Substitution of lead with tin suppresses ionic transport in halide perovskite optoelectronics

Despite the rapid rise in the performance of a variety of perovskite optoelectronic devices with vertical charge transport, the effects of ion migration remain a common and longstanding Achilles' heel limiting the long-term operational stability of lead halide perovskite devices. However, there...

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Bibliographic Details
Published in:Energy & environmental science 2024-01, Vol.17 (2), p.76-769
Main Authors: Dey, Krishanu, Ghosh, Dibyajyoti, Pilot, Matthew, Pering, Samuel R, Roose, Bart, Deswal, Priyanka, Senanayak, Satyaprasad P, Cameron, Petra J, Islam, M. Saiful, Stranks, Samuel D
Format: Article
Language:English
Subjects:
Charge transport
Chemistry
Current loss
Electrical measurement
First principles
Iodides
Ion dynamics
Ion migration
Lead
Lead compounds
Metal halides
Optoelectronic devices
Perovskites
Photovoltaic cells
Short circuit currents
Short-circuit current
Solar cells
Spectroscopy
Substitutes
Temperature dependence
Tin
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Summary:Despite the rapid rise in the performance of a variety of perovskite optoelectronic devices with vertical charge transport, the effects of ion migration remain a common and longstanding Achilles' heel limiting the long-term operational stability of lead halide perovskite devices. However, there is still limited understanding of the impact of tin (Sn) substitution on the ion dynamics of lead (Pb) halide perovskites. Here, we employ scan-rate-dependent current-voltage measurements on Pb and mixed Pb-Sn perovskite solar cells to show that short circuit current losses at lower scan rates, which can be traced to the presence of mobile ions, are present in both kinds of perovskites. To understand the kinetics of ion migration, we carry out scan-rate-dependent hysteresis analyses and temperature-dependent impedance spectroscopy measurements, which demonstrate suppressed ion migration in Pb-Sn devices compared to their Pb-only analogues. By linking these experimental observations to first-principles calculations on mixed Pb-Sn perovskites, we reveal the key role played by Sn vacancies in increasing the iodide ion migration barrier due to local structural distortions. These results highlight the beneficial effect of Sn substitution in mitigating undesirable ion migration in halide perovskites, with potential implications for future device development. Mobile ions cause deterioration in both device performance and stability of lead halide perovskite devices. This study provides direct evidence for substantial suppression of ionic migration effects in tin-containing perovskite compositions.
ISSN:1754-5692
1754-5706
DOI:10.1039/d3ee03772j