergo ‘buckification’,90,99–101 relative to systems with the same number of car-
that might be responsible for the observed spheri- bon atoms in bulk diamond and hydrogen atoms
cal shapes of diamond particles. Particles con- as H2 molecules. The results of DFT/LDA calcu-
taining (100) bare surfaces reconstructed in a lations by Kern and Hafner186 on energetics of
manner similar to bulk diamond surfaces.99–101 In reconstructed (001)(2 × 1):H and (111)(1 × 1):H
addition, relaxation and geometrical parameters diamond surfaces were used for the calculations
of hydrogenated nanodiamond surfaces were quite (summarized in Table 11). A dimer reconstruc-
similar to those of bulk diamond.99–101 Based on tion of all (100) diamond surfaces has been as-
these facts, we performed simple evaluations of sumed.
binding energies of hydrogenated clusters with The calculations suggest that a truncated oc-
different morphologies. tahedron cluster is more stable than a cubo-octa-
Results of binding energies of fully hydroge- hedron or a spherical cluster with the same num-
nated spherical, cubo-octahedron and truncated in ber of atoms (Figure 43a). As apparent from the
one direction octahedron clusters are plotted in figure, the difference in binding energy between

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FIGURE 43. Binding energies of hydrogenated diamond clusters as a function of particle size.
Binding energies calculated relative to systems with the same number of carbon atoms in bulk
diamond and hydrogen atoms as H2 molecules. LDA data186 (Table 11) on energetics of (001) and
(111) diamond surfaces are used for the calculations.

287
spherical and cubo-octahedron clusters is small, tron beam irradiation can even induce phase tran-
on the order of ~0.01 to 0.02 eV/atom (for a sitions, such as carbon onions to nanodiamond
comparison, the difference in cohesive energies structures and vice versa. Similarly, Ijima and
of bulk diamond and graphite is about 0.02 eV/ Ichihasi187 showed that at the nanoscale, the shape
atom). These results can be explained using simple of metallic particles is not necessarily constant
arguments about the relative fractions of surface because the energy of a nanoparticle shows many
atoms with favorable and unfavorable energies local minimum energy configurations, correspond-
for clusters with particular shapes. As follows ing to different structures. A gold particle ~2 nm
from Table 11, one-, two-, and three-coordinated in size that was exposed to strong electron beam
carbon atoms at a diamond surface have different irradiation with a beam intensity between 15 and
energies. Thus, a larger number of atoms with 80 amp/cm2 fluctuated between the cubo-octahe-
unfavorable on-site energies (such as, for example, dral, icosahedral, and single-twinned structures.187
twofold coordinated atoms at a (001) facet) would Although not quite realistic, energetic char-
result in lower cluster stability. Indeed, as illus- acteristics of all-carbon nonreconstructed diamond
trated in Figure 44, the fraction of two-coordi- clusters were evaluated using a bond order poten-
nated atoms (accordingly dimerized and hydroge- tial,188 which indicated stable relaxed diamond
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nated in a final structure) is larger for cubo-octahedron structures contrary to the first principle simula-
clusters, resulting in the greatest cluster stability tions. The results of these calculations indicated
compared with the spherical and octahedron struc- that cohesion energy, surface excess energies, and
tures. It should be noted that spherical clusters re- stiffness of spherical diamond clusters with
semble truncated octahedrons (Figure 45a) with nanoscale dimensions deviate considerably from
additional adatoms (for bigger clusters — atomic their macroscopic values. For clusters of 2.2 nm
islands) at the center of their facets and are interme- (1100 atoms) and 4.8 nm (104 atoms), the calcu-
diate shapes between octahedron and cubo-octahe- lated cohesive energy, was about of 95% and 99%
dron regarding the number of surface atoms with of the bulk value, respectively. From an analysis
nonfavorable energies. The fraction of atoms with of the asymptotic value of surface energy it was
three dangling bonds at the surface of a spherical concluded that the spherical surface possess pri-
cluster is relatively small (Figure 45a). An analysis marily a (100) character. Regarding stiffness, it
of their location at a surface of a spherical cluster was found that for clusters 2.2 nm and 5.8 nm
show that they do not have undercoordinated near- (2 × 104 atoms) in diameter the stiffness was about
est neighbors with which to form a (2 × 1) surface 92% and 99% of the bulk value, respectively.
reconstruction. Thus, singly coordinated atoms would A current conclusion is that hydrogenated all-
be rather etched or terminated by three hydrogen diamond clusters are the most energetically pref-
atoms. In general, from the analysis above, it can be erable forms, especially octahedrons and partially
concluded that the most stable shape of a fully hy- truncated octahedrons. Starting with CH 4 ,
drogenated diamond cluster is that with the maxi- adamante (C10H8), etc., all hydrogenated diamond
mum number of ‘energetically favorable’ surface clusters are mechanically stable.
atoms, for example, hydrogenated atoms with three In contrast, if the (111) surface of a
carbon atoms as neighbors. The octahedron or slightly nanodiamond particle is not hydrogen terminated,
truncated octahedron cluster are primary candidates the resulting structure would be an encapsulated
satisfying this condition. fullerene at small particle sizes and ‘bucky dia-
Due to the very small difference in stability mond’ with a diamond core and fullerene-like
between different carbon structures, it can be also outer shell91,99–101 (Figure 45c). Buckification has
expected that excitation (for instance, by an elec- been observed for spherical particles at least up to
tron microscope) may be sufficient to induce tran- 3 nm in diameter.91 The authors91 performed ab
sitions in particle shape. This may be the primary initio calculations using the GGA density func-
reason that different shapes of diamond clusters tional for the smallest size clusters, and a
such as spherical (Figure 42a) or faceted (Figure semiempirical tight-binding Hamiltonian for sys-
15) are observed. As discussed in Section II, elec- tems up to 3 nm (2425 atoms) in diameter. Both

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FIGURE 44. Fractions of one-, two-, and three-coordinated surface atoms


(relative to the total number of surface atoms) for cubo-octahedron (a), spherical
(b), and truncated in one direction octahedron clusters (c) as a function of
number of atoms in a cluster.

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FIGURE 45. Structural models of nanodiamond clusters. Spherical (a) or polyhedral (b) (cubo-octahedron) shapes
with all four-coordinated carbon atoms can be preserved if the cluster surface is terminated by hydrogen. Two-
coordinated atoms on the surface of a spherical cluster are dark colored (a). This illustrates that a spherical cluster
represents truncated octahedron with several adatoms in the center of its (001) or (111) facets. Bare surface of
nonhydrogenated diamond clusters experience surface reconstruction resulting in a cluster with a diamond core and
a fullerene-like shell(c) (courtesy of Guilia Galli90).

methods gave similar structural models for the spectra of nanodiamond agglomerates.90 The pre-
smallest cluster sizes, indicating validity of the edge signal of the nanodiamond spectra differs
results for structures of larger clusters obtained significantly from those of diamond and graphite
with the tight-binding method. According to Ref. and exhibits a characteristic 2-peak feature re-
91, starting from ideally terminated diamond par- sembling that of a buckyball and C70. These
ticles, the reconstruction occurs spontaneously at nanodiamond peaks had been interpreted as the
low temperature. The barrier between the ideal signature of a mixture of pentagons and hexagons
surface structure and the reconstructed surface is on the reconstructed surface of the diamond core.
size dependent and increases as the size of the
cluster is increased, achieving a value of the order
of several tens of eV for the largest clusters as b. Simulations of Diamond Clusters:
found in bulk diamond.189 It is interesting to de- Electronic Properties
fine the critical size, when diamond clusters will
have an all-diamond structure (probably with re- Relationships between various electronic prop-
constructed (111) surfaces forming Pandey chains erties and cluster size were explored with a self-
similar to bulk diamond surfaces). consistent environment dependent tight-binding
In support of their fullerene-like structural (SCEDTB) model with the C-H terms fit to first
model, the authors provide an X-ray absorption principles electronic structure results for ethane,

290
methane, benzene, and hydrogenated <111> and eV for the largest cluster examined (913 carbon
<100> diamond surfaces.191 Plotted in Figure 46 atom; ~2 nm diameter), which leads to the con-
is the density of states for four diamond clusters clusion that any band gap size effect is insignifi-
and for bulk diamond. The bulk density of states cant for cluster sizes larger than about 2 to 2.5
is shifted by the averaged Coulomb potential due nm. Minor deviations from the bulk spectrum for
to the surface dipole layer (cf. Figure 47) experi- the largest cluster are due mainly to the presence
enced by carbon atoms in the cluster. All four of hydrogen states and not to the finite dimen-
clusters demonstrate a size dependence of the sions of the cluster. This result apparently dis-
band gap (Figure 48). Dimensional effects are agrees with indirect X-ray measurements, which
most apparent with respect to the states in the indicate that in a 3.6-nm cluster the conduction
valence band; the highest-occupied molecular band edge position is 1.2 eV above the conduc-
orbitals for the 34 and 161 atom clusters lie ap- tion band edge for bulk diamond.170 At the same
proximately 2.5 eV and 1.25 eV, respectively, time, however, the results are consistent with re-
below the bulk valence band edge. At the same cent ab initio calculations90 (Figure 48b). De-
time even for the smallest cluster the energy of pending on the simulation approach, the authors
the lowest-unoccupied molecular orbitals coin- conclude, the band gap for diamond clusters ap-
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cide with the bulk conduction band edge. This proaches that for bulk diamond at cluster sizes of
result can be intuitively expected because the states about 2 nm according to Quantum Monte Carlo
with higher energies and smaller wavelengths are calculations, and about 1 to 1.2 nm according to
less sensitive to the dimensions of the system. density functional calculations using the general-
Dimensional band gap widening is less than 0.4 ized gradient approximation.90 According to the

FIGURE 46. Electronic density of states for the four clusters with a truncated octahedron shape (histogram) and for
bulk diamond (solid line). The histogram at the bottom of the pane (a) is a spectrum generated from density functional
theory. (After Ref. 191.)

291
FIGURE 47. Coulomb potential distributions for the nanodiamond clusters\plotted along the <100> and <111>
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directions passing through the centers of mass of the clusters. Octahedron clusters are truncated along the <001>
axis and contain 34 (a), 161 (b), 435 (c) and 915 carbon atoms (d), correspondingly. (After Ref. 172.)

FIGURE 48. Band gap vs. cluster size for fully hydrogenated diamond clusters calculated with a SCTB model190 (a),
and DFT /GGA (generalized gradient approximation) and DFT/TDLDA (time dependent LDA) methods90 (b). In
Figure 48b the HOMO-LUMO gaps are indicated by triangles. The dashed line indicates the bulk (indirect) gap
calculated with DFT/GGA. Open circles correspond to calculations with TDLDA.90 The fact that for larger clusters
the band gap is lower than that for the bulk structure is due to a stress effect induced by hydrogen on the surface.90
The bulk band gap calculated with the SCTB approach (a) is 5.5. eV.

292
results on X-ray adsorbtion and emission experi- dependent tight binding calculations191 are plotted
ments, no appreciable changes in band gap is in Figure 47. The main feature of the potential
observed for nanodiamond clusters with sizes distribution is a sharp rise at the cluster surface
exceeding 2 nm.90 produced by hydrogen termination. Cluster size
Illustrated by Figure 49 are electronic proper- effects are apparently only significant for the
ties of carbon nanoclusters with highly distorted smallest cluster. For the larger clusters the calcu-
bonds (consisting completely of 5 to 7 rings) as lations predict that the potential inside the cluster
well as clusters with sp2/sp3 bonding. According does not change appreciably with increasing clus-
to the figure, the band gap becomes filled with the ter size. In conjunction with the spectra plots the
presence of sp2 bonding. potential rise at the boundary gives a -1.4 5 eV
Coulomb potential distributions for the clus- electron affinity of the hydrogenated <111> sur-
ters obtained with the self-consistent environment face. This value is close to the experimentally
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FIGURE 49. Density of states of two nanocarbon clusters with highly disordered
sp3 bonds (a) as well as with mixed sp2/sp3 bonding (b). Clusters contain 435
carbon atoms. (After Ref. 190.)

293
measured electron affinity,192 while density func- unless some assumptions related to particular struc-
tional theory usually overestimates experimental tures are made. Below we compare the mechani-
values by ~0.6 to 0.8 eV.193 cal properties of these two materials at equal condi-
One of the major focuses in nanoelectronic tions, assuming that it is possible to make diamond
applications of nanodiamond is the possibility of nanorods, and briefly discuss the routes for syn-
n- and p-type doping of the clusters. Recent first thesis of one-dimensional diamond.
principles calculations addressed the structural When extrapolating the mechanical proper-
stability of nanodiamond clusters doped with B, ties of carbon nanotubes to the macroscale, an
N, and P in substitutional positions.194,195 Small ambitious assumption has to be made regarding
hydrogenated diamond clusters (a few tens of their wall thickness; it is usually assumed to be
C atoms) containing B, N, or P atoms in the center equal to the interplanar spacing of graphite. At the
maintained the diamond lattice during relaxation. nanoscale, an unambiguious characteristic of
For future research, it would be interesting to strength would be maximum force before failure
evaluate substitutional energies of different for a given structure, rather than maximum stress.
dopants in the subsurface positions vs. position in At least, it would be a useful characteristic for
the inner parts of nanoparticles, as well as their comparison of fiber-like nanostructures from dif-
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diffusional properties. Another interesting issue ferent materials with similar diameters. For this
would be the difference in dopant behavior in force–based definition of a nanostructure strength,
nanoclusters as compared to that in bulk diamond Figure 50 illustrates the dependence of fracture
when well with diamond surfaces at the load vs. diameter for single wall nanotubes and
macroscale. diamond nanorods for three orientations, corre-
A major conclusion of the studies of elec- sponding to the low-index axis (<111>,<110>,
tronic properties of nanodiamond clusters is that <100>).196 The calculations for nanotubes were
quantum confinement effects disappear at cluster done using ideal strength values for graphene
sizes larger than approximately 2 nm, in contract sheets from ab-initio pseudopotential total energy
to silicon and germanium clusters where quantum calculations within the local density approxima-
confinement effects persist up to 6 to 7 nm clus- tion228 (values are summarized in Tables 12 and
ters.90 A practical realization of the size depen- 13). Similar strength values for different diamond
dence of quantum confinement effects in ND clus- orientations were obtained by the same authors197
ters is likely difficult because of the very small and by similar techniques,198 so all the input pa-
cluster size (below ~1000 atoms for 2 nm cluster). rameters for the evaluations are self-consistent.
In addition, according to the size distribution func- Fracture forces are evaluated for MWNTs with a
tion of the UDD particles, only a small fraction of variable outer diameter and a fixed inner diameter
the clusters is produced with a 2 nm diameter. of 4 nm, which corresponds to typical experimen-
tal values.39
The results of Figure 50 demonstrate that at
c. Diamond Nanorods small diameters, carbon nanotubes are stronger than
diamond rods because of the superior strength of
Would Diamond Nanorods be Stronger the single bonds in graphene over those in diamond
than Fullerene Nanotubes? (Table 13). However, as the load-bearing area and,
correspondingly, the number of bonding sites in-
Diamond was always considered the stron- creases with diameter, the diamond rods become
gest material in the macroscopic world until the stronger than SWNTs. The corresponding critical
extreme mechanical properties of carbon diameters for the three orientations of diamond
nanotubes were discovered (Table 13). After that nanorods are summarized in Table 13. While the
discovery, numerous papers claimed that carbon strength of SWNT increases linearly with diam-
nanotubes were the strongest material. It is diffi- eter, the strength of nanorods grows as the square
cult to make a fair comparison between two rep- of diameter. Figure 50 also illustrates that the
resentatives from the macro- and nano-worlds strength of a MWNT is comparable to that of a

