Sulvanite (Cu3VS4) nanocrystals for printable thin film photovoltaics

Ching-Chin Chen a, Kevin H. Stone b, Cheng-Yu Lai a, Kevin D. Dobson c, Daniela Radu a,d,⇑
a
Department of Chemistry, Delaware State University, 1200 N. DuPont Highway, Dover, DE 19901, USA
b
SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA
c
Institute of Energy Conversion, University of Delaware, Newark, DE 19716, USA
d
Department of Material Science and Engineering, University of Delaware, Newark, DE 19716, USA

a r t i c l e i n f o

Article history:
Received 19 July 2017
Received in revised form 3 September 2017
Accepted 17 September 2017Available
online 21 September 2017

Keywords:
Nanocrystalline materials
Nanoparticles
Colloidal processing
Thin films
Solar energy materials
Electronic materials

a b s t r a c t

Copper Vanadium Sulfide (Cu3VS4), also known as sulvanite, has recently emerged as a suitable absorber material for thin film photovoltaics. The
synthesis of Cu3VS4 nanocrystals via a rapid solvothermal route is reported for the first time. The phase purity of the Cu3VS4 nanocrystals has been
confirmed by X-ray powder diffraction (XRD) and Raman spectroscopy, while the nanoparticle size, of about 10 nm, was eval-uated by transmission
electron microscopy (TEM). Successful ligand exchange with sulfide, an inorganic ligand, demonstrated that the nanoparticles are amenable to surface
modifications, key element in solu-tion processing.

Further annealing of as-synthesized nanocrystals under a sulfur/argon atmosphere at 600 °C, rendered highly crystalline Cu3VS4 powders exhibiting an
impurity that could be potentially mitigated by anneal-ing temperature optimization. Thus, Cu3VS4, formed solely from Earth-abundant elements, could
provide an inexpensive, reliable approach to fabricating solution processed thin film photovoltaic absorbers.

