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Chemical control of the dimensionality of the octahedral network of solar absorbers from the CuI-AgI-BiI3 phase space by synthesis of 3D CuAgBiI5

Abstract:
A newly reported compound, CuAgBiI5, is synthesized as powder, crystals, and thin films. The structure consists of a 3D octahedral Ag+/Bi3+ network as in spinel, but occupancy of the tetrahedral interstitials by Cu+ differs from those in spinel. The 3D octahedral network of CuAgBiI5 allows us to identify a relationship between octahedral site occupancy (composition) and octahedral motif (structure) across the whole CuI–AgI–BiI3 phase field, giving the ability to chemically control structural dimensionality. To investigate composition–structure–property relationships, we compare the basic optoelectronic properties of CuAgBiI5 with those of Cu2AgBiI6 (which has a 2D octahedral network) and reveal a surprisingly low sensitivity to the dimensionality of the octahedral network. The absorption onset of CuAgBiI5 (2.02 eV) barely changes compared with that of Cu2AgBiI6 (2.06 eV) indicating no obvious signs of an increase in charge confinement. Such behavior contrasts with that for lead halide perovskites which show clear confinement effects upon lowering dimensionality of the octahedral network from 3D to 2D. Changes in photoluminescence spectra and lifetimes between the two compounds mostly derive from the difference in extrinsic defect densities rather than intrinsic effects. While both materials show good stability, bulk CuAgBiI5 powder samples are found to be more sensitive to degradation under solar irradiation compared to Cu2AgBiI6.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1021/acs.inorgchem.1c02773

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Institution:
University of Oxford
Division:
MPLS
Department:
Physics
Sub department:
Condensed Matter Physics
Role:
Author
ORCID:
0000-0003-0329-2822
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Role:
Author
ORCID:
0000-0003-2044-6774


Publisher:
American Chemical Society
Journal:
Inorganic Chemistry More from this journal
Volume:
60
Issue:
23
Pages:
18154-18167
Place of publication:
United States
Publication date:
2021-11-09
DOI:
EISSN:
1520-510X
ISSN:
0020-1669
Pmid:
34751565


Language:
English
Keywords:
Pubs id:
1210267
Local pid:
pubs:1210267
Deposit date:
2021-12-03

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