Suppression of phase transitions and glass phase signatures in mixed cation halide perovskites

Mantas Simenas; Sergejus Balciunas; Jacob N. Wilson; Sarunas Svirskas; Martynas Kinka; Andrius Garbaras; Vidmantas Kalendra; Anna Gagor; Daria Szewczyk; Adam Sieradzki; Miroslaw Maczka; Vytautas Samulionis; Aron Walsh; Robertas Grigalaitis; Juras Banys

doi:10.1038/s41467-020-18938-z

Suppression of phase transitions and glass phase signatures in mixed cation halide perovskites

Mantas Simenas, Sergejus Balciunas, Jacob N. Wilson, Sarunas Svirskas, Martynas Kinka, Andrius Garbaras, Vidmantas Kalendra, Anna Gagor, Daria Szewczyk, Adam Sieradzki, Miroslaw Maczka, Vytautas Samulionis, Aron Walsh, Robertas Grigalaitis, Juras Banys

Department of Physics

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

56 Scopus citations

Abstract

Cation engineering provides a route to control the structure and properties of hybrid halide perovskites, which has resulted in the highest performance solar cells based on mixtures of Cs, methylammonium, and formamidinium. Here, we present a multi-technique experimental and theoretical study of structural phase transitions, structural phases and dipolar dynamics in the mixed methylammonium/dimethylammonium MA_1-xDMA_xPbBr₃ hybrid perovskites (0 ≤ x ≤ 1). Our results demonstrate a significant suppression of the structural phase transitions, enhanced disorder and stabilization of the cubic phase even for a small amount of dimethylammonium cations. As the dimethylammonium concentration approaches the solubility limit in MAPbBr₃, we observe the disappearance of the structural phase transitions and indications of a glassy dipolar phase. We also reveal a significant tunability of the dielectric permittivity upon mixing of the molecular cations that arises from frustrated electric dipoles.

Original language	English
Article number	5103
Journal	Nature Communications
Volume	11
Issue number	1
DOIs	https://doi.org/10.1038/s41467-020-18938-z
State	Published - 1 Dec 2020

Bibliographical note

Funding Information:
This project has been funded by the Research Council of Lithuania (LMTLT) (agreement No. S-MIP-19-4) and by EPSRC (Grant No. EP/K016288/1). AW is supported by a Royal Society University Research Fellowship and J.N.W. acknowledges useful discussions with Jarvist Frost on the Starrynight code. We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/ P020194/1).

Publisher Copyright:
© 2020, The Author(s).

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Simenas, M., Balciunas, S., Wilson, J. N., Svirskas, S., Kinka, M., Garbaras, A., Kalendra, V., Gagor, A., Szewczyk, D., Sieradzki, A., Maczka, M., Samulionis, V., Walsh, A., Grigalaitis, R., & Banys, J. (2020). Suppression of phase transitions and glass phase signatures in mixed cation halide perovskites. Nature Communications, 11(1), Article 5103. https://doi.org/10.1038/s41467-020-18938-z

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title = "Suppression of phase transitions and glass phase signatures in mixed cation halide perovskites",

abstract = "Cation engineering provides a route to control the structure and properties of hybrid halide perovskites, which has resulted in the highest performance solar cells based on mixtures of Cs, methylammonium, and formamidinium. Here, we present a multi-technique experimental and theoretical study of structural phase transitions, structural phases and dipolar dynamics in the mixed methylammonium/dimethylammonium MA1-xDMAxPbBr3 hybrid perovskites (0 ≤ x ≤ 1). Our results demonstrate a significant suppression of the structural phase transitions, enhanced disorder and stabilization of the cubic phase even for a small amount of dimethylammonium cations. As the dimethylammonium concentration approaches the solubility limit in MAPbBr3, we observe the disappearance of the structural phase transitions and indications of a glassy dipolar phase. We also reveal a significant tunability of the dielectric permittivity upon mixing of the molecular cations that arises from frustrated electric dipoles.",

