Materials Letters 126 (2014) 181–184

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Synthesis, characterization and optoelectronic properties

of iron pyrite nanohusks
M. Alam Khan a,b,n, M.O. Manasreh a, Yong-Mook Kang b
a
Optoelectronic Laboratory, Department of Electrical Engineering, University of Arkansas, Fayetteville, 72701 AR, United States
b
Department of Energy and Materials Engineering, Dongguk University-Seoul, Seoul 100-715, Republic of Korea

art ic l e i nf o a b s t r a c t

Article history: Poly-sized iron pyrite nanohusks with an average length of
6 nm were synthesized in ethanolamine
Received 4 February 2014 which acts as a solvent and a surfactant at 210 1C in a Schlenk flask. An X-ray diffraction pattern and
Accepted 10 April 2014 Raman spectra show a cubic iron pyrite structure with prominent Raman peaks at the 339.5 and 378
Available online 18 April 2014
positions, typical of cubic iron pyrite. UV–vis spectra show an increased band gap of 1.34 eV due to
Keywords: quantum size effects. The synthesized semiconducting iron pyrite nanohusks owing to lighter weight
Iron pyrite and strong visible light coverage have advantages over large pyrite nanocrystals, since the larger
Photovoltaics particles usually sink down to the bottom on spin casting due to unavoidable gravity effects. When such
Band gap nanohusks were applied in a bulk-heterojunction type solar cell with an n-type fullerene (PCBM), an
Optical properties
efficiency of 0.23% was observed with a JSC of 1.4 mA/cm  2, a VOC of 0.17 V and a fill factor of 32. The
Nanohusks
morphology and optoelectronic properties of the synthesized nanohusks were elucidated by TEM, XRD,
Raman spectra
micro-Raman spectra, UV–vis, SEM, XPS, TEM-EDX and J–V techniques.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction
It is increasingly clear that the finite supply of the traditional
fuels (fossil, coal and gas) must shift in the favor of renewable
energy resources in order to fulfill the growing global energy
needs (20 TW) [1,2]. Among several promising resources, photo-
voltaic energy is perceived as reliable, clean and inexhaustible;
however, significant cost reduction is necessary to compete with
fossil fuels. At present silicon based solar cells dominate the
photovoltaic market; however, their significant cost and complex
technology impede their wide use. Hence alternative technologies
such as CIGS and CdTe are explored [3]. Most of the alternative
structures use either toxic or trace elements such as Cd, In, and Pb
[4]. Instead, non-toxic, abundant, and thus cheap materials such as
FeS2, Cu2O, Cu2S and SnS are typical p-type and earth abundant,
are much more promising and could make an impact even with
overall low efficiencies. Among all these materials iron pyrite
(FeS2) is the most attractive in both cost and abundance [5].
Recently iron pyrite (FeS2, fool’s gold) has been getting resurgent
interest owing to its promising attributes such as abundance, non-
toxicity, high absorption coefficient (
5  105 cm  1 for hν 41.3 eV)
n
Corresponding author at: Department of Energy and Materials Engineering,
Dongguk University-Seoul, Seoul 100-715, Republic of Korea.
Tel.: þ 1 479 575 5444; fax: þ 1 479 575 7967.
E-mail address: alamkhan77@gmail.com (M. Alam Khan).
and a very suitable band gap (0.95 eV) [6,7]. The high natural
abundance of iron pyrite translates into an estimated 0.000002 ¢/W
of material extraction cost. Recently, Wadia et al. placed it among
the top 23 promising potential candidates for solar electricity
generation [8]. The Schottky junction type pyrite photovoltaic
devices reported so far exhibit high quantum efficiency and photo-
current but low photovoltage which is often less than 20% of the
band gap [9]. The causes of such low voltage and efficiencies are
material issues, such as phase impurity, intrinsic bulk, surface
defects and mid gap defect states which cause Fermi level pinning.
But, the theoretical limit of the power conversion efficiency of FeS2
is reported to be better than those of CuInSe2, CdTe, and Si based
photovoltaic devices [10]. This is mainly due to the major advantage
of the diffusion/drift length (0.1–1.0 μm) in iron pyrite. The optical
and electrical properties can be improved by increasing the energy
band gap (Eg) of FeS2 by tuning the crystal sizes [11,12] where Eg
increases with respect to the size of nanocrystals. Although it is
reported that in pyrite based photovoltaics less than a micron of
total thickness (
30–300 nm) is enough to absorb all visible
spectrums, most of the time it is difficult to make high quality
films because of the large nanocrystals [13], resulting in uneven film
surface, particle aggregation and non-uniformity with nanoscale
separation. Quantum sized pyrite particles owing to lighter weight
can be suspended well and expected to form better and uniform
films. Herein, we report phase pure semiconducting iron pyrite
nanohusks with excellent light absorption properties and processed

