The Ferroelectric-Ferroelastic Debate About Metal Halide Perovskites

Overview

Journal J Phys Chem Lett

Publisher American Chemical Society

Specialty Chemistry

Date 2022 Aug 15

PMID 35969174

Authors

Francesco Ambrosio

Filippo De Angelis

Alejandro R Goni

Affiliations

Soon will be listed here.

Abstract

Metal halide perovskites (MHPs) are solution-processed materials with exceptional photoconversion efficiencies that have brought a paradigm shift in photovoltaics. The nature of the peculiar optoelectronic properties underlying such astounding performance is still controversial. The existence of ferroelectricity in MHPs and its alleged impact on photovoltaic activity have fueled an intense debate, in which unanimous consensus is still far from being reached. Here we critically review recent experimental and theoretical results with a two-fold objective: we argue that the occurrence of ferroelectric domains is incompatible with the A-site cation dynamics in MHPs and propose an alternative interpretation of the experiments based on the concept of ferroelasticity. We further underline that ferroic behavior in MHPs would not be relevant at room temperature or higher for the physics of photogenerated charge carriers, since it would be overshadowed by competing effects like polaron formation and ion migration.

Citing Articles

Strong Dependence of Point Defect Properties in Metal Halide Perovskites on Description of van der Waals Interaction.

Deng L, Ran J, Wang B, Boziki A, Tkatchenko A, Jiang J J Phys Chem Lett. 2024; 15(42):10465-10472.

PMID: 39392450 PMC: 11514007. DOI: 10.1021/acs.jpclett.4c02390.

Anomalous Polarons in Two-Dimensional Organometallic Perovskite Ferroelectric.

Yu J, Han Y, Yang Y, Zhang H, Liu Y, Xu J Adv Sci (Weinh). 2024; 11(43):e2406885.

PMID: 39312912 PMC: 11578327. DOI: 10.1002/advs.202406885.

Phase Transitions and Dynamics in Mixed Three- and Low-Dimensional Lead Halide Perovskites.

Simenas M, Gagor A, Banys J, Maczka M Chem Rev. 2024; 124(5):2281-2326.

PMID: 38421808 PMC: 10941198. DOI: 10.1021/acs.chemrev.3c00532.

Cation Dynamics as Structure Explorer in Hybrid Perovskites-The Case of MAPbI.

Druzbicki K, Gila-Herranz P, Marin-Villa P, Gaboardi M, Armstrong J, Fernandez-Alonso F Cryst Growth Des. 2024; 24(1):391-404.

PMID: 38188269 PMC: 10768891. DOI: 10.1021/acs.cgd.3c01112.

Topic E, Senjug P, Barisic D, Loncaric I, Pajic D, Rubcic M Cryst Growth Des. 2023; 23(6):4262-4272.

PMID: 37304397 PMC: 10251751. DOI: 10.1021/acs.cgd.3c00066.

References

Kojima A, Teshima K, Shirai Y, Miyasaka T . Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J Am Chem Soc. 2009; 131(17):6050-1. DOI: 10.1021/ja809598r. View

Zhu X, Podzorov V . Charge Carriers in Hybrid Organic-Inorganic Lead Halide Perovskites Might Be Protected as Large Polarons. J Phys Chem Lett. 2015; 6(23):4758-61. DOI: 10.1021/acs.jpclett.5b02462. View

Leguy A, Goni A, Frost J, Skelton J, Brivio F, Rodriguez-Martinez X . Dynamic disorder, phonon lifetimes, and the assignment of modes to the vibrational spectra of methylammonium lead halide perovskites. Phys Chem Chem Phys. 2016; 18(39):27051-27066. DOI: 10.1039/c6cp03474h. View

Stroppa A, Quarti C, De Angelis F, Picozzi S . Ferroelectric Polarization of CH3NH3PbI3: A Detailed Study Based on Density Functional Theory and Symmetry Mode Analysis. J Phys Chem Lett. 2015; 6(12):2223-31. DOI: 10.1021/acs.jpclett.5b00542. View

Miyata K, Meggiolaro D, Trinh M, Joshi P, Mosconi E, Jones S . Large polarons in lead halide perovskites. Sci Adv. 2017; 3(8):e1701217. PMC: 5553817. DOI: 10.1126/sciadv.1701217. View

