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Alloying a single and a double perovskite: a Cu+/2+ mixed-valence layered halide perovskite with strong optical absorption

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Abstract

Introducing heterovalent cations at the octahedral sites of halide perovskites can substantially change their optoelectronic properties. Yet, in most cases, only small amounts of such metals can be incorporated as impurities into the three-dimensional lattice. Here, we exploit the greater structural flexibility of the two-dimensional (2D) perovskite framework to place three distinct stoichiometric cations in the octahedral sites. The new layered perovskites AI4[CuII(CuIInIII)0.5Cl8] (1, A = organic cation) may be derived from a CuI–InIII double perovskite by replacing half of the octahedral metal sites with Cu2+. Electron paramagnetic resonance and X-ray absorption spectroscopy confirm the presence of Cu2+ in 1. Crystallographic studies demonstrate that 1 represents an averaging of the CuI–InIII double perovskite and CuII single perovskite structures. However, whereas the highly insulating CuI–InIII and CuII perovskites are colorless and yellow, respectively, 1 is black, with substantially higher electronic conductivity than that of either endmember. We trace these emergent properties in 1 to intervalence charge transfer between the mixed-valence Cu centers. We further propose a tiling model to describe how the Cu+, Cu2+, and In3+ coordination spheres can pack most favorably into a 2D perovskite lattice, which explains the unusual 1 : 2 : 1 ratio of these cations found in 1. Magnetic susceptibility data of 1 further corroborate this packing model. The emergence of enhanced visible light absorption and electronic conductivity in 1 demonstrates the importance of devising strategies for increasing the compositional complexity of halide perovskites.

Graphical abstract: Alloying a single and a double perovskite: a Cu+/2+ mixed-valence layered halide perovskite with strong optical absorption

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Article information


Submitted
27 Feb 2021
Accepted
13 May 2021
First published
14 May 2021

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2021, Advance Article
Article type
Edge Article

Alloying a single and a double perovskite: a Cu+/2+ mixed-valence layered halide perovskite with strong optical absorption

B. A. Connor, R. W. Smaha, J. Li, A. Gold-Parker, A. J. Heyer, M. F. Toney, Y. S. Lee and H. I. Karunadasa, Chem. Sci., 2021, Advance Article , DOI: 10.1039/D1SC01159F

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    [Original citation] - Published by The Royal Society of Chemistry.

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