Solution Aging Promotes the Formation of Hexagonal Polytypes in Mixed-Cation/-Halide Perovskites

Gianluca Bravetti; Nicola Taurisano; Anna Moliterni; Jose Manuel Vicent-Luna; Davide Altamura; Federica Aiello; Nadir Vanni; Agostina Lina Capodilupo; Sonia Carallo; Giuseppe Gigli; Gloria Uccello-Barretta; Federica Balzano; Cinzia Giannini; Shuxia Tao; Silvia Colella; Aurora Rizzo

doi:10.1021/acs.chemmater.3c02694

Solution Aging Promotes the Formation of Hexagonal Polytypes in Mixed-Cation/-Halide Perovskites

Gianluca Bravetti
, Nicola Taurisano
, Anna Moliterni
, Jose Manuel Vicent-Luna
, Davide Altamura
, Federica Aiello
, Nadir Vanni
, Agostina Lina Capodilupo
, Sonia Carallo
, Giuseppe Gigli
, Gloria Uccello-Barretta
, Federica Balzano
, Cinzia Giannini
, Shuxia Tao (Corresponding author)
, Silvia Colella (Corresponding author)
, Aurora Rizzo (Corresponding author)

Research output: Contribution to journal › Article › Academic › peer-review

11 Citations (Scopus)

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Abstract

Mixed-cation/-halide perovskite compositions are becoming increasingly popular, allowing the convenient tuning of photophysical and optoelectronic properties of photoactive films. However, the presence of multiple components in the solution and the demonstrated reactivity between some of them make the ink formulation quite complex and difficult to connect to the film properties and to a fundamental understanding, leading to the fabrication of reproducible and efficient optoelectronic devices. Herein, we report for the first time on the straightforward relationship between the ubiquitous presence of the N-methylformamidinium (MFA) adduct into MA/FA aged solutions and the formation of hexagonal polytypes (6H and 4H) during FA_0.85MA_0.15Pb(I_0.85Br_0.15)₃ perovskite crystallization. The aging process in solution is evaluated through nuclear magnetic resonance (NMR), supported by optical, morphological, and crystalline structure characterizations. Density functional theory calculations unravel how the conformation of the MFA deeply alters the crystallization pathways, preferentially stabilizing the hexagonal yellow phases, known to be detrimental to the perovskite film performances in optoelectronic devices.

Original language	English
Pages (from-to)	3150–3163
Number of pages	14
Journal	Chemistry of Materials
Volume	36
Issue number	7
DOIs	https://doi.org/10.1021/acs.chemmater.3c02694
Publication status	Published - 9 Apr 2024

Funding

This work was partly funded by the research project: “nuovi Concetti, mAteriali e tecnologie per l’iNtegrazione del fotoVoltAico negli edifici in uno scenario di generazione diffuSa” [CANVAS], funded by the Italian Ministry of the Environment and the Energy Security, through the Research Fund for the Italian Electrical System (type-A call, published on G.U.R.I. n. 192 on 18-08-2022), CUP-B53C22005670005. S.T. acknowledges funding from VIDI (Project No. VI.Vidi.213.091) from NWO, the Netherlands. A.R. gratefully acknowledges the PRIN 22 and PRIN PNRR 22 projects LEAD-OUT (2022B3C94E) and MASTER (P2022ZYTJY) founded by the European Community-Next Generation EU. A.M., D.A., and C.G gratefully thank F. Baldassarre and R. Lassandro for their technical assistance.

Funders
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

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Bravetti, G., Taurisano, N., Moliterni, A., Vicent-Luna, J. M., Altamura, D., Aiello, F., Vanni, N., Capodilupo, A. L., Carallo, S., Gigli, G., Uccello-Barretta, G., Balzano, F., Giannini, C., Tao, S., Colella, S., & Rizzo, A. (2024). Solution Aging Promotes the Formation of Hexagonal Polytypes in Mixed-Cation/-Halide Perovskites. Chemistry of Materials, 36(7), 3150–3163. https://doi.org/10.1021/acs.chemmater.3c02694