http://dx.doi.org/10.1016/j.matlet.2014.04.060
0167-577X/& 2014 Elsevier B.V. All rights reserved.
182 M. Alam Khan et al. / Materials Letters 126 (2014) 181–184
for photovoltaic testing. To the best of our knowledge such quantum
sized and band tuned phase pyrite nanohusks have not been
reported.
2. Experimental
Iron pyrite (FeS2) cubic quantum dots were prepared by a
colloidal synthetic route similar to that reported by our group [14].
In a typical synthesis, 10 ml of ethanolamine (90%, Acros) was
injected into a 100 ml Schlenk flask, then 600 mg of FeCl2.4H2O
(Alfa Aesar) was mixed in it in N2 atmosphere with mild stirring at
115 1C for 1.5 h to degas it, and then in another Schlenk flask
600 mg of Sulfur (99.9%, Sigma-Aldrich) was mixed in 15 ml of
diphenyl ether (Merck) and degassed in N2 atmosphere at 85 1C
for 1 h. Then the later lot was injected into the first flask at 210 1C
with a total reaction time of 1 h with vigorous stirring in N2
atmosphere and cooled down promptly using an oil bath. Then
few drops of chloroform (Merck) were added to prevent coagula-
tion of FeS2 nanocrystals at a suitable temperature and lastly it was
washed with methanol (99.5%, Merck) several times using a
centrifuge at 5000 rpm for 10 min.
For the solar cell application: An ITO glass was masked, etched
and cleaned with ethanol, detergent, and acetone successively
with 10 min sonication, respectively. Highly conducting poly (3,4-
ethylene-dioxylenethiophene): polystyrene sulfonic acid (PEDOT:
PSS) was spin casted (4000 rpm for 50 s). After that it was
annealed at 140 1C for 10 min. In 1.0 ml of chloroform solvent
FeS2 (10 mg) and PCBM (20 mg) were added in a vial in a glove box
and then sonicated for 15 min to dissolve homogeneously; after
that the mixture was magnetically stirred for 24 h. Then the active
layer was spin casted at 1600 rpm for 30 s and dried at room
temperature. Then with the use of a cotton bud the spilled active
layer was carefully wiped out at the sides of PN electrodes. After
this procedure an Al (80 nm) electrode was deposited by vacuum
evaporation at 10  6 Torr. Post-annealing was carried out at 120 1C
for 10 min and the active area was 0.04 cm2.
Photocurrent–voltage (J–V) curves of the cell were measured by
current–voltage characteristic measurement (digital source meter;
model 2400, Keithly) with illuminating conditions (AM1.5G, model
ORIEL-Sol-3A, Newport). The morphology of the samples was
imaged with a transmission electron microscope (A FEI Titan
80–300, Transmission Electron Microscope at 300 kV). X-ray
diffraction (XRD) analysis was performed by Philips PW3040
X’Pert MRD High Resolution XRD and Ni-filtered with CuKα
radiation. Absorption spectra dispersed in chloroform were
recorded on a Cary 5000 UV–vis-NIR spectrophotometer. Micro-
Raman spectra were measured by making a film by drop casting
on a glass slide using the HORIBA Jobin Yvon’s LabRAM.
X-ray photo-electron spectroscopy (XPS, PHI 5000, Versa Probe,
ULVAC-PHI, Inc., Japan) was performed at 1.1  10  7 Pa with Al Kα
radiation.
3. Results and discussion
The optical properties of the synthesized quantum nanohusks
were analyzed by UV–vis spectra which are shown in Fig. 1. The
figure clearly indicates that the absorption onset is at 920 nm on
extrapolating the spectral curves with the estimated band gap of
1.34 eV. It is interesting to observe a shoulder at 2.56 eV which
shows monotonic absorption rise. The nanocrystal shows visible
