Electronic structure and optoelectronic properties of bismuth Ooxyiodide robust against percent-level iodine-, oxygen- and bismuth-related surface defects
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Supporting information
Published version
Author(s)
Type
Journal Article
Abstract
In the search for nontoxic alternatives to lead‐halide perovskites, bismuth oxyiodide (BiOI) has emerged as a promising contender. BiOI is air‐stable for over three months, demonstrates promising early‐stage photovoltaic performance and, importantly, is predicted from calculations to tolerate vacancy and antisite defects. Here, whether BiOI tolerates point defects is experimentally investigated. BiOI thin films are annealed at a low temperature of 100 °C under vacuum (25 Pa absolute pressure). There is a relative reduction in the surface atomic fraction of iodine by over 40%, reduction in the surface bismuth fraction by over 5%, and an increase in the surface oxygen fraction by over 45%. Unexpectedly, the Bi 4f7/2 core level position, Fermi level position, and valence band density of states of BiOI are not significantly changed. Further, the charge‐carrier lifetime, photoluminescence intensity, and the performance of the vacuum‐annealed BiOI films in solar cells remain unchanged. The results show BiOI to be electronically and optoelectronically robust to percent‐level changes in surface composition. However, from photoinduced current transient spectroscopy measurements, it is found that the as‐grown BiOI films have deep traps located ≈0.3 and 0.6 eV from the band edge. These traps limit the charge‐carrier lifetimes of BiOI, and future improvements in the performance of BiOI photovoltaics will need to focus on identifying their origin. Nevertheless, these deep traps are three to four orders of magnitude less concentrated than the surface point defects induced through vacuum annealing. The charge‐carrier lifetimes of the BiOI films are also orders of magnitude longer than if these surface defects were recombination active. This work therefore shows BiOI to be robust against processing conditions that lead to percent‐level iodine‐, bismuth‐, and oxygen‐related surface defects. This will simplify and reduce the cost of fabricating BiOI‐based electronic devices, and stands in contrast to the defect‐sensitivity of traditional covalent semiconductors.
Date Issued
2020-03-24
Date Acceptance
2020-01-10
Citation
Advanced Functional Materials, 2020, 30 (13), pp.1-11
ISSN
1616-301X
Publisher
Wiley
Start Page
1
End Page
11
Journal / Book Title
Advanced Functional Materials
Volume
30
Issue
13
Copyright Statement
© 2020 The Authors. Published by WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
Sponsor
Downing College, Cambridge
Royal Academy of Engineering
Royal Academy Of Engineering
Identifier
https://onlinelibrary.wiley.com/doi/full/10.1002/adfm.201909983
Grant Number
RF\201718\17101
RF\201718\17101
Subjects
Science & Technology
Physical Sciences
Technology
Chemistry, Multidisciplinary
Chemistry, Physical
Nanoscience & Nanotechnology
Materials Science, Multidisciplinary
Physics, Applied
Physics, Condensed Matter
Chemistry
Science & Technology - Other Topics
Materials Science
Physics
bismuth-based solar absorbers
defect tolerance
perovskite-inspired materials
photoinduced current transient spectroscopy
photovoltaics
CURRENT TRANSIENT SPECTROSCOPY
RESISTIVITY BULK MATERIALS
PEROVSKITE SOLAR-CELLS
TOLERANCE
LOSSES
BIOI
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Materials
Publication Status
Published
Date Publish Online
2020-02-14