294
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diamond rod oriented in the <100> direction and for synthesis, molecular modeling has been used
exceeds those for <111> and <110>-oriented to explore structures and to characterize binding
nanorods. Although the load-bearing properties of energies for several example diamond nanorod
MWNTs are quite impressive, in practical applica- configurations illustrated in Figure 51a.196 Plotted
tions, special precautions must be taken to exploit in Figure 51b are energies as a function of the
this property. Experiments by Yu et al.249 have hydrogen-to-carbon ratio for the four diamond
shown that when clamps of a particular kind are nanorods illustrated in Figure 51a, calculated with
applied to the outermost shell of a tensile loaded the bond-order analytic potential.218 Also plotted
MWNT, failure occurs only in the outermost shell. are energies for (17,0) nanotubes of finite length
This result suggests little load transfer between the whose ends have been hydrogen terminated. The
outer shell and inner shells, and therefore the inner energies reported are relative to systems with the
shells do not contribute to the load bearing cross- same number of carbon and hydrogen atoms in
sectional area of the system. Because of the integ- graphite and as H2 molecules, respectively. For
rity of diamond rods, this problem is absent from large carbon-to-hydrogen ratios, the diamond
the structures. It was also shown196 that by no nanorods and the single-walled fullerenes are
means do carbon nanotubes posses the highest roughly comparable in binding energy, while for
strength-to-weight ratio. small ratios the sp3-bonded structures are ener-
To futhur explore whether diamond nanorods getically favored, in agreement with a previous
represent an important and viable target structure analysis of carbon-hydrogen clusters (Section II).

295
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To explore the size dependence of the Atomistic simulations196 indicate that diamond
Young’s modulus of diamond nanorods, the nanorods represent an important and viable target
second derivative of strain energy in the system structure for synthesis. Given the number of meth-
was been calculated196 as a function of strain ods that have been used to produce covalently
for a nanorod of 1.4 nm in diameter (Table 13). bonded whiskers, the prospects for synthesizing
This value is an unambiguious characteristic diamond nanorods appears to be very promising.
and can easily be converted to Young’s modu- For example, impressive results have been
lus (see Section III.B.2 below). While an aver- achieved in the growth of β-SiC nanorods and
age value of the second derivative of strain whiskers with radii as small as 10 nm. Synthesis
energy is similar to that of bulk diamond, the has been accomplished by a number of methods,
strain energy changed in a different manner for including hot filament chemical vapor deposi-
subsurface carbon atoms and those in the rod tion,219 laser ablation,220 reduction-carburization,226
center. The ‘strengthening’ of the atoms in the and sol-gel reactions followed by carbothermal
rod center (Table 13) had been observed Ref. reduction of xerogels.267 However, as described
196. in Section III.A.1, aligned diamond whiskers have

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FIGURE 50. Fracture force as a function of diameter for different one-dimensional carbon
structural components: diamond nanorods with different crystallographic orientations, SWNTs
and MWNTs. The types of nanotubes correspond to those with a zigzag arrangement of
atoms. In the case of MWNTs, the outer diameter is a variable and the inner diameter is
assumed 4 nm for all MWNTs. (After Ref. 196.)

FIGURE 51. Illustrations of representative diamond nanorods (a). Binding energies given by a bond-order potential
as a function of hydrogen-to-carbon ratio (b). Energies were calculated using a dimer reconstruction for all surfaces
with structures corresponding to the (100) diamond surface. Open triangles: diamond nanorods. Solid circles: (17,0)
nanotubes of different lengths whose ends are hydrogen terminated. (After Ref. 196.)

297
been formed so far only by a ‘top down’ approach tous carbon;203 this method is based on the de-
using air plasma etching of polycrystalline dia- composition of carbon-containing gases on metal
mond films, particularly of as-grown diamond catalysts at reaction temperatures below 1000oC.
films and films with molybdenum deposited as an Arc discharge and laser ablation methods are based
etch-resistant mask.33 In addition to the ‘top-down’ on the condensation of carbon atoms generated
methods of diamond nanorod synthesis, direct from the evaporation of solid carbon sources. The
conversion of carbon nanotubes to diamond evaporation temperature involved in these pro-
nanorods might be also considered. It is known cesses is close to the melting temperature of graph-
that carbon onions can be converted to structures ite, 3000 to 4000oC. The multiwall nanotubes
containing nanodiamond cores under MeV e-beam reported by Iijima13 in 1991 were produced by an
irradiation93 or ion beam irradiation.123 So far, arc-discharge method. Before the discovery of
electron beam induced formation of amorphous nanotubes, both arc discharge and laser ablation
carbon nanorods 10 to 20 nm in diameter from techniques had been used to produce fullerenes,
CVD-deposited carbon nanotubes has been real- but the optimal conditions to produce fullerenes
ized in situ under HRSEM.268 Similarly, it has is different that the optimal conditions required to
been observed that carbon nanotubes can be trans- produce nanotubes. In 1985 Smalley and col-
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formed into amorphous carbon rods under irra- leagues 12 reported that they had produced
diation with an Ar ion beam.269 fullerenes by a laser vaporization method. The
Interestingly, diamond rods with diameters as chronology of the major events in the synthesis of
small as 10 µm and several hundred micrometers nanotubes and fullerenes is summarized in Table
long were fabricated by a variety of techniques 14.
back in the 1960s.270–272 The monocrystalline rods In an arc-discharge, carbon atoms are evapo-
were grown epitaxially on diamond seed crystals rated by a helium plasma generated by high a
from a gaseous phase under low pressure condi- current between the anode and cathode. This
tions in the presence of a Ni, Fe, or Mn catalyst.270 method can produce both high-quality MWNTs
Diamond whiskers were also grown in an elec- and SWNTs (Figure 52). Growth of MWNTs by
tron microscope on the sharp edges of diamond or this method does not require, in principle, a cata-
other dielectric crystals under electron beam irra- lyst.39,204 MWNTs can be obtained by controlling
diation from carbon-containing residual gases at the growth conditions such as the pressure of the
low pressure.271 Diamond whisker growth in a inert gas (optimal for MWNT ~500 Torr, for C60–
metal-carbon system at high pressures and tem- below 100Torr39) and the arc current. The synthe-
peratures conditions was also reported.272 sized MWNTs typically have a length on the
order of 10 µm and diameters in the range of 5 to
10 nm. They typically form tight bundles, but
B. Carbon Nanotubes nanotubes themselves are very straight. The puri-
fication of MWNTs can be achieved by heating
1. Synthesis and Properties as-grown material in an oxygen environment.
While a standard arc-evaporation method pro-
Synthesis and properties of nanotubes are duces only multilayered nanotubes, the addition
topics comprehensively addressed in a variety of of metals such as cobalt to the graphite electrodes
books.39,199–203 Below we provide a brief summary results in extremely fine nanotubes with single-
of these topics. layer walls.47,48 The optimization of SWNT growth
There are three most commonly used meth- was achieved using a carbon anode containing
ods to produce carbon nanotubes: arc discharge, yttrium and nickel as a catalyst.204
laser ablation, and chemical vapor deposition. An alternative method of growth of high-
There are also several nontraditional methods that quality SWNTs in large quantities was suggested
have been developed (discussed, for example, in in 1996.49 Like the original method of preparing
Ref. 39, 224). CVD methods have been used for C60, this involved the laser vaporization of a graph-
at least 4 decades for the production of filamen- ite target containing a small amount of catalyst

298
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and resulted in a high yield of single-walled nanoparticles formed on a support substrate such
nanotubes with unusually uniform diameters. as alumina. For MWNT growth, mostly ethylene
These highly uniform nanotubes had a greater or acetylene is used as a hydrocarbon feedstock,
tendency to form aligned ropes than those pre- and the growth temperature is typically in the
pared using arc evaporation. The ropes consist of range of 550 to 750oC.204 There are the same
tens of individual nanotubes close-packed into typical catalytic metals (iron, cobalt, nickel) for
hexagonal crystals. The initial experiments indi- the CVD process, as for laser ablation and arc
cated that the rope samples contained a very high discharge methods. The drawback of the CVD
proportion of nanotubes with a specific armchair growth of MWNT is the high defect density, a
structure, but later other types of SWNT were problem that still needs to be addressed.204 Re-
grown. SWNTs grown both by laser ablation and cent progress in the fabrication of MWNT using
arc discharge typically contain by products of the catalytic CVD method shows that narrow
fullerenes, graphitic polyhedrons with encapsu- diameter double and triple walled nanotubes can
lated metal particles, and amorphous carbon par- be grown with high yield.210 Growth of bulk
ticles or overcoatings on SWNT walls. A widely amounts of SWNTs with a high degree of struc-
used purification method developed by Smalley tural perfection was enabled by a CVD method204
and co-workers207 involves refluxing the as-grown using an appropriate catalyst, a temperature range
SWNTs in a nitric acid solution for an extended of 800 to 1000oC, and preferably methane as the
period of time. carbon feedstock. Optimization of the catalyst to
The CVD growth process involves heating a grow highly aligned SWNTs nanotubes is de-
catalyst material to high temperatures in a fur- scribed in Ref. 204. The maximum length of
nace and flowing a hydrocarbon gas through the individual SWNTs grown by this method is 150
reactor (Figure 52). The key parameters of the micrometers.204 The SWNT produced can be
CVD nanotube growth are the hydrocarbons, separated from the support material by acidic
catalysts, and growth temperature. The catalyst treatment. The high interest in CVD nanotube
species are typically transition-metal growth is also due to the fact that aligned and

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FIGURE 52. Schematic representation of the experimental setup for the three most common
methods of nanotube growth (adapted from Ref. 204). Type of nanotube grown (MWNT or
SWNT), necessity to use a catalyst, as well as the possibility to grow fullerenes by the same
method are also specified. Available data on nanotube yield are also provided.

ordered nanotube structures can be grown on substrates make catalytic CVD the method of
specific growth sites of prepatterned substrates choice for nanotube device development.
with control that is not possible with the arc To illustrate how the diameter of the nanotubes
discharge or laser ablation techniques.204 Thus, depends on the method of growth and specific
using the CVD method in combination with growth conditions, we refer the reader to Table 15
microfabrication techniques, individual SWNT (adapted from Ref. 205). On the basis of the
can be integrated into nanotube-based electronic analysis of experimental data in the literature,
and chemical-mechanical devices that are func- summarized in Table 15, the authors205 concluded
tional on the molecular scale. The relatively low that the majority of the catalytic mechanisms un-
temperatures of the process and the ability to derlying the formation of various nanocarbon
pattern the catalyst material directly on device deposits on catalytic substrates include some com-

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mon steps. A thermodynamic analysis of carbon SWNTs with identical diameters and chirality.
nucleation on the metal surface demonstrates that The precursor material for SWNT growth con-
a variation of the reaction parameters, such as the sisted of a heterostructure composed of alternate
temperature and the nature of the metal catalyst layers of buckyballs and thermally evaporated
and promoters, can lead to the formation of differ- nickel that resulted in very small nucleation sites
ent carbon deposits, such as filamentous carbon, and subsequent self-assembly of the SWNT crys-
multiwall nanotubes, or single-wall nanotubes. tals. Even more recently,32 long nanotube strands,
As an opposite extreme to the challenge of up to several centimeters in length, consisting of
growth of an individual nanotube at a predeter- aligned SWNT were synthesized by the catalytic
mined site, the synthesis of large uniform and pyrolysis of n-hexane with an enhanced vertical
ordered micro- and eventually macrostructures of floating technique. The long strands of nanotubes
SWNTs has been pursued rigorously. Recently, were assembled from arrays of nanotubes, which
the self-assembly of single crystals of SWNTs were intrinsically long.
using thermolysis of nanopatterned precursors has The industrial capacity for the production of
been reported.51 Micrometer-sized crystals of carbon nanotubes is steadily increasing. Informa-
SWNTs were composed of arrays of thousands of tion on leading commercial suppliers of carbon

301
nanofibers and nanotubes is provided in Ref. 224. tail in a later section. Depending on their precise
As a particular example of services provided by structure, nanotubes can be either metallic con-
one of the current SWNT suppliers, we refer the ductors or semiconductors. The semiconducting
reader to Carbon Nanotechnologies, Inc, (CNI) nanotubes are of two types: one has a band gap of
Texas. In addition to the production of SWNTs a few hundredths of an electron volt, while others
(in the CNI case, by laser ablation method), the have about a 1-eV band gap depending on the
list of services provided by the vendors includes radius. Ropes have been measured with a resistiv-
derivatization of end-of-tube and the sidewall of ity of 10–4 ohm-cm at 300 K,49 making them the
nanotubes, which is important for modifying physi- most conductive fibers known. Individual
cal properties, cross-linking, and enhancing solu- nanotubes have been observed to conduct elec-
bility and dispersion; enabling technology for end- trons ballistically, for example, without scatter-
use applications such as cutting, alignment, ing, with coherence lengths of several microns.211
dispersion, solubilization, and wrapping with poly- In addition, they can carry the highest current
mer surfactants. density of any known material, measured212 as
In general, major challenges in nanotube high as 109 A/cm2. Quantum conductance of
growth remain the ability to gain control over the SWNTs has been reported213 as well as their in-
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nanotube chirality and diameter, and the ability to trinsic superconductivity.214 Selected properties
directly grow semiconducting or metallic of SWNTs are summarized in Table 16.
nanotubes from and to any desired sites.204
There is a long list of unique properties of
nanotubes that make them one of the most impor- 2. Mechanical Properties of Carbon
tant structural and functional materials for Nanotubes
nanotechnological applications. One of the strik-
ing features of nanotubes is their combination of The mechanics of carbon nanotubes is a topic
widely variable electronic properties and extreme of very intensive research as confirmed by the
mechanical properties. These are discussed in de- number of excellent reviews published within the

