Antimony selenosulfide, Sb2(S,Se)3, has attracted attention over the last few years as a light-harvesting material for photovoltaic technology owing to its phase stability, earth abundancy and low toxicity. However, the lack of a suitable material processing approach to obtain Sb2(S,Se)3 films with optimal optoelectronic properties and morphology severely hampers prospects for efficiency improvement. Here we demonstrate a hydrothermal approach to deposit high-quality Sb2(S,Se)3 films. By varying the Se/S ratio and the temperature of the post-deposition annealing, we improve the film morphology, increase the grain size and reduce the number of defects. In particular, we find that increasing the Se/S ratio leads to a favourable orientation of the (Sb4S(e)6)n ribbons (S(e) represents S or Se). By optmizing the hydrothermal deposition parameters and subsequent annealing, we report a Sb2(S,Se)3 cell with a certified 10.0% efficiency. This result highlights the potential of Sb2(S,Se)3 as an emerging photovoltaic material.
Subscribe to Journal
Get full journal access for 1 year
only $4.92 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
All data generated or analysed during this study are included in the published article and its Supplementary Information and Source Data files. Source data are provided with this paper.
Green, M. A. et al. Solar cell efficiency tables (version 54). Progress. Photovolt. Res. Appl. 27, 565–575 (2019).
Kondrotas, R., Chen, C. & Tang, J. Sb2S3 solar cells. Joule 2, 857–878 (2018).
Wang, L. et al. Stable 6%-efficient Sb2Se3 solar cells with a ZnO buffer layer. Nat. Energy 2, 17046 (2017).
Li, Z. et al. 9.2%-efficient core-shell structured antimony selenide nanorod array solar cells. Nat. Commun. 10, 125 (2019).
Wang, X. et al. Development of antimony sulfide-selenide Sb2(S,Se)3-based solar cells. J. Energy Chem. 27, 713–721 (2018).
Yun, H. et al. Efficient nanostructured TiO2/SnS heterojunction solar cells. Adv. Energy Mater. 9, 1901343 (2019).
Bernecheal, M. et al. Solution-processed solar cells based on environmentally friendly AgBiS2 nanocrystals. Nat. Photonics 10, 521–525 (2016).
Xue, D. et al. GeSe thin-film solar cells fabricated by self-regulated rapid thermal sublimation. J. Am. Chem. Soc. 139, 958–965 (2017).
Shockley, W. & Queisser, H. J. Detailed balance limit of efficiency of p-n junction solar cells. J. Appl. Phys. 32, 510–519 (1961).
Scheer, R. & Schock, H. W. Chalcogenide Photovoltaics: Physics, Technologies, and Thin Film Devices Ch. 3 (John Wiley & Sons, 2011).
Park, J.-S., Kim, S. Y., Xie, Z. & Walsh, A. Point defect engineering in thin-film solar cells. Nat. Rev. Mater. 3, 194–210 (2018).
Yan, C. et al. Cu2ZnSnS4 solar cells with over 10% power conversion efficiency enabled by heterojunction heat treatment. Nat. Energy 3, 764–772 (2018).
Zhou, Y. et al. Thin-film Sb2Se3 photovoltaics with oriented one-dimensional ribbons and benign grain boundaries. Nat. Photonics 9, 409–416 (2015).
Wu, C. et al. Interfacial engineering by indium-doped CdS for high efficiency solution processed Sb2(S1-xSex)3 solar cells. ACS Appl. Mater. Inter. 11, 3207–3213 (2019).
Yang, B. et al. In situ sulfurization to generate Sb2(Se1-xSx)3 alloyed films and their application for photovoltaics. Progress. Photovolt. Res. Appl. 25, 113–122 (2017).
Ishaq, M. et al. Efficient double buffer layer Sb2(SexS1-x)3 thin film solar cell via single source evaporation. Sol. RRL 2, 1800144 (2018).
Jaramillo-Quintero, O. A. et al. Influence of the electron buffer layer on the photovoltaic performance of planar Sb2(SxSe1-x)3 solar cells. Progress. Photovolt. Res. Appl. 26, 709–717 (2018).
Choi, Y. C. et al. Efficient inorganic-organic heterojunction solar cells employing Sb2(Sx/Se1-x)3 graded-composition sensitizers. Adv. Energy Mater. 4, 1301680 (2014).
Wu, C. et al. Water additive enhanced solution processing of alloy Sb2(S1-xSex)3-based solar cells. Sol. RRL 4, 1900582 (2020).
Jiang, Q. et al. Surface passivation of perovskite film for efficient solar cells. Nat. Photonics 13, 460–466 (2019).
Wang, W. et al. Device characteristics of CZTSSe thin-film solar cells with 12.6% efficiency. Adv. Energy Mater. 4, 1301465 (2014).
Wang, X. et al. Interfacial engineering for high efficiency solution processed Sb2Se3 solar cells. Sol. Energ. Mater. Sol. Cells 189, 5–10 (2019).
Wang, W. et al. Promising Sb2(S,Se)3 solar cells with high open voltage by application of a TiO2/CdS double buffer layer. Sol. RRL 2, 1800208 (2018).
