Exploring Responses of Contact Kelvin Probe Force Microscopy in Triple-Cation Double-Halide Perovskites

Kim, Dohyung; Vasudevan, Rama K.; Higgins, Kate; Morozovska, Anna N.; Eliseev, Eugene A.; Ziatdinov, Maxim; Kalinin, Sergei V.; Ahmadi, Mahshid

doi:10.1021/acs.jpcc.1c02474

Title: Exploring Responses of Contact Kelvin Probe Force Microscopy in Triple-Cation Double-Halide Perovskites

Journal Article · Fri May 28 00:00:00 EDT 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c02474· OSTI ID:1818661

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Univ. of Tennessee, Knoxville, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
National Academy of Science of Ukraine, Kyiv (Ukraine)

Hybrid organic–inorganic perovskite (HOIP) solar cells have undergone unprecedentedly rapid improvement in power conversion efficiencies during the last decade, but controversy remains regarding the role of local phenomena and heterogeneity in grain by grain. These challenges in turn necessitate understanding the fundamental mechanisms operating at individual grains and exploring how these mechanisms give rise to the collective behaviors of the films. Although numerous efforts have targeted local phenomena in these materials using classical scanning probe microscopy modalities, the measurements remain difficult to interpret due to intrinsic coupling between possible ferroelectric, ion migration, bulk and surface electrochemical phenomena, and the effects of light on these behaviors. Here, we explore the electromechanical responses in (Cs_0.05FA_0.85MA_0.15)Pb(I_0.85Br_0.15)₃ perovskite thin film in the dark and under illumination using band excitation-piezoresponse force microscopy (BE-PFM). To identify and separate ferroic, electrostatic, and electrochemical responses, we utilize contact-Kelvin probe force microscopy (cKPFM). The cKPFM responses show weak variability with morphological features in the dark, while such variability significantly increases under illumination. Deconvolution of the cKPFM responses via principal component analysis (PCA) shows heterogeneity in grain to grain possibly due to variation in migration and segregation of halide ions in mixed perovskites at specific grains. Further, we propose an electrostatic mechanism based on the physics of semiconductors, which can directly link the observed cKPFM behaviors with the ionic and electronic density of states (DOS) and their time dynamics. Here, these findings suggest that cKPFM is a powerful probe of local ionic behaviors on the nanoscale, both in HOIPs and other materials.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1818661

Journal Information:: Journal of Physical Chemistry. C, Vol. 125, Issue 22; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (68)