302
last year.221–225 The focus of much of the research uniformity of a material and is defined as a mate-
has been on properties of individual NTs, such as rial property (a characteristic intrinsic to the
their Young’s modulus, bending stiffness, buck- material independent on specimen geometry). As
ling criteria, tensile and compressive strength. the specimen size diminishes, the discrete struc-
Advanced mechanical properties of nanotubes are ture of the material can no longer be homog-
important in projected applications such as enized into a continuum. As has been pointed out
nanoelectromechanical systems, nanosensors, by Yakobson et al.,221 if one considers graphene
nanocircuits, drug delivery devices, and reinforc- as a two-dimensional material, a MWNT should
ing structures in nanocomposites.223–225 Recently, be considered as an engineered structure com-
a super-hard bulk material consisting solely of posed of rolled graphene sheets rather than a
nanotubes has been created, suggesting that mac- material. However, the definition of material-like
roscopic structures consisting exclusively of characteristics, such as Young’s modulus, never-
nanotubes might be possible.51 theless has been applied to nanotubes when con-
Below we summarize experimental and theo- sidering their application as an engineering mate-
retical data reported to date on two important me- rial. Below we consider in more detail the
chanical characteristics of nanotubes, their Young’s discrepancy between Young’s modulus calculated
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modulus, and tensile strength. There is a surpris- by two means, both of which originate in con-
ingly wide variation within the measured and pre- tinuum mechanics, that do not contradict one
dicted values of these properties. For example, there another if applied to macroscale materials, but
is fivefold variation in measured properties of give a fivefold difference in predicted Young’s
SWNTs and a 40-fold variation in the predicted modulus of nanotubes. This result has been pointed
fracture strengths of SWNT.227,228 To a large extent, out by Yakobson et al. by applying a shell model
this discrepancy can be attributed to the fact that to carbon nanotubes235 that served an otherwise
definitions characterizing macroscopic material be- very useful role in predicting of buckling behav-
havior under load should be used with caution in ior of nanotubes. This is probably the most strik-
describing nanometer-scale objects. To address this ing inconsistency in the application of continuum
important issue, the area of nanomechanics is emerg- mechanics approaches to the nanoscale.
ing as a new discipline that describes the behavior of
materials and structures at the nanoscale.221–223 New
mechanical characteristics that are different from Yakobson’s Paradox
those used in conventional continuum mechanics
will likely be defined to describe the deformation Calculating a Young’s modulus is straight-
behavior of nanostructures in the near future. De- forward if the potential energy functions describ-
pending on the demands of applications taking place ing interatomic interactions are known. The cal-
solely at the nanoscale (in contrast to macroscopic culations involve the second derivative of the
applications in composites, for instance), mechani- strain energy with respect to the applied strain:
cal characteristics might be introduced along with
materials characteristics that depend on a specimen’s 1  ∂2 E 
Yb = (8)
geometry. This issue has been partially addressed in V  ∂ε 2  ε = 0
the Section III.A.3.c on the comparison of the frac-
ture strengths of carbon nanotubes and hypothetical
diamond nanorods and is briefly touched on in the where V=Sh is the volume of the object, h in the
discussion of the fracture strengths of nanotubes. object’s thickness, and S is the surface area of the
nanotube at zero strain. The value of ∂2E/∂ε2 is a
unique characteristic independent of the structure
a. Young Modulus of Nanotubes or material under consideration. The average value
for nanotubes obtained from recent first principle
The definition of Young’s modulus relies on simulations is 56 eV/atom and that of graphite is
the continuum hypothesis that assumes spatial 57.3 eV/atom (Table 17).229 For simulations using

303
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many-body interatomic potentials, the value of axial and circumferential directions of a shell.
∂2E/∂ε2 is comparable.221 Assuming h=0.34 nm Using the shell model, a wide variety of shell
(the interplanar distance in graphite), the calcu- buckling behavior, particularly critical strains or
lated Young’s modulus of nanotubes with Eq. 6 curvatures vs. applied load such as compression,
using first principles data 229 are slightly lower bending, torsion can be predicted. Molecular dy-
than that of graphite (1030 GPa). This value is namics simulations of transformations of shapes
comparable to the lowest reported experimental of SWNTs subject to large nonlinear deforma-
values of SWNT extracted from data on thermal tions demonstrated remarkable agreement with
oscillations and bending tests, which are about tube buckling behavior predicted from the shell
1.2 to 1.3 TPa,233,234 where the same assumption model.235 The only material parameters required
on the tube thickness had also been made in the in the shell model are in-plane stiffness C,
corresponding expressions for the thermal vibra- Poisson’s ratio ν, and the flexural rigidity D that
tions amplitude and for the nanotube deflection can be obtained from first principle simulations.
under bending used to extract the Young’s modu- The simulation of the axial tension of a nanotube
lus. provides values for Poisson’s ratio ν and the in-
The contradiction with the values reported plane stiffness C
above appears when the Young’s modulus of
SWNT and wall thickness are estimated from the 1  ∂2 E 
C= (9a)
in-plane stiffness and flexural rigidity calculated S  ∂ε 2  ε = 0
in the shell model,235 where a SWNT is approxi-
mated by a continuum isotropic shell. The defor-
mation energy of a nanotube is a function of in- The flexural rigidity, the dependence of the strain
plane strain ε and the changes of curvature k in the energy on its curvature, D can be calculated from

304
a comparison of strain energy U of tubes of dif- of Y is valid, the Young’s modulus would unam-
ferent diameters d: biguously be recovered as:

D = Ud 2 / 2 (9b) ρb ∂ 2 E
Y= (11)
m ∂ε 2
Recent first principles-based estimations229 pro-
vide D=3.9 eVÅ2/atom and show no dependency where ρb is the bulk density and m is the mass of
on tube chirality. The in-plain stiffness for dif- the atom. First principles Y values for SWNT
ferent types of nanotubes are given in Table 17. ropes are of the order of ~1 TPa (Table 18).
As we can see so far, the nanotube thickness is Thus, there is an interesting situation in the
not involved in the estimations of C and D in the application of the continuum shell model to tubu-
shell model. On the other hand, a continuum lar nanostructures. On the one hand, the descrip-
shell can be assigned the modulus Ysh and the tion of nanotube characteristics within the shell
thickness h unambiguously, to formally match model is intrinsically self-consistent and is very
the ν, C and D: useful for predicting tube buckling behavior. On
the other hand, there is remarkable discrepancy
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C = Ysh h , (10a) between the Young’s modulus of SWNT recov-


ered from the shell model and that corresponding
Ysh h 3 to SWNT ropes or graphite. To avoid this prob-
D= (10b)
12(1 − ν 2 ) lem, Ru236 proposed an intrinsic bending stiffness
for carbon NTs in order to decouple the bending
shell stiffness of NTs from their ill-defined effec-
Using the first principles parameters reported tive thickness and to ensure a consistent use of the
above for C and D and a first principle’s Poisson classic shell theory (i.e, shell thickness — only
ratio ν=0.15,229 the shell Young modulus would for shell theory).
be 3.86 TPa (~5 TPa with an analytic potential for At present, theoretical issues on the Young’s
describing interatomic interactions) and with a modulus of nanotubes can be summarized as fol-
shell thickness h=0.9 Å. These values differ sig- lowing.221,229,236
nificantly from those reported above. Based on
this discussion, these questions remain until we 1. The elastic properties of a cage graphite
can apply a material definition to an atomically structure can be characterized unambigu-
thick structure, as well as on limitation of the ously only by its in-plane and flexural rigid-
applicability of Eq. 10 to nanostructures. ity parameters (Eq. 9), both of which can be
The in-plane stiffness C is an unambiguous calculated from first principles.
parameter, and considering only axial tension, 2. Using these rigidity parameters (and Pois-
according to Eq. 8a and h can take any values son ratio), SWNT buckling behavior can be
satisfying . If we assume h=0.34 nm, the resulting predicted very well from the macroscopic
Young’s modulus of a SWNT will be of the order shell model, as confirmed by atomistic simu-
of ~1 TPa using the first principles in-plane stiff- lations.
ness value.229 It should be noted that for nanotubes 3. Using rigidity parameters, the shell Young’s
with diameters less than 0.68 nm (doubled modulus and shell thickness can be defined
interplanar space in graphite), using h=0.34 nm unambiguously (Eq. 10). Currently, the fact
makes no sense, although in many articles this is that these characteristic are inconsistent
value is used for estimations of Y for nanotubes with Young’s modulus and thickness of 3-D
of any diameter. Nanotubes with small radii in materials such as SWNT ropes and MWNTs
principle should be considered as rods with corre- and therefore are attributed only to the shell
sponding cross-sectional areas.230 model for understanding its high resilience.236
For SWNT ropes, which are a three-dimen- 4. If cage structures are distributed statistically
sional material and therefore the classic definition uniformly over a large cross-sectional area

305
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306
(as SWNT ropes or MWNT with relatively ting. The theory links interatomic potentials and
big radius), the bulk Young’s modulus can atomic structure of a material to a constitutive
be recovered unambiguously (Eq. 4). model on the continuum level. Reported Young’s
5. An appropriate estimation of the bulk moduli are within the range 500 to 700 GPa,
Young’s modulus of a SWNT cannot be depending on the type of the interatomic potential
made using Equations 9 and 8a due to the used in the calculations. These values are some-
uncertainty of nanotube bulk density or an what lower than those obtained from first prin-
arbitrary geometrical thickness, respectively. ciples or pure atomistic simulations with analytic
Nevertheless, by convention, h=0.34 nm is potentials.
usually presumed so that calculated results
on in-plane rigidity of SWNTs are reported
in terms of Young’s modulus. Experimental and Theoretical Young’s
6. Experiments addressing the Young’s modu- Modulus for CNTs
lus of SWNT (Table 18) use analytical ex- Currently, measured Young’s moduli of CNTs
pressions relating measured values and are typically of the order of 1.0 to 1.3 TPa (Table
Young’s modulus. An assumption on SWNT 18), and those predicted from first-principle simu-
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wall thickness is also required in these esti- lations are of the order of 1 TPa (Table 19).
mations, and it is assumed to be 0.34 nm. However, the maximum observed and predicted
values are up to 5 Tpa, which is probably an
Within the above summary, questions still artifact in the experimental measurements and the
exist such as, for example, when can a MWNT be Young’s modulus for the shell model in the theo-
considered a ‘bulk’ material so that the Eq. 4 can retical analysis as discussed above.
be applied. For example, Govindjee and A number of experimental methods have been
Sackman237 considered an elastic multisheet model used to date to deduce Y (Table 18). These meth-
to show the explicit dependence of material prop- ods include transmission electron microscopy
erties on the system size when a continuum cross- (TEM) observations of thermally excited vibra-
section assumption is made for a multishell sys- tions,240 thermal stresses monitored by micro-
tem subjected to bending. The continuum Raman spectroscopy,241 atomic force microscopy
assumption is shown to hold when more than 201 (AFM)-based measurements of lateral deflection
shells are present in the macromechanical system of CNTs,242 and a direct pulling technique by
considered. applying an axial force to a long NT rope23,24 or to
There is an additional consideration in the a single MWNT25 (Figure 53).
nanomechanics of SWNT related to the possible According to Table 18, the TEM-based meth-
changing of the nature of bonding when π− and ods suffer from relatively large margins of error
σ- bonds experience a different influence of de- margin of the order of 100%. For AFM-based
formation during, for example, a bending test, so techniques, the error margin can be of the order of
that when, for example, a nanotube is bent, its 50%. Significant errors mostly arise from diffi-
effective tension-related properties are different culties in anchoring the ends of the nanotube.246
from those in a pure tension test. In addition, to extract a Young’s modulus most
Probably useful atomistic simulations can be experimental techniques make some assumptions
done with sheets of diamond of different thick- regarding the mechanical behavior of the system
ness. Unlike nanotubes, the thickness can be con- and assume that continuum elasticity theory is
tinuously increased and tendencies in in-plane valid so that well-established expressions from
stiffness and flexural rigidity can be analyzed. elasticity theory for loaded tubes can be used at
A different approach for analyzing the linear the nanoscale. However, the resulting values can
elastic modulus of a SWNT is described in,239 be very sensitive to geometrical assumptions. For
where nanoscale continuum theory is established example, measured values of Y of Mo-based nano-
to directly incorporate interatomic potentials into whiskers varied by about a factor of two depend-
a continuum analysis without any parameter fit- ing on the assumed geometry of the cross-sec-

307
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308
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FIGURE 53. Illustration of a multiwall carbon nanotube (~11 nm diameter) prior to


tensile testing (a). Arrows indicate direction of loading (white is the actual pulling
direction); (b) fracture surfaces of both ends of the tube after breakage. (Reprinted from
Ref. 245, with permission from Elsevier Science.)

tional area of the nanocrystal.246 An excellent re- nanotubes (approaching that of graphene) with
view of instrumentation for measuring Young’s increasing radius (Table 17). The Poisson’s ratio
moduli is provided in Ref. 223. also retains graphitic values except for a possible
In contrast to the experimental results, there slight reduction for small radii. It shows, how-
are no appreciable differences between the ever, chirality dependence (Tables 17 and 19).
Young’s modulus for nanotubes and for a single
graphene sheet predicted from first principles
simulations (Table 19). Also, the results from Limitations of Continuum Mechanics at
Table 19 indicate that the effect of curvature and the Nanoscale
chirality on the elastic properties of NTs is small. Atomistic simulations of buckling of selected
More detailed analysis of variations in the strength nanotubes235 demonstrated that bifurcation-buck-
of C-C bonding as the graphene sheet is rolled ling equations from shell theory can be applied, in
into a tube had been performed in Ref. 227. Based principle, at the nanoscale. However, the defor-
on a first principles cluster method, the authors mation behavior of every nanotube cannot be sat-
adopted the Mulliken population analysis to esti- isfactorily described using a shell model. A com-
mate the overlap integrals between carbon atoms prehensive analysis of the limitations on the
that measure the strength of the covalent bond. applicability of continuum shell models to the
According to these results, the binding energy, entire class of nanotubes has been performed by
elastic modulus, and tensile strength of carbon Harik.230,248
nanotubes must be less than that of graphite. In- A scaling analysis has been used to identify
deed, results of first principles calculations232 and229 the key nondimensional geometrical parameters
indicate an increase in the in-plane rigidity of that control the buckling behavior of NTs. Based

309
on the relationship between buckling behavior their global mechanical behavior. Thus, NT shells
and NT structure, four broad classes of CNTs had behave either as thin shells or thick shells (hollow
been identified (Figure 54a): thin and thick shells, cylinders) depending on the thickness-to-radius
high aspect ratio (long) NTs, and NT beams. A ratio. The long NTs (class II) have structural be-
representative applicability map according to the havior similar to the behavior of columns. The
NT classes had been also constructed (Figure 54b). NT beams (class III) deform like macroscopic
The descriptive name of each class indicates the beams.
structural properties of NTs as well as the poten- The results of the analysis have important
tial continuum models that can be used to predict practical applications. For NTs with the same
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FIGURE 54. Schematic representation of four classes of nanotube geometries (a) used in the applica-
bility map for the continuum beam model (b). Ranges of values for non-dimensional geometric param-
eters of nanotubes define NT classes and indicate the limits in the applicability of the thin-shell model
for NTs. Parameters LNT, RNT, and a1 represent the three length scales involved in the nano-mechanical
problem. a1 is the width of the hexagonal carbon rings, which is about 0.24 nm. LNT, RNT, dNT are nanotube
length, radius and diameter, respectively. (Reprinted from Ref. 230 with permission from V. Harik.)

