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Cu–In Halide Perovskite Solar Absorbers
Open accessAbstract
The long-term chemical instability and the presence of toxic Pb in otherwise stellar solar absorber APbX 3 made of organic molecules on the A site and halogens for X have hindered their large-scale commercialization. Previously explored ways to achieve Pb-free halide perovskites involved replacing Pb 2+ with other similar M 2+ cations in n s 2 electron configuration, e.g., Sn 2+ or by Bi 3+ (plus Ag + ), but unfortunately this showed either poor stability (M = Sn) or weakly absorbing oversized indirect gaps (M = Bi), prompting concerns that perhaps stability and good optoelectronic properties might be contraindicated. Herein, we exploit the electronic structure underpinning of classic Cu[In,Ga]Se 2 (CIGS) chalcopyrite solar absorbers to design Pb-free halide perovskites by transmuting 2Pb to the pair [B IB + C III ] such as [Cu + Ga] or [Ag + In] and combinations thereof. The resulting group of double perovskites with formula A 2 BCX 6 (A = K, Rb, Cs; B = Cu, Ag; C = Ga, In; X = Cl, Br, I) benefits from the ionic, yet narrow-gap character of halide perovskites, and at the same time borrows the advantage of the strong Cu( d )/Se( p ) → Ga/In( s / p ) valence-to-conduction-band absorption spectra known from CIGS. This constitutes a new group of CuIn-based Halide Perovskite (CIHP). Our first-principles calculations guided by such design principles indicate that the CIHPs class has members with clear thermodynamic stability, showing direct band gaps, and manifesting a wide-range of tunable gap values (from zero to about 2.5 eV) and combination of light electron and heavy-light hole effective masses. Materials screening of candidate CIHPs then identifies the best-of-class Rb 2 [CuIn]Cl 6, Rb 2 [AgIn]Br 6, and Cs 2 [AgIn]Br 6, having direct band gaps of 1.36, 1.46, and 1.50 eV, and theoretical spectroscopic limited maximal efficiency comparable to chalcopyrites and CH 3 NH 3 PbI 3 . Our finding offers a new routine for designing new-type Pb-free halide perovskite solar absorbers.
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Metadata
- Authors
- Zhao, X.-G., Yang, D., Sun, Y., Li, T., Zhang, L., Yu, L., & Zunger, A.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2017-05-04
- Volume
- 139
- Issue
- 19
- Pages
- 6718-6725
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2606374948
- Cited by
- 428
- References
- 66
- FWCI
- 17.56
- Type
- journal article
- Language
- en
- Open access
- green
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