light absorption throughout indicating a promising material for
photovoltaic application. The inset in Fig. 1 shows the X-ray diff-
raction (XRD) analysis which depicts that the synthesized nano-
husks show a diffraction pattern similar to a cubic FeS2 structure
4 (311)
400
(200)
Intensity (arb. units)
(210)
(220)
300 (211)
3
Intensity (arb. units)
(111)
200
2
100
20 30 40 50 60
1 2Theta
0
400 600 800 1000 1200
Wavelength (nm)
Fig. 1. UV–vis spectra of the synthesized iron pyrite nanohusks in ethanolamine;
inset: X-ray diffraction patterns of the sample.
without a trace of detectable marcasite, pyrrotite, greigyte and
other impurities. The dominant peak position can be matched
with JCPDS no. 42-1340 and peaks assigned to 28.21, 32.81, 36.91,
40.51, 47.31, and 56.21 corresponding to crystal phases of (111),
(200), (210), (211), (220), and (311). It is worth noting that the
samples prepared in ethanolamine indicate a preferred crystal
orientation of (200).
The morphology and size of the synthesized samples were
analyzed by transmission electron microscopy (TEM) and are
represented in Fig. 2(a and b). It clearly shows that the synthesized
nanocrystals are poly-sized with an average length of
6 nm with
the morphology matching a rice husk. The corresponding high
resolution image is shown in Fig. 2(b) where the clarity of the
particle husks is more prominent with tapering ends and being
relatively thicker in the center. An image of Fast Fourier Transform
(FFT) of the iron pyrite nanohusks (inset (a)) shows a ring pattern
and can be indexed as crystalline in nature.
Micro-Raman spectroscopy analysis is depicted in Fig. 3(a). The
Raman analysis was conducted to further check out any trace
peaks of marcasite, greigyte, FeS or any other pyrite phases. The
dominant phonon mode at 339.5 and 378, and a small shoulder at
360 can be assigned to the Ag (S2 dumbel liberation), Eg (S2
dumbell stretching), Tg(1) and Tg(3) vibrational modes. A fifth band
which was expected to appear in the Raman spectra at position
377 cm  1 (Tg (2) mode) is possibly buried within the dominant Eg
peak. Micro-Raman mapping of films at several positions of the
sample shows only homogeneous pyrite peaks with no sign of
marcasite or other impurity phase peaks. Fig. 3(b) shows the J–V
characteristics of the nanohusks when processed for the photo-
voltaic test in a bulk-heterojunction type. The device architecture
was made as ITO/PEDOT:PSS/FeS2:PCBM/Al. The prepared device
shows an efficiency of η ¼0.23% with a JSC of 1.4 mA/cm  2, a VOC of
0.17 V and a fill factor of 32. The inset in Fig. 3(b) shows a cross-
sectional SEM image of the active layer (FeS2:PCBM) which shows
a thickness of
250 nm.
Tailoring the optoelectronic properties without changing any
chemical composition opens up the curiosity of the colloidal
method where the electronic and optical properties of any
semiconductor could be altered. The iron pyrite has a promising
absorption coefficient of α ¼6  105 cm  1 and a suitable band gap
of 0.95 eV which are very attractive for the thin absorber layer for
photovoltaic applications. Moreover, the solution based processes
offer other appealing traits such as substantial cost reduction,
flexibility and ease of handling, ideally suited for PV technology.
Most of the films for photovoltaic applications are spin casted
where the size of inorganic nanocrystals plays a crucial role and
 M. Alam Khan et al. / Materials Letters 126 (2014) 181–184 183