310
values of the nondimensional parameters, they tally are summarized in Tables 19 and 20, respec-
must have identical critical strain and buckling tively. Measurements were done on individual
modes, even if the individual structural features MWNTs and SWNT ropes. Yu et al. obtained the
are different. This can help to reduce the number tensile strength of individual MWNTs by scan-
of MD simulations needed to describe a whole ning electron microscopy.249 The MWNTs broke
class of NTs. In experimental studies, specific in the outermost layer, and the tensile strength of
equivalent-continuum models should be used for the MWNT layer ranged from 11 to 63 GPa.
a system under investigation according to the Analysis of the stress-strain curves for the indi-
applicability map for data reduction or NT probe vidual MWNTs indicated that the corresponding
design. Young’s modulus of the outer layers varied from
270 to 950 GPa. More recently, the first observa-
tion of the actual breaking of a MWNT in tension
b. Nanotube Tensile Strength in TEM has been reported245 (Figure 53). Figure
CNT tensile strengths predicted using first 53b reveals that the nanotube has apparently
principles calculations and obtained experimen- ‘healed’ itself after failure by forming a closed
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311
end-cap. Based on the observation of the force Molecular dynamics simulations of nanotubes
required to break the nanotube a tensile strength under tension had been performed using a bond
of 150 GPa (experimental uncertainties ~30%) order analytic potential in Ref. 261 However,
was estimated. The corresponding deformation while using the bond order potential for estimat-
was ~5%. This is the highest reported fracture ing elastic properties for moderate deformation
strength of any material and is relatively close to (up to 15%) is reasonable, the bond-order poten-
the ideal fracture strength of graphene. From cor- tial used in the simulations261 is not appropriate
responding bending studies on such nanotubes, for simulating system behavior at deformations
the Young’s modulus was estimated to be 0.9 TPa above approximately 15% due to acut-off via a
(±20%). Ab initio estimations of ideal fracture switching function of the interatomic potential.
strengths along the directions corresponding to When bond lengths exceed 1.7 Å (the beginning
the zigzag and armchair atoms arrangements at of the cut-off range), a steep nonphysical increase
the edge are 209 GPa and 226 GPa, respectively.228 in the interatomic forces results in very high val-
This ideal tensile strength had been obtained for ues of ultimate tensile strength. When developing
an ideal situation where there is no symmetry an interatomic potential suitable for fracture simu-
breaking (no defects, no stress inhomoginities lations, it is important that any cut-off function be
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due to temperature, for example), and hence it used at distances beyond the inflection point in
establishes an upper limit on the strength. In simi- the potential function. The inflection point relates
lar simulation conditions, ideal fracture strengths to the peak interatomic force and therefore influ-
for diamond range from ~95 GPa in the <111> ences fracture stresses in a system. In our previ-
direction198,228 to 225 GPa in the <001> direc- ous work on diamond cleavage, we avoided this
tion.198 It would be valuable to study the failure of problem by shifting the cut-off function beyond
deformed graphene in conditions of small pertur- the inflection point and keeping a list of nearest
bations using the first principles approaches. neighbors during the run.42 Recently,43 a modified
The only reported first principles-based esti- Morse function was developed to specifically
mation of a (6,6) nanotube tensile strength in address fracture of CNTs by adjusting the posi-
elongated nanotubes is surprisingly very low (~6 tion of the inflection point to provide an ultimate
1  ∂Etot  fracture strain of nanotubes that reproduces the
GPa).227 It was calculated as σ TH =   ,
s  ∂ε  ε = ε CR value obtained from the Yu et al. experiment
(~10%).249 The corresponding fracture stress un-
where s is the surface area of cross-section, and der conditions of symmetry breaking (tempera-
εCR is maximum strain in the system (~0.4). The ture, presence of vacancies) was estimated to be
corresponding Young’s modulus is also lower ~90 GPa. However, a reliable value can probably
(0.76 TPa) than those reported in other studies only be obtained with quantum mechanics–based
(Table 19). Thus alternative first principles calcu- dynamic simulations.
lations are required. Recently, the ductile behav- Interesting results on the tensile strengths of
ior of carbon nanotubes was investigated by large- SWNTs under hydrostatic pressure have been
scale quantum calculations.256 While the formation reported in Ref. 44. Simulations used the bond-
energy of strain-induced topological defects de- order potential with DFT simulations of selected
termines the thermodynamic limits of the elastic configurations. Hydrostatic pressure on the
response and of the mechanical resistance to ap- nanotube walls was simulated by encapsulating
plied tension, it was found that the activation hydrogen molecules to capped nanotubes. The
barriers for the formation of such defects are much reported failure strength under hydrostatic pres-
larger than estimated previously. Unfortunately, sure was 63 GPa for a (5,5) nanotube, and that for
ultimate tensile stress values had not been evalu- a nanotube containing twinned 7-5-5-7 pairs was
ated in Ref. 256. A comprehensive analysis of only 3 GPa lower.
nanotube ductile behavior is provided in the re- Finally, regarding the practical aspects of
view,221 but recent results256 should be taken in nanotube strength, the first kinetic approach to
the account. CNT real-time strength has been discussed in

312
Ref. 45 predicting the yield strain range. It was and 3.7 for <001> and <111> diamond orienta-
found that the value depends on the NT chirality, tions, correspondingly. The higher the value, the
in a way very different from the thermodynamic more weak/heavy is the nano-specimen.
assessments.
Estimating a three-dimensional ideal strength
for nanotubes suffers from the same problem of 3. Assemblies of Carbon Nanotubes and
uncertainty in defining the cross-sectional area of Nanodiamond
a nanotube as in the estimation of Young’s modu-
lus. According to Roundy,266 depending on the Certain types of nanocarbons such as
application a more useful metric might be force fullerenes, nanotubes, and diamond clusters can
divided by the mass per unit length (i.e., the stress serve as basic building blocks for constructing
divided by mass density) (Figure 55). This would more complicated structures that might exhibit
assume a strength-to-weight ratio characteristic new properties and find novel applications. In this
of the structural material and can provide a single section the feasibility of assembling carbon
nanotube with an ideal strength that would be nanotubes and nanodiamond clusters is discussed.
independent of the spatial arrangement of the tubes There is a geometrical similarity between the
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(e.g., MWNT vs. NT ropes). It would also be {111} planes of diamond and individual graphene
convenient to perform a comparison of the char- sheets in which pairs of diamond planes resemble
acteristic for nano-specimens from different ma- “puckered” graphite. This relationship, together
terials. For example, the ratio between the strength- with the lengthening of carbon-carbon bonds from
to-weight characteristic for graphite and diamond 1.42 Å in graphite to 1.54 Å in diamond, results
(using data from Tables 12 and 21) would be 1.56 in the near epitaxial relations

FIGURE 55. Illustration as a convenient strength characteristic of a nanostructure can be defined. It


would be the maximum force before failure divided by the mass per unit length. This definition does
not involve the problematic definition of cross-sectional area and is independent of the dimensionality
of the nanostructure.

313
Graphite (0001) || diamond (111) nanotube-diamond structures. In experiments by
Kuznetsov et al.,82,277 the formation of nanometric
Graphite [1120] || diamond [101] closed curved graphitic structures with tubular or
conical forms attached to the surface of a dia-
mond particle were observed in HRTEM images
between graphite and diamond planes. These re- of diamond particles after high-temperature an-
lations have been utilized in several models for nealing. The TEM images show concentric gra-
understanding important structures and processes phitic shells corresponding to the top view of
in carbon materials, including diamond nucle- nested carbon nanotubes (Figure 56a) as well as a
ation on graphite275 and graphitization of diamond side view of nanotubes on the edges of particles
surfaces and clusters.82,189,276,277 There are also simi- (Figure 56b). The authors suggest that multilay-
lar but less obvious relations between fullerene ered graphitic caps that form during the initial
nanotubes and diamond that lead to a number of annealing of micron-sized diamond particles at
mechanically and chemically stable structures with 1800 to 2000 K transform into closed carbon
potential structural materials and nanoelectronic nanotubes attached to the diamond surface via
device applications. reconstruction of the edges of diamond (111)
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Several recent experiments have provided planes orthogonal to the surface into graphite
compelling evidence for stable hybrid carbon (0001) planes.277

FIGURE 56. TEM images of carbon nanotubes/nanofolds attached to a diamond surface. Top
view (a) and side view (b). (Reprinted from Ref. 277, with permission from Elsevier Science.)

314
Guidelines for creating a range of robust ing in bonding (Figure 57). For example, the total
nanotube-diamond structures have been devel- mismatch for a (6,0) nanotube is 6.7%, while that
oped recently278 and tested with the bond-order for (24,0) nanotube would be only 2.6%. To cre-
potential.218 The analysis was restricted to (n,0) ate a strong chemical interface between a (n,0)
and (n,n) nanotubes perpendicularly attached to nanotube and the corresponding n-sided polygon
diamond (001) and (111) facets. These rules were formed by dangling bonds on a diamond surface,
derived based on geometrical considerations in the shape of the polygon should be as close to
combination with energies and stresses estimated circular as possible to match that of a nanotube
from atomic modeling using an analytic potential edge. Thus, in addition to total mismatch, a local
function.278 Geometrical considerations include mismatch can be defined as the distance between
analysis of the total and local mismatches be- a single vertex of a polygon on a diamond surface
tween a nanotube and the diamond surface. A and the point of the projection of a corresponding
total mismatch is a mismatch between the perim- atom from a nanotube edge. Atomic level simula-
eter of a nanotube and the perimeter of a polygon tions have suggested that local lateral mismatches
on a diamond surface formed by atoms participat- as large as about 1 Å do not necessarily inhibit
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FIGURE 57. Schemes of the possible connection between the (111) diamond surface and zigzag nanotubes. Dots
connected by solid lines correspond to the atomic sites available for bonding at nanotube edges. Crosses
correspond to atomic sites at the (111) diamond surface. Dashed lines connect sites on the diamond surface
participating in the bonding with the specific nanotube. Stars at the contours of nanotubes (e,f) denote the dangling
bonds at the interface diamond/nanotube after the nanotube attachment. (Reprinted from Ref. 278.)

315
strong bond formation. For (6,0) and (24,0) Because of the fourfold symmetry of (100)
nanotubes this local mismatch would be 0.17 Å diamond facets, a general scheme like that out-
and 0.68 Å, respectively. Nanotubes with larger lined above for the attachment of nanotubes to
radii posses less total mismatch but higher local (111) facets could not be developed. Analysis of
mismatch, thus the interface energy of the relaxed bonding geometries together with molecular mod-
structures is higher for nanotubes with larger radii eling studies, however, has been able to identify
(Table 22). specific cases of strong bonding.278 One such ex-
Based on criteria related to the total and local ample is a (12,0) nanotube attached to the (100)
mismatches and relative symmetry of a nanotube facet of a diamond cluster, which is illustrated in
and site available for bonding on a diamond sur- Figure 58b. The total mismatch between the sur-
face, six distinct groups of (n,0) nanotubes with face sites and the nanotube is only 4.9%. Interface
different degrees of bond formation with a dia- energies for selected zigzag nanotubes attached to
mond (111) facet can be identified depending on an (001) diamond surface are provided in Table
the nanotube parameter n (Figure 56).278 The stron- 22.
gest interfaces are formed by nanotubes from the Depending on a nanotubes morphology, some
first two groups that correspond to nanotubes with types of open nanotubes can be chemically con-
sixfold (6 × M,0) and threefold (6 × M+3,0) sym-
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nected with different diamond surfaces, atom-to-


metry, where M is an integer. The energetic char- atom. Structures without dangling bonds at the
acteristics of nanotubes of different groups are interface can be formed; this is important for
summarized in Table 22. nanoelectronic applications, because dangling
The symmetry of (n,n) nanotubes do not bonds at the interface can trap electrons and sup-
match well with that of a defect-free diamond press conductivity through the interface. By com-
(111) facet, and therefore interfaces of this type bining metallic or semiconducting nanotubes with
will not in general show strong bonding. How- diamond clusters or substrates, different types of
ever, there is a strong similarity between the heterojunctions can be designed for carbon-based
five-fold symmetric (111) facets of adiamond nanoelectronics applications. For example, a hy-
pentaparticle and the ends of (5 × M, 5 × M) brid structure consisting of a short nanotube sand-
nanotubes that can result in strong bonding.278 wiched between two diamond clusters mimics the
The total mismatch between a pentaparticle of a double barrier structure of a resonant tunneling
nanoscopic size and (5,5) nanotube (Figure 58a) diode.
is about –4.1%. Simulations predict that the lo- The nanotube/nanodiamond composite, illus-
cal mismatch can be accommodated for (5 × M, trated in Figure 58, may, in principle, serve as tips
5 × M) nanotubes at least up to M=3. As dis- for a field emitting array.172,191 According to self-
cussed in Section III.A, pentaparticles are often consistent tight binding simulations,191 the work
observed among nanodiamond clusters. functions of a single closed nanotube and a single

316
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FIGURE 58. Illustration of the relaxed hybrid interface structure between a diamond pentaparticle and a (5,5)
nanotube (a) and diamond truncated octahedron cluster and the (12,0) nanotube (b). The nanotube is attached to
the (100) facet of the cluster. (Reprinted from Ref. 278.)

317
nanotube with an edge terminated by hydrogen are Recently,279 partitioned real-space density func-
about 4.5 to 5 eV. The barrier at the back contact tional calculations of field evaporation of carbon
of the diamond cluster/metallic nanotube varies clusters from SWNT were performed. The calcu-
from 4.5 to 2-3 eV, depending if the nanodiamond lations demonstrate that the activation-energy bar-
cluster consists of pure diamond phase (Figure 58) rier for field evaporation of carbon clusters and
or contains the tetrahedrally coordinated (ta-C) hydrocarbon clusters from SWNT’s decreases as
carbon phase.191 Taking into account the negative the electric field increases. It was also found that
electron affinity at the hydrogenated surface of a evaporation from an open-ended carbon nanotubes
diamond cluster, the resulting emission barrier for occurs more easily than from capped nanotubes.
the hybrid structure is comparable or lower than Another interesting result is that adsorbed hydro-
that for a single nanotube (Figure 59). Calculations gen weakens the C-C bonds and significantly re-
also indicate the presence of the wave functions duces the activation-energy barrier for field evapo-
with energies near the Fermi level that are continu- ration.
ously extended along both the nanotube and dia- Regarding nanotechnology applications, a
mond cluster.191 This enhances the possibility of nanotube forming strong chemical bonds with a
current flow from a nanotube to a diamond cluster. diamond cantilever can be a good candidate for a
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Probably, the major advantage of the above proximal probe tip.


design of a nanotube capped with a nanodiamond The nanodiamond/nanotube hybrid structures
particle is the potential reduction of nanotube discussed above can, in principle, be synthesized
erosion resulting in increased device lifetime. by manipulating diamond clusters with a proxi-
Indeed, the current density for emission from a mal probe tip with a nanotube mounted at the end
single nanotube is high in compared with a of the tip. While this method of assembling
nanotube capped with a nanodiamond particle nanoscale building blocks would be a powerful
that posses more emission sites. Based on esti- tool to test a concept, it is not suitable for the mass
mates using the bond order potential, an hydroge- production. One of the more practical ways of
nated diamond surface is more mechanically stable fabricating the suggested hybrid structures might
than a capped or hydrogenated nanotube edge. be electrophoresis/dielectrophoresis techniques

FIGURE 59. Homogeneous emission through a nanodiamond cluster. Band structure for graphite/
diamond/vacuum when (a) no field is applied and (b) under applied field. The difference between the
Fermi level and CB edge depends on geometry and may vary between 5.5 eV and 3.0 eV. CB edge
position in tetrahedrally coordinated a-C depends on the amorphization degree. Band structures in
applied fields for a-C with zero (c) and positive (d) EA. (Reprinted from Ref.191.)

