Abstract
Sinnerite (Cu6As4S9) is a semiconductor computed to have attractive optoelectronic properties, but little attention has been paid to its experimental synthesis and characterization. Here, the authors report the first synthesis of polycrystalline sinnerite thin films. By heating Cu3AsS4 nanoparticles in sealed ampoules with As2S2 powder, a phase transformation to Cu6As4S9 is achieved along with the formation of micronsized dense grains appropriate for device applications. The films display a bandgap of ~1.2 eV, significant photocurrent generation under simulated AM1.5 illumination, and carrier lifetimes nearing 1 ns, demonstrating the promise of sinnerite for use in photovoltaic applications.
Similar content being viewed by others
References
C. Wadia, A.P. Alivisatos, and D.M. Kammen: Materials availability expands the opportunity for large-scale photovoltaics deployment. Environ. Sci. Technol. 43, 2072 (2009).
W. Wang, M.T. Winkler, O. Gunawan, T. Gokmen, T.K. Todorov, Y. Zhu, and D.B. Mitzi: Device characteristics of CZTSSe thin-film solar cells with 12.6% efficiency. Adv. Energy Mater. 4, 1301465 (2014).
T. Gershon, T. Gokmen, O. Gunawan, R. Haight, S. Guha, and B. Shin: Understanding the relationship between Cu2ZnSn(S,Se)4 material properties and device performance. MRS Commun. 4, 159 (2014).
C.K. Miskin, W.-C. Yang, C.J. Hages, N.J. Carter, C.S. Joglekar, E.A. Stach, and R. Agrawal: 9.0% efficient Cu2ZnSn(S,Se)4 solar cells from selenized nanoparticle inks. Prog. Photovoltaics Res. Appl. 23, 654 (2015).
W.A. Dunlap-Shohl, Y. Zhou, N.P. Padture, and D.B. Mitzi: Synthetic approaches for halide perovskite thin films. Chem. Rev. 119, 3193 (2019).
T. Shi, W.-J. Yin, M. Al-Jassim, and Y. Yan: Structural, electronic, and optical properties of Cu3-V-VI4 compound semiconductors. Appl. Phys. Lett. 103, 152105 (2013).
R.B. Balow, E.J. Sheets, M.M. Abu-Omar, and R. Agrawal: Synthesis and characterization of copper arsenic sulfide nanocrystals from earth abundant elements for solar energy conversion. Chem. Mater. 27, 2290 (2015).
R.B. Balow, C.K. Miskin, M.M. Abu-Omar, and R. Agrawal: Synthesis and characterization of Cu3(Sb1-xAsx)S4 semiconducting nanocrystal alloys with tunable properties for optoelectronic device applications. Chem. Mater. 29, 573 (2017).
T. Pauporté and D. Lincot: Electrical, optical and photoelectrochemical properties of natural enargite, Cu3AsS4. Adv. Mater. Opt. Electron. 5, 289 (1995).
A. Das, A. Shamirian, and P.T. Snee: Arsenic silylamide: an effective precursor for arsenide semiconductor nanocrystal synthesis. Chem. Mater. 28, 4058 (2016).
S.A. McClary, J. Andler, C.A. Handwerker, and R. Agrawal: Solution-processed copper arsenic sulfide thin films for photovoltaic applications. J. Mater. Chem. C 5, 6913 (2017).
L. Yu, R.S. Kokenyesi, D.A. Keszler, and A. Zunger: Inverse design of high absorption thin-film photovoltaic materials. Adv. Energy Mater. 3, 43 (2013).
S.K. Wallace, K.L. Svane, W.P. Huhn, T. Zhu, D.B. Mitzi, V. Blum, and A. Walsh: Candidate photoferroic absorber materials for thin-film solar cells from naturally occurring minerals: enargite, stephanite, and bournonite. Sustain. Energy Fuels 1, 1339 (2017).
S.K. Wallace, K.T. Butler, Y. Hinuma, and A. Walsh: Finding a junction partner for candidate solar cell absorbers enargite and bournonite from electronic band and lattice matching. J. Appl. Phys. 125, 055703 (2019).
R. Zhang, K. Chen, B. Du, and M.J. Reece: Screening for Cu–S based thermoelectric materials using crystal structure features. J. Mater. Chem. A 5, 5013 (2017).
S.A. McClary, R.B. Balow, and R. Agrawal: Role of annealing atmosphere on the crystal structure and composition of tetrahedrite–tennantite alloy nanoparticles. J. Mater. Chem. C 6, 10538 (2018).
