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 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
It is increasingly clear that the finite supply of the traditional of material extraction cost. Recently, Wadia et al. placed it among
fuels (fossil, coal and gas) must shift in the favor of renewable the top 23 promising potential candidates for solar electricity
energy resources in order to fulfill the growing global energy generation [8]. The Schottky junction type pyrite photovoltaic
needs (20 TW) [1,2]. Among several promising resources, photo- devices reported so far exhibit high quantum efficiency and photo-
voltaic energy is perceived as reliable, clean and inexhaustible; current but low photovoltage which is often less than 20% of the
however, significant cost reduction is necessary to compete with band gap [9]. The causes of such low voltage and efficiencies are
fossil fuels. At present silicon based solar cells dominate the material issues, such as phase impurity, intrinsic bulk, surface
photovoltaic market; however, their significant cost and complex defects and mid gap defect states which cause Fermi level pinning.
technology impede their wide use. Hence alternative technologies But, the theoretical limit of the power conversion efficiency of FeS2
such as CIGS and CdTe are explored [3]. Most of the alternative is reported to be better than those of CuInSe2, CdTe, and Si based
structures use either toxic or trace elements such as Cd, In, and Pb photovoltaic devices [10]. This is mainly due to the major advantage
[4]. Instead, non-toxic, abundant, and thus cheap materials such as of the diffusion/drift length (0.1–1.0 μm) in iron pyrite. The optical
FeS2, Cu2O, Cu2S and SnS are typical p-type and earth abundant, and electrical properties can be improved by increasing the energy
are much more promising and could make an impact even with band gap (Eg) of FeS2 by tuning the crystal sizes [11,12] where Eg
overall low efficiencies. Among all these materials iron pyrite increases with respect to the size of nanocrystals. Although it is
(FeS2) is the most attractive in both cost and abundance [5]. reported that in pyrite based photovoltaics less than a micron of
Recently iron pyrite (FeS2, fool’s gold) has been getting resurgent total thickness (
30–300 nm) is enough to absorb all visible
interest owing to its promising attributes such as abundance, non- spectrums, most of the time it is difficult to make high quality
toxicity, high absorption coefficient (
5  105 cm  1 for hν 41.3 eV) 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
n
Corresponding author at: Department of Energy and Materials Engineering, can be suspended well and expected to form better and uniform
Dongguk University-Seoul, Seoul 100-715, Republic of Korea.
Tel.: þ 1 479 575 5444; fax: þ 1 479 575 7967.
films. Herein, we report phase pure semiconducting iron pyrite
E-mail address: alamkhan77@gmail.com (M. Alam Khan). 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 4 (311)
400
sized and band tuned phase pyrite nanohusks have not been (200)

Intensity (arb. units)

reported. (210)
(220)
300 (211)
3

Intensity (arb. units)

(111)
2. Experimental 200

Iron pyrite (FeS2) cubic quantum dots were prepared by a 2

100
colloidal synthetic route similar to that reported by our group [14].
In a typical synthesis, 10 ml of ethanolamine (90%, Acros) was 20 30 40 50 60

injected into a 100 ml Schlenk flask, then 600 mg of FeCl2.4H2O 1 2Theta

(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
0
400 600 800 1000 1200
for 1 h. Then the later lot was injected into the first flask at 210 1C
Wavelength (nm)
with a total reaction time of 1 h with vigorous stirring in N2
atmosphere and cooled down promptly using an oil bath. Then Fig. 1. UV–vis spectra of the synthesized iron pyrite nanohusks in ethanolamine;
few drops of chloroform (Merck) were added to prevent coagula- inset: X-ray diffraction patterns of the sample.