318
involving directional movement of charged/po- for cold cathode fabrication.180,181 Similar to the
larized diamond particles in the suspensions un- above results, deposition of nanodiamond pow-
der an applied electric field. Electrophoretic depo- der on arrays of carbon nanotubes can be consid-
sition of nanosized diamond particles from ered.
isopropyl alcohol suspensions on highly oriented
pyrolytic graphite (HOPG) substrates has
been thoroughly investigated in Ref. 71. The IV. APPLICATIONS OF CARBON
nanoparticles acquire a negative surface charge in NANOSTRUCTURES
aqueous and organic suspensions. However, in
isopropyl alcohol suspensions, H+ ions generated In the worldwide study “Nanostructure Sci-
in situ by the reaction between iodine and ac- ence and Technology” 1999,281 four broadly de-
etone adsorbed on the diamond particles, result- fined and, in principle overlapping, application
ing in a positive surface charge and deposition areas for nanostructure science and technology
of particles on a cathode. SEM and AFM pic- were suggested as a classification scheme. These
tures demonstrated that nanodiamond deposited areas are dispersions and coatings, high surface
as individual particles has a spherical shape. It area materials, functional nanodevices, and con-
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was also revealed that the defect sites, such as solidated materials. Figure 60 illustrates how this
steps on HOPG surface, are favorable for the classification can be applied specifically for car-
deposition of particles. These techniques have bon-based nanostructures, which due to their abun-
been also used successfully for the deposition of dant forms fill all four categories of the applica-
nanodiamond powder on arrays of silicon tips tion fields.

FIGURE 60. Schematic representation of four major areas of the applicability of the carbon nanostructures drawn
according to the general classification of nanostructures in Ref. 281.

319
Nanocarbon materials possess remarkable example, aggregate-free nanodiamond-metal so-
properties, and the potential applications look lutions for electroplating have been developed for
unlimited. While nanostructural materials from industrial production in Germany.285 Among
the graphite family have a well-established repu- nanotube foundries, bulk quantity production is
tation in a variety of applications,4 broad market listed on the websites of Hyperion (MWNT),
acceptance of more esoteric nanocarbon-based Rosseter Holdings Ltd, INP Toulouse France
technologies, however, will be enabled only if the (MWNTs), Nanoledge (arc-grown SWNTs). For
fabrication costs are reduced and bulk production example, Guangzhou reports production of
realized. For example, in 1998 a standard price of MWNT as 10 kg/day (95% purity) and SWNT as
first gram- and subgram-sized nanotube samples of 100 g/day (50% purity).
was about $2000 per gram. Currently, prices vary In addition to the necessity of having effec-
from $500 a gram down to tens of dollars a gram tive and inexpensive methods of fabricating high
for unpurified multiwall nanotubes. According to quality nanostructures in bulk quantities (e.g.,
Fortune Magazine,282 Carbon Nanotechnologies, for applications in nanocomposites), it is also
Inc., TX, projects that as nanotube prices drop, important to develop controllable methods of
more and more markets will open up with a total nanostructure integration that can be scaled-up
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market value totaling $100 billion a year. Accord- for volume production of functional devices. For
ing to Ref. 282, projecting the price of nanotubes example, for nanotube-based electronics, the
down to $15,000 a pound, or about $33 a gram, a strategies under development for achieving scale-
yearly supply of one ton would be able to support up are self-assembly of nanospecies or self-align-
the manufacture of several billion dollars’ worth ment through controlled CVD growth on sur-
of flat-panel displays for PCs and television sets. faces patterned with catalytic particles combined
In Table 23 we provide a tentative price list for with microfabrication techniques.204
nanodiamond particles, carbon nanotubes, and Below we discuss the applications of UDD in
fullerenes as of 2002. Because the quality, purity, more detail as a field less familiar to many audi-
and exact form of the final product (powders, sus- ences. The applications of ultrananocrystalline dia-
pensions, etc.) vary, it is difficult to make mean- mond films and carbide-derived diamond are
ingful price comparisons between different found- briefly outlined because these topics are thor-
ries, so the information provided does not pretend oughly described in a number of recent publica-
to advertise or diminish products of any of the tions.2,14,63 Among the most popular nanotube ap-
companies listed. As can be seen from Table 23, plications that have been described in recent
prices for the highest purity nanodiamond par- reviews, we have chosen to discuss only the rap-
ticles, fullerenes, and nanotubes are all different by idly evolving areas of cold cathodes and func-
an order of magnitude in increasing order. An tional devices. We conclude the section with a
analysis of the economic impact of nanocarbon use brief description of medical applications of
shows that it increases the price of traditional prod- fullerenes and the ever-increasing role that com-
ucts. For example, the utilization of ultradispersed putational methods play in the development of
diamond for polymer (rubber) composites in the new applications of carbon materials.
amount of 1 gram per 1 kg of polymer1 requires an
additional investment of $2 per 1 kg of polymer
composite. This sounds reasonable. A. Diamond-Based Nanostructured
Nanodiamond production by a single com- Materials for Macroscopic Applications
pany currently can be of the order of tons per
year,1,3 so it is a quite mature technology. Tech- Below we discuss in more detail current and
nologies for purification and application in differ- potential applications of three different classes of
ent areas are quite developed also (at least in nanodiamond, which, in our opinion, are the major
countries of the Former Soviet Union (FSU)).1,3 classes of diamond-based materials on the
Novel applications continue to emerge as the tech- nanotechnology market. Those materials are
nology is developed on an industrial scale. For ultradispersed diamond particles (UDD), which has

320
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321
been on the market in FSU countries for decades, Dolmatov.1 The material is used in the form of a
and two recently synthesized nanodiamond struc- powder, suspension, or paste. Below we provide
tures, namely, ultrananocrystalline diamond films the digest of UDD applications according to Ref
and carbide-derived nanodiamond. While UNCD 1.
films possess very unique properties, carbide-de-
rived diamond is distinct by the simplicity of its
production. These three materials are synthesized a. Metal-Diamond Galvanic Coatings
by completely different techniques and have rather
different properties, providing each of them spe- Electrochemical and chemical deposition of
cific application niches (Figure 61). UDD together with metals using standard gal-
vanic equipment has been demonstrated to be
beneficial in a variety of applications in machine
1. Applications of Ultradispersed building, shipbuilding, the aircraft industry, tools
Diamond for electronics, electrical engineering, medicine,
and the watch and jewelry industry. The advan-
An extended review on the technological ap- tages of adding UDD to galvanic coatings include
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plications of UDD had been written recently by an increase in wear-resistance and microhardness

FIGURE 61. Schematic representation of major areas of current and prospective applications of UDD,
ultrananocrystalline diamond films and carbide-derived diamond films.

322
(Table 24); an increase in corrosion resistance information for different metals where UDD has
and a decrease in porosity; a dramatic decrease of been used successfully to enhance the performance
friction coefficient; considerable improvement of of galvanic coatings. According to Dolmatov,284
adhesion and cohesion; and high throwing power metal-UDD galvanic coatings are a major market
of electrolyte. According to Ref. 1, 283, the ser- niche for the current UDD consumption from Dia-
vice life of products is increased 2 to 10 times, mond Center, Inc. followed by applications such as
even when the coating thicknesses is decreased polishing materials and nanocomposites.
by a factor of 2 to 3. The strengthening effect is In the near future PlasmaChem GmbH, Inc.
observed in coatings of many metals, including will commercialize a new high purity aggregate-
silver, gold, and platinum, which are employed in free ND product for application in the electroplat-
numerous electronics applications. Particularly, ing/electroless processes based on industrial pro-
UDD is most widely used in strengthening chro- cesses/compositions developed in the framework
mium coatings deposited using an electrolytic of a European project.285
process. In this process, UDD-containing addi-
tives are added to the chrome-plating electrolyte
without any modification to the standard produc- b. UDD for Polishing Pastes and
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tion line. Such coatings increase by a few times Suspensions


the operating life of molds, high-precision bear-
ing surfaces, and other similar components. UDD UDD pastes are being used for finishing pre-
is also used in the production of cutting and razor cision polished materials for electronics, radio
tools. engineering, optics, medical, machine building,
The UDD content in a metal coating averages and jewelry industries1. The compositions with
0.3 to 0.5 wt. %. The amount of UDD consumed UDD allow one to obtain a surface of any geo-
for a metal layer thickness of 1 mm is 0.2 g metrical form with a relief height roughness of
(1 carat) / m2. Table 24 provides more detailed 2 to 8 nm. Recently, 4 Å roughness has been

323
achieved for Al2O3, and SiC surfaces using UDD elastomers and polysiloxanes were developed;
suspensions (according to the Alit, Inc., Ukraine). the elastic strength of rubbers based on
UDD is employed in polishing compositions used polyisoprene, butadiene-styrene, butadiene-ni-
for the final treatment of silicon wafers in the trile, and natural rubbers were considerably im-
microelectronics industry. UDD has been also proved.1,286 For example, for fluoroelastomers
used in the electronics industry as a component of filled with UDD particles the stretch modulus
heat-removal pastes and compounds for chip pack- at 100% elongation and the conditional rupture
aging, replacing the highly toxic beryllium oxide strength increased more than tenfold (from 8.5
that has been used traditionally. to 92 MPa and from 15.7 to 173 MPa, respec-
The amount of UDD consumed for this appli- tively). In this case, the elongation increased by
cation is 1 to 10 g/m2. a factor of 1.6 (from 280 to 480%). One of the
mechanisms that have been attributed to the
influence of UDD particles on the strength prop-
c. UDD for Polymer Compositions erties of polymer composites is an increase in
cross-linking.1 Additives of UDD into the rub-
Polymer composites with enhanced me- bers decrease attrition wear by an average of 3
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chanical properties are required by the aircraft, to 5 times, increase rupture strength by 30%,
motor and tractor, ship building, medical, chemi- and breaking temperature by 15%. Epoxy adhe-
cal, and petrochemical industries, as well as in sives that incorporate UDD have high adhesion
the manufacture of seals, stop valves for vari- and cohesion properties.
ous purposes, and protective and antifriction The specific consumption of UDD or dia-
coatings. The addition of UDD to polymers mond blend (mix containing UDD and significant
provides an increase in their mechanical percent of other carbon based products of detona-
strength, wear-resistance, and heat-ageing re- tion explosion) is 1 to 5 kg per 1000 kg of rubber
sistance (Table 25). Highly effective coatings (polymer) and 1 to 5 kg per 1000 m2 of polymer
based on the incorporation of UDD in fluoro- coating or film.

324
d. UDD for Lubricating Oils, Greases, and agent) in oncology, gastroenterology, vascular
Lubricant Coolants disease, and an efficient remedy for the afteref-
fects of burns and skin diseases. The beneficial
Modified lubricant compositions are used in property of UDD for medical applications is its
machinery, metal treatment, engine building, ship anomalously high adsorbtion capacity, high spe-
building, and the aircraft and transportation indus- cific surface areas, abundance of free electrons on
tries. The addition of UDD and diamond blend to oils the surface (a multiple radical donor), nanoscale
allow one to obtain sedimentation-stable and environ- size, significant amount of oxygen-containing
mentally safe systems with particle sizes of less than functional groups on the surface, chemically inert
0.5 µm.1 The use of nanodiamonds in oils increases cores and hydrophoblicity of the surface. Due to
the service life of motors and transmissions. Friction their high adsorption capacities, UDD exhibits
torque is reduced by 20 to 40%, and the wear of extremely high absorbing/bonding activities with
rubbed surfaces is decreased by 30 to 40%. respect to pathogenic viruses, microbes, and bac-
The specific consumption of UDD or DB in teria. The absorbing/bonding may be selective to
these applications is 0.01 to 0.2 kg per 1000 kg of particular drugs, which can enhance the drug’s
oil. activity. According to Refs. 1, 289, UDD exhibits
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no carcinogenic or mutagenic properties and is


not toxic.
e. UDD for Systems of Magnetic Recording The use of UDD in the form of aqueous and
oil suspensions showed promising results for cur-
UDD is also used as an antifriction additive ing cancer by removing toxins from organism,
and a physical modifier for ferro-lacquer coatings normalizing peristaltic of the bowels, and im-
of magnetic tapes and disks, and also as an additive proving blood characteristics.289 The use of UDD
to electrochemical deposition of composite mag- in chemical and radiotherapy appears to be prom-
neto-recording tapes to improve the properties of ising in the cure of malignant tumors by prevent-
magnetic recording devices.287 The addition of UDD ing the mutagenic effect of drags. According to
decreases ferro-magnetic grain size, thus allowing Ref. 289, a theraupeutic course requires ~0.02 to
an increase in recording density while reducing 0.5 g of UDD. While preliminary results, particu-
abrasive wear and friction coefficient larly in oncology, are encouraging,289 this area of
reseach has been explored very little because of
insufficient funding for the research in the coun-
f. UDD for Application in Intermetallics tries of the FSU where the application was first
Based on Copper, Zinc, and Tin developed.
A research group from the Ukraine also re-
UDD can be used in specific application fields cently reported a study on the use of UDD as an
such as when surfaces experience high frictional adsorbent for the purification of biological me-
forces produced by very harsh working condi- dia.290
tions that displace plastic and liquid lubricating
materials. UDD is an ideal composite material for
intermetallics based on copper with zinc or tin h. UDD Dinter as an Adsorbent of a New
(the UDD content is no more than 15 volume %). Type
The addition of UDD decreases the frictional
forces two to six times.288 Carbon-containing adsorbents are widely used
in various industries such as medicine and phar-
macology. The most abundant of these adsorbents
g. UDD for Biology and Medicine are activated coals and graphitized thermal car-
bon black. Synthetic diamond, particularly sub-
According to Refs. 1, 289 UDD is considered micron diamond composites as well as sintered
a potential medical agent (not just drug delivery UDD, represents a new class of carbon containing

