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Is Photoluminescence Spectroscopy a Suitable Probe of Halide Segregation?

Abstract:
Mixed-halide perovskites exhibit ideal band gaps for use in perovskite-based multijunction photovoltaics, but stable performance is compromised by light-induced halide segregation. Photoluminescence (PL) tracking is universally used to monitor such photoinstability; however, here we reveal that such data do not accurately quantify halide segregation. We utilize a combination of simultaneously recorded PL and X-ray diffraction (XRD) measurements to explore CH3NH3Pb­(I1–x Br x )3 films across 18 different halide ratios. While PL data suggests that segregation rates increase exponentially with bromide fraction x, XRD patterns reveal that they are actually unchanged. We demonstrate that PL cannot accurately reflect the rate and extent of halide segregation because it is governed by charge funneling to iodide-rich minority domains, which is strongly influenced by additional factors, including luminescence efficiency, band energetics, and charge extraction. To assess the efficacy of treatments to suppress such photoinstabilities, it is therefore essential to probe changes across the full material volume, e.g. by monitoring XRD or absorption spectra.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1021/acsenergylett.6c00432

Authors

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Institution:
University of Oxford
Division:
MPLS
Department:
Physics
Sub department:
Physics - Central
Role:
Author
ORCID:
0009-0007-2899-1829
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Physics
Sub department:
Physics - Central
Role:
Author
ORCID:
0000-0002-9726-0436
More by this author
Role:
Author
ORCID:
0000-0001-5132-1232
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Physics
Sub department:
Physics - Central
Role:
Author
More by this author
Institution:
University of Oxford
Division:
MPLS
Department:
Physics
Sub department:
Physics - Central
Role:
Author
ORCID:
0000-0002-9226-6943


More from this funder
Funder identifier:
https://ror.org/0439y7842
Grant:
EP/W007975/2


Publisher:
American Chemical Society
Journal:
ACS Energy Letters More from this journal
Volume:
11
Issue:
5
Pages:
3953-3961
Publication date:
2026-04-21
Acceptance date:
2026-04-16
DOI:
EISSN:
2380-8195
ISSN:
2380-8195


Language:
English
Keywords:
Source identifiers:
4032791
Deposit date:
2026-05-11
ARK identifier:
This ORA record was generated from metadata provided by an external service. It has not been edited by the ORA Team.

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