100 nm 50 nm

Fig. 2. TEM image of the synthesized sample: (a) low resolution and (b) corresponding high resolution image; inset (a): Fast fourier transform (FFT) pattern of iron pyrite
nanocrystals.

800 2.0
= 0.23%
Raman Intensity (arb. units)

600 1.5
250 nm
JSC (mA/cm-2)

400 1.0
300nm

200 0.5

0 0.0
300 350 400 450 0.05 0.10 0.15 0.20 0.25 0.30
Wavenumber (cm ) -1
VOC (volt)

Fig. 3. (a) Micro-Raman analysis indicating phonon modes of as synthesized iron pyrite nanohusks, and (b) J–V characteristic of the photovoltaic response; inset shows a
cross-sectional image of thin films.

bigger crystals tend to sink to the bottom which results in
nanoscale separation or renders the film unsuitable/inefficient
for photovoltaic application.
So in the present study size tuned pyrite nanohusks that are
lighter in nature are expected to cast uniform and smooth films
with better efficiency; however, an efficiency of 0.23% was quite
low, which can be attributed to poor contact with the substrate,
particle boundary involvement, non-perfect ratio of Fe:S (1:1.97)
as analyzed by TEM-EDX (Supporting information; Fig. S1) and
nanoscale separation in the films of fullerene and inorganic FeS2
due to different physio-chemical natures. X-ray photoelectron
spectra (XPS) were further analyzed to investigate the pyrite
nanohusks and the details are shown in Fig. S2 (supporting
information) where the observed Fe2p spectra clearly show two
resolved peaks at 710 eV and 723 eV, corresponding to Fe 2p3/2, Fe
2p1/2. However, signals of spin orbital S 2p components are weak
at 162 eV and can be attributed to S2p which is in good agreement
with the bulk iron pyrite reported elsewhere [15]. Since ethano-
lamine acts both as a solvent and a surfactant and with a suitable
temperature (210 1C) the precursor breaks and rearrange to form
iron-amine complexes. With the injection of molecular sulfur
reaction takes place and a large number of pyrite nuclei are
generated in the fast growth process. Since no bulky surfactant
(TOPO) was used here, a short chain of ethanolamine results in a
large degree of super saturation swiftly with a fast release of
excess free energy. The cohesive energy between the nuclei are not
strong enough to hold the nanocrystals together at this mild
temperature leading to a fast bursting of quantum nanohusks.
The band gap tuning (1.34 eV) and light crystal size of the
nanohusks make it appealing as a solar absorber material due to
superior optoelectronic properties and visible light coverage. The
band gap tunability of several semiconductors has led to many
pioneering applications such as light emitting devices [16], lasers
[17], high luminescence [18] and low thermal conductivity [19].
The details of the film morphology, solvent effects, and crystals
size effects on ITO glass, nanoscale separation, and resistance are
under study.
4. Conclusion
Phase pure poly-sized pyrite nanohusks with tapering ends and
an average length of
6 nm were synthesized in a high aspect
ratio using ethanolamine as a solvent and a surfactant at 210 1C in
a Schlenk flask. The band gap was found to be 1.34 eV by optical
absorption spectra and XRD and Raman spectra show a phase pure
pyrite semiconducting structure. A photovoltaic response of 0.23%
184 M. Alam Khan et al. / Materials Letters 126 (2014) 181–184
was observed with a JSC of 1.4 mA/cm  2, a VOC of 0.17 V and a fill
factor of 32.
Acknowledgment
This work is partially supported by the Air Force Office of
Scientific Research (Grant FA9550-10-1-0136), the NSF-EPSCoR
program (Grant EPS-1003970), and the NASA-EPSCoR program
(Grant 242026-1BBX11AQ36A).
Appendix A. Supporting information
Supplementary data associated with this paper can be found in
the online version at http://dx.doi.org/10.1016/j.matlet.2014.04.060.
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