325
adsorbents,291 characterized by chemical inertness Ultrananocrystalline diamond has been also
and high strength. Another beneficial effect is the grown with the incorporation of nitrogen up to 8
possibility of using the adsorbent repeatedly by × 1020 atoms/cm3 with the addition of nitrogen to
modifying and recovering the diamond surface. plasmas during the CVD growth of diamond
In addition to the application areas listed films.292 This is the highest carrier concentrations
above, UDD is used as a component in the pro- seen for any n-type diamond material to date
duction of diamond ceramics and molds made of resulting in several orders of magnitude increase
diamond-containing materials. UDD had also been in UNCD conductivity that promise applications
employed for seeding substrates used in the CVD in heterojunction electronic devices.
growth of diamond films. Dry UDD is known to UNCD electrodes exhibit a wide working
absorb and retain water in amounts that are four potential window, a low background current, and
times the weight of the UDD. This allows its use high degree of electrochemical activity for redox
as an inert solid water absorber in materials whose systems. These results, in combination with the
quality is determined by the residual water con- biocompatibility properties of UNCD, could lead
tent, for example, in magnetic carriers. to the application of UNCD electrodes for nerve
stimulation.2
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Future MEMS applications that involve sig-


2. Applications of Pure Phase nificant rolling or sliding contact (MEMS moving
Ultrananocrystalline Diamond Films mechanical assemblies (MEMS MMAs)) will re-
quire the use of new materials with significantly
As discussed in Section III.A, ultrananocrystalline improved mechanical and tribological properties
diamond is grown using a new plasma deposition and the ability to perform in harsh environments.
process that utilizes a high content of noble gas. This Because the feature resolution in polycrystalline
process was developed at Argonne National Labora- MEMS is limited by grain size, the use of MEMS
tory and produces films with ultrasmall (2 to 5 nm) made by conventional CVD diamond methods is
grains with atomically abrupt grain boundaries. UNCD limited. In addition, the conventional CVD dia-
films are superior in many ways to traditional micro- mond films typically have large grain sizes (~1
crystalline diamond films: they are smooth, dense, mm), high internal stress, poor intergranular adhe-
pinhole free, and phase-pure, and can be conformally sion, and rough surfaces (rms ~1 µm). Alterna-
coated on a wide variety of materials and high-aspect- tively, diamond-like coatings, generally grown by
ratio structures. The set of unique properties include physical vapor deposition, cannot cover high as-
mechanical (high hardness ~100 GPa, and Young’s pect ratio MEMS features conformally and require
modulus ~960 GPa), tribological (extremely low fric- high-temperature post-deposition processing to
tion ~0.01), transport (tunable electrical conductivity, relieve stress, which compromises their mechani-
high thermal conductivity), electrochemical (wide cal properties. Ultrananocrystalline diamond coat-
working potential window), and electron emission ings possess morphological and mechanical prop-
(low, stable threshold voltage) characteristics. The erties that are ideally suited for MEMS applications
UNCD has been considered for a variety of applica- in general, and MMA use in particular.2,293 The
tions, including MEMS and moving mechanical as- roughness of the film is about 20 to 40 nm and the
sembly devices, surface acoustic wave (SAW) de- friction coefficient can be as low as 0.01. The
vices, biosensors and electrochemical sensors, coatings surfaces are very smooth (rms~30 to 40 nm) and
for field emission arrays, photonic and RF switching, the hardness is as high as ~100 GPa. When com-
and neural prostheses. pared with Si-based MEMS, the brittle fracture
Studies of UNCD-coated flat substrates and strength is 23 times that of Si, and the projected
microtip arrays for cold cathodes applications2,292 wear life of MEMS MMAs from diamond is 10,000
have yielded consistently low threshold fields times greater than that of Si MMAs. The group
(1 to 2 V/µm), high total emission currents (up to from Argonne National Laboratory demonstrated
10 mA), and stable emission during long-duration three-dimensional MEMS structures fabricated
testing (up to 14 days). from UNCD material, including cantilevers and

326
multilevel devices, acting as precursors to We would like to conclude this subsection by
microbearings and gears (Figure 62). outlining the medial application of diamond from a
Applications of UDNC as biocompatible MEMS completely different perspective. Within the con-
devices, biosensors and biological electrodes are being cepts of the molecular nanotechnology,308 carbon-
also explored. A special program is funded by the DOE based materials could play an important role in build-
to develop UDNC-based artificial retinas to restore ing “nanorobots”, structures that have been
sight to people blinded by the retinitis picmentosa envisioned for applications in nanomedicine309 (Fig-
condition.294 Functionalization of UNCD to attach DNA ure 64). Nanomedicine may be defined as the moni-
molecules has been demonstrated also.294 toring, repair, construction, and control of human
Nanocrystalline diamond coatings on suitable biological systems at the molecular level using en-
substrates are promising materials for medical gineered nanodevices and nanostructures. 309
implants, cardiovascular surgery, and for the coat- Fullerene nanotube–based rotors, shuffles, and
ing of certain components of artificial heart valves gears310 have been computationally designed as well
due to their extremely high chemical inertness, as those based on so-called diamonoid materials.311
smoothness of the surface, and good adhesion of
the coatings to the substrate.295 Nanocrystalline
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diamond coatings (reported grain size ~nm) de- 3. Applications of Carbide-Derived


posited by RF-PCVD of methane with nitrogen Diamond-Structured Carbon
on mm-sized steel implants that had been inserted
to tissue and bones for up to 52 weeks295 demon- Recently, a method for the synthesis of dia-
strated excellent biocompatibility and biostability mond-structured carbon in bulk quantities by ex-
(Figure 63). tracting silicon from silicon carbide or metal car-

FIGURE 62. A UNCD MEMS cantilever strain gauge with a 100-nm feature resolution
produced by UNCD blanket film deposition and etching through a hard oxide mask.
The UNCD film is 3.3 µm thick, and it is separated from the substrate by 2 µm.
(Reprinted from Ref. 293, with permission from Elsevier Science.)

327
FIGURE 63. Illustration of a very good biotolerance of the implants coated with the nanocrystalline
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diamond layers. In subcutaneous tissue, muscles and bones, thin connective tissue capsules
built from fibrocytes and collagen fibers were formed. Optical microscope analysis of the wall
of the capsule after 52 weeks did not reveal any phagocytic reaction or products of corrosion.
(Reprinted from Ref. 295, with permission from Elsevier Science.)

FIGURE 64. Science fiction: using diamond in medical nanorobots. The picture is adapted
from M. D. Lemonick, “...And Will They Go Inside Us? Given the Promise of Nanotechnology,
It’s a Safe Bet,” Time Magazine 154 (8 November 1999):93. Artist: Joe Letrola.

328
bide was developed.14 In principle, chlorination of ability of the films produced by chlorination of SiC
carbides for the production of carbon-based materials and an extremely narrow pore size distribution in
and, particularly, nanoporous carbon, is a relatively carbide-derived carbon provide effective molecu-
mature technology that has been commercialized (see, lar sieves, high-surface area electrodes and other
for example, http://www.skeleton-technologies.com). applications, where vapor-deposited diamond films
However, the synthesis of nanocrystalline diamond cannot be applied. The large-scale solid-state syn-
by this technique14 is a recent achievement. Coatings thesis of technical diamond at ambient pressure
of diamond-structured carbon produced by this route and moderate temperatures with no plasma activa-
show hardness values in excess of 50 GPa and Young’s tion can provide diamond materials at a low cost
moduli up to 800 GPa. for a variety of high-volume applications such as
The carbide-derived carbon and diamond coat- brake pads, where diamond could not be used be-
ings show excellent tribological behavior in both room fore because of its cost.
air and dry nitrogen and are at the stage of commer-
cialization for tribilogical applications, particularly as
nanodiamond coatings for SiC dynamic seals for B. Carbon Nanotubes in Advanced
water pumps.296 The coatings are self-lubricating, with Electron Sources: Are Carbon
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remarkably low friction coefficients that can be tai- Nanotubes Exceptional Electron
lored by altering the reaction parameters and show no Sources?
measurable wear.296 Favorable tribological properties
of carbide-derived nanodiamond make it a favored Advanced electron sources often are regarded
candidate for applications in the manufacturing of as the most important short-term application of
different types of prosthesis.297 carbon nanotubes. In this section, we summarize
Conformal coatings produced by selective etch- the technical parameters of nanocarbon electron
ing can be useful in micro-electro-mechanical sys- emitters and provide critical assessments of their
tems (MEMS) applications, where very thin and status and prospects. Electron emission properties
uniform coatings are required. In addition, perme- of carbon nanotubes are considered.

329
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330
1. Practical Issues of Field Emission a great deal of recent speculation regarding field
Electron Sources emission from carbon nanotubes, with some re-
searchers claiming properties that are far superior
Field emitters are cold electron sources whose to more conventional field emitting structures. In
operation is based on geometry effects. Despite this section we attempt to critically review carbon
their apparent simplicity and the expectations about nanotubes field emission cathodes from the view-
device applications, field emitters are rarely used point of the field emission community, including
in real-world devices. The reason is that so far candid comparisons to other well-established field
field emitters do not satisfy the practical technical emitters. In our comparison, we categorize differ-
requirements of high current density and emis- ent types of field emitters as “low-voltage emit-
sion stability,314,315 as well as a low operating ters”, “high-current emitters”, and “gated emit-
voltage. ters”.
The two major designs of electron sources are
a single point electron source (e.g., a single
nanotube) and a large area electron source, which a. Low-Voltage Emitters
could be either an array of tips (e.g., nanotubes)
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or a continuous film of emitting material. Low-voltage (10 to 20 V) field emission from


In this section we provide critical assessments carbon nanotubes was reported recently in Ref.
of the status of carbon emitters by comparison 319, where a very small emitter-to-anode dis-
with their most recently reported emission param- tance (6 µm) was used. We note that similar
eters to those of field emitters made from other effects can be achieved with other types of field
materials (Figures 65 and 66). emitters. The first field emission diode that oper-
ated at less than 10 V applied was reported in
1989 by Makhov.314 It consisted of sharp wedges
2. Carbon Nanotubes Emitters of single crystal silicon operated at a cathode-to-
anode distance of less than 1 µm. Since then,
Typical carbon nanotubes field emitters are several similar devices have been demonstrated,
shown in Figure 67. With their high aspect ratio including recent results from diamond tips (see
and unique conducting properties, there has been Table 26). In all cases, the low-voltage operation

FIGURE 65. Conventional field emission technologies: (a) Single Mo tip field emitter (etched wire);
(b) ungated Si field emitter arrays. (Reprinted from Ref. 316, Copyright 1994, with permission from
American Institute of Physics.)

331
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FIGURE 66. Gated Mo field emitters. (Reprinted from Ref. 317, Copyright
1998, with permission from American Institute of Physics.)

was achieved by using very small vacuum gaps of cathode area αtotal (independent of the number of
less than 10 µm. Unfortunately, this type of de- emission sites). All of the reported data regarding
vice has limited usefulness; they are all essen- carbon nanotubes field emission has been ob-
tially diodes with little or no advantages com- tained using a proximity probe of very small area
pared with solid-state diodes. Table 26 compares (1 to 100 µm2), with the total current measured in
recently reported low-voltage operation of carbon these experiments typically only 1 to 100 µA.
nanotubes field emission diodes with previously Nevertheless, claims of high-current densities and
reported field emission devices. device applications for microwave tubes have been
made. The practical question, however, is “what
will the current be when the anode diameter is
b. High-Current Emitters increased to 1 cm?” It is likely that the current
will be much less than 10,000 amperes. As was
The potential for high-emission currents has shown by Göhl et al.,323 an increase in probe
always been an attractive feature of field emitters, diameter results in a drastic decrease in probe
and there are many reports of “high current den- current density.
sities” from novel emission materials. However, The parameter of merit for device applica-
these reports can be misleading and must be inter- tions is the integral current density, that is, the
preted carefully in terms of practical applications. total current emitted divided by the entire cath-
For example, a small total current of 10 µA can ode area. That is, a very high current density is
result both in very high and very low current obtained only from a very small cathode area.
density depending on the choice of emission area. (The record current density of about 2500 A/
The emission area of practical merit is the total cm2324 was obtained from an array of emitters

332
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FIGURE 67. Fragments of typical CNT field emitters: (a) supported single nanotube;329 (b)
array of CNT grown by CVD (at different magnifications);326 (c) attached CNTs.332 (Re-
printed from Ref. 329 with permission from Springer-Verlag GmbH & Co. KG (a) and Ref.
326 (b) and Ref. 332 (c) with permission from the American Institute of Physics.)

333
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with an integral area of 25 × 25 µm2 and a total nanotubes on conventional silicon gated field
current of a few mA.) A realistic challenge is to emitters with 2.5 µm gate aperture. The silicon
demonstrate a total current of 1 A (or more) from tips in these particular emitters were relatively
a macroscopic area of 1 cm2. Overall judgements blunt. A gated field emitter cell with carbon
about the potential usefulness of new cathode nanotubes grown on Si tips is shown in Figure 68.
materials cannot be made without data from a However, it was found from SEM examination
minimum set of practical parameters: maximum that only 10% of Si tips had carbon nanotubes.328
total current at failure Imax, integral current den- Figure 69 shows emission current-voltage char-
sity Jmax, operating voltages Vth (threshold volt- acteristics from Si field emission arrays with and
age), and Vmax (voltage for maximum current or without carbon nanotubes. As can be seen, emit-
failure) and transconductance gm~ Imax / Vmax.315 ters without carbon nanotubes had a much higher
Note that the typical maximum current of “high- threshold voltage. Field emission arrays with car-
current” carbon nanotubes emitters is within 0.1 bon nanotubes showed threshold voltages near 20
to 2 mA. For comparison, 4 mA of current was V. Table 28 compares emission characteristics of
obtained from a single ZrC tip.327 Table 27 com- carbon nanotubes328 and Mo317 gated field emit-
pares maximum current and transconductance of ters. Indeed, carbon nanotubes allow for the re-
different field emitters. duction of the operational voltage for emitters
with relatively large gate aperture. However, the
current per cell and total current of a carbon
c. Gated Emitters nanotubes field emission array is considerably
lower than metal field emitters.
Gated field emitters shown in Figure 66 are
basic components of field emission displays (FED)
and microtriodes for vacuum microelectronics d. Maximum Current from Individual
devices.314 Typical gate voltages of metal field Nanotubes
emitters prepared by standard technique is in the
range 50 to 100 V. To date, only a few reports on Experiments with individual carbon nanotubes
gated carbon nanotubes emitters have been pub- s mounted on metal tips have shown maximum
lished. Hsu and Shaw328 grew multiwalled carbon emission currents of the order of 100 µA.329

334
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FIGURE 68. Gated carbon nanotubes-on-silicon post field emitter cell.


