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Title: Light–ferroelectric interaction in two-dimensional lead iodide perovskites

Abstract

The unique physical properties of two-dimensional (2D) metal halide perovskites (MHPs) such as nonlinear optics, anisotropic charge transport, and ferroelectricity have made these materials promising candidates for multifunctional applications. Recently, fluorine derivatives such as 4,4-difluoropiperidinium lead iodide perovskite or (4,4-DFPD, C5H10F2N)2PbI4 have shown strong ferroelectricity as compared to other 2D MHPs. Although it was previously addressed that the ferroelectricity in MHPs can be affected by illumination, the underlying physical mechanisms of light–ferroelectricity interaction in 2D MHPs are still lacking. Here, we explore the electromechanical responses in 4,4-(DFPD)2PbI4 thin films using advanced scanning probe microscopy techniques revealing ferroelectric domain structures. In this work, hysteretic ferroelectric loops measured by contact-Kelvin probe force microscopy are dependent on domain structures under dark conditions, while ferroelectricity weakens under illumination. The X-ray diffraction patterns exhibit significant changes in preferential orientation of individual lattice planes under illumination. Particularly, the reduced intensity of the (1 1 1) lattice plane under illumination leads to transitioning from a ferroelectric to a paraelectric phase. The instability of positive ions, especially molecular organic cations, is observed under illumination by time-of-flight secondary ion mass spectrometry. The combination of crystallographic orientation and chemical changes under illumination clearly contributes to the origin of light–ferroelectricity interactionmore » in 2D (4,4-DFPD, C5H10F2N)2PbI4.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [2]; ORCiD logo [1]
  1. Univ. of Tennessee, Knoxville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), High Energy Physics (HEP); USDOE Office of Science (SC), Nuclear Physics (NP); USDOE Office of Science (SC), Fusion Energy Sciences (FES)
OSTI Identifier:
1883740
Grant/Contract Number:  
AC05-00OR22725; 2043205
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 10; Journal Issue: 18; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kim, Dohyung, Ievlev, Anton V., Ovchinnikova, Olga S., Kalinin, Sergei V., and Ahmadi, Mahshid. Light–ferroelectric interaction in two-dimensional lead iodide perovskites. United States: N. p., 2022. Web. doi:10.1039/d1ta10944h.
Kim, Dohyung, Ievlev, Anton V., Ovchinnikova, Olga S., Kalinin, Sergei V., & Ahmadi, Mahshid. Light–ferroelectric interaction in two-dimensional lead iodide perovskites. United States. https://doi.org/10.1039/d1ta10944h
Kim, Dohyung, Ievlev, Anton V., Ovchinnikova, Olga S., Kalinin, Sergei V., and Ahmadi, Mahshid. Mon . "Light–ferroelectric interaction in two-dimensional lead iodide perovskites". United States. https://doi.org/10.1039/d1ta10944h. https://www.osti.gov/servlets/purl/1883740.
@article{osti_1883740,
title = {Light–ferroelectric interaction in two-dimensional lead iodide perovskites},
author = {Kim, Dohyung and Ievlev, Anton V. and Ovchinnikova, Olga S. and Kalinin, Sergei V. and Ahmadi, Mahshid},
abstractNote = {The unique physical properties of two-dimensional (2D) metal halide perovskites (MHPs) such as nonlinear optics, anisotropic charge transport, and ferroelectricity have made these materials promising candidates for multifunctional applications. Recently, fluorine derivatives such as 4,4-difluoropiperidinium lead iodide perovskite or (4,4-DFPD, C5H10F2N)2PbI4 have shown strong ferroelectricity as compared to other 2D MHPs. Although it was previously addressed that the ferroelectricity in MHPs can be affected by illumination, the underlying physical mechanisms of light–ferroelectricity interaction in 2D MHPs are still lacking. Here, we explore the electromechanical responses in 4,4-(DFPD)2PbI4 thin films using advanced scanning probe microscopy techniques revealing ferroelectric domain structures. In this work, hysteretic ferroelectric loops measured by contact-Kelvin probe force microscopy are dependent on domain structures under dark conditions, while ferroelectricity weakens under illumination. The X-ray diffraction patterns exhibit significant changes in preferential orientation of individual lattice planes under illumination. Particularly, the reduced intensity of the (1 1 1) lattice plane under illumination leads to transitioning from a ferroelectric to a paraelectric phase. The instability of positive ions, especially molecular organic cations, is observed under illumination by time-of-flight secondary ion mass spectrometry. The combination of crystallographic orientation and chemical changes under illumination clearly contributes to the origin of light–ferroelectricity interaction in 2D (4,4-DFPD, C5H10F2N)2PbI4.},
doi = {10.1039/d1ta10944h},
journal = {Journal of Materials Chemistry. A},
number = 18,
volume = 10,
place = {United States},
year = {Mon Apr 11 00:00:00 EDT 2022},
month = {Mon Apr 11 00:00:00 EDT 2022}
}

Works referenced in this record:

Differentiating Ferroelectric and Nonferroelectric Electromechanical Effects with Scanning Probe Microscopy
journal, May 2015


Effects of light on ferroelectric polarization and leakage current
journal, July 2018


Molecular ferroelectric contributions to anomalous hysteresis in hybrid perovskite solar cells
journal, August 2014

  • Frost, Jarvist M.; Butler, Keith T.; Walsh, Aron
  • APL Materials, Vol. 2, Issue 8
  • DOI: 10.1063/1.4890246

Applications of Modern Ferroelectrics
journal, February 2007


A lead-halide perovskite molecular ferroelectric semiconductor
journal, May 2015

  • Liao, Wei-Qiang; Zhang, Yi; Hu, Chun-Li
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8338

Two-Dimensional Layered Perovskite Ferroelectric with Giant Piezoelectric Voltage Coefficient
journal, December 2019

  • Chen, Xiao-Gang; Song, Xian-Jiang; Zhang, Zhi-Xu
  • Journal of the American Chemical Society, Vol. 142, Issue 2
  • DOI: 10.1021/jacs.9b12368

The First 2D Hybrid Perovskite Ferroelectric Showing Broadband White‐Light Emission with High Color Rendering Index
journal, December 2018

  • Ji, Chengmin; Wang, Sasa; Li, Lina
  • Advanced Functional Materials, Vol. 29, Issue 6
  • DOI: 10.1002/adfm.201805038

Confinement-Driven Ferroelectricity in a Two-Dimensional Hybrid Lead Iodide Perovskite
journal, May 2020

  • Chen, Xiao-Gang; Song, Xian-Jiang; Zhang, Zhi-Xu
  • Journal of the American Chemical Society, Vol. 142, Issue 22
  • DOI: 10.1021/jacs.0c03710

Critical Role of Grain Boundaries for Ion Migration in Formamidinium and Methylammonium Lead Halide Perovskite Solar Cells
journal, May 2016

  • Yun, Jae S.; Seidel, Jan; Kim, Jincheol
  • Advanced Energy Materials, Vol. 6, Issue 13
  • DOI: 10.1002/aenm.201600330

Photoinduced Bulk Polarization and Its Effects on Photovoltaic Actions in Perovskite Solar Cells
journal, September 2017


Two-dimensional hybrid organic–inorganic perovskites as emergent ferroelectric materials
journal, August 2020

  • Hou, Yuchen; Wu, Congcong; Yang, Dong
  • Journal of Applied Physics, Vol. 128, Issue 6
  • DOI: 10.1063/5.0016010

Local Crystal Misorientation Influences Non-radiative Recombination in Halide Perovskites
journal, December 2019


Mutual Insight on Ferroelectrics and Hybrid Halide Perovskites: A Platform for Future Multifunctional Energy Conversion
journal, August 2019


Record Enhancement of Phase Transition Temperature Realized by H/F Substitution
journal, July 2020


Role of Ferroelectric Nanodomains in the Transport Properties of Perovskite Solar Cells
journal, January 2016


Effect of crystallographic orientation on ferroelectric properties of PbZr 0.2 Ti 0.8 O 3 thin films
journal, August 1993

  • Ramesh, R.; Sands, T.; Keramidas, V. G.
  • Applied Physics Letters, Vol. 63, Issue 6
  • DOI: 10.1063/1.109943

Photo-induced ferroelectric switching in perovskite CH 3 NH 3 PbI 3 films
journal, January 2017

  • Wang, Peiqi; Zhao, Jinjin; Wei, Liyu
  • Nanoscale, Vol. 9, Issue 11
  • DOI: 10.1039/C6NR09310H

Ferroelectric Domain Wall Induced Band Gap Reduction and Charge Separation in Organometal Halide Perovskites
journal, February 2015

  • Liu, Shi; Zheng, Fan; Koocher, Nathan Z.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 4
  • DOI: 10.1021/jz502666j

Metal halide perovskite nanostructures for optoelectronic applications and the study of physical properties
journal, February 2019


Spatially Resolved Carrier Dynamics at MAPbBr 3 Single Crystal–Electrode Interface
journal, October 2019

  • Ahmadi, Mahshid; Collins, Liam; Higgins, Kate
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 44
  • DOI: 10.1021/acsami.9b16287

Ferroelectric and Charge Transport Properties in Strain-Engineered Two-Dimensional Lead Iodide Perovskites
journal, May 2021


Photodriven Dipole Reordering: Key to Carrier Separation in Metalorganic Halide Perovskites
journal, March 2019


Light- and bias-induced structural variations in metal halide perovskites
journal, January 2019


Highly sensitive X-ray detector made of layered perovskite-like (NH4)3Bi2I9 single crystal with anisotropic response
journal, June 2019


A Layered Hybrid Perovskite Solar-Cell Absorber with Enhanced Moisture Stability
journal, September 2014

  • Smith, Ian C.; Hoke, Eric T.; Solis-Ibarra, Diego
  • Angewandte Chemie International Edition, Vol. 53, Issue 42
  • DOI: 10.1002/anie.201406466

Suppressed Ion Migration in Low-Dimensional Perovskites
journal, June 2017


Probing Facet-Dependent Surface Defects in MAPbI 3 Perovskite Single Crystals
journal, May 2019

  • Kim, Dohyung; Yun, Jung-Ho; Lyu, Miaoqiang
  • The Journal of Physical Chemistry C, Vol. 123, Issue 23
  • DOI: 10.1021/acs.jpcc.9b00943

Bandgap Engineering of Lead-Halide Perovskite-Type Ferroelectrics
journal, February 2016

  • Ye, Heng-Yun; Liao, Wei-Qiang; Hu, Chun-Li
  • Advanced Materials, Vol. 28, Issue 13
  • DOI: 10.1002/adma.201505224

Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells
journal, April 2014

  • Frost, Jarvist M.; Butler, Keith T.; Brivio, Federico
  • Nano Letters, Vol. 14, Issue 5
  • DOI: 10.1021/nl500390f

Crystallographic Orientation Dependence on Electrical Properties of (Bi,Na)TiO3 -based Thin Films
journal, August 2013

  • Ding, Rui; Wang, Danyang; Chu, Dewei
  • Journal of the American Ceramic Society, Vol. 96, Issue 11
  • DOI: 10.1111/jace.12524

Toward the Targeted Design of Molecular Ferroelectrics: Modifying Molecular Symmetries and Homochirality
journal, March 2019


Ferroelectric or non-ferroelectric: Why so many materials exhibit “ferroelectricity” on the nanoscale
journal, June 2017

  • Vasudevan, Rama K.; Balke, Nina; Maksymovych, Peter
  • Applied Physics Reviews, Vol. 4, Issue 2
  • DOI: 10.1063/1.4979015

Exploring Responses of Contact Kelvin Probe Force Microscopy in Triple-Cation Double-Halide Perovskites
journal, May 2021

  • Kim, Dohyung; Vasudevan, Rama K.; Higgins, Kate
  • The Journal of Physical Chemistry C, Vol. 125, Issue 22
  • DOI: 10.1021/acs.jpcc.1c02474

Molecular Design Principles for Ferroelectrics: Ferroelectrochemistry
journal, August 2020

  • Liu, Hui-Yu; Zhang, Han-Yue; Chen, Xiao-Gang
  • Journal of the American Chemical Society, Vol. 142, Issue 36
  • DOI: 10.1021/jacs.0c07055

Ferroionic states in ferroelectric thin films
journal, May 2017

  • Morozovska, Anna N.; Eliseev, Eugene A.; Morozovsky, Nicholas V.
  • Physical Review B, Vol. 95, Issue 19
  • DOI: 10.1103/PhysRevB.95.195413

Quantification of ion migration in CH 3 NH 3 PbI 3 perovskite solar cells by transient capacitance measurements
journal, January 2019

  • Futscher, Moritz H.; Lee, Ju Min; McGovern, Lucie
  • Materials Horizons, Vol. 6, Issue 7
  • DOI: 10.1039/C9MH00445A

Exploring Local Electrostatic Effects with Scanning Probe Microscopy: Implications for Piezoresponse Force Microscopy and Triboelectricity
journal, October 2014

  • Balke, Nina; Maksymovych, Petro; Jesse, Stephen
  • ACS Nano, Vol. 8, Issue 10
  • DOI: 10.1021/nn505176a

Exploring Anomalous Polarization Dynamics in Organometallic Halide Perovskites
journal, January 2018

  • Ahmadi, Mahshid; Collins, Liam; Puretzky, Alexander
  • Advanced Materials, Vol. 30, Issue 11
  • DOI: 10.1002/adma.201705298

Two-Dimensional Organic–Inorganic Perovskite Ferroelectric Semiconductors with Fluorinated Aromatic Spacers
journal, October 2019

  • Shi, Ping-Ping; Lu, Si-Qi; Song, Xian-Jiang
  • Journal of the American Chemical Society, Vol. 141, Issue 45
  • DOI: 10.1021/jacs.9b10048

Exciton diffusion in two-dimensional metal-halide perovskites
journal, April 2020

  • Seitz, Michael; Magdaleno, Alvaro J.; Alcázar-Cano, Nerea
  • Nature Communications, Vol. 11, Issue 1
  • DOI: 10.1038/s41467-020-15882-w

Fluoridation Achieved Antiperovskite Molecular Ferroelectric in [(CH 3 ) 2 (F-CH 2 CH 2 )NH] 3 (CdCl 3 )(CdCl 4 )
journal, February 2019

  • Wang, Zhong-Xia; Zhang, Yi; Tang, Yuan-Yuan
  • Journal of the American Chemical Society, Vol. 141, Issue 10
  • DOI: 10.1021/jacs.8b13109

Dielectric Response: Answer to Many Questions in the Methylammonium Lead Halide Solar Cell Absorbers
journal, May 2017

  • Anusca, Irina; Balčiūnas, Sergejus; Gemeiner, Pascale
  • Advanced Energy Materials, Vol. 7, Issue 19
  • DOI: 10.1002/aenm.201700600

Crystallographic Orientation Dependent Ferroelectric Characteristics of (Bi3.3,La0.8)Ti3O12 (BLT) Capacitors
journal, April 2005

  • Kim, Nam-Kyeong; Yeom, Seung-Jin; Kweon, Soon-Yong
  • Integrated Ferroelectrics, Vol. 70, Issue 1
  • DOI: 10.1080/10584580490892854

Mixed electrochemical–ferroelectric states in nanoscale ferroelectrics
journal, May 2017

  • Yang, Sang Mo; Morozovska, Anna N.; Kumar, Rajeev
  • Nature Physics, Vol. 13, Issue 8
  • DOI: 10.1038/nphys4103

Electric-Field-Driven Reversible Conversion Between Methylammonium Lead Triiodide Perovskites and Lead Iodide at Elevated Temperatures
journal, December 2015

  • Yuan, Yongbo; Wang, Qi; Shao, Yuchuan
  • Advanced Energy Materials, Vol. 6, Issue 2
  • DOI: 10.1002/aenm.201501803

Promises and challenges of perovskite solar cells
journal, November 2017

  • Correa-Baena, Juan-Pablo; Saliba, Michael; Buonassisi, Tonio
  • Science, Vol. 358, Issue 6364
  • DOI: 10.1126/science.aam6323

Hysteretic Ion Migration and Remanent Field in Metal Halide Perovskites
journal, August 2020

  • Liu, Yongtao; Borodinov, Nikolay; Lorenz, Matthias
  • Advanced Science, Vol. 7, Issue 19
  • DOI: 10.1002/advs.202001176

Unraveling the hysteretic behavior at double cations-double halides perovskite - electrode interfaces
journal, November 2021


Chiral-perovskite optoelectronics
journal, March 2020

  • Long, Guankui; Sabatini, Randy; Saidaminov, Makhsud I.
  • Nature Reviews Materials, Vol. 5, Issue 6
  • DOI: 10.1038/s41578-020-0181-5

Dimensional tailoring of hybrid perovskites for photovoltaics
journal, November 2018


The First 2D Homochiral Lead Iodide Perovskite Ferroelectrics: [ R ‐ and S ‐1‐(4‐Chlorophenyl)ethylammonium] 2 PbI 4
journal, February 2019

  • Yang, Chen‐Kai; Chen, Wang‐Nan; Ding, Yan‐Ting
  • Advanced Materials, Vol. 31, Issue 16
  • DOI: 10.1002/adma.201808088

Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite
journal, July 2016


Correlating Crystallographic Orientation and Ferroic Properties of Twin Domains in Metal Halide Perovskites
journal, March 2021


Ferroic Halide Perovskite Optoelectronics
journal, June 2021

  • Liu, Yongtao; Kim, Dohyung; Ievlev, Anton V.
  • Advanced Functional Materials, Vol. 31, Issue 36
  • DOI: 10.1002/adfm.202102793

An organic–inorganic hybrid ferroelectric with strong luminescence and high Curie temperature
journal, January 2020

  • Fu, Hanmei; Jiang, Chunli; Lao, Jie
  • CrystEngComm, Vol. 22, Issue 8
  • DOI: 10.1039/C9CE01888C

Observation of Vortex Domains in a Two-Dimensional Lead Iodide Perovskite Ferroelectric
journal, February 2020

  • Zhang, Han-Yue; Song, Xian-Jiang; Chen, Xiao-Gang
  • Journal of the American Chemical Society, Vol. 142, Issue 10
  • DOI: 10.1021/jacs.0c00371

Role of Decomposition Product Ions in Hysteretic Behavior of Metal Halide Perovskite
journal, May 2021


Local polarization dynamics in ferroelectric materials
journal, April 2010

  • Kalinin, Sergei V.; Morozovska, Anna N.; Chen, Long Qing
  • Reports on Progress in Physics, Vol. 73, Issue 5, Article No. 056502
  • DOI: 10.1088/0034-4885/73/5/056502

Exploring Transport Behavior in Hybrid Perovskites Solar Cells via Machine Learning Analysis of Environmental‐Dependent Impedance Spectroscopy
journal, June 2021

  • Kim, Dohyung; Muckley, Eric S.; Creange, Nicole
  • Advanced Science, Vol. 8, Issue 15
  • DOI: 10.1002/advs.202002510

Selective enhancement of optical nonlinearity in two-dimensional organic-inorganic lead iodide perovskites
journal, September 2017


Ferroelectric large polarons
journal, April 2018


Chemically diverse and multifunctional hybrid organic–inorganic perovskites
journal, February 2017


Photoinduced Giant Dielectric Constant in Lead Halide Perovskite Solar Cells
journal, June 2014

  • Juarez-Perez, Emilio J.; Sanchez, Rafael S.; Badia, Laura
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 13
  • DOI: 10.1021/jz5011169

Polarization Switching and Light-Enhanced Piezoelectricity in Lead Halide Perovskites
journal, April 2015

  • Coll, Mariona; Gomez, Andrés; Mas-Marza, Elena
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 8
  • DOI: 10.1021/acs.jpclett.5b00502

Giant enhancement in ferroelectric polarization under illumination
journal, March 2018


Piezoresponse force microscopy and nanoferroic phenomena
journal, April 2019