Growth of BaZrS3 Chalcogenide Perovskite Thin Films Without Post Annealing
Abstract
Tandem solar cells based on hybrid organic–inorganic metal halide perovskites have achieved power conversion efficiencies of up to 28%. However, issues related to long-term stability and lead (Pb) toxicity have prompted the search for earth-abundant, chemically stable, and non-toxic alternatives. In this work, we report the first vacuum evaporation synthesis of BaZrS₃ (barium zirconium sulfide) thin films at a substrate temperature of 550 °C. The resulting films exhibit near-stoichiometric Ba:Zr ratios and strong light absorption, with absorption coefficients exceeding 10⁵ cm⁻¹ near 1.9 eV. Under controlled conditions, a baseline oxygen content of 4–6% was consistently observed. The absence of an additional sulfurization step markedly increased the resistance of the thin film and suppressed the dark current by approximately three orders of magnitude, indicating a substantial reduction in carrier density likely resulting from a decreased concentration of sulfur vacancies. These findings highlight the potential of BaZrS3 as a stable, lead-free absorber for next-generation photovoltaics.
Downloads
References
D.W. de Quilettes, S.M. Vorpahl, S.D. Stranks, H. Nagaoka, G.E. Eperon, M.E. Ziffer, H.J. Snaith, and D.S. Ginger, “Impact of microstructure on local carrier lifetime in perovskite solar cells,” Science, 348, 683-686 (2015). https://doi.org/10.1126/science.aaa5333
S. Suragtkhuu, S. Sunderiya, P. Myagmarsereejid, S. Purevdorj, A.S.R. Bati, B. Bold, et al., “Graphene-Like Monoelemental 2D Materials for Perovskite Solar Cells,” Adv. Energy Mater. 13, 2204074 (2023). https://doi.org/10.1002/aenm.202204074
A. Swarnkar, W.J. Mir, R. Chakraborty, M. Jagadeeswararao, T. Sheikh, A. Nag, “Are Chalcogenide Perovskites an Emerging Class of Semiconductors for Optoelectronic Properties and Solar Cell?” Chem. Mater. 31, 565−575 (2019). https://doi.org/10.1021/acs.chemmater.8b04178
K.V. Sopiha, C. Comparotto, J.A. Márquez, and J.J.S. Scragg, “Chalcogenide Perovskites: Tantalizing Prospects, Challenging Materials,” Advanced Optical Materials, 10, 2101704 (2022). https://doi.org/10.1002/adom.202101704
M. Buffiere, D.S. Dhawale, and F. El-Mellouhi, “Chalcogenide Materials and Derivatives for Photovoltaic Applications,” Energy Technology, 7, 1900819 (2019). https://doi.org/10.1002/ente.201900819
C. Comparotto, P. Ström, O. Donzel-Gargand, T. Kubart, and J.J.S. Scragg, “Synthesis of BaZrS3 Perovskite Thin Films at a Moderate Temperature on Conductive Substrates,” ACS Appl. Energy Mater. 5(5), 6335–6343 (2022). https://doi.org/10.1021/acsaem.2c00704
C. Wang, R. Nie, Y. Dai, H. Tai, B. Zhu, L. Zhao, Y. Wu, et al., “Enhancing the inherent stability of perovskite solar cells through chalcogenide-halide combinations,” Energy Environ. Sci. 17, 1368-1386 (2024). https://doi.org/10.1039/D3EE03612J
R. Jaramillo, and J. Ravichandran, “In praise and in search of highly- polarizable semiconductors: Technological promise and discovery strategiesm,” APL Materials, 7, 100902 (2019). https://doi.org/10.1063/1.5124795
Y. Nishigaki, T. Nagai, M. Nishiwaki, T. Aizawa, M. Kozawa, K. Hanzawa, Y. Kato, et al., “Extraordinary Strong Band-Edge Absorption in Distorted Chalcogenide Perovskites,” Solar RRL, 4, 1900555 (2020). https://doi.org/10.1002/solr.201900555
X. Wu, W. Gao, J. Chai, C. Ming, M. Chen, H. Zeng, P. Zhang, et al., “Defect tolerance in chalcogenide perovskite photovoltaic material BaZrS3,” Science China Materials, 64, 2976−2986 (2021). https://doi.org/10.1007/s40843-021-1683-0
W. Meng, B. Saparov, F. Hong, J. Wang, D.B. Mitzi, and Y. Yan, “Alloying and Defect Control within Chalcogenide Perovskites for Optimized Photovoltaic Application,” Chem. Mater. 28, 821 829 (2016). https://doi.org/10.1021/acs.chemmater.5b04213
M. Ishii, and M. Saeki, “Raman and Infrared Spectra of BaTiS3 and BaNbS3,” Phys. Stat. Sol. (b), 170, K49 (1992). https://doi.org/10.1002/pssb.2221700149
M. Ishii, M. Saeki, and M. Sekita, “Vibrational spectra of barium-zirconium sulfides,” Mater. Res. Bull. 28, 493-500 (1993). https://doi.org/10.1016/0025-5408(93)90132-W
S. Perera, H. Hui, C. Zhao, H. Xue, F. Sun, C. Deng, N. Gross, et al., “Chalcogenide perovskites – an emerging class of ionic semiconductors,” Nano Energy, 22, 129-135 (2016). https://doi.org/10.1016/j.nanoen.2016.02.020
R. Yang, J. Nelson, C. Fai, H.A. Yetkin, C. Werner, M. Tervil, A.D. Jess, et al., “A Low-Temperature Growth Mechanism for Chalcogenide Perovskites,” Chemistry of Materials, 35(12), 4743–4750 (2023). https://doi.org/10.1021/acs.chemmater.3c00494
T.M. Razykov, K.М. Kuchkarov, B.A. Ergashev, L. Schmidt-Mende, T. Mayer, M. Tivanov, М. Makhmudov, et al., “Growth and characterization of Sb2(SxSe1-x)3 thin flms prepared by chemical-molecular beam deposition for solar cell applications,” Thin Solid Films, 807, 140554 (2024). https://doi.org/10.1016/j.tsf.2024.140554
S. Agarwal, K.C. Vincent, and R. Agrawal, “From synthesis to application: a review of BaZrS3chalcogenide perovskites,” Nanoscale, 17, 4250-4300 (2025). https://doi.org/10.1039/D4NR03880K
Copyright (c) 2025 T.M. Razykov, K.M. Kuchkarov, R.T. Yuldoshov, M.P. Pirimmatov, R.R. Khurramov, D.Z. Isakov, M.A. Makhmudov, S.A. Muzafarova, A. Matmuratov
This work is licensed under a Creative Commons Attribution 4.0 International License.
Authors who publish with this journal agree to the following terms:
- Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License that allows others to share the work with an acknowledgment of the work's authorship and initial publication in this journal.
- Authors are able to enter into separate, additional contractual arrangements for the non-exclusive distribution of the journal's published version of the work (e.g., post it to an institutional repository or publish it in a book), with an acknowledgment of its initial publication in this journal.
- Authors are permitted and encouraged to post their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work (See The Effect of Open Access).