(Reprinted from Ref. 328, Copyright 2002, with permission from the
American Institute of Physics.)

335
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FIGURE 69. Emission current-voltage characteristics (anode current vs gate


voltage) from arrays with and without CNTs. (Reprinted from Ref. 328, Copy-
right 2002, with permission from the American Institute of Physics.)

336
Nilsson et al.330 studied the emission-degradation has to keep in mind that such an application must
behavior of carbon nanotubes thin-film electron compete with existing fluorescent tubes. In gen-
emitters. The authors investigated MWNT arrays eral, to achieve a brightness of 10 000 cd/m2, the
grown by CVD on a silicon wafer. They found emission current density should be about 0.5 to 1
that current-dependent emission degradation µa/cm2 at voltages of 3 to 5 kV. For luminescent
started at about 300 nA per emitter. This result is tubes of practical size these conditions will result
consistent with Ref. 328 (see Table 28). In the in high power consumption. Indeed, the power
authors’ opinion, the primary degradation mecha- consumption of the reported carbon nanotubes
nism of a carbon nanotubes film on Si was the field emission lamp is more than 10 times higher
Joule heating at the carbon nanotubes /silicon than for a conventional fluorescent tube.334 The
interface.330 The authors330 discuss the difference authors334 believe that it would be possible to
between their result and the result reported by decrease the power consumption by phosphor
Bonard et al.,329 where a maximum current of 100 optimization. It should be noted, however, that
µA was obtained from an individual MWNT the phosphor efficiency by electron excitation is
mounted on the tip of an etched gold wire. This always lower than the efficiency by UV excita-
difference can be explained in part by the differ- tion for fundamental physical reasons, and there-
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ent contact resistance between carbon nanotubes fore it may not be possible to fabricate field emis-
and gold and carbon nanotubes and Si.329 sion lamps with efficiencies comparable with
In general, the average current per emission fluorescent tubes.
site in a carbon nanotubes emitter is smaller than Among other proposals for using carbon
in metal field emission arrays. The maximum nanotubes as field emission electron sources, we
current of 100 µA obtained from individual mention X-ray tubes,335 electron guns for electron
nanotubes is also typically the maximum current microscopy,336 and vacuum microtriodes.337 How-
for metal (e.g., Mo) emitters,314 though emitters ever, unless considerable improvement in integral
from metal carbides,327 or metal tips with dia- current density and emitter lifetime is shown,
mond coatings,331 result in larger maximum cur- major breakthroughs in the performance or appli-
rents, up to few mA per tip.327 cation of these devices will be difficult to achieve.

3. Field Emission Devices 4. Emission Mechanism and Specific


Features of Carbon Nanotubes
a. Displays and Lamps
In general, carbon nanotubes emitters are
Field emission flat panel displays are often based on the same operation principle as more
cited as one of the most promising applications of traditional emitters, such as metal tips. As a gen-
carbon nanotube field emitters, and several groups eral observation, the open-ended carbon nanotubes
have demonstrated the operation of carbon appear to emit better than those with caps, and
nanotubes displays. Probably, the most advanced SWNTs emit better than MWNTs.
FED prototypes were made at Samsung.332,333 We The key factor determining emission proper-
note somewhat pessimistically, however, that ties of carbon nanotubes is the geometrical field
many different kinds of field emission displays enhancement, which for individual emitters is
have been demonstrated during the last 12 years, roughly proportional to their aspect ratio. The
with but so far none have proven to be a success- difference between carbon nanotubes and con-
ful commercial alternative to other technologies ventional field emitters and the potential advan-
such as LEDs, electroluminescent, and plasma tage of carbon nanotubes is their cylindrical shape,
displays. which may enable higher field enhancement.
One of the recently proposed applications of However, this advantage turns into a drawback
carbon nanotubes was in the luminescent tubes when we consider the maximum current from
for general lighting purposes.334 However, one individual nanotube emission sites. It is limited to

337
hundreds of nA,328,330 for example, very different Doped Carbon Nanotubes Structures
from tens of µA for metal tips.314,317
Another difference between carbon nanotubes As-grown semiconducting carbon nanotubes
and conventional metal field emitters is the fact have p-type conductivity.340–343 Carbon nanotubes
that carbon nanotubes can be flexed, bent, and can be doped chemically by controlling surface
reoriented by an electric field.338 For moderate adsorbates.341–343 Doped structures with p-n junc-
electric fields, the flexing and reorienting is re- tions were formed on individual single-walled
versible, but under high-field conditions suffi- carbon nanotubes by doping with alkaline metals
cient to extract large field emission currents, the and organic molecules. Doped structures with both
nanotube remains irreversibly deformed. negative differential conductance341 and unipolar
Nanotubes that field emitted at a high cur- conductance (rectification)342 were demonstrated.
rents for long times were foreshortened338, sug- In a recent work by Kong et al.340 a p-n-p junction
gesting a lifetime-limiting mechanism for vacuum was chemically defined on an individual carbon
microelectronic devices. nanotubes. The n-doped region was produced by
local deposition of potassium on a p-type carbon
nanotubes. From transport measurements, the
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Conclusion on Field Emission from Carbon authors340 concluded that nanometer-scale width
Nanotubes tunnel barriers at the p-n junctions dominate the
electrical characteristics of the system. Figure 70.
Despite statements claiming carbon nanotubes shows a schematic p-n-p carbon nanotubes device
to be “excellent”, high-current, and low-field and the corresponding band diagram. At low tem-
emitters, realistic assessment suggests that carbon peratures, the structure can be regarded as a quan-
nanotubes may ultimately offer few advantages tum dot confined between the two p-n junctions.
over alternative field emission technologies. In Single electron transistor behavior of this carbon
fact, a more precise comparison of conventional nanotubes p-n-p structure was reported.340 In prin-
metal field emitters and carbon nanotubes emit- ciple, by local doping of carbon nanotubes, the
ters (see Tables 26 to 28) does not reveal any realization of such functional devices as Esaki
remarkable advantages of the latter. tunnel diodes or Shokley p-n-p-n diodes should
be possible.

C. Carbon Nanotubes as
Nanoelectronics Components Field Effect Transistors

Carbon nanotubes are considered as a very The possibility for modulating the conduc-
important subset of nanoelectronic materials.339 tance through a carbon nanotubes by a gate elec-
Semiconducting properties of carbon nanotubes trode was first demonstrated by Dekker et al. in
made them interesting for electronics applications. 1998.344 Since then, several groups have demon-
One of the requirements for a material for active strated field effect transistor (FET ) device struc-
electronic devices is the ability to control its elec- tures in which a gate electrode modulates the
tron transport properties. In CNTs such control conductivity of a conducting channel by a factor
can be achieved by geometry (e.g., diameter, shape, of 105.345 Large arrays of carbon nanotube FETs
helicity) or surface adsorbates. have been fabricated.346 Simple prototypes of elec-
The operational principle of most electronic tronic circuit elements were demonstrated, such
devices is based on either conductivity modula- as a voltage inverter or NOT gate circuit using
tion of a channel or on highly nonlinear I-V one n-channel and one p-channel FET.
characteristics. Both field effect transistors In carbon nanotubes FETs, the carbon
(FETs) and intratube p-n junctions made from nanotubes acts as a channel, connecting two metal
individual semiconducting nanotubes have been electrodes. The channel conductance is modu-
demonstrated. lated by third gate electrode. Several different

338
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FIGURE 70. (a) Schematic CNT p-n-p structure; (b) AFM image showing a 200-
nm wide window (dark), corresponding to potassium doped n-type region; (c)
corresponding band diagram. (Reprinted from Ref. 340, Copyright 2002, with
permission from American Institute of Physics.)

types of carbon nanotubes FET were reported: mance of a carbon nanotubes FET is much better
“bottom gate”,344 “top gate”,347 and vertical.348 than a Si FET. It should be noted, however, that in
The top gate structure shown in Figure 71347 ap- their comparision the authors used electrical
pears the most promising one, because it allows charcteristics normalized per channel width, which
for a thinner gate insulator, protects the carbon was assumed to be 1.4 nm. Another assumption
nanotubes channel from exposure to air, and can was that only one nanotube was present in the
be made suitable for high-frequency operation.347 channel. The third assumption is that the
Wind et al.347 recently reported top gate transconductance will increase proportional to the
p-channel carbon nanotubes FET with channel number of parallel nanotubes in the channel. All of
length of 260 nm and having a maximum these assumptions need to be carefully investi-
transconductance of 3.25 µS. The authors com- gated. For circuit operation of a FET, the total
pared the parameters of the carbon nanotubes FET transconductance is one of the key parameters. The
to the state-of-the art Si transistors (see table in total transconductance reported in Ref. 347 is
Figure 71c). In the authors’ opinion, the dc perfor- 3.25 µS, which is much smaller than the

339
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FIGURE 71. (a) Schematic cross-section of the top gate CNT FET showing the gate
and source and drain electrodes. (b) Output characteristic of a top gate p-type
CNFET with a Ti gate and a gate oxide thickness of 15 nm. The gate voltage values
range from 20.1 to 21.1 V above the threshold voltage, which is 20.5 V. Inset:
Transfer characteristic of the CNFET for Vds= 20.6 V. (c) Comparison of key device
parameters for CNT and Si FET. (Reprinted from Ref. 328, Copyright 2002, with
permission from American Institute of Physics.)

340
transconductance of practical Si FETs. Javey et local gate voltage of -40 V and a source-drain bias
al.349 reported fabrication nanotube FET arrays with of 20 V for 5 min. The authors note, however, that
local bottom gates. some of the p-FETs become rather insulating over
While as-made FETs are all p-type, a local a large gate range after this electrical manipulation
electrical manipulation method was used to con- step. The yield of p- to n-conversion by our local
vert specified nanotube FETs into n-type. The au- manipulation method was about 50%.
thors349 found that a p-type FET can be converted This local doping approach leads to multiple
into n-type by applying a high local gate voltage n-FETs coexisting with p-FETs on a chip. Comple-
combined with a large source-drain bias for a cer- mentary logic gates with up to six complementary
tain duration. This conversion is shown in the cur- transistors and three stage ring oscillators were
rent vs bottom gate voltage (I-Vg) curves in Figure realized by connecting the n- and p-transistors.
72a for a transistor before and after applying a Figure 72b shows the output characteristics of an
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FIGURE 72. Local manipulation for n-type tube FETs for complementary devices. (a)
Source-drain current vs. gate voltage (I-Vg) curves of a SWNT-FET in air and after local
electrical manipulation in vacuum, showing the p- to n-type conversion. Bias = 10 mV. (b)
Transfer characteristics of an inverter made from a p-type nanotube FET and an n-type FET
obtained by electrical manipulation. The operating voltage applied is VDD = -5 V. (Reprinted
from Ref. 349, Copyright 2002, with permission from the American Chemical Society.)

341
inverter (NOT gate). It consists of an as-made p- nanotube electronic devices is probably the most
type tube FET and an n-type FET, and obtained important issue for assessments of the feasibility
by electrical manipulation. This complementary of nanotube electronics.
NOT logic gate exhibits a high voltage gain of 8. The theoretical understanding of the opera-
Complementary NOR, OR, NAND, and AND tion of a carbon nanotubes FET remains incom-
logic gates are built with up to six (3 p-type/3 n- plete.351 While initially it was believed that the
type) SWNT-FETs.349 gate voltage changes the conductivity of carbon
All published characteristics of carbon nanotubes channel, later there was increasing
nanotubes electronic logic gates are static I-V evidence that the Schottky barriers at the carbon
characteristics. Data on the dynamic time-depen- nanotubes/metal contacts may play a key role.
dent response of these components are very im- Heinze et al.,351 based on their theoretical results,
portant for fair assessments of their usefulness for concluded that carbon nanotubes FETs operate as
practical nanoelectronic devices. At this point, unconventional Schottky barrier transistors in
there are only very few reports on the operational which switching occurs primarily by modulation
speed of carbon nanotubes devices. Ring oscilla- of the contact resistance rather than the channel
tors with an oscillation frequency of 5 Hz made resistance. Clearly, more work is needed for a
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using three unipolar p-type carbon nanotubes FETs complete understanding of carbon nanotubes FET
and resistors were reported in Ref. 350. Javey et operation.
al.349 reported a complementary carbon nanotubes Besides the specific technical issues discussed
FET ring oscillator with three SWNT based in- above, there is a more fundamental question con-
verters. The oscillating frequency of the device cerning possible nanoelectronic applications of
was measured to be about 220 Hz (Figure 73). carbon nanotubes: What is the best direction to
Thus, the speed of carbon nanotubes devices, re- pursue for alternate information processing tech-
ported at this point, is very slow. The authors349 nologies, for example, carbon nanotubes, molecu-
explain this as due to “extrinsic” factors such as lar electronics, etc.? Today’s attempts in most
external resistance and capacitance of the circuit. cases replicate silicon technology with new
The demonstration of high-speed operation of switches, or integrate nonsilicon components, such

FIGURE 73. Ouput characteristics of a ring oscillator made of three complementary nanotube
inverters. The output frequency is 220 Hz. VDD = -4 V. (Reprinted from Ref. 349, Copyright 2002,
with permission from American Chemical Society.)