Liu, M., Gong, Y., Li, Z., Dou, M. & Wang, F. A green and facile hydrothermal approach for the synthesis of high-quality semi-conducting Sb2S3 thin films. Appl. Surf. Sci. 387, 790–795 (2016).
Filip, M. R., Patrick, C. E. & Giustino, F. GW quasiparticle band structures of stibnite, antimonselite, bismuthinite, and guanajuatite. Phys. Rev. B 87, 205125 (2013).
Jiménez, T., Seuret-Jiménez, D., Vigil-Galán, O., Basurto-Pensado, M. A. & Courel, M. Sb2(S1-xSex)3 solar cells: the impact of radiative and non-radiative loss mechanisms. J. Phys. D Appl. Phys. 51, 435501 (2018).
Zhou, Y. et al. Buried homojunction in CdS/Sb2Se3 thin film photovoltaics generated by interfacial diffusion. Appl. Phys. Lett. 111, 013901 (2017).
Tang, R. et al. Vacuum assisted solution processing for highly efficient Sb2S3 solar cells. J. Mater. Chem. A 6, 16322–16327 (2018).
Hu, W. et al. Low-temperature in situ amino functionalization of TiO2 nanoparticles sharpens electron management reaping over 21% efficient planar perovskite solar cells. Adv. Mater. 31, 1806095 (2019).
Jung, E. H. et al. Efficient, stable and scalable perovskite solar cells using poly(3-hexylthiophene). Nature 567, 511–515 (2019).
Qin, X. et al. Recent progress in stability of perovskite solar cells. J. Semicond. 38, 011002 (2017).
Kukimoto, H., Henry, C. H. & Merritt, F. R. Photocapacitance studies of the oxygen donor in GaP. I. Optical cross sections, energy levels, and concentration. Phys. Rev. B 7, 2486–2499 (1973).
Whight, K. R. Junction structure effects on constant capacitance DLTS and ODLTS spectra. Solid State Electron. 25, 893–901 (1982).
Cai, Z., Dai, C.-M. & Chen, S. Intrinsic defect limit to the electrical conductivity and a two-step p-type doping strategy for overcoming the efficiency bottleneck of Sb2S3-based solar cells. Sol. RRL 4, 1900503 (2020).
Wen, X. et al. Vapor transport deposition of antimony selenide thin film solar cells with 7.6% efficiency. Nat. Commun. 9, 2179 (2018).
Huang, M. et al. Complicated and unconventional defect properties of the quasi-one-dimensional photovoltaic semiconductor Sb2Se3. ACS Appl. Mater. Interfaces 11, 15564–15572 (2019).
Liu, X. et al. Enhanced Sb2Se3 solar cell performance through theory-guided defect control. Progress. Photovolt. Res. Appl. 25, 861–870 (2017).
Christopher, N. S. & David, O. S. The complex defect chemistry of antimony selenide. J. Mater. Chem. A 7, 10739–10744 (2019).
Christians, J. A. & Kamat, P. V. Trap and transfer. Two-step hole injection across the Sb2S3/CuSCN interface in solid-state solar cells. ACS Nano 7, 7967–7974 (2013).
Christians, J. A., Leighton, J. D. T. & Kamat, P. V. Rate limiting interfacial hole transfer in Sb2S3 solid-state solar cells. Energy Environ. Sci. 7, 1148–1158 (2014).
Giovanni, D. Coherent spin and quasiparticle dynamics in solution‐processed layered 2D lead halide perovskites. Adv. Sci. 5, 1800664 (2018).
This research was mainly supported by the National Key Research and Development Program of China (2019YFA0405600), the National Natural Science Foundation of China (U1732150) and the Australian Renewable Energy Agency (ARENA). X.H., M.A.G. and J.H. acknowledge funding support from the Australian Renewable Energy Agency (grant RND011). S.C. acknowledges support from National Natural Science Foundation of China under grant nos 61722402 and 91833302 and Shanghai Academic/Technology Research Leader (19XD1421300). The authors appreciate the technical assistance of and the use of facilities at the Electron Microscope Unit, University of New South Wales. The authors acknowledge the use of facilities and the assistance at the University of Wollongong (UOW) Electron Microscopy Centre.
The authors declare no competing interests.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Compressed folder containing source data for Fig. 1b–d,f,g.
Compressed folder containing source data for Fig. 2b–g.
Compressed folder containing source data for Fig. 3a–f.
O-DLTS source data for Fig. 4.
TA source data for Fig. 5.
About this article
Cite this article
Tang, R., Wang, X., Lian, W. et al. Hydrothermal deposition of antimony selenosulfide thin films enables solar cells with 10% efficiency. Nat Energy 5, 587–595 (2020). https://doi.org/10.1038/s41560-020-0652-3
Applied Physics Letters (2021)
ACS Photonics (2021)
Suppressing the Trapping Process by Interfacial Charge Extraction in Antimony Selenide Heterojunctions
ACS Energy Letters (2021)
Journal of Energy Chemistry (2021)