Cs+ incorporation into CH3NH3PbI3 perovskite: substitution limit and stability enhancement

Ralf G. Niemann, Laxman Gouda, Jiangang Hu, Shay Tirosh, Ronen Gottesman, Petra J. Cameron, Arie Zaban

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Abstract

In this study we systematically explored the mixed cation perovskite Csx(CH3NH3)1-xPbI3. We exchanged the A-site cation by dipping MAPbI3 films into a CsI solution, thereby incrementally replacing the MA+ in a time-resolved dipping process and analysed the resulting thin-films with UV-Vis, XRD, EDAX, SEM and optical depth-analysis in a high-throughput fashion. Additional in situ UV-Vis and time-resolved XRD measurements allowed us to look at the kinetics of the formation process. The results showed a discontinuity during the conversion. Firstly, small amounts of Cs+ are incorporated into the structure. After a few minutes, the Cs content approaches a limit and grains of δ-CsPbI3 occur, indicating a substitution limit. We compared this cation exchange to a one-step crystallisation approach and found the same effect of phase segregation, which shows that the substitution limit is an intrinsic feature rather than a kinetic effect. Optical and structural properties changed continuously for small Cs incorporations. Larger amounts of Cs result in phase segregation. We estimate the substitution limit of CsxMA1-xPbI3 to start at a Cs ratio x = 0.13, based on combined measurements of EDAX, UV-Vis and XRD. The photovoltaic performance of the mixed cation perovskite shows a large increase in device stability from days to weeks. The initial efficiency of mixed CsxMA1-xPbI3 devices decreases slightly, which is compensated by stability after a few days.

Original languageEnglish
Pages (from-to)17819-17827
Number of pages9
JournalJournal of Materials Chemistry A
Volume4
Issue number45
DOIs
Publication statusPublished - 7 Dec 2016

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Perovskite
Cations
Substitution reactions
Positive ions
Energy dispersive spectroscopy
Kinetics
Crystallization
Structural properties
Ion exchange
Optical properties
Throughput
Thin films
Scanning electron microscopy
perovskite

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Cs+ incorporation into CH3NH3PbI3 perovskite : substitution limit and stability enhancement. / Niemann, Ralf G.; Gouda, Laxman; Hu, Jiangang; Tirosh, Shay; Gottesman, Ronen; Cameron, Petra J.; Zaban, Arie.

In: Journal of Materials Chemistry A, Vol. 4, No. 45, 07.12.2016, p. 17819-17827.

Research output: Contribution to journalArticle

Niemann, Ralf G. ; Gouda, Laxman ; Hu, Jiangang ; Tirosh, Shay ; Gottesman, Ronen ; Cameron, Petra J. ; Zaban, Arie. / Cs+ incorporation into CH3NH3PbI3 perovskite : substitution limit and stability enhancement. In: Journal of Materials Chemistry A. 2016 ; Vol. 4, No. 45. pp. 17819-17827.
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