Small-Band-Gap Halide Double Perovskites

Slavney, Adam H.; Leppert, Linn; Valdes, Abraham Saldivar; Bartesaghi, Davide; Savenije, Tom J.; Neaton, Jeffrey B.; Karunadasa, Hemamala I.

doi:10.1002/anie.201807421

Title: Small-Band-Gap Halide Double Perovskites

Journal Article · Tue Aug 07 00:00:00 EDT 2018 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201807421· OSTI ID:1475457

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^[2]; Valdes, Abraham Saldivar ^[1];

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Stanford Univ., Stanford, CA (United States)
Univ. of Bayreuth, Bayreuth (Germany)
Delft Univ. of Technology, Delft (Netherlands); Materials Innovation Institute, Delft (Netherlands)
Delft Univ. of Technology, Delft (Netherlands)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Kavli Energy NanoScience, Berkeley, CA (United States)

Abstract Despite their compositional versatility, most halide double perovskites feature large band gaps. Herein, we describe a strategy for achieving small band gaps in this family of materials. The new double perovskites Cs ₂ AgTlX ₆ (X=Cl ( 1 ) and Br ( 2 )) have direct band gaps of 2.0 and 0.95 eV, respectively, which are approximately 1 eV lower than those of analogous perovskites. To our knowledge, compound 2 displays the lowest band gap for any known halide perovskite. Unlike in A ^I B ^II X ₃ perovskites, the band‐gap transition in A ^I ₂ BB′X ₆ double perovskites can show substantial metal‐to‐metal charge‐transfer character. This band‐edge orbital composition is used to achieve small band gaps through the selection of energetically aligned B‐ and B′‐site metal frontier orbitals. Calculations reveal a shallow, symmetry‐forbidden region at the band edges for 1 , which results in long (μs) microwave conductivity lifetimes. We further describe a facile self‐doping reaction in 2 through Br ₂ loss at ambient conditions.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-76SF00515; DMR-1708892; ECCS-1542152

OSTI ID:: 1475457

Alternate ID(s):: OSTI ID: 1467925

Journal Information:: Angewandte Chemie (International Edition), Vol. 57, Issue 39; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 120 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
absorber
band gap
band structure
doping
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