Sulvanite (Cu3VS4) Nanocrystals for Printable Thin Film

Photovoltaics

Ching-Chin Chena
a
Department of Chemistry, Delaware State University, 1200 N. DuPont Highway, Dover, DE

19901, USA

Kevin H. Stoneb
b
SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA

Cheng-Yu Laia
a
Department of Chemistry, Delaware State University, 1200 N. DuPont Highway, Dover, DE

19901, USA

Kevin D. Dobsonc
c
Institute of Energy Conversion, University of Delaware, Newark, DE 19716, USA

Daniela Radu*,a,d
a
Department of Chemistry, Delaware State University, 1200 N. DuPont Highway, Dover, DE

19901, USA
d
Department of Material Science and Engineering, University of Delaware, Newark, DE 19716,

USA

* dradur@desu.edu

© 2017. This manuscript version is made available under the Elsevier user license
http://www.elsevier.com/open-access/userlicense/1.0/
Abstract

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 evaluated 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

solution 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 annealing temperature optimization. Thus, Cu3VS4, formed solely

from Earth-abundant elements, could provide an inexpensive, reliable approach to

fabricating solution processed thin film photovoltaic absorbers.

Keywords: nanocrystalline materials; nanoparticles; colloidal processing; thin films; solar

energy materials; electronic materials

1. Introduction

Solar photovoltaic (PV) absorber materials have been extensively explored toward

harnessing solar energy with high efficiency. As part of second generation PV, thin film

technologies have been regarded as inexpensive alternatives to Gen1 silicon PV, and have

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recently reached comparable power conversion efficiencies.1, 2 The commercial thin film

PV is championed by two absorber materials: copper indium gallium diselenide

Cu2(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 alternative 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 fabrication

of solution-processed thin-film absorbers from nanocrystal precursors represent a feasible

and economically advantageous approach. Nevertheless, the stagnation in CZTS/CZTSSe

development, 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 structures a new group of p-

type semiconductors: Cu3MCh4 (M = V, Nb, Ta; Ch = S, Se, Te),14, 15 highlighting their

potential as photovoltaic absorbers given their direct bandgaps in the proximity of 1.5 eV.

Among these materials, Cu3VS4 (CVS) stands out for its elemental 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

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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 semiconductor

nanocrystals benefit from facile solution synthesis routes, at moderate temperatures in

comparison with their bulk counterparts, and allow control of nanoparticle stoichiometry,

phase purity, 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 modification. 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 microscopy (TEM).

2. Materials and Methods

2.1 Chemicals. Vanadium(III) acetylacetonate (97%), sodium sulfide, and oleylamine

(70%) were purchased from Sigma-Aldrich. Copper(II) acetylacetonate (98%), sulfur

powder (-100 mesh, 99.5%), and formamide (99%) were purchased from Alfa Aesar.

Hexane, toluene, chloroform (all ACS grade), and ethanol (200 proof), were purchased

from VWR International. All reagents and solvents were used without further purification.

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 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 oC and the mixture was further degassed under vacuum at 120 oC for 30 minutes.

Sulfur (256.5 mg, 8 mmol) was separately dissolved in oleylamine (10 mL) and heated at

150 oC. The temperature of the Cu-V solution was increased to 230 oC over a 15-minute

period and held at 230 oC for another 30 minutes, followed by dropwise injection of the

sulfur solution. The final reaction mixture was stirred at 230 oC for 30 minutes. After

cooling to room temperature by removing the heating source, 10 mL of hexane were added

and the suspension 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 minutes. 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 by

centrifugation at 7500 rpm for 5 minutes. 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 oC.

The sulfur atmosphere was obtained by placing sulfur powder (1 g) in another crucible in

the 350 oC 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 published procedures.22, 23 In a typical experiment, as-

synthesized nanocrystals (20 mg) were washed with hexane and either isopropanol or

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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 minutes.

2.5 Characterization. The crystal structure of bulk sulvanite Cu3VS4 used for reference

were obtained from The Database “The RRUFF™ Project”24 and the simulation of

diffraction pattern was performed with the Mercury software from the Cambridge

Structural Database.25

X-ray diffraction (XRD) was performed on a Rigaku MiniFlex600 system equipped with

a Cu Kα radiation source (λ=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 (λ= 532 nm). TEM images were recorded on a Zeiss LIBRA 120

instrument. Thermogravimetric Analysis (TGA) was performed on a Discover TGA (RT

Instruments). High resolution synchrotron powder diffraction data were collected at SSRL

beamline 2-1 with 17 keV X-rays (λ= 0.729 Å) and Rietveld refinement performed using

the software TOPAS-Academic.26

3. Results and Discussion

3.1 Characterization of Phase Purity.

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 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 (Figure 1(a)) and the powder X-ray diffraction pattern

(Mercury software). The crystallographic parameters of CVS are listed in Table 1.

Table 1. Crystallographic Parameters of Cu3VS4

The simulated pattern is showed in Figure 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.

Figure 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.

The identity of CVS NCs was further demonstrated by Raman spectroscopy. Figure 2

shows Raman spectra of both as-synthesized and annealed Cu3VS4 nanocrystals. A

spectrum of bulk CVS is shown for comparison (Fig 2 inset).

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 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

Figure 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 RRUFF™
Project”, reference [24]); (b) TGA analysis (in N2 atmosphere) of the annealed Cu3VS4 powder

Upon annealing in sulfur/argon atmosphere at 600 oC for 1 h, TGA data were collected

for the annealed Cu3VS4 from ambient temperature (25 °C) to 900 °C, at a ramping

Figure 3. (a) Synchrotron XRD pattern and (b) refinement of Cu3VS4 annealed powder

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 temperature of 10 °C/minute under nitrogen atmosphere. The weight loss starting around

390 oC (inset 1) could be correlated with further decomposition of residual carbon

originated in the synthesis of the nanocrystals, while the loss starting around 640 oC could

be associated 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 (Figure 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

Figure 4. TEM image of ligand-exchanged Cu3VS4 nanocrystals (inset shows ligand exchange
experiment)

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 The inset in Figure 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 surface. 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 (Figure 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 demonstrated that the

nanocrystals could be solution processed. Synchrotron XRD of Cu3VS4 powders upon

annealing in a sulfur/argon atmosphere at 600 oC show a highly crystalline Cu3VS4

sulvanite 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.

5. Acknowledgements

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 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 Lightsource, SLAC

National Accelerator Laboratory, was supported by the U.S. Department of Energy, Office

of Basic Energy Sciences under Contract No. DE-AC02-76SF00515.

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