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      Strategic review of secondary phases, defects and defect-complexes in kesterite CZTS–Se solar cells

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          Abstract

          This article presents a strategic review of secondary phases, defects and defect-complexes in kesterite CZTS–Se solar cells responsible for performance gap from CIGS solar cells.

          Earth abundant kesterite copper-zinc-tin-sulfide–selenide (CZTS–Se) is considered as cost-effective material for next generation solar cells. However, current CZTS–Se solar cells have much lower efficiency than CIGS solar cells. Rapid progress in achieving the target efficiency in CZTS–Se solar cells is hindered by the narrow phase stability of the quaternary phase, Cu 2ZnSn(S xSe 1−x) 4, and the existence of other competitive and complex secondary phases and defects. This resulted in structural inhomogeneity, local fluctuation of open circuit voltage and high carrier recombination that finally lead to poor device performance and repeatability issues. The higher performance of off-stoichiometric CZTS materials, copper-poor and zinc-rich, and their inherent association with secondary phases and defects force the scientific community to investigate them together. This work aims to provide a comprehensive review for optimum growth conditions to achieve efficient kesterite CZTS–Se material under different conditions, complementary characterization techniques to detect unwanted phases, defects and defect-complexes and various approaches to reduce the secondary phases, defects and defect-complexes for higher performance in CZTS–Se solar cells. Understanding and addressing the structural inhomogeneity, control growth and material characterization are expected to yield closer performance parity between CZTS–Se and CIGS solar cells.

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          Device Characteristics of CZTSSe Thin-Film Solar Cells with 12.6% Efficiency

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            New world record efficiency for Cu(In,Ga)Se2 thin-film solar cells beyond 20%

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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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                Author and article information

                Journal
                EESNBY
                Energy & Environmental Science
                Energy Environ. Sci.
                Royal Society of Chemistry (RSC)
                1754-5692
                1754-5706
                2015
                2015
                : 8
                : 11
                : 3134-3159
                Article
                10.1039/C5EE02153G
                c141a039-85ed-4fe1-bfd6-82eb22025ceb
                © 2015
                Product
                Self URI (article page): http://xlink.rsc.org/?DOI=C5EE02153G

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