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Chemical Vapor Deposition (#06682G)
Chapter 1
J. R. Creighton and P. Ho
Sandia National Laboratories
P.O. Box 5800, MS0601
Albuquerque, NM 87185-0601
39.098 40.08 44.956 47.90 50.942 51.996 54.938 55.847 58.933 58.70 63.546 65.39 69.72 72.61 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.468 87.62 88.906 91.22 92.906 95.94 (99) 101.07 102.905 106.4 107.868 112.4 114.8 118.7 121.8 127.6 126.9 131.30
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn
132.905 137.33 138.9 178.49 180.948 183.85 186.2 190.2 192.22 195.09 196.966 200.59 204.37 207.2 209.0 (210) (210) (222)
87 88 89
Fr Ra Ac
(223) (226) 227.0
57 58 59 60 61 62 63 64 65 66 67 68 69 70 71
LANTHANIDES La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
138.9 140.115 140.1 144.2 (145) 150.4 152.0 157.2 158.9 162.5 164.9 167.3 168.9 173.0 174.96
89 90 91 92 93 94 95 96 97 98 99 100 101 102 103
ACTINIDES Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
227.0 232.0 231.0 238.0 237.0 (244) (243) (247) (247) (251) (252) (257) (256) (259) (257)
Fig. 1: Periodic table, where shaded boxes indicate elements that have been deposited using CVD.
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2001 ASM International. All Rights Reserved. www.asminternational.org
Chemical Vapor Deposition (#06682G)
In its simplest incarnation, CVD involves surface to be coated and the source. Another
flowing a precursor gas or gases into a chamber advantage of CVD is that, in addition to the wide
containing one or more heated objects to be variety of materials that can be deposited, they
coated. Chemical reactions occur on and near can be deposited with very high purity. This
the hot surfaces, resulting in the deposition of a results from the relative ease with which
thin film on the surface. This is accompanied by impurities are removed from gaseous precursors
the production of chemical by-products that are using distillation techniques. Other advantages
exhausted out of the chamber along with include relatively high deposition rates, and the
unreacted precursor gases. As would be expected fact that CVD often doesnt require as high a
with the large variety of materials deposited and vacuum as PVD processes.
the wide range of applications, there are many CVD also has a number of disadvantages.
variants of CVD. It is done in hot-wall reactors One of the primary disadvantages lies in the
and cold-wall reactors, at sub-torr total pressures properties of the precursors. Ideally, the
to above-atmospheric pressures, with and precursors need to be volatile at near-room
without carrier gases, and at temperatures temperatures. This is non-trivial for a number
typically ranging from 200-1600C. There are of elements in the periodic table, although the
also a variety of enhanced CVD processes, use of metal-organic precursors has eased this
which involve the use of plasmas, ions, photons, situation. CVD precursors can also be highly
lasers, hot filaments, or combustion reactions to toxic (Ni(CO)4), explosive (B2H6), or corrosive
increase deposition rates and/or lower deposition (SiCl4). The byproducts of CVD reactions can
temperatures. There are also many derivatives also be hazardous (CO, H2, or HF). Some of
of the CVD terminology, such as metal-organic these precursors, especially the metal-organic
chemical vapor deposition (MOCVD)16,17 or, less precursors, can also be quite costly. The other
commonly, organo-metallic chemical vapor major disadvantage is the fact that the films are
deposition (OMCVD), which are sometimes usually deposited at elevated temperatures. This
used to note the class of molecules used in the puts some restrictions on the kind of substrates
deposition process. Some practitioners chose to that can be coated. More importantly, it leads to
differentiate epitaxial film deposition from stresses in films deposited on materials with
polycrystalline or amorphous film deposition, different thermal expansion coefficients, which
so they introduced a variety of terms that include can cause mechanical instabilities in the
epitaxy in the acronym. Two of the more deposited films.
common variants are organometallic vapor phase CVD processes can be categorized
epitaxy (OMVPE) 7 and metalorganic vapor according to the type of:
phase epitaxy (MOVPE)18 which are often used 1. Application,
in the compound semiconductor epitaxy 2. Process and reactor used, or
3. Precursor and chemical reaction used.
literature.
The next three sections of this chapter are
CVD has a number of advantages as a
method for depositing thin films. One of the arranged around such subdivisions. These
primary advantages is that CVD films are sections are followed by a discussion of the
generally quite conformal, i.e., that the film fundamental processes underlying CVD, such
thickness on the sidewalls of features is as mass transport, thermodynamics, and
comparable to the thickness on the top. This chemical kinetics. Finally, we present a brief
means that films can be applied to elaborately analysis of the historical and current status of
shaped pieces, including the insides and CVD R & D.
undersides of features, and that high-aspect ratio
holes and other features can be completely filled. CVD Applications
In contrast, physical vapor deposition (PVD)
techniques, such as sputtering or evaporation, One of the earliest examples of a large-scale
generally require a line-of-sight between the CVD application was a carbonyl process for
2001 ASM International. All Rights Reserved. www.asminternational.org
Chemical Vapor Deposition (#06682G)
4 Creighton and Ho
Fig. 2: Cross section of a silicon microelectronic memory circuit showing several materials
deposited by CVD; polycrystalline silicon, tungsten (W), SiO2, and Si3N4. Photo courtesy
of Pat Shea, Sandia National Laboratories.
CVD or PECVD. The CVD steps define the these devices contain two dimensional (2-D)
structure of the device perpendicular to the quantum wells or superlattices composed of
silicon substrate, while numerous lithographic strained epitaxial layers that are 1-10 nm thick.
and etching steps define the structure in the other An example of a strained layer superlattice is
two dimensions. CVD is sometimes used to shown in Figure 4. In addition to quantum wells,
apply coatings to reduce friction after the 3-D laser structures such as the vertical cavity surface
structure is created. Work is also being done to emitting laser (VCSEL) contain mirror stacks
integrate MEMS devices with silicon composed of a large number of alternating layers
microelectronic devices on the same chip. of semiconductor material that are typically
The field of nanotechnology has generated 50-100 nm thick. The thickness of each layer
a lot of recent interest, and focused research often must be controlled with a precision better
programs have been initiated in almost all than 1 nm. Despite this requirement these
industrialized countries in the last five years. In devices can be grown routinely with relatively
2000 the U.S. launched the National Nano- high yield in finely tuned and calibrated OMVPE
technology Initiative, with plans to nearly double reactors. 28 A related CVD technique that
the nanoscale R & D effort.26 Nano-technology automatically yields subnanometer control is
is an extremely diverse topic, but some of the known as atomic layer epitaxy (ALE).29
best examples of existing nanoscale R & D are in An extension of 2-D quantum well R & D
the area of epitaxial heterostructures for laser involves the generation of quantum wires (1-D)
diodes and LEDs grown by CVD.7,23,27 Many of and quantum dots (0-D).27,30 Quantum dots are
2001 ASM International. All Rights Reserved. www.asminternational.org
Chemical Vapor Deposition (#06682G)
6 Creighton and Ho
Fig. 3: Example of a silicon surface micromachined gear train. Courtesy of the Intelligent
Micromachine Initiative, Sandia National Laboratories.
Fig. 4: Strained layer superlattice of InAsSb on InSb with 10 nm layer thickness. Photo courtesy
of R. M. Biefeld, Sandia National Laboratories.
2001 ASM International. All Rights Reserved. www.asminternational.org
Chemical Vapor Deposition (#06682G)
Fig. 5: Indium arsenide quantum dots deposited on gallium arsenide by OMVPE. Photo courtesy
of Jeff Cederberg and R. M. Biefeld, Sandia National Laboratories.
often considered to be artificial atoms, where a thick Rhenium CVD coating is applied to a
the effect of quantum confinement significantly sacrificial molybdenum mandrel, which is later
perturbs the normal bulk electronic properties removed by etching. Another example is the
of the material. One method of growing quantum production of large-scale infrared optical materials
dots involves depositing one material on another (ZnSe and/or ZnS up to several feet across).32
with a large lattice mismatch. The example in
Figure 5 is InAs on GaAs(100) by CVD. Due to CVD Reactor Types
the interfacial properties of this highly strained
layer, InAs spontaneously forms islands on the As mentioned in the introduction, CVD
10-nm scale with a relatively narrow size encompasses a wide range of reactor and process
distribution. The electronic and optical types. The choice of process/reactor is
properties of the InAs quantum dots are determined by the application via the
dramatically different from bulk InAs, allowing requirements for substrate material, coating
for novel device fabrication. material and morphology, film thickness and
In addition to the numerous electronic and uniformity, availability of precursors, and cost.
optoelectronic applications mentioned above, Here, we discuss the general types of reactors
novel applications of CVD are also being used used for CVD, and refer the reader to the other
to generate macroscopic components (10 cm as chapters in this and other books for detailed
opposed to 1 nm). One interesting example is information on specific systems.
the production of Ir/Re thrust chambers for liquid Hot wall reactors represent one of the major
rocket motors (see Figure 6).31 For this structure categories of CVD reactors. In such systems,
2001 ASM International. All Rights Reserved. www.asminternational.org
Chemical Vapor Deposition (#06682G)
8 Creighton and Ho
Fig. 6: Rhenium rocket thrust chamber fabricated using CVD. Photo courtesy of B. H. Tuffias,
Ultramet.31
shown schematically in Figure 7, the chamber relatively uniform substrate temperatures and
containing the parts is surrounded by a furnace thus coating thicknesses. The primary
that heats the system. The parts are loaded into disadvantages are that the walls get heavily
the system, it is heated to the desired coated, requiring frequent cleaning and causing
temperature, then the reactive gases are particle problems, and that it involves higher
introduced. The reactor may be equipped with thermal loads and energy usage.
shelves for coating many parts at once, or be Cold wall reactors are the other major
sized for specific large parts. These systems are category of CVD reactors. In such systems, the
often run at very high temperatures, limited only substrates are heated but the walls are cooled.
by the materials used in constructing the furnace, Figure 9 shows an example of a cold wall
and at reduced pressures, on the order of Torr to rotating disk CVD reactor.28,33 This system has
tens of Torr. Figure 8 shows a schematic for a water-cooled quartz walls, with a rotating holder
hot-wall reactor that has been tailored to low- for (silicon or compound semiconductor) wafers
pressure CVD (LPCVD) batch processing in the that is resistively heated from below. Other
microelectronics industry. In this case, a commercial cold-wall reactors include lamp
specialized support holds a large number (over heated single-wafer reactors that are widely used
a hundred) of closely-spaced silicon wafers for in microelectronics fabrication, and inductively
simultaneous processing. In general, hot wall heated horizontal flow reactors. Cold-wall
reactors have the advantages of being able to reactors are often run at relatively high pressures,
process large batches of substrates, and having several hundred torr to atmospheric total
2001 ASM International. All Rights Reserved. www.asminternational.org
Chemical Vapor Deposition (#06682G)
Gas Inlet
Heating
Elements
Parts
Being
Coated
Shelves
Exhaust
to Pump
Fig. 7: Schematic drawing of hot-wall CVD reactor used to coat multiple parts.
Gas Inlet
Heating
Elements
Wafers
Exhaust to Pump
Fig. 8: Schematic drawing of LPCVD furnace for batch processing of multiple silicon wafers.
2001 ASM International. All Rights Reserved. www.asminternational.org
Chemical Vapor Deposition (#06682G)
10 Creighton and Ho
Gas Inlet
Rotating
Water Holder Water Cooled
Quartz Walls
Stationary
Heater
Exhaust
to Pump
Fig. 9: Schematic diagram of a cold-wall rotating disk CVD reactor used for depositing thin films
on semiconductor wafers.
pressure, and usually have the reactive precursors over a set of rollers. In other cases, such as the
diluted in a carrier gas. Most compound large-scale application of optical coatings (i.e.
semiconductor CVD processes use reactors of low-E coatings) to glass, the moving belt could
this type. Cold wall reactors have the advantages be the float-glass sheet itself. These systems are
of reduced deposition of material on the walls, essentially open to atmosphere the reactive
which means less cleaning, lower thermal loads gases are contained by curtains of inert gas
on the substrates because of faster heat-up and on either side of the deposition zone. Such
cool-down times, lower energy consumption, and systems have the advantage that they can do very
the avoidance of vacuum equipment. The primary large scale production, and avoid vacuum
disadvantages are larger temperature non- equipment. The disadvantages are a relatively
uniformities on the substrate, which may lead to high rate of gas consumption, potential non-
film thickness non-uniformities, the smaller batch uniformities in film thickness, relatively low
sizes, and possible thermal stresses on the operating temperatures because of the high
substrates if the heating/cooling is too rapid. volumes of gas involved, and relatively low
A specialized variation of a cold wall reactor efficiency for precursor use.
is the continuous reactor shown schematically Plasma-enhanced (PECVD) or plasma-
in Figure 10. In this system, the surface to be assisted (PACVD) CVD, (see chapters in
coated moves underneath a set of gas injectors Refs. 5, 14, and 15), constitute a smaller category
and is heated from below. In some cases, the of CVD processes that also involves a variety of
substrates (wafers) are placed on a belt moving reactor designs. In these systems, a plasma is
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