1. Introduction approach. Nevertheless, the stagnation in CZTS/CZTSSe develop-

Solar photovoltaic (PV) absorber materials have been exten-
sively explored toward harnessing solar energy with high effi-
ciency. As part of second generation PV, thin film technologies
have been regarded as inexpensive alternatives to Gen1 silicon
PV, and have recently reached comparable power conversion
efficiencies [1,2]. The commercial thin film PV is championed by
two absorber materials: copper indium gallium diselenide
Cu(InxGa1 x)S2 (CIGS) and cadmium telluride (CdTe). Nevertheless,
indium and tellurium scarcity and their price escalation impact
tremendously CdTe and CIGS module production costs [3]; along
with cadmium toxicity, these concerns drove attention to alterna-
tive PV absorbers, composed of Earth-abundant, sustainable, and
preferably non-toxic elements. Isostructural with CIGS, copper zinc
tin sulfide and sulfo-selenides, Cu2ZnSnS4 (CZTS) and Cu2ZnSn(S,
Se)4 (CZTSSe), gained exponential interest as solar absorbers in
the past two decades. Since the first CZTS report in 1988 [4],
increases in power conversion efficiency reached a 12.6% record
[5–11]. Importantly, CZTS research also demonstrated that fabrica-
tion of solution-processed thin-film absorbers from nanocrystal
precursors represent a feasible and economically advantageous
⇑ Corresponding author at: Department of Chemistry, Delaware State University,
1200 N. DuPont Highway, Dover, DE 19901, USA.
ment, primarily due to open-circuit voltage (Voc) deficiencies and
the inability to eliminate structural defects [12,13], has further
fueled the quest for alternative materials.
Recently, Kehoe et al. have reported the calculated band struc-
tures a new group of p-type semiconductors: Cu3MCh4 (M = V, Nb,
Ta; Ch = S, Se, Te) [14,15], highlighting their potential as photo-
voltaic absorbers given their direct bandgaps in the proximity of
1.5 eV. Among these materials, Cu3VS4 (CVS) stands out for its ele-
mental composition, which includes only Earth-abundant
elements.
Bulk CVS powder was previously synthesized through a solid
state method, and the energy bandgap was estimated to be
1.3 eV [16]. Recently, nano-CVS thin films were prepared by pulsed
laser deposition (PLD). The reported bandgap of 1.35 eV and
absorption coefficient >105 cm 1 have demonstrated the potential
of CVS as a thin film PV absorber.
Success in solution processed CIGS and CZTSSe encouraged
investigation of nanoscale precursor routes in fabricating thin film
absorbers. Sintering of colloidal nanocrystals led to low-cost, high-
efficiency chalcogenide solar cells [5–7,17,18]. Colloidal semicon-
ductor nanocrystals benefit from facile solution synthesis routes,
at moderate temperatures in comparison with their bulk counter-
parts, and allow control of nanoparticle stoichiometry, phase pur-
ity, and particle size [19–21]. Crystalline nanoparticles
(nanocrystals) dispersed in adequate solvents (‘‘inks”) could be
readily deposited onto substrates through simple coating methods
(spin-, dip-, spray-coating), as a preamble to the ultimately desired
roll-to-roll processing technologies on flexible substrates, toward
enabling low-cost thin film PV.
In this report, we demonstrate the first synthesis of colloidal
CVS nanocrystals (NCs) and their amenability to surface modifica-
tion. The CVS NCs were characterized by powder X-ray diffraction
(XRD) and Raman spectroscopy to validate phase purity. Their
morphology was characterized by transmission electron micro-
scopy (TEM).
2. Materials and methods
2.1. Chemical reagents
Vanadium(III) acetylacetonate (97%), sodium sulfide, and oley-
lamine (70%) were purchased from Sigma-Aldrich. Copper(II)
acetylacetonate (98%), sulfur powder ( 100 mesh, 99.5%), and for-
mamide (99%) were purchased from Alfa Aesar. Hexane, toluene,
chloroform (all ACS grade), and ethanol (200 proof), were pur-
chased from VWR International. All reagents and solvents were
used without further purification.
2.2. Preparation of Cu3VS4 nanocrystals
All solution syntheses were conducted in an argon atmosphere
and all steps of the nanocrystals purification were conducted in air.
In a typical experiment, vanadium(III) acetylacetonate
(870.7 mg, 2.5 mmol) and copper(II) acetylacetonate (1570.6 mg,
6 mmol) were dissolved in oleylamine (30 mL) at 120 °C and the
mixture was further degassed under vacuum at 120 °C for
