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      Improvement of CZTSSe film quality and superstrate solar cell performance through optimized post-deposition annealing

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          Abstract

          Improving the performance of kesterite solar cells requires high-quality, defect-free CZTS(Se) films with a reduced number of secondary phases and impurities. Post-annealing of the CZTS films at high temperatures in a sulfur or selenium atmosphere is commonly used to improve the quality of the absorbing material. However, annealing at high-temperatures can promote material decomposition, mainly due to the loss of volatile elements such as tin or sulfur. In this work, we investigate how the additional step of sulfurization at reduced temperatures affects the quality and performance of CZTSSe based solar cells. A comprehensive structural analysis using conventional and high resolution XRD as well as Raman spectroscopy revealed that the highest CZTSSe material quality with the lowest structural disorder and defect densities was obtained from the CZTS films pre-sulfurized at 420 °C. Furthermore, we demonstrate the possibility of using Sb 2Se 3 as a buffer layer in the superstrate configuration of CZTSSe solar cells, which is possible alternative to replace commonly employed toxic CdS as a buffer layer. We show that the additional low-temperature selenization process and the successful use of Sb 2Se 3 as a buffer layer could improve the performance of CZTSSe-based solar cells by up to 3.48%, with an average efficiency of 3.1%.

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          High-Efficiency Perovskite Solar Cells

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            Classification of lattice defects in the kesterite Cu2ZnSnS4 and Cu2ZnSnSe4 earth-abundant solar cell absorbers.

            The kesterite-structured semiconductors Cu2ZnSnS4 and Cu2ZnSnSe4 are drawing considerable attention recently as the active layers in earth-abundant low-cost thin-film solar cells. The additional number of elements in these quaternary compounds, relative to binary and ternary semiconductors, results in increased flexibility in the material properties. Conversely, a large variety of intrinsic lattice defects can also be formed, which have important influence on their optical and electrical properties, and hence their photovoltaic performance. Experimental identification of these defects is currently limited due to poor sample quality. Here recent theoretical research on defect formation and ionization in kesterite materials is reviewed based on new systematic calculations, and compared with the better studied chalcopyrite materials CuGaSe2 and CuInSe2 . Four features are revealed and highlighted: (i) the strong phase-competition between the kesterites and the coexisting secondary compounds; (ii) the intrinsic p-type conductivity determined by the high population of acceptor CuZn antisites and Cu vacancies, and their dependence on the Cu/(Zn+Sn) and Zn/Sn ratio; (iii) the role of charge-compensated defect clusters such as [2CuZn +SnZn ], [VCu +ZnCu ] and [ZnSn +2ZnCu ] and their contribution to non-stoichiometry; (iv) the electron-trapping effect of the abundant [2CuZn +SnZn ] clusters, especially in Cu2ZnSnS4. The calculated properties explain the experimental observation that Cu poor and Zn rich conditions (Cu/(Zn+Sn) ≈ 0.8 and Zn/Sn ≈ 1.2) result in the highest solar cell efficiency, as well as suggesting an efficiency limitation in Cu2ZnSn(S,Se)4 cells when the S composition is high. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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              Vapor transport deposition of antimony selenide thin film solar cells with 7.6% efficiency

              Antimony selenide is an emerging promising thin film photovoltaic material thanks to its binary composition, suitable bandgap, high absorption coefficient, inert grain boundaries and earth-abundant constituents. However, current devices produced from rapid thermal evaporation strategy suffer from low-quality film and unsatisfactory performance. Herein, we develop a vapor transport deposition technique to fabricate antimony selenide films, a technique that enables continuous and low-cost manufacturing of cadmium telluride solar cells. We improve the crystallinity of antimony selenide films and then successfully produce superstrate cadmium sulfide/antimony selenide solar cells with a certified power conversion efficiency of 7.6%, a net 2% improvement over previous 5.6% record of the same device configuration. We analyze the deep defects in antimony selenide solar cells, and find that the density of the dominant deep defects is reduced by one order of magnitude using vapor transport deposition process.
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                Author and article information

                Contributors
                marius.franckevicius@ftmc.lt
                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group UK (London )
                2045-2322
                28 September 2022
                28 September 2022
                2022
                : 12
                : 16170
                Affiliations
                [1 ]GRID grid.425985.7, Center for Physical Sciences and Technology, ; Sauletekio Av. 3, 10257 Vilnius, Lithuania
                [2 ]GRID grid.6441.7, ISNI 0000 0001 2243 2806, Institute of Biochemistry, Life Sciences Center, , Vilnius University, ; Sauletekio 7, 10257 Vilnius, Lithuania
                [3 ]GRID grid.450974.b, Institute of Applied Physics, ; 5 Academiei Str., Chişinău, 2028 Moldova
                Article
                20670
                10.1038/s41598-022-20670-1
                9519875
                36171263
                7772a99c-7156-4f81-9a05-947d24c71721
                © The Author(s) 2022

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 6 June 2022
                : 16 September 2022
                Funding
                Funded by: FundRef http://dx.doi.org/10.13039/100018694, HORIZON EUROPE Marie Sklodowska-Curie Actions;
                Award ID: 778357
                Award Recipient :
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                © The Author(s) 2022

                Uncategorized
                materials science,materials for devices
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                materials science, materials for devices

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