tion of FeS2 nanocrystals at a suitable temperature and lastly it was

washed with methanol (99.5%, Merck) several times using a without a trace of detectable marcasite, pyrrotite, greigyte and
centrifuge at 5000 rpm for 10 min. other impurities. The dominant peak position can be matched
For the solar cell application: An ITO glass was masked, etched with JCPDS no. 42-1340 and peaks assigned to 28.21, 32.81, 36.91,
and cleaned with ethanol, detergent, and acetone successively 40.51, 47.31, and 56.21 corresponding to crystal phases of (111),
with 10 min sonication, respectively. Highly conducting poly (3,4- (200), (210), (211), (220), and (311). It is worth noting that the
ethylene-dioxylenethiophene): polystyrene sulfonic acid (PEDOT: samples prepared in ethanolamine indicate a preferred crystal
PSS) was spin casted (4000 rpm for 50 s). After that it was orientation of (200).
annealed at 140 1C for 10 min. In 1.0 ml of chloroform solvent The morphology and size of the synthesized samples were
FeS2 (10 mg) and PCBM (20 mg) were added in a vial in a glove box analyzed by transmission electron microscopy (TEM) and are
and then sonicated for 15 min to dissolve homogeneously; after represented in Fig. 2(a and b). It clearly shows that the synthesized
that the mixture was magnetically stirred for 24 h. Then the active nanocrystals are poly-sized with an average length of
6 nm with
layer was spin casted at 1600 rpm for 30 s and dried at room the morphology matching a rice husk. The corresponding high
temperature. Then with the use of a cotton bud the spilled active resolution image is shown in Fig. 2(b) where the clarity of the
layer was carefully wiped out at the sides of PN electrodes. After particle husks is more prominent with tapering ends and being
this procedure an Al (80 nm) electrode was deposited by vacuum relatively thicker in the center. An image of Fast Fourier Transform
evaporation at 10  6 Torr. Post-annealing was carried out at 120 1C (FFT) of the iron pyrite nanohusks (inset (a)) shows a ring pattern
for 10 min and the active area was 0.04 cm2. and can be indexed as crystalline in nature.
Photocurrent–voltage (J–V) curves of the cell were measured by Micro-Raman spectroscopy analysis is depicted in Fig. 3(a). The
current–voltage characteristic measurement (digital source meter; Raman analysis was conducted to further check out any trace
model 2400, Keithly) with illuminating conditions (AM1.5G, model peaks of marcasite, greigyte, FeS or any other pyrite phases. The
ORIEL-Sol-3A, Newport). The morphology of the samples was dominant phonon mode at 339.5 and 378, and a small shoulder at
imaged with a transmission electron microscope (A FEI Titan 360 can be assigned to the Ag (S2 dumbel liberation), Eg (S2
80–300, Transmission Electron Microscope at 300 kV). X-ray dumbell stretching), Tg(1) and Tg(3) vibrational modes. A fifth band
diffraction (XRD) analysis was performed by Philips PW3040 which was expected to appear in the Raman spectra at position
X’Pert MRD High Resolution XRD and Ni-filtered with CuKα 377 cm  1 (Tg (2) mode) is possibly buried within the dominant Eg
radiation. Absorption spectra dispersed in chloroform were peak. Micro-Raman mapping of films at several positions of the
recorded on a Cary 5000 UV–vis-NIR spectrophotometer. Micro- sample shows only homogeneous pyrite peaks with no sign of
Raman spectra were measured by making a film by drop casting marcasite or other impurity phase peaks. Fig. 3(b) shows the J–V
on a glass slide using the HORIBA Jobin Yvon’s LabRAM. characteristics of the nanohusks when processed for the photo-
X-ray photo-electron spectroscopy (XPS, PHI 5000, Versa Probe, voltaic test in a bulk-heterojunction type. The device architecture
ULVAC-PHI, Inc., Japan) was performed at 1.1  10  7 Pa with Al Kα was made as ITO/PEDOT:PSS/FeS2:PCBM/Al. The prepared device
radiation. 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
3. Results and discussion a thickness of
250 nm.
Tailoring the optoelectronic properties without changing any
The optical properties of the synthesized quantum nanohusks chemical composition opens up the curiosity of the colloidal
were analyzed by UV–vis spectra which are shown in Fig. 1. The method where the electronic and optical properties of any
figure clearly indicates that the absorption onset is at 920 nm on semiconductor could be altered. The iron pyrite has a promising
extrapolating the spectral curves with the estimated band gap of absorption coefficient of α ¼6  105 cm  1 and a suitable band gap
1.34 eV. It is interesting to observe a shoulder at 2.56 eV which of 0.95 eV which are very attractive for the thin absorber layer for
shows monotonic absorption rise. The nanocrystal shows visible photovoltaic applications. Moreover, the solution based processes
light absorption throughout indicating a promising material for offer other appealing traits such as substantial cost reduction,
photovoltaic application. The inset in Fig. 1 shows the X-ray diff- flexibility and ease of handling, ideally suited for PV technology.
raction (XRD) analysis which depicts that the synthesized nano- Most of the films for photovoltaic applications are spin casted
husks show a diffraction pattern similar to a cubic FeS2 structure 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 large degree of super saturation swiftly with a fast release of
nanoscale separation or renders the film unsuitable/inefficient excess free energy. The cohesive energy between the nuclei are not
for photovoltaic application. strong enough to hold the nanocrystals together at this mild
So in the present study size tuned pyrite nanohusks that are temperature leading to a fast bursting of quantum nanohusks.
lighter in nature are expected to cast uniform and smooth films The band gap tuning (1.34 eV) and light crystal size of the
with better efficiency; however, an efficiency of 0.23% was quite nanohusks make it appealing as a solar absorber material due to
low, which can be attributed to poor contact with the substrate, superior optoelectronic properties and visible light coverage. The
particle boundary involvement, non-perfect ratio of Fe:S (1:1.97) band gap tunability of several semiconductors has led to many
as analyzed by TEM-EDX (Supporting information; Fig. S1) and pioneering applications such as light emitting devices [16], lasers
nanoscale separation in the films of fullerene and inorganic FeS2 [17], high luminescence [18] and low thermal conductivity [19].
due to different physio-chemical natures. X-ray photoelectron The details of the film morphology, solvent effects, and crystals
spectra (XPS) were further analyzed to investigate the pyrite size effects on ITO glass, nanoscale separation, and resistance are
nanohusks and the details are shown in Fig. S2 (supporting under study.
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 4. Conclusion
with the bulk iron pyrite reported elsewhere [15]. Since ethano-
lamine acts both as a solvent and a surfactant and with a suitable Phase pure poly-sized pyrite nanohusks with tapering ends and
temperature (210 1C) the precursor breaks and rearrange to form an average length of
6 nm were synthesized in a high aspect
iron-amine complexes. With the injection of molecular sulfur ratio using ethanolamine as a solvent and a surfactant at 210 1C in
reaction takes place and a large number of pyrite nuclei are a Schlenk flask. The band gap was found to be 1.34 eV by optical
generated in the fast growth process. Since no bulky surfactant absorption spectra and XRD and Raman spectra show a phase pure
(TOPO) was used here, a short chain of ethanolamine results in a pyrite semiconducting structure. A photovoltaic response of 0.23%
184 M. Alam Khan et al. / Materials Letters 126 (2014) 181–184

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