30 min. Sulfur (256.5 mg, 8 mmol) was separately dissolved in
oleylamine (10 mL) and heated at 150 °C. The temperature of the
Cu-V solution was increased to 230 °C over a 15-min period and
held at 230 °C for another 30 min, followed by dropwise injection
of the sulfur solution. The final reaction mixture was stirred at
230 °C for 30 min. After cooling to room temperature by removing
the heating source, 10 mL of hexane were added and the suspen-
sion was separated into two 50 mL centrifuge tubes. Further,
20 mL of ethanol were added to each tube and the CVS NCs were
collected by centrifugation at 7500 rpm for 5 min. Next, CVS NCs
were washed by redispersion in a mixture of 10 mL hexane and
5 mL chloroform, and precipitated in 25 mL of ethanol followed
Fig. 1. (a) Crystal structure of sulvanite Cu3VS4; (b) Powder XRD patterns of as-synthesized (top) and annealed (middle) Cu3VS4 nanocrystals, and simulated crystal structure
of Cu3VS4.
by centrifugation at 7500 rpm for 5 min. The washing step was
repeated once, replacing ethanol with isopropanol as an anti-
solvent. The final NCs were stored under vacuum.
2.3. Annealing of as-synthesized nanocrystals
An amount of 700 mg CVS NCs was placed in a graphite crucible
and annealed under a sulfur and argon atmosphere at 600 °C. The
sulfur atmosphere was obtained by placing sulfur powder (1 g) in
another crucible in the 350 °C zone of the tube furnace, preceding
the graphite crucible in the argon flow.
2.4. Sulfide (S2 ) ligand exchange of as-synthesized nanocrystals
The ligand exchange method was adapted from previously pub-
lished procedures [22,23]. In a typical experiment, as-synthesized
nanocrystals (20 mg) were washed with hexane and either iso-
propanol or ethanol (hexane to alcohol ratio 1:1), recovered by
centrifugation, and dispersed in toluene (5 mL). A sodium sulfide
Na2S solution in formamide (FA) (5 mL, 0.18 M) was added to the
nanocrystals dispersion and the final dispersion was vigorously
stirred overnight. Upon transfer of CVS NCs from the toluene to
the FA layer, the toluene layer was removed and the NCs in the
FA layer were washed three times with toluene (3 mL each time).
Ethanol (5 mL) was added to the FA dispersion to precipitate the
CVS NCs, which were further recovered by centrifugation at
7500 rpm for 5 min.
2.5. Characterization
The crystal structure of bulk sulvanite Cu3VS4 used for reference
were obtained from The Database ‘‘The RRUFFTM Project” [24] and
the simulation of diffraction pattern was performed with the Mer-
cury software from the Cambridge Structural Database [25].
X-ray diffraction (XRD) was performed on a Rigaku MiniFlex600
system equipped with a Cu Ka radiation source (k = 1.5405 Å) and
operated at 30 mV and 10 mA. Raman spectroscopy analysis was
carried out on Horiba Scientific XploRA PLUS equipped with an
Ar-laser source (k = 532 nm). TEM images were recorded on a Zeiss
LIBRA 120 instrument. Thermogravimetric Analysis (TGA) was per-
formed on a Discover TGA (RT Instruments). High resolution syn-
chrotron powder diffraction data were collected at SSRL beamline
2–1 with 17 keV X-rays (k = 0.729 Å) and Rietveld refinement per-
formed using the software TOPAS-Academic [26].
3. Results and discussion
3.1. Characterization of phase purity
Crystal structure information of sulvanite Cu3VS4 from the
American Mineralogist Crystal Structure Database (AMCSD) [27],
based a report from Pauling et al. [28] were used to simulate the
crystal structure (Fig. 1(a)) and the powder X-ray diffraction
pattern (Mercury software). The crystallographic parameters of
CVS are listed in Table 1.
The simulated pattern is showed in Fig. 1(b), along with the
X-ray diffraction pattern of as-synthesized CVS powder and the
annealed powder, both in good agreement with the simulated
pattern.
The identity of CVS NCs was further demonstrated by Raman
spectroscopy. Fig. 2 shows Raman spectra of both as-synthesized
and annealed Cu3VS4 nanocrystals. A spectrum of bulk CVS is
shown for comparison (Fig. 2 inset).
The Raman pattern of the synthesized Cu3VS4 nanocrystals is in
agreement with literature reported data, showing an enhanced
peaks intensity and signal-to-noise ratio after annealing [16].
Upon annealing in sulfur/argon atmosphere at 600 °C for 1 h,
TGA data were collected for the annealed Cu3VS4 from ambient
temperature (25 °C) to 900 °C, at a ramping temperature of