342
as carbon nanotubes with silicon, for example, chains, and the water solubility increases with the
CMOS channel replacement technologies. How- number of polar groups. A number of useful
ever, as long as electron transport and energy fullerene-based therapeutics have been reported,
barriers govern device operation, use of carbon including antiviral agents and anti-cancer drugs, as
nanotubes to replace the channel of a silicon well as biosensors for diagnostic applications;300,301
MOSFET would not measurably extend silicon as a protective agent against iron-induced oxida-
CMOS technology. tive stress;306 or as an in vitro antibacterial agent.307
Three important parameters in the realization Fullerenes had been demonstrated to be useful
of digital systems are the device switching speed, in DNA-templated assemblies of inorganic-organic
switching energy dissipation, and integration den- building blocks.312 The fullerene-DNA complex-
sity. The question that should be examined is ation significantly altered the structure of DNA
“What are the ultimate limits to the speed, size, (DNA become very condensed). This complexe
density and dissipated energy of a carbon might be potentially useful for gene delivery.
nanotubes switch (e.g., a FET switch)? The exploration of nanotubes in biomedical
In addition, several issues need to be addressed applications is also underway. Cells have been
to assess the practical feasibility of nanotube based shown to grow on nanotubes, so they have no
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integrated electronics. Possibilities for integra- toxic effect.313 The cells also do not adhere to the
tion of individual carbon nanotubes components nanotubes, potentially giving rise to applications
in a complex circuit (billions of components per such as coatings for prosthetics, and antifouling
cm2) are unclear at this point. coatings for ships. The ability to chemically modify
the sidewalls of nanotubes can be considered for
biomedical applications such as vascular stents,
D. Medical Applications of Fullerene- and neuron growth and regeneration.313
Based Materials Thus, all major forms of carbon at the
nanoscale appear to be valuable resources for
The field of fullerene and carbon nanotube biomedical applications.
biology, as well as applications of fullerene deriva-
tives in biology and medicine, has become increas-
ingly popular.298,299 In the mid-1990s it was dem- E. Atomic Modeling of Carbon
onstrated that fullerene compounds have biological Nanostructures as a Tool for Developing
activity and their potential as therapeutic products New Materials and Technologies
for the treatment of several diseases had been re-
ported. Recently, a private biopharmaceutical com- The results of a number of modeling and simu-
pany, C Sixty Inc. was created with a primary lation studies on carbon nanostructures have been
focus on the discovery and the development of a discussed in appropriate places elsewhere in this
new class of therapeutics based on the fullerene article. For completeness, we include in this sec-
molecule. C Sixty’s lead products are based on the tion a brief discussion of some situations in which
modification of the fullerene molecule and are theory and modeling has led to experiments in
aimed at the treatment of cancer, AIDS, and developing new technologies and applications in-
neurodegenerative diseases.301 volving carbon nanostructures. In some cases the
The flexible chemical reactivity of C60 has experiment has confirmed the theoretical predic-
already resulted in numerous fullerene compounds tions, while in other cases the corresponding ex-
that are now available for study. In addition, at 7.2 perimental measurements have yet to be made.
Å in diameter, C60 is similar in size to steroid
hormones or peptide alpha-helices, and thus
fullerene compounds are ideal molecules to serve 1. Fullerene Structures
as ligands for enzymes and receptors.298 While
fullerene C60 itself shows no solubility in water, Probably the most celebrated triumph of theory
many fullerene compounds can be very water in the area of carbon structures is the prediction
soluble. Such derivatives of C60 contain polar side that the electronic properties of carbon nanotubes,

343
specifically the absence or presence of a band Based on the predicted nanotube wrapping-
gap, depends on the tubule’s helical structure and band gap prediction, several groups have sug-
radius.199,280,353,354 Using simple tight binding gested that joining two nanotubes with similar
theory based on near-neighbor π bonding, it can radii but different helical structures could create a
be shown that when the relation (2n1+n2)=3q is metal-semiconductor junction.355,356 Calculations
satisfied, a nanotube is predicted to have a zero have shown that such a junction is energetically
band gap, with all other structures being semicon- feasible without introducing undesirable radical
ductors. In this expression, n1 and n2 are the inte- electronic states. Similarly, theory proposed that
ger values of the in-plane graphite lattice vectors the electronic properties of nanotubes could be
that define the wrapping of a nanotube, and q is an tuned further by chemisorbing species to their
integer. Further analysis shows that with the ex- walls.95,357 An example structure of this type is
ception of the n1=n2 structures, the zero band gaps illustrated in Figure 74, where ethylene molecules
predicted by simple tight binding theory are due are chemisorbed along part of a (6,0) nanotube at
to a degeneracy of the highest occupied molecular positions that are predicted to open a band gap.
orbital (HOMO) and the lowest unoccupied mo- Based on tight binding calculations, the structure
lecular orbital (LUMO) at the Gamma point, that shown is predicted to have a Schottky barrier of
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is, these structures are semimetals. More detailed 0.44 eV, and metal-induced gaps states that decay
calculations show that s-p mixing removes this from the metallic to the semiconducting region of
degeneracy and introduces a band gap, albeit with the nanotube.95,357 The decay behavior of these
a value that is much smaller than the structures states is quantitatively similar to those at more
predicted to be semiconductors by simple tight conventional interfaces such as Al-Si boundaries.
binding theory, and that the magnitude of the White and Todorov have predicted that
small band gap decreases with increasing nanotube nanotubes display ballistic electron conduction,
radius.354 In the case of the n1=n2 structures, theory with localization lengths of the order of hundreds
has shown that the zero band gap is due to a of nanometers (or more).358 This is exceptional
crossing of the HOMO and the LUMO, resulting behavior, which strongly suggests applications of
in a true metal. nanotubes as efficient nanoscale wires. Additional

FIGURE 74. Illustration of a region of a nanotube containing a metal-semiconductor junction due


to ethylene chemisorption.

344
details regarding transport in nanotubes can be retically for nanotubes used as molecular
found in Ref. 359. indentors,368,369 a property that supports experi-
Theory has also predicted that the value of a mental applications of nanotubes in nanometer-
band gap in a semiconducting nanotube can be scale metrology.370 Similar to kink formation,
changed by an applied stress, and that band gaps theory predicted that nanotubes with large radii
can even be added or removed for large will collapse into ribbon structures due to van der
stresses.357,360,361 This has led to suggestions of Waals attraction between opposing walls of the
nanoscale strain and vibration gauges using nanotube.371,372 These structures have been ob-
nanotubes as sensors in which changes in conduc- served experimentally.372,302
tivity due to strain are utilized.357 Structures with An interesting example of theory and experi-
this specialized function have not yet been con- ment working together is the prediction that kinks
structed. in nanotubes may act as sites of enhanced reactiv-
Recently, Srivastava and co-workers have ity.303 Using molecular modeling and a tight bind-
modeled the structure and electron transport ing model, theory predicted that the ridges along
through both symmetric and asymmetric nanotube the top and bottom of kinks on nanotubes produce
“Y junctions”.362,363 These structures, which when atomic geometries that resemble sp3 bonding,
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appropriately connected resemble neuro-networks, which result in the formation of radical states in
were found to be energetically stable and elec- the band gap of a (17,0) nanotube. Furthermore,
tronically robust with respect to defect states. The these radical states, theory predicted, are sites for
transport calculations suggest that switching and strong chemisorption of hydrogen atoms, and
rectification properties of these structures depend therefore kinks should display enhanced reactiv-
strongly on the symmetry, and to a lesser degree ity. Experimental studies carried out in parallel
on chirality. For symmetric junctions, for example, with the calculations showed that kink sites are
the calculations show that perfect rectification more susceptible to attack by dilute nitric acid
across a junction is possible depending on the than are nonkinked regions of nanotubes. From a
helical structure of the nanotubes, but that for technology viewpoint, these results suggest that
asymmetric junctions rectification is not possible. combining mechanical bending with chemical
Recent simulations and experiments have indi- interactions is a viable route for controlling the
cated that nanotube junctions can be created by cutting of nanotubes to precise lengths for various
electron beam heating of cross nanotubes.364 Taken electronic device applications.
together, the predictions relating band gaps to Several modeling studies have been carried
structure and chemisorption, ballistic electron out to explore the properties of nanotube-polymer
transport models, and the apparently rich behav- composites, particularly how load transfer between
ior and structures possible with Y junctions makes the nanofiber and matrix can be maintained.
a strong case for using these structures for Molecular modeling has suggested that polymers
nanoscale electronic device applications, with the can optimize nonbonded interactions with a
caveats mentioned above.365 nanotube by wrapping helically around the
As discussed above, molecular modeling in nanotubes.304 Molecular modeling studies have
conjunction with continuum treatments of also shown that chemical cross-linking between a
nanotubes showed that severely bent nanotubes nanotube and a polymer matrix can significantly
will kink (much like a garden hose), and that kink enhance load transfer,305 and that somewhat sur-
formation is largely reversible as nanotubes are prisingly such cross links may not significantly
straightened.366,235 The kink structures observed decrease the high modulus that make nanotubes
in these early simulations were remarkably simi- attractive for composite applications in the first
lar to those subsequently seen with electron and place.95
atomic force microscopies.366,367 Both indicate a Molecular modeling studies using classic, tight
flattened region behind the kink, and ridges along binding, and first principles atomic forces have
the top and the bottom of the kink. Reversible also been used to characterize the plastic defor-
kink formation has also been characterized theo- mation of uniaxially strained nanotubes.66,256 These

345
calculations predicted a Stone-Whales transfor- the application of these structures as localized
mation that leads to what can be interpreted as electron sources for templating at scales below
dislocation formation and motion. Because the more traditional lithographies.
kink motion involves bond rotation, and bonds
can have different orientations with respect to the
nanotube axis for different helical wrappings, the 2. Nanodiamond Clusters
calculations predicted that the strength of
nanotubes depends strongly on their structure. The high symmetry of nanotubes helped to
Interestingly, the formation of a dislocation re- facilitate much of the successful theory and mod-
sults in an interface between two nanotubes with eling done on these and related systems. In the
different helical properties but similar radii, which, case of nanodiamond clusters, there is a much
depending on the structures of the nanotube, can greater variation in structure and perhaps fewer
result in a metal-semiconductor junction like that clear-cut technological applications, and so less
discussed above. Hence, these calculations lead has been done in terms of theory leading applica-
to predictions for specific conditions under which tions.
these junctions could potentially be made, as well Galli and co-workers used accurate first prin-
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as predictions of structures with optimized plastic ciples methods to characterize the dependence of
properties for structural materials applications. band gap on the size of hydrogen-terminated nano-
Modeling has indicated that another poten- diamond clusters, as well as to predict surface
tially important application of nanotubes is the reconstructions of clusters without chemisorbed
separation of organic molecular mixtures.70 Simu- hydrogen that are unique to these clusters.90 The
lations of diffusive flow of methane/isobutene, calculations indicate that for the hydrogen-termi-
methane/n-butane, and methane/ethane binary nated structures the HOMO-LUMO gap, which is
mixtures through single nanotubes and nanotube given as 8.9 eV for methane, becomes compa-
bundles were carried out. The simulations showed rable to the band gap for bulk diamond for clus-
effective separation of the butane structures from ters as small as 1 nm. This result is in sharp
methane, but that because of the similarity in size contrast to silicon and germanium clusters, which
separation of methane and ethane was as effec- show quantum confinement effects for larger clus-
tive. The simulations also showed that the helical ters. The lack of quantum confinement effects in
structure of nanotubes has little effect on the dif- diamond clusters is consistent with experimental
fusion coefficients and hence the separation prop- emission and adsorption studies. The first prin-
erties, but that the radius had a large effect with ciples calculations also predicted surface recon-
smaller radii structures showing better discrimi- structions without hydrogen termination that had
nation between different molecules. significant π character. These structures resemble
Molecular modeling and tight binding meth- diamond clusters encapsulated in fullerenes and
ods have also been used to characterize the struc- have been termed “bucky diamond” clusters.
tural and electronic properties of fullerene While not necessarily suggesting new technologi-
nanocones and nanostructures assembled from cal applications of these structures, the results of
nanocones.352 The calculations suggested that de- these studies do point toward potential limitations
pending on their radius, these carbon nanocones and opportunities for using nano-diamond clus-
can exhibit conventional cone shapes or can form ters for nanoelectronics applications.
concentric wave-like metastable structures. Fur- Modeling has also been used to characterize
thermore, the calculations showed that single the bonding and stability of hybrid nanodiamond-
nanocones can be assembled into extended two- nanotube structures.278 The modeling studies,
dimensional structures that can be in a self-simi- which included both a many-body classic poten-
lar fashion with fivefold symmetry. Predicted elec- tial and tight-binding calculations, showed that
tronic properties of nanocones indicated that the several classes of hybrids exist with reasonably
pentagon in the center of a cone is the most prob- low-strain structures interfaces. There are several
able spot for electron field emission, suggesting possible applications of these systems, including

346
as arrays of field emitters (Figure 75) and as tures, suggests that nano-diamond clusters could
nanoscale diodes (Figure 76). While there are be useful in computing applications.
indications that such structures have been real-
ized experimentally, deliberate experimental stud-
ies aimed at technological applications of these V. CONCLUSIONS AND FUTURE
structures have not to date been carried out. OUTLOOK
In an interesting set of calculations, Park,
Srivastava, and Cho used first principles calcula- It is an interesting period in the science of
tions to examine a 31P atom positioned at the carbon, when the different communities such as
center of a diamond nanocrystallite as a solid- those conducting research on graphite-based ma-
state binary qubit.195 The calculations indicated terials, fullerene nanotubes, and diamond, which
that the impurity is much more stable at a substi- were working rather independently and are now
tutional site than an interstitial site, and that the merging into one discipline as their interests con-
placement of the impurity is robust with respect verge at the nanoscale. There is a clear tendency
to diffusion. The calculations also indicated that to understand the properties of all-carbon entities
coupling between the nuclear spin and the weakly at the nanoscale within a unified framework, in-
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bound (valance) donor electrons is suitable for cluding interrelationships between the various
single qubit applications. This result, together with forms of nanocarbon, conditions under which one
the stability of nanotube-diamond hybrid struc- form transforms to another, and the possibility of

FIGURE 75. Illustration of a “mushroom” array of nanodiamond-tubule hybrid structures.

347
FIGURE 76. Illustration of a resonance tunneling diode created from a nanodiamond-
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fullerene hybrid structure.

combining nanocarbon entities into hierarchical ultradispersed diamond has a long history of ap-
structures. plication in the countries of FSU, before
There is increased research activity in the ther- nanotechnology became a popular topic, in such
modynamics and kinetics of carbon at the nanoscale. traditional areas as galvanic coatings, polymer
Ab initio level of sophisticated computer simula- composites, polishing, and additions to lubricants.
tions outlined the sequence of the most stable forms It can be easily produced in ton quantities; how-
of carbon at the nanoscale, which are rings, ever, it is very hard to produce UDD completely
fullerenes, diamond clusters, and graphite particles free of contamination due to the incombustible
as the system size is increased. Interesting forms of impurities (metals, nonmetals, and their oxides)
nonhydrogenated nanodiamond such as bucky-dia- that are located in interparticle areas within ag-
mond have been discovered, and experimental glomerates of UDD particles. A high purity of
confirmation has been provided. Presumably, there UDD is not required, however, for the traditional
are enough data accumulated for the development applications mentioned above. Depending on the
of the three-dimensional carbon phase diagram at application, earlier developed technologies for
the nanoscale, where the third parameter is ths size UDD purification, surface modification as well as
of the carbon entity. Tremendous tasks remain to aggregate-free UDD suspensions are being devel-
be done in order to develop an understanding of the oped for industrial-scale use. It should be empha-
general mechanisms of the nucleation and the sized that developing an understanding of the
growth of carbon nanospecies under a variety of relationship between the complex structure of the
conditions as well as the kinetics of transformation surface of UDD and their physical properties are
between different carbon forms. areas of recent very active research.384 Especially
Special attention in the current review had important, although very challenging, is develop-
been devoted to nanodiamond, which has very ing an understanding of the properties of indi-
diverse structures at the nanoscale, ranging from vidual nanodiamond particles. Regarding novel
individual clusters to high-purity films. As dis- applications of UDD, we pointed out their bio-
cussed in the review, these nanodiamond forms medical applications, an area of research that has
can be produced by very diverse techniques, rang- just started to emerge.
ing from the detonation explosive method to the The properties of carbon nanotubes as well
low-pressure CVD method or by the method of as their prospective applications have been the
chlorinating carbides. It is interesting that focus of a variety of reviews and books. In the

348
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