author = "Mantas Simenas and Sergejus Balciunas and Wilson, {Jacob N.} and Sarunas Svirskas and Martynas Kinka and Andrius Garbaras and Vidmantas Kalendra and Anna Gagor and Daria Szewczyk and Adam Sieradzki and Miroslaw Maczka and Vytautas Samulionis and Aron Walsh and Robertas Grigalaitis and Juras Banys",

note = "Funding Information: This project has been funded by the Research Council of Lithuania (LMTLT) (agreement No. S-MIP-19-4) and by EPSRC (Grant No. EP/K016288/1). AW is supported by a Royal Society University Research Fellowship and J.N.W. acknowledges useful discussions with Jarvist Frost on the Starrynight code. We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/ P020194/1). Publisher Copyright: {\textcopyright} 2020, The Author(s).",

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Simenas, M, Balciunas, S, Wilson, JN, Svirskas, S, Kinka, M, Garbaras, A, Kalendra, V, Gagor, A, Szewczyk, D, Sieradzki, A, Maczka, M, Samulionis, V, Walsh, A, Grigalaitis, R & Banys, J 2020, 'Suppression of phase transitions and glass phase signatures in mixed cation halide perovskites', Nature Communications, vol. 11, no. 1, 5103. https://doi.org/10.1038/s41467-020-18938-z

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T1 - Suppression of phase transitions and glass phase signatures in mixed cation halide perovskites

AU - Simenas, Mantas

AU - Balciunas, Sergejus

AU - Wilson, Jacob N.

AU - Svirskas, Sarunas

AU - Kinka, Martynas

AU - Garbaras, Andrius

AU - Kalendra, Vidmantas

AU - Gagor, Anna

AU - Szewczyk, Daria

AU - Sieradzki, Adam

AU - Maczka, Miroslaw

AU - Samulionis, Vytautas

AU - Walsh, Aron

AU - Grigalaitis, Robertas

AU - Banys, Juras

N1 - Funding Information: This project has been funded by the Research Council of Lithuania (LMTLT) (agreement No. S-MIP-19-4) and by EPSRC (Grant No. EP/K016288/1). AW is supported by a Royal Society University Research Fellowship and J.N.W. acknowledges useful discussions with Jarvist Frost on the Starrynight code. We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/ P020194/1). Publisher Copyright: © 2020, The Author(s).

PY - 2020/12/1

Y1 - 2020/12/1

N2 - Cation engineering provides a route to control the structure and properties of hybrid halide perovskites, which has resulted in the highest performance solar cells based on mixtures of Cs, methylammonium, and formamidinium. Here, we present a multi-technique experimental and theoretical study of structural phase transitions, structural phases and dipolar dynamics in the mixed methylammonium/dimethylammonium MA1-xDMAxPbBr3 hybrid perovskites (0 ≤ x ≤ 1). Our results demonstrate a significant suppression of the structural phase transitions, enhanced disorder and stabilization of the cubic phase even for a small amount of dimethylammonium cations. As the dimethylammonium concentration approaches the solubility limit in MAPbBr3, we observe the disappearance of the structural phase transitions and indications of a glassy dipolar phase. We also reveal a significant tunability of the dielectric permittivity upon mixing of the molecular cations that arises from frustrated electric dipoles.

AB - Cation engineering provides a route to control the structure and properties of hybrid halide perovskites, which has resulted in the highest performance solar cells based on mixtures of Cs, methylammonium, and formamidinium. Here, we present a multi-technique experimental and theoretical study of structural phase transitions, structural phases and dipolar dynamics in the mixed methylammonium/dimethylammonium MA1-xDMAxPbBr3 hybrid perovskites (0 ≤ x ≤ 1). Our results demonstrate a significant suppression of the structural phase transitions, enhanced disorder and stabilization of the cubic phase even for a small amount of dimethylammonium cations. As the dimethylammonium concentration approaches the solubility limit in MAPbBr3, we observe the disappearance of the structural phase transitions and indications of a glassy dipolar phase. We also reveal a significant tunability of the dielectric permittivity upon mixing of the molecular cations that arises from frustrated electric dipoles.

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DO - 10.1038/s41467-020-18938-z

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SN - 2041-1723

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ER -

Suppression of phase transitions and glass phase signatures in mixed cation halide perovskites

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