Reactive Passivation of Wide-Bandgap Organic–Inorganic Perovskites with Benzylamine

While amines are widely used as additives in metal-halide perovskites, our understanding of the way amines in perovskite precursor solutions impact the resultant perovskite film is still limited. In this paper, we explore the multiple effects of benzylamine (BnAm), also referred to as phenylmethylamine, used to passivate both FA<sub>0.75</sub>Cs<sub>0.25</sub>Pb(I<sub>0.8</sub>Br<sub>0.2</sub>)<sub>3</sub> and FA<sub>0.8</sub>Cs<sub>0.2</sub>PbI<sub>3</sub> perovskite compositions. We show that, unlike benzylammonium (BnA<sup>+</sup>) halide salts, BnAm reacts rapidly with the formamidinium (FA<sup>+</sup>) cation, forming new chemical products in solution and these products passivate the perovskite crystal domains when processed into a thin film. In addition, when BnAm is used as a bulk additive, the average perovskite solar cell maximum power point tracked efficiency (for 30 s) increased to 19.3% compared to the control devices 16.8% for a 1.68 eV perovskite. Under combined full spectrum simulated sunlight and 65 °C temperature, the devices maintained a better <i>T</i><sub>80</sub> stability of close to 2500 h while the control devices have <i>T</i><sub>80</sub> stabilities of <100 h. We obtained similar results when presynthesizing the product BnFAI and adding it directly into the perovskite precursor solution. These findings highlight the mechanistic differences between amine and ammonium salt passivation, enabling the rational design of molecular strategies to improve the material quality and device performance of metal-halide perovskites.

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Publication Details

Journal
Journal of the American Chemical Society
Published
2024-09-30
DOI
https://doi.org/10.1021/jacs.4c06659
Citations
35
Primary Topic
Perovskite Materials and Applications
Type
article
Field-Weighted Citation Impact
7.30

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article

Reactive Passivation of Wide-Bandgap Organic–Inorganic Perovskites with Benzylamine

Declan P. McCarthy, Suer Zhou, Benjamin M. Gallant, Rachel C. Kilbride et al.
35 citations
Journal of the American Chemical Society
Perovskite Materials and Applications
7.30
article

Reactive Passivation of Wide-Bandgap Organic–Inorganic Perovskites with Benzylamine

Declan P. McCarthy, Suer Zhou, Benjamin M. Gallant, Rachel C. Kilbride, Jian Wang, Seth R. Marder, Pattarawadee Therdkatanyuphong, Yangwei Shi, Dominik J. Kubicki, Margherita Taddei, Akash Dasgupta, James N. Drysdale, Joel A. Smith, Ashley R. Marshall, Stephen Barlow, David S. Ginger, Henry James Snaith, Junxiang Zhang
article en
35 citations

Abstract

While amines are widely used as additives in metal-halide perovskites, our understanding of the way amines in perovskite precursor solutions impact the resultant perovskite film is still limited. In this paper, we explore the multiple effects of benzylamine (BnAm), also referred to as phenylmethylamine, used to passivate both FA<sub>0.75</sub>Cs<sub>0.25</sub>Pb(I<sub>0.8</sub>Br<sub>0.2</sub>)<sub>3</sub> and FA<sub>0.8</sub>Cs<sub>0.2</sub>PbI<sub>3</sub> perovskite compositions. We show that, unlike benzylammonium (BnA<sup>+</sup>) halide salts, BnAm reacts rapidly with the formamidinium (FA<sup>+</sup>) cation, forming new chemical products in solution and these products passivate the perovskite crystal domains when processed into a thin film. In addition, when BnAm is used as a bulk additive, the average perovskite solar cell maximum power point tracked efficiency (for 30 s) increased to 19.3% compared to the control devices 16.8% for a 1.68 eV perovskite. Under combined full spectrum simulated sunlight and 65 °C temperature, the devices maintained a better <i>T</i><sub>80</sub> stability of close to 2500 h while the control devices have <i>T</i><sub>80</sub> stabilities of <100 h. We obtained similar results when presynthesizing the product BnFAI and adding it directly into the perovskite precursor solution. These findings highlight the mechanistic differences between amine and ammonium salt passivation, enabling the rational design of molecular strategies to improve the material quality and device performance of metal-halide perovskites.

Journal of the American Chemical SocietyVol. 146(40)
University of Colorado Boulder (US), University of Washington (US), University of Oxford (GB), Vidyasirimedhi Institute of Science and Technology (TH), University of Birmingham (GB), University of Sheffield (GB)
National Science Foundation, Vidyasirimedhi Institute of Science and Technology, Horizon 2020 Framework Programme, Engineering and Physical Sciences Research Council, Office of Naval Research, Office of Naval Research Global
Openalex Percentile: Top 2%
Perovskite Materials and Applications
7.30
DOIOpen Access PDFOpenAlex
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