Kubicki D, Prochowicz D, Hofstetter A, Pechy P, Zakeeruddin S, Gratzel M . Cation Dynamics in Mixed-Cation (MA)(FA)PbI Hybrid Perovskites from Solid-State NMR. J Am Chem Soc. 2017; 139(29):10055-10061. DOI: 10.1021/jacs.7b04930. View

Crothers T, Milot R, Patel J, Parrott E, Schlipf J, Muller-Buschbaum P . Photon Reabsorption Masks Intrinsic Bimolecular Charge-Carrier Recombination in CHNHPbI Perovskite. Nano Lett. 2017; 17(9):5782-5789. DOI: 10.1021/acs.nanolett.7b02834. View

Frost J, Butler K, Brivio F, Hendon C, van Schilfgaarde M, Walsh A . Atomistic origins of high-performance in hybrid halide perovskite solar cells. Nano Lett. 2014; 14(5):2584-90. PMC: 4022647. DOI: 10.1021/nl500390f. View

Marronnier A, Lee H, Geffroy B, Even J, Bonnassieux Y, Roma G . Structural Instabilities Related to Highly Anharmonic Phonons in Halide Perovskites. J Phys Chem Lett. 2017; 8(12):2659-2665. DOI: 10.1021/acs.jpclett.7b00807. View

10.

Bakulin A, Selig O, Bakker H, Rezus Y, Muller C, Glaser T . Real-Time Observation of Organic Cation Reorientation in Methylammonium Lead Iodide Perovskites. J Phys Chem Lett. 2016; 6(18):3663-9. DOI: 10.1021/acs.jpclett.5b01555. View

11.

Strelcov E, Dong Q, Li T, Chae J, Shao Y, Deng Y . CHNHPbI perovskites: Ferroelasticity revealed. Sci Adv. 2017; 3(4):e1602165. PMC: 5392022. DOI: 10.1126/sciadv.1602165. View

12.

Ghosh D, Aziz A, Dawson J, Walker A, Islam M . Putting the Squeeze on Lead Iodide Perovskites: Pressure-Induced Effects To Tune Their Structural and Optoelectronic Behavior. Chem Mater. 2020; 31(11):4063-4071. PMC: 7011759. DOI: 10.1021/acs.chemmater.9b00648. View

13.

Wei J, Zhao Y, Li H, Li G, Pan J, Xu D . Hysteresis Analysis Based on the Ferroelectric Effect in Hybrid Perovskite Solar Cells. J Phys Chem Lett. 2015; 5(21):3937-45. DOI: 10.1021/jz502111u. View

14.

Liu Y, Collins L, Proksch R, Kim S, Watson B, Doughty B . Chemical nature of ferroelastic twin domains in CHNHPbI perovskite. Nat Mater. 2018; 17(11):1013-1019. DOI: 10.1038/s41563-018-0152-z. View

15.

Leguy A, Azarhoosh P, Alonso M, Campoy-Quiles M, Weber O, Yao J . Experimental and theoretical optical properties of methylammonium lead halide perovskites. Nanoscale. 2015; 8(12):6317-27. DOI: 10.1039/c5nr05435d. View

16.

Kutes Y, Ye L, Zhou Y, Pang S, Huey B, Padture N . Direct Observation of Ferroelectric Domains in Solution-Processed CH3NH3PbI3 Perovskite Thin Films. J Phys Chem Lett. 2015; 5(19):3335-9. DOI: 10.1021/jz501697b. View

17.

Ivanovska T, Dionigi C, Mosconi E, De Angelis F, Liscio F, Morandi V . Long-Lived Photoinduced Polarons in Organohalide Perovskites. J Phys Chem Lett. 2017; 8(13):3081-3086. DOI: 10.1021/acs.jpclett.7b01156. View

18.

Miyata K, Zhu X . Ferroelectric large polarons. Nat Mater. 2018; 17(5):379-381. DOI: 10.1038/s41563-018-0068-7. View

19.

Liu Y, Trimby P, Collins L, Ahmadi M, Winkelmann A, Proksch R . Correlating Crystallographic Orientation and Ferroic Properties of Twin Domains in Metal Halide Perovskites. ACS Nano. 2021; 15(4):7139-7148. DOI: 10.1021/acsnano.1c00310. View

20.

Zhang X, Zhao D, Liu X, Bai R, Ma X, Fu M . Ferroelastic Domains Enhanced the Photoelectric Response in a CsPbBr Single-Crystal Film Detector. J Phys Chem Lett. 2021; 12(35):8685-8691. DOI: 10.1021/acs.jpclett.1c02606. View