P. Levinsky, C. Candolfi, A. Dauscher, J. Tobola, J. Hejtmánek, and B. Lenoir: Thermoelectric properties of the tetrahedrite–tennantite solid solutions Cu12Sb4-xAsxS13 and Cu10Co2Sb4-yAsyS13 (0 = x, y = 4). Phys. Chem. Chem. Phys. 21, 4547 (2019).
S. Maske and B.J. Skinner: Studies of the sulfosalts of copper I. Phases and phase relations in the system Cu-As-S. Econ. Geol. 66, 901 (1971).
E. Makovicky and B.J. Skinner: Studies of the sulfosalts of copper II. The crystallography and composition of sinnerite, Cu6As4S9. Am. Mineral. 57, 824 (1972).
J. Hautala and P.C. Taylor: A review of optical properties of metal chalcogenide glasses. J. Non-Cryst. Solids 141, 24 (1992).
B. Yan, S. Girlani, and P.C. Taylor: Defect structure and conductivity in tetrahedrally coordinated metal chalcogenide amorphous semiconductors. Phys. Rev. B 56, 10249 (1997).
L. Bindi, E. Makovicky, F. Nestola, and L. De Battisti: Sinnerite, Cu6As4S9, from the Lengenbach Quarry, Binn Valley, Switzerland: description and re-investigation of the crystal structure. Can. Mineral. 51, 851 (2013).
M.V. Kovalenko, M.I. Bodnarchuk, J. Zaumseil, J.-S. Lee, and D.V. Talapin: Expanding the chemical versatility of colloidal nanocrystals capped with molecular metal chalcogenide ligands. J. Am. Chem. Soc. 132, 10085 (2010).
Z. Xia, J. Zhong, M. Leng, L. Hu, D.-J.J. Xue, B. Yang, Y. Zhou, X. Liu, S. Qin, Y.-B.B. Cheng, and J. Tang: Generalized water-processed metal chalcogenide complexes: synthesis and applications. Chem. Mater. 27, 8048 (2015).
W. Wu, Y. Cao, J.V. Caspar, Q. Guo, L.K. Johnson, I. Malajovich, H.D. Rosenfeld, and K.R. Choudhury: Studies of the fine-grain sub-layer in the printed CZTSSe photovoltaic devices. J. Mater. Chem. C 2, 3777 (2014).
T.J. Huang, X. Yin, C. Tang, G. Qi, and H. Gong: Influence of ligands on the formation of kesterite thin films for solar cells: a comparative study. ChemSusChem 9, 1032 (2016).
C.J. Hages, M.J. Koeper, C.K. Miskin, K.W. Brew, and R. Agrawal: Controlled grain growth for high performance nanoparticle-based kesterite solar cells. Chem. Mater. 28, 7703 (2016).
S. McLeod, E. Alruqobah, and R. Agrawal: Liquid assisted grain growth in solution processed Cu(In,Ga)(S,Se)2. Sol. Energy Mater. Sol. Cells 195, 12 (2019).
P. Kubelka and F. Munk: Ein Beitrag zur Optik der Farbanstriche (A contribution to the optics of pigments). Z. Tech. Phys. 12, 593 (1931).
R.R. Gagne, C.A. Koval, and G.C. Lisensky: Ferrocene as an internal standard for electrochemical measurements. Inorg. Chem. 19, 2854 (1980).
Acknowledgments
The authors acknowledge the National Science Foundation for funding under grant #1534691-DMR (Rapid Design of Earth Abundant Inorganic Materials for Future PVs). S.A.M. acknowledges Purdue University for a Bilsland Dissertation Fellowship. The authors thank Kyle Weideman, Yining Feng, and Professor Luna Lu for Hall effect measurements; Joseph Andler, Essam AlRuqobah, and Xianyi Hu for providing Mo films; Apurva Pradhan for helpful comments on the manuscript; Alexei Lagoutchev for helpful discussions regarding the collection of reflectance data; and Joseph Andler for the assistance with the abstract graphic.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Supplementary material
Supplementary material
The supplementary material for this article can be found at https://doi.org/10.1557/mrc.2020.11.
Rights and permissions
About this article
Cite this article
McClary, S.A., Agrawal, R. Synthesis and characterization of semiconducting sinnerite (Cu6As4S9) thin films. MRS Communications 10, 188–193 (2020). https://doi.org/10.1557/mrc.2020.11
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1557/mrc.2020.11