Chemical Management for Colorful, Efficient, and Stable Inorganic–Organic Hybrid Nanostructured Solar Cells Noh, Jun Hong; Im, Sang Hyuk; Heo, Jin Hyuck Nano Letters, Vol. 13, Issue 4, p. 1764-1769 https://doi.org/10.1021/nl400349b	journal	March 2013
Ionic transport in hybrid lead iodide perovskite solar cells Eames, Christopher; Frost, Jarvist M.; Barnes, Piers R. F. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8497	journal	June 2015
Differentiating Ferroelectric and Nonferroelectric Electromechanical Effects with Scanning Probe Microscopy Balke, Nina; Maksymovych, Petro; Jesse, Stephen ACS Nano, Vol. 9, Issue 6 https://doi.org/10.1021/acsnano.5b02227	journal	May 2015
Hysteresis and transient behavior in current–voltage measurements of hybrid-perovskite absorber solar cells Unger, E. L.; Hoke, E. T.; Bailie, C. D. Energy Environ. Sci., Vol. 7, Issue 11 https://doi.org/10.1039/C4EE02465F	journal	January 2014
Acoustic microscopy by atomic force microscopy Rabe, U.; Arnold, W. Applied Physics Letters, Vol. 64, Issue 12 https://doi.org/10.1063/1.111869	journal	March 1994
Electrostrictive and electrostatic responses in contact mode voltage modulated scanning probe microscopies Eliseev, Eugene A.; Morozovska, Anna N.; Ievlev, Anton V. Applied Physics Letters, Vol. 104, Issue 23 https://doi.org/10.1063/1.4882861	journal	June 2014
Identification of the physical origin behind disorder, heterogeneity, and reconstruction and their correlation with the photoluminescence lifetime in hybrid perovskite thin films Berhe, Taame Abraha; Cheng, Ju-Hsiang; Su, Wei-Nien J. Mater. Chem. A, Vol. 5, Issue 39 https://doi.org/10.1039/C7TA04615D	journal	January 2017
Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics Hoke, Eric T.; Slotcavage, Daniel J.; Dohner, Emma R. Chemical Science, Vol. 6, Issue 1 https://doi.org/10.1039/C4SC03141E	journal	January 2015
Electrochemical strain microscopy with blocking electrodes: The role of electromigration and diffusion Morozovska, A. N.; Eliseev, E. A.; Kalinin, S. V. Journal of Applied Physics, Vol. 111, Issue 1 https://doi.org/10.1063/1.3675508	journal	January 2012
Critical Role of Grain Boundaries for Ion Migration in Formamidinium and Methylammonium Lead Halide Perovskite Solar Cells Yun, Jae S.; Seidel, Jan; Kim, Jincheol Advanced Energy Materials, Vol. 6, Issue 13 https://doi.org/10.1002/aenm.201600330	journal	May 2016
Local Crystal Misorientation Influences Non-radiative Recombination in Halide Perovskites Jariwala, Sarthak; Sun, Hongyu; Adhyaksa, Gede W. P. Joule, Vol. 3, Issue 12 https://doi.org/10.1016/j.joule.2019.09.001	journal	December 2019
Local probing of ionic diffusion by electrochemical strain microscopy: Spatial resolution and signal formation mechanisms Morozovska, A. N.; Eliseev, E. A.; Balke, N. Journal of Applied Physics, Vol. 108, Issue 5 https://doi.org/10.1063/1.3460637	journal	September 2010
Theoretical description of the transfer of vibrations from a sample to the cantilever of an atomic force microscope Hirsekorn, S.; Rabe, U.; Arnold, W. Nanotechnology, Vol. 8, Issue 2 https://doi.org/10.1088/0957-4484/8/2/003	journal	June 1997
Giant switchable photovoltaic effect in organometal trihalide perovskite devices Xiao, Zhengguo; Yuan, Yongbo; Shao, Yuchuan Nature Materials, Vol. 14, Issue 2 https://doi.org/10.1038/nmat4150	journal	December 2014
Ion Migration in Organometal Trihalide Perovskite and Its Impact on Photovoltaic Efficiency and Stability Yuan, Yongbo; Huang, Jinsong Accounts of Chemical Research, Vol. 49, Issue 2 https://doi.org/10.1021/acs.accounts.5b00420	journal	January 2016
Spatially Resolved Carrier Dynamics at MAPbBr ₃ Single Crystal–Electrode Interface Ahmadi, Mahshid; Collins, Liam; Higgins, Kate ACS Applied Materials & Interfaces, Vol. 11, Issue 44 https://doi.org/10.1021/acsami.9b16287	journal	October 2019
Heterogeneity at multiple length scales in halide perovskite semiconductors Tennyson, Elizabeth M.; Doherty, Tiarnan A. S.; Stranks, Samuel D. Nature Reviews Materials, Vol. 4, Issue 9 https://doi.org/10.1038/s41578-019-0125-0	journal	July 2019
Light- and bias-induced structural variations in metal halide perovskites Kim, Dohyung; Yun, Jae Sung; Sharma, Pankaj Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08364-1	journal	January 2019
