Letter

pubs.acs.org/NanoLett

Synthesis and Properties of Semiconducting Iron Pyrite (FeS2)

Nanowires
Miguel Caban-Acevedo, Matthew S. Faber, Yizheng Tan, Robert J. Hamers, and Song Jin*
Department of Chemistry, University of WisconsinMadison, 1101 University Avenue, Madison, Wisconsin 53706, United States
*
S Supporting Information

ABSTRACT: We report the growth and structural, electrical,

and optical characterization of vertically oriented single-
crystalline iron pyrite (FeS2) nanowires synthesized via thermal
sulfidation of steel foil for the first time. The pyrite nanowires
have diameters of 410 nm and lengths greater than 2 m.
Their crystal phase was identified as cubic iron pyrite using
high-resolution transmission electron microscopy, Raman
spectroscopy, and powder X-ray diffraction. Electrical transport
measurements showed the pyrite nanowires to be highly p-doped, with an average resistivity of 0.18 0.09 cm and carrier
concentrations on the order of 1021 cm3. These pyrite nanowires could provide a platform to further study and improve the
physical properties of pyrite nanostructures toward solar energy conversion.
KEYWORDS: Iron pyrite (FeS2), nanowire, semiconductor, solar energy conversion, photovoltaics, photoelectrochemistry

ron pyrite (cubic -FeS2, fools gold) is an earth-abundant

I and nontoxic semiconductor that is very promising for solar
energy conversion.1 Based on the band gap of pyrite (0.95 eV,
indirect; 1.03 eV, direct), a 28% photovoltaic conversion
efficiency is theoretically possible, according to the Shockley
Queisser estimate. Furthermore, the high absorption coefficient
of pyrite ( = 6 105 cm1 for h > 1.3 eV), which is several
orders of magnitude larger than that of crystalline silicon,
enables thin absorber layers, reducing material demand.1 Single-
crystalline pyrite is reported to have a high carrier mobility of
360 cm2 V1 s1 and an estimated carrier diffusion length of
0.11 m.2 Pyrite solar cells have demonstrated a high
quantum efficiency of 90% and photocurrents as high as 42 mA
cm2.3 Moreover, in photoelectrochemical (PEC) applications,
pyrite displays excellent stability against photocorrosion in
comparison with other chalcogenide semiconductors (e.g., CdS,
CdSe).3 Together, these favorable attributes make pyrite very
attractive among the inexpensive, earth-abundant candidate
solar materials that have the potential to satisfy the annual
worldwide energy demand.4,5
Despite these advantages, the conversion efficiency of pyrite-
based solar cells remains below 3%, and significant challenges
remain before pyrite can become a useful solar material.1,6 Such
low efficiencies have been attributed to various material issues,
such as phase impurity and intrinsic bulk and surface defects,
driving a need for high-quality pyrite materials. However,
despite the demonstrated growth of high-quality single crystals
via chemical vapor transport, previous efforts to grow pyrite
thin films using methods such as metalorganic chemical vapor
deposition and thermal sulfidation of iron1,710 yielded poor-
quality thin films. On the other hand, advances in nano-
technology can offer new approaches to study the physical
properties of semiconductor materials and improve their
performance toward solar applications.1114 Specifically,
single-crystalline pyrite nanowires (NWs) could be an attractive
platform to study the properties of pyrite relevant to solar
energy conversion and, furthermore, investigate the inherent
material challenges, such as doping control and surface state
passivation. Moreover, since bulk recombination losses are
proportional to volume, NWs could enable the high open-
circuit voltages predicted for very thin films (100 nm)
without the low short-circuit currents,6 due to the advantages of
their one-dimensional (1D) morphology:1318 NWs can
effectively absorb incident sunlight along their long axial
direction and efficiently separate the photogenerated carriers in
the short radial direction.19 Nanocrystals of pyrite have recently
been reported in the literature,2022 and they are being actively
pursued for low-cost pyrite thin film preparation. However, the
synthesis of single-crystalline pyrite NWs remains under-
studied.23 Here, we report a simple synthetic approach for
single-crystal pyrite NWs via thermal sulfidation of steel foil for
the first time. Several methods of structural characterization
convincingly show that the NW products are single-crystalline
pyrite phase, and electrical and surface photovoltage character-
ization shows that the as-synthesized pyrite NWs are p-type
semiconductors.
We have successfully synthesized pyrite NWs by heating a
low-carbon steel foil at 350 C for 2 h under a sulfur
atmosphere. In a home-built reactor consisting of a fused silica
tube equipped with pressure and argon gas flow control, sulfur
powder evaporated upstream reacted with shot-peened and
cleaned steel substrates placed near the hot zone of the tube
Received: December 23, 2011
Revised: February 21, 2012
Published: March 19, 2012

2012 American Chemical Society 1977 dx.doi.org/10.1021/nl2045364 | Nano Lett. 2012, 12, 19771982
Nano Letters
furnace (see Supporting Information for full experimental
details). Representative scanning electron microscopy (SEM)
images of as-synthesized samples (Figure 1a) reveal smooth,
Figure 1. Structural characterization of the as-synthesized pyrite NWs.
(a) A 90 tilt SEM view of the as-synthesized NWs on the steel
substrate. (b) PXRD of an as-synthesized substrate (top trace), in
comparison to the standard diffraction patterns for pyrite (JCPDS no.
65-3321)), pyrrhotite-7T (JCPDS no. 20-0534), iron monosulfide
(JCPDS no. 65-9124), and iron (JCPDS no. 06-0696). (c) Confocal
micro-Raman spectroscopy of the as-synthesized NW substrate.
high-aspect ratio, vertically oriented NWs growing from the
substrate in high density. The NW diameters and lengths range
between 410 nm and 26 m, respectively. The average NW
length does not change significantly with reaction time after 1
h.
The phase identity of the products was determined using
powder X-ray diffraction (PXRD) of the as-synthesized
substrate (Figure 1b). All peaks in the PXRD pattern can be
indexed to pyrite (cubic -FeS2, JCPDS no. 65-3321; space
group Pa3, a = 5.419 ), pyrrhotite-7T (hexagonal Fe9S10,
JCPDS no. 20-0534; space group P6, a = 6.894 , and c =
1978
Letter
40.140 ), iron monosulfide (hexagonal FeS, JCPDS no. 65-
9124; space group P63/mmc, a = 3.450 , and c = 5.670 ), and
iron (cubic Fe, JCPDS no. 06-0696; space group Im3m, a =
2.866 ). The iron disulfide polymorph, marcasite (ortho-
rhombic -FeS2, JCPDS no. 65-2567; space group Pnnm, a =
4.445 , b = 5.425 , and c = 3.388 ), was not detectable in
the PXRD pattern. The sulfide scale layers that formed on the
surface of the steel foil after the thermal sulfidation reaction
accounted for the pyrrhotite-7T and FeS peaks in the PXRD
(additional discussion below). Furthermore, we used confocal
micro-Raman spectroscopy to probe the surface layer of the as-
synthesized substrate. The Raman spectrum (Figure 1c) shows
three peaks at 343, 379, and 430 cm1, which are the
characteristic active modes for pyrite corresponding to the S2
libration (Eg), SS in-phase stretch (Ag), and coupled libration
and stretch (Tg) modes, respectively.24,25 Raman peaks for
marcasite (386 and 323 cm1) were not observed. Note that,
due to the high absorption coefficient of pyrite, the light
penetration depth (defined as 1/) for pyrite at a laser
wavelength of 532 nm is about 16 nm; therefore, Raman
spectroscopy primarily probes the top pyrite layer and the
NWs, in contrast to PXRD, which probes deeper through the
sample.
The most conclusive evidence for single-crystalline pyrite
NWs came from high-resolution transmission electron
microscopy (HRTEM) and 2D fast Fourier transform (FFT)
analysis. Representative HRTEM images (Figure 2a,c) show
Figure 2. HRTEM characterization of the pyrite NWs. Bright-field
HRTEM image and the corresponding FFT of a single pyrite NW
oriented along the (a,b) [100] and (c,d) [110] ZA. (e) HRTEM image
of a single NW along the [010] ZA displaying planar defects along the
NW axis (indicated by arrows).
lattice-resolved single-crystalline NWs oriented along the [100]
and [110] zone axes (ZAs), respectively, for pyrite. The
corresponding FFTs (Figure 2b,d) can be indexed to cubic
pyrite -FeS2. The observed lattice spacings of 5.4 and 3.8
correspond exactly to the (002) and (110) lattice spacings of
pyrite, respectively. All pyrite NWs analyzed exhibit the same
001 axial growth direction. It should be noted that FFT
dx.doi.org/10.1021/nl2045364 | Nano Lett. 2012, 12, 19771982
Nano Letters
Figure 3. (ad) SEM images of as-synthesized samples at reaction temperatures ranging from 325400 C at 45 tilt view, and (eh) the
corresponding cross-sectional SEM images showing the temperature dependence of pyrite NW growth density and the sulfide layer thicknesses,
respectively.
analysis along the [100] ZA alone is not sufficient to identify
the pyrite crystal structure. Cubic pyrite and its orthorhombic
polymorph marcasite share many structural similarities: The
iron atoms in both are octahedrally coordinated, but in pyrite
the octahedra share corners, while in marcasite they share
edges. More importantly, there is only a 1.5% mismatch
between the pyrite lattice parameter a and the two marcasite
dimensions b and (a2 + c2)1/2.26,27 Such a small mismatch
makes the zone axis pattern (ZAP) for pyrite along the [100]
ZA nearly identical to that along the [101] ZA for marcasite
(see simulated ZAPs in Figure S1, Supporting Information).
However, the ZAP along [110] ZA for pyrite is unique and
distinguishable from the ZAP along [010] for marcasite (see
simulated ZAPs in Figure S1, Supporting Information).
Therefore, HRTEM and FFT analysis along the [110] ZA, or
other unique ZAs, must be carried out in order to differentiate
the pyrite structure from the marcasite structure, as
demonstrated in Figure 2.
In addition, planar defects were often observed at the center
of pyrite NWs along their axial length (Figure 2e) when viewed
along the 010 ZA, which have been identified as stacking
faults. Stacking faults have been observed in pyrite, and those
along a [100] pyrite projection have a displacement vector of R
= 0.115[001],28 in agreement with our observations. Due to the
atomic rearrangement, the resulting boundary between both
sides of such stacking fault can be described as a single
marcasite layer (or lamella).28,29 The formation mechanism for
these observed stacking faults remains unclear. It may also be
possible that such stacking faults could seed marcasite inner- or
overgrowth on pyrite NWs or perhaps are the result of
interconversion between the two phases.28
All of the structural characterization evidence makes it clear
that the NWs formed are exclusively pyrite phase. While scale
layers of other iron sulfide phases formed on the growth
substrate, as detected by PXRD, the pyrite NWs can be
harvested from the substrate by gentle sonication for property
studies or applications. We have further investigated and
compared various NW synthesis conditions (Figure 3), with
particular attention given to the thickness and composition of
the resultant transition scale layers. It is clear that NW
formation occurs readily at sulfidation temperatures between
325 to 350 C but only sparsely at 375 and 400 C. The NW
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Letter
density and morphology is optimal at 350 C. The NW
diameter does not depend on the reaction temperature or sulfur
vapor pressure. Distinct sulfide scale layers form on the steel
foil surface, underneath the NW forest, as shown in the cross-
sectional views of spalled flakes of the surface for various
synthesis temperatures (Figure 3eh). Following previous
studies on scale layer formation upon iron sulfidation7,30 and in
accordance with our reported confocal micro-Raman and
PXRD analysis, we have concluded that the top layer of fine,
uniform grains is pyrite, while the bottom layer of coarse,
columnar grains is pyrrhotite. Furthermore, a disorganized
granular pyrrhotite layer was observed below the columnar
pyrrhotite at the surface of the steel substrate (Figure S2,
Supporting Information). The total transition layer thickness
increases with sulfidation temperature, but the pyrite layer
thickness peaks at around 350 C, where the pyrite NW growth
density is highest. This temperature dependence of the
transition layer thickness can be explained by the fact that
iron diffusion toward the surface is the rate-limiting step in the
sulfidation reaction.7 At low temperatures, the overall mass
transport of iron and sulfur species through the steel substrate
is low and relatively equal, so the overall thickness of the film is
small. As the temperature increases, iron diffusion through the
pyrrhotite transition layer increases rapidly relative to the
diffusion of sulfur through the pyrite layer, so the total
thickness of the sulfide layers increases, with the bottom
pyrrhotite layer thickness becoming greater than that of the top
pyrite layer. The decrease in NW density with increasing
temperature and pyrrhotite layer thickness suggests the
importance of slow iron diffusion (relative to that of sulfur)
for NW growth.
Pyrite NW growth by thermal sulfidation has not been
previously reported, even though the sulfidation of iron under
similar conditions for pyrite thin film growth has been
explored.710 The precise reason for this is not clear, but it is
possible that due to their small diameter, the pyrite NWs could
have been overlooked in earlier studies. Alternatively, the
pyrrhotite XRD peaks at 2 42 and 49 have not been
previously observed,7 suggesting a unique composition of the
sulfidation products presented here. Analogies can be drawn
between this synthesis and the thermal oxidation synthesis of
various metal oxide NWs on metal substrates31,32 and the
dx.doi.org/10.1021/nl2045364 | Nano Lett. 2012, 12, 19771982
Nano Letters Letter

synthesis of Cu2S NWs via sulfidation of Cu metal that have

been reported and investigated in detail33,34 to explain the
driving force for the anisotropic growth of pyrite NWs. Note
that, however, Cu2S is the lower sulfide species in the CuS
system, which would be more suitably compared to Fe1xS in
the FeS system. There is also a difference in the sulfidation of
Cu where H2S gas was used as the sulfur source. If H2S is used
for thermal sulfidation, the formation of pyrite is slow.30 The
mass transport through the transition iron sulfide layer is likely
important for pyrite NW growth, as similarly explained for
hematite (-Fe2O3) NW growth via thermal oxidation of
iron.3537 In that case, the transition layer, composed of the
lower iron oxides, reduces overall iron diffusion, but grain
boundaries and defects enhance iron delivery to the surface,
which facilitates 1D growth. As a result, there is a critical iron
thickness for hematite NW growth.35 Similarly, we found that
no significant pyrite NW growth can be observed on
evaporated iron films thinner than 1 m. The stacking faults
observed in the pyrite NWs might also facilitate iron diffusion,
enhancing 1D growth.37 However, there are differences
between the hematite and the pyrite NW syntheses: At their
respective optimal NW growth temperature, sulfur is the more
mobile species during pyrite NW growth, while iron diffuses
faster during hematite NW growth. This relative diffusion
argument explains the thick pyrite layer relative to the
pyrrhotite transition layer at the optimal NW growth condition
(Figure 3f).
We have also characterized the physical properties of these
pyrite NWs. To probe their electrical properties, we fabricated
four-probe single NW devices using standard e-beam
lithography techniques followed by the deposition of Au
contacts (see Supporting Information for full fabrication
details). Representative room temperature electrical measure-
ments of a typical pyrite NW device show linear current (Isd)
versus voltage (Vsd) behavior (Figure 4a), indicating ohmic
contact. Through four-probe measurement (red solid line in
Figure 4a), a resistivity of 0.27 cm was calculated for this
representative NW using the diameter and length measured
through SEM imaging (inset of Figure 4a), with the accuracy of
the diameter measurements confirmed by atomic force
microscopy (Figure S3, Supporting Information).The measure-
ment of 10 independent four-probe NW devices revealed an
average resistivity of 0.18 0.09 cm. Furthermore, we
utilized degenerately doped silicon substrates coated with a 100 Figure 4. (a) IV curve for two (black) and four (red) probe
nm thick Al2O3 dielectric layer as back gate to probe the pyrite measurements of a single pyrite NW device, with an SEM image of a
NW devices in a field-effect transistor (FET) configuration. typical device (inset). (b) IV curves for a pyrite NW FET under an
The conductance of the pyrite NW FETs increased slightly applied Vg of 20, 0, and 20 V (black, blue, and red trace,
respectively). The inset shows Isd versus Vg plotted at Vsd = 1 V. (c)
with a negative applied gate voltage (Vg), indicating p-type
The wavelength dependence of the peak areas extracted from the TR-
behavior. The plot of Isd versus Vg at Vsd = 1 V (Figure 4b, SPV transients (inset), normalized by the photon energy for an as-
inset) yielded a small transconductance of 0.41 nA/V. The synthesized pyrite NW sample.
weak gating behavior suggests high dopant concentration and
low carrier mobility. The field mobility can be estimated from films that are heavily doped.6,9,40 From the measured resistivity
the transconductance, dI/dVg = (C/L2)Vsd, where is the () of this pyrite NW, a carrier concentration (N) of 4 1021
carrier mobility, C is the capacitance, and L is the length of the cm3 was estimated using N = 1/q (where q is the electron
NW. The NW device capacitance is given by C = 2keff0L/
charge), which is consistent with the low mobility. Analogous
ln(2tox/r),38,39 where keff and tox are the effective dielectric
constant and the thickness of the Al2O3 layer, and r is the pyrite to previously studied pyrite thin films, unintentionally highly p-
NW radius. Here, we use keff = 0.5Al2O3 (4.7), in accordance doped pyrite can result from iron vacancies and interstitial
with previous studies.39 The representative pyrite NW FET sulfur.6 Controllable doping and elimination of vacancies and
shown in Figure 4b yielded an estimated hole mobility of 0.03 other defects would be desirable for future solar applications of
cm2 V1 s1, which is very low compared to that reported for these pyrite NWs. This might be achieved by intentional
natural and synthetic pyrite single crystals (360 cm2 V1 s1) doping with other metals or appropriate annealing procedures,
but comparable to the values reported for p-type pyrite thin which are currently under investigation.
1980 dx.doi.org/10.1021/nl2045364 | Nano Lett. 2012, 12, 19771982
Nano Letters
The as-synthesized pyrite NWs on as-grown substrates were
further studied by the time-resolved surface photovoltage (TR-
SPV) technique using a capacitor-like arrangement41 (exper-
imental details in the Supporting Information). SPV is a
contactless technique that can reveal information on charge
separation at the semiconductor surface. In TR-SPV, the
sample is illuminated with brief laser pulses, and charge
separation generates a change in surface potential that can be
sensed using a pickup electrode located in close proximity.41
Band bending in a semiconductor affects charge separation near
the surface, resulting in the surface localization of either holes
or electrons, depending on the doping type.42 We measured the
TR-SPV transients in ambient conditions at a series of
excitation wavelengths (Figure S4, Supporting Information).
This capacitive measurement produces a photocurrent, with the
total charge proportional to the area under the SPV peak. The
TR-SPV signal (Figure 4c, inset) corresponds to electron
accumulation at the surface and confirms that the as-
synthesized pyrite NWs and the top pyrite surface are of p-
type. Because the signal lies within the measurement pulse
width of the laser, the kinetics of the charge separation and
recombination could not be resolved. To extract the peak area,
we mathematically modeled the SPV signal (Figure 4c, inset) as
an exponential convoluted with a Gaussian (transient fitting
procedure in the Supporting Information), the fitted peak areas
were normalized to the photon energy at each wavelength and
plotted against wavelength (Figure 4c). The resulting curve
matches the absorption of pyrite.2,3,22 Linear extrapolation of
the SPV spectrum reveals an estimate for the absorption onset
around 0.89 eV (1386 nm), which would correspond to the
indirect band gap transition for pyrite.
In conclusion, we demonstrated the first example of vertically
oriented, single-crystalline iron pyrite NW synthesis through
thermal sulfidation of a steel substrate. The crystalline phase of
the NWs was confirmed to be the cubic iron pyrite by HRTEM
analysis and corroborated by PXRD and Raman spectroscopy.
Electrical transport measurements revealed highly doped p-type
semiconducting pyrite NWs with resistivity, carrier mobility,
and carrier concentration similar to values reported for p-type
pyrite thin films. The direct use of these pyrite NWs on as-
grown substrates for solar devices may be difficult due to the
underlying sulfide scale layer. However, the NW products can
be harvested from the growth substrates, and the throughput of
the synthesis can be improved by employing high surface area
substrates. Though the physical properties of the as-synthesized
pyrite NWs could be improved through control of the dopant
concentration, their semiconducting behavior and optical
characteristics make these pyrite NWs a versatile platform to
study and improve the fundamental physical properties of
pyrite toward applications in photovoltaic or photoelectro-
chemical solar energy conversion.
ASSOCIATED CONTENT
*
S Supporting Information
Experimental details, TR-SPV transient peak fitting, and other
materials as mentioned in the text. This material is available free
of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*E-mail: jin@chem.wisc.edu
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Letter
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This research is supported by the U.S. Department of Energy,
Office of Basic Energy Sciences, Division of Materials Sciences
and Engineering under award DE-FG02-09ER46664 (to both
S.J. and R.J.H.). M.C.-A. and M.S.F. also thank the NSF
Graduate Research Fellowship for support. S.J. also thanks the
Research Corporation SciaLog Award for Solar Energy
Conversion for support.
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