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title = "Solution Aging Promotes the Formation of Hexagonal Polytypes in Mixed-Cation/-Halide Perovskites",

abstract = "Mixed-cation/-halide perovskite compositions are becoming increasingly popular, allowing the convenient tuning of photophysical and optoelectronic properties of photoactive films. However, the presence of multiple components in the solution and the demonstrated reactivity between some of them make the ink formulation quite complex and difficult to connect to the film properties and to a fundamental understanding, leading to the fabrication of reproducible and efficient optoelectronic devices. Herein, we report for the first time on the straightforward relationship between the ubiquitous presence of the N-methylformamidinium (MFA) adduct into MA/FA aged solutions and the formation of hexagonal polytypes (6H and 4H) during FA0.85MA0.15Pb(I0.85Br0.15)3 perovskite crystallization. The aging process in solution is evaluated through nuclear magnetic resonance (NMR), supported by optical, morphological, and crystalline structure characterizations. Density functional theory calculations unravel how the conformation of the MFA deeply alters the crystallization pathways, preferentially stabilizing the hexagonal yellow phases, known to be detrimental to the perovskite film performances in optoelectronic devices.",

author = "Gianluca Bravetti and Nicola Taurisano and Anna Moliterni and Vicent-Luna, \{Jose Manuel\} and Davide Altamura and Federica Aiello and Nadir Vanni and Capodilupo, \{Agostina Lina\} and Sonia Carallo and Giuseppe Gigli and Gloria Uccello-Barretta and Federica Balzano and Cinzia Giannini and Shuxia Tao and Silvia Colella and Aurora Rizzo",

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Bravetti, G, Taurisano, N, Moliterni, A, Vicent-Luna, JM, Altamura, D, Aiello, F, Vanni, N, Capodilupo, AL, Carallo, S, Gigli, G, Uccello-Barretta, G, Balzano, F, Giannini, C, Tao, S, Colella, S & Rizzo, A 2024, 'Solution Aging Promotes the Formation of Hexagonal Polytypes in Mixed-Cation/-Halide Perovskites', Chemistry of Materials, vol. 36, no. 7, pp. 3150–3163. https://doi.org/10.1021/acs.chemmater.3c02694

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AU - Bravetti, Gianluca

AU - Taurisano, Nicola

AU - Moliterni, Anna

AU - Vicent-Luna, Jose Manuel

AU - Altamura, Davide

AU - Aiello, Federica

AU - Vanni, Nadir

AU - Capodilupo, Agostina Lina

AU - Carallo, Sonia

AU - Gigli, Giuseppe

AU - Uccello-Barretta, Gloria

AU - Balzano, Federica

AU - Giannini, Cinzia

AU - Tao, Shuxia

AU - Colella, Silvia

AU - Rizzo, Aurora

PY - 2024/4/9

Y1 - 2024/4/9

N2 - Mixed-cation/-halide perovskite compositions are becoming increasingly popular, allowing the convenient tuning of photophysical and optoelectronic properties of photoactive films. However, the presence of multiple components in the solution and the demonstrated reactivity between some of them make the ink formulation quite complex and difficult to connect to the film properties and to a fundamental understanding, leading to the fabrication of reproducible and efficient optoelectronic devices. Herein, we report for the first time on the straightforward relationship between the ubiquitous presence of the N-methylformamidinium (MFA) adduct into MA/FA aged solutions and the formation of hexagonal polytypes (6H and 4H) during FA0.85MA0.15Pb(I0.85Br0.15)3 perovskite crystallization. The aging process in solution is evaluated through nuclear magnetic resonance (NMR), supported by optical, morphological, and crystalline structure characterizations. Density functional theory calculations unravel how the conformation of the MFA deeply alters the crystallization pathways, preferentially stabilizing the hexagonal yellow phases, known to be detrimental to the perovskite film performances in optoelectronic devices.

AB - Mixed-cation/-halide perovskite compositions are becoming increasingly popular, allowing the convenient tuning of photophysical and optoelectronic properties of photoactive films. However, the presence of multiple components in the solution and the demonstrated reactivity between some of them make the ink formulation quite complex and difficult to connect to the film properties and to a fundamental understanding, leading to the fabrication of reproducible and efficient optoelectronic devices. Herein, we report for the first time on the straightforward relationship between the ubiquitous presence of the N-methylformamidinium (MFA) adduct into MA/FA aged solutions and the formation of hexagonal polytypes (6H and 4H) during FA0.85MA0.15Pb(I0.85Br0.15)3 perovskite crystallization. The aging process in solution is evaluated through nuclear magnetic resonance (NMR), supported by optical, morphological, and crystalline structure characterizations. Density functional theory calculations unravel how the conformation of the MFA deeply alters the crystallization pathways, preferentially stabilizing the hexagonal yellow phases, known to be detrimental to the perovskite film performances in optoelectronic devices.

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DO - 10.1021/acs.chemmater.3c02694

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SN - 0897-4756

VL - 36

SP - 3150

EP - 3163

JO - Chemistry of Materials

JF - Chemistry of Materials

IS - 7

ER -

Solution Aging Promotes the Formation of Hexagonal Polytypes in Mixed-Cation/-Halide Perovskites

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