Table 1
Crystallographic parameters of sulvanite Cu3VS4 structure.

Space group: P-43 m, a = b = c = 5.3921(1) Å, a = b = c = 90°

Atom x y z Occupancy
Cu 0.500 0.000 0.000 1
V 0.000 0.000 0.000 1
S 0.2391(2) 0.2391(2) 0.2391(2) 1

Fig. 2. (a) Raman spectra of as-synthesized (blue) and annealed (red) Cu3VS4 nanocrystals. Inset: Raman spectrum of bulk Cu3VS4 sample (Courtesy of The Database ‘‘The
RRUFFTM Project”, reference [24]); (b) TGA analysis (in N2 atmosphere) of the annealed Cu3VS4 powder.

Fig. 3. (a) Synchrotron XRD pattern and (b) refinement of Cu3VS4 annealed powder.

Fig. 4. TEM image of ligand-exchanged Cu3VS4 nanocrystals (inset shows ligand
exchange experiment).
10 °C/minute under nitrogen atmosphere. The weight loss starting
around 390 °C (inset 1) could be correlated with further decompo-
sition of residual carbon originated in the synthesis of the
nanocrystals, while the loss starting around 640 ° C could be asso-
ciated with material decomposition.
Synchrotron XRD analysis of the annealed CVS powder enabled
quantification of powder purity, showing with a 92.6% Cu3VS4
sulvanite content (Rietveld refinement), while Cu1.8S (digenite)
accounted for the other 7.4% of the product (Fig. 3). FWHM of X-ray
diffraction peaks decreased in comparison with the Cu3VS4 NCs
spectrum, suggesting an increase in primary crystallite size.
3.2. Ligand exchange results
Nanocrystals synthesized in long-alkyl chain solvents retain
carbon on their surfaces, which could be detrimental in electronic
applications, given the layer created around the nanocrystals [29].
The inset in Fig. 4 shows the results of the ligand exchange of
CVS NCs, which transferred from the non-polar (toluene) into the
polar (formamide) layer, indicating polarity change of the NCs sur-
face. This experiment validates the capability of CVS NCs to
undergo surface modifications, thus opening the opportunity to
utilize them in thin film solar cells.
3.3. Cu3VS4 nanocrystals size
TEM imaging of as-synthesized CVS NCs was performed after
ligand exchange. As showed in the TEM micrograph (Fig. 4), CVS
NCs present a narrow particle size distribution, with the average
particle size of 10 nm.
4. Conclusion
A solution-based method for Cu3VS4 nanocrystals fabrication is
reported. The Cu3VS4 nanocrystals showed phase purity by XRD
and Raman spectroscopy. A narrow particle size distribution, with
particle size of 10 nm was shown by TEM. Successful surface
modification by ligand exchange of Cu3VS4 nanocrystals demon-
strated that the nanocrystals could be solution processed. Syn-
chrotron XRD of Cu3VS4 powders upon annealing in a sulfur/
argon atmosphere at 600 °C show a highly crystalline Cu3VS4 sul-
vanite phase, accounting for 92.6% of the product along with 7.4%
Cu1.8S (digenite) impurity. The reported Cu3VS4 nanocrystal have
potential for serving as precursor materials in fabrication of thin-
film solar photovoltaics.
Acknowledgements
This material is based upon work supported in part by the
National Science Foundation under grants No. 1435716 and No.
1535876, and by the U.S. DOE Sunshot Initiative, Award No.
DE-EE0006322. Use of the Stanford Synchrotron Radiation Light-
source, SLAC National Accelerator Laboratory, was supported by
the U.S. Department of Energy, Office of Basic Energy Sciences
under Contract No. DE-AC02-76SF00515.
References
[1] W. Jaegermann, A. Klein, T. Mayer, Adv. Mater. 21 (42) (2009) 4196–4206.
[2] M.A. Green, K. Emery, Y. Hishikawa, W. Warta, E.D. Dunlop, Prog.
Photovoltaics: Res. Appl. 24 (1) (2016) 3–11.
[3] C. Candelise, M. Winskel, R. Gross, Prog. Photovoltaics Res. Appl. 20 (6) (2012)
816–831.
[4] I. Kentaro, N. Tatsuo, Jpn. J. Appl. Phys. 27 (11R) (1988) 2094.
[5] Y. Cao, M.S. Denny, J.V. Caspar, W.E. Farneth, Q. Guo, A.S. Ionkin, L.K. Johnson,
M. Lu, I. Malajovich, D. Radu, H.D. Rosenfeld, K.R. Choudhury, W. Wu, J. Am.
Chem. Soc. 134 (38) (2012) 15644–15647.
[6] Q. Guo, G.M. Ford, W.-C. Yang, B.C. Walker, E.A. Stach, H.W. Hillhouse, R.
Agrawal, J. Am. Chem. Soc. 132 (49) (2010) 17384–17386.
[7] W.-C. Hsu, H. Zhou, S. Luo, T.-B. Song, Y.-T. Hsieh, H.-S. Duan, S. Ye, W. Yang, C.-
J. Hsu, C. Jiang, B. Bob, Y. Yang, ACS Nano 8 (9) (2014) 9164–9172.
[8] H. Katagiri, Thin Solid Films 480–481 (2005) 426–432.
[9] W. Wang, M.T. Winkler, O. Gunawan, T. Gokmen, T.K. Todorov, Y. Zhu, D.B.
Mitzi, Adv. Energy Mater. 4 (7) (2014) 1301465.
[10] K. Jimbo, R. Kimura, T. Kamimura, S. Yamada, W.S. Maw, H. Araki, K. Oishi, H.
Katagiri, Thin Solid Films 515 (15) (2007) 5997–5999.
[11] D.A.R. Barkhouse, O. Gunawan, T. Gokmen, T.K. Todorov, D.B. Mitzi, Prog.
Photovoltaics Res. Appl. 20 (1) (2012) 6–11.
[12] S. Siebentritt, Thin Solid Films 535 (2013) 1–4.
[13] R. Aninat, L.-E. Quesada-Rubio, E. Sanchez-Cortezon, J.-M. Delgado-Sanchez,
Thin Solid Films 633 (2017) 146–150.
[14] B.K. Aoife, O.S. David, W.W. Graeme, J. Phys.: Condens. Matter 28 (17) (2016)
175801.
[15] A.B. Kehoe, D.O. Scanlon, G.W. Watson, J. Mater. Chem. C 3 (47) (2015) 12236–
12244.
[16] D. Petritis, G. Martinez, C. Levy-Clement, O. Gorochov, Phys. Rev. B 23 (12)
(1981) 6773–6786.
[17] J. Jasieniak, B.I. MacDonald, S.E. Watkins, P. Mulvaney, Nano Lett. 11 (7) (2011)
2856–2864.
[18] M.G. Panthani, J.M. Kurley, R.W. Crisp, T.C. Dietz, T. Ezzyat, J.M. Luther, D.V.
Talapin, Nano Lett. 14 (2) (2014) 670–675.
[19] M.G. Panthani, C.J. Stolle, D.K. Reid, D.J. Rhee, T.B. Harvey, V.A. Akhavan, Y. Yu,
B.A. Korgel, J. Phys. Chem. Lett. 4 (12) (2013) 2030–2034.
[20] I. Gur, N.A. Fromer, M.L. Geier, A.P. Alivisatos, Science 310 (2005) 462.
[21] C. Wadia, Y. Wu, S. Gul, S.K. Volkman, J. Guo, A.P. Alivisatos, Chem. Mater. 21
(13) (2009) 2568–2570.
[22] A. Nag, M.V. Kovalenko, J.-S. Lee, W. Liu, B. Spokoyny, D.V. Talapin, J. Am.
Chem. Soc. 133 (27) (2011) 10612–10620.
[23] Q. Lin, H.J. Yun, W. Liu, H.-J. Song, N.S. Makarov, O. Isaienko, T. Nakotte, G.
Chen, H. Luo, V.I. Klimov, J.M. Pietryga, J. Am. Chem. Soc. 139 (19) (2017)
6644–6653.
[24] B. Lafuente, D. R. T., H. Yang, N. Stone, in: T. Armbruster, R.M. Danisi (Eds.),
Highlights in Mineralogical Crystallography, W. De Gruyter, Berlin, Germany,
2015, pp. 1–30.
[25] C.R. Groom, I.J. Bruno, M.P. Lightfoot, S.C. Ward, Acta Crystallogr. B Struct. Sci.
Cryst. Eng. Mater. 72 (Pt 2) (2016) 171–179.
[26] A. Coelho, Topas Academic, version 6 by Alan Coelho, Bruker-AXS.
[27] R.T. Downs, Michelle Hall-Wallace, Am. Mineral. 88 (2003) 247–250.
[28] L. Pauling, H. R, Zeitschrift fur Kristallographie 84 (1932) 204–212.
[29] D.V. Talapin, J.S. Lee, M.V. Kovalenko, E.V. Shevchenko, Chem. Rev. 110 (1)
(2010) 389–458.