Vibrations of free and surface‐coupled atomic force microscope cantilevers: Theory and experiment Rabe, U.; Janser, K.; Arnold, W. Review of Scientific Instruments, Vol. 67, Issue 9 https://doi.org/10.1063/1.1147409	journal	September 1996
Probing Facet-Dependent Surface Defects in MAPbI ₃ Perovskite Single Crystals Kim, Dohyung; Yun, Jung-Ho; Lyu, Miaoqiang The Journal of Physical Chemistry C, Vol. 123, Issue 23 https://doi.org/10.1021/acs.jpcc.9b00943	journal	May 2019
Unique Properties of Halide Perovskites as Possible Origins of the Superior Solar Cell Performance Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa Advanced Materials, Vol. 26, Issue 27 https://doi.org/10.1002/adma.201306281	journal	May 2014
Correlating Photoluminescence Heterogeneity with Local Electronic Properties in Methylammonium Lead Tribromide Perovskite Thin Films Moerman, David; Eperon, Giles E.; Precht, Jake T. Chemistry of Materials, Vol. 29, Issue 13 https://doi.org/10.1021/acs.chemmater.7b00235	journal	June 2017
Ferroelectric or non-ferroelectric: Why so many materials exhibit “ferroelectricity” on the nanoscale Vasudevan, Rama K.; Balke, Nina; Maksymovych, Peter Applied Physics Reviews, Vol. 4, Issue 2 https://doi.org/10.1063/1.4979015	journal	June 2017
High-Efficiency Rubidium-Incorporated Perovskite Solar Cells by Gas Quenching Zhang, Meng; Yun, Jae S.; Ma, Qingshan ACS Energy Letters, Vol. 2, Issue 2 https://doi.org/10.1021/acsenergylett.6b00697	journal	January 2017
The Importance of Distributed Loading and Cantilever Angle in Piezo-Force Microscopy Huey, Bryan D.; Ramanujan, Chandra; Bobji, Musuvathi Journal of Electroceramics, Vol. 13, Issue 1-3 https://doi.org/10.1007/s10832-004-5114-y	journal	July 2004
Benign ferroelastic twin boundaries in halide perovskites for charge carrier transport and recombination Xiao, Xun; Li, Wenhao; Fang, Yanjun Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-16075-1	journal	May 2020
Quantitative Electromechanical Atomic Force Microscopy Collins, Liam; Liu, Yongtao; Ovchinnikova, Olga S. ACS Nano, Vol. 13, Issue 7 https://doi.org/10.1021/acsnano.9b02883	journal	July 2019
Violin Plots: A Box Plot-Density Trace Synergism Hintze, Jerry L.; Nelson, Ray D. The American Statistician, Vol. 52, Issue 2 https://doi.org/10.1080/00031305.1998.10480559	journal	May 1998
Ultrafast ion migration in hybrid perovskite polycrystalline thin films under light and suppression in single crystals Xing, Jie; Wang, Qi; Dong, Qingfeng Physical Chemistry Chemical Physics, Vol. 18, Issue 44 https://doi.org/10.1039/C6CP06496E	journal	January 2016
Solid-State Ionics of Hybrid Halide Perovskites Senocrate, Alessandro; Maier, Joachim Journal of the American Chemical Society, Vol. 141, Issue 21 https://doi.org/10.1021/jacs.8b13594	journal	April 2019
Exploring Local Electrostatic Effects with Scanning Probe Microscopy: Implications for Piezoresponse Force Microscopy and Triboelectricity Balke, Nina; Maksymovych, Petro; Jesse, Stephen ACS Nano, Vol. 8, Issue 10 https://doi.org/10.1021/nn505176a	journal	October 2014
Piezoresponse force spectroscopy of ferroelectric-semiconductor materials Morozovska, Anna N.; Svechnikov, Sergei V.; Eliseev, Eugene A. Journal of Applied Physics, Vol. 102, Issue 11 https://doi.org/10.1063/1.2818370	journal	December 2007
How the formation of interfacial charge causes hysteresis in perovskite solar cells Weber, Stefan A. L.; Hermes, Ilka M.; Turren-Cruz, Silver-Hamill Energy & Environmental Science, Vol. 11, Issue 9 https://doi.org/10.1039/C8EE01447G	journal	January 2018
Self-Regulation Mechanism for Charged Point Defects in Hybrid Halide Perovskites Walsh, Aron; Scanlon, David O.; Chen, Shiyou Angewandte Chemie International Edition, Vol. 54, Issue 6 https://doi.org/10.1002/anie.201409740	journal	December 2014
Research on electrostrictive effect of second-order phase transition ferroelectrics Qu, Shao H.; Cao, Wan Q.; Fang, Fan Ferroelectrics Letters Section, Vol. 44, Issue 4-6 https://doi.org/10.1080/07315171.2017.1397447	journal	November 2017
The band excitation method in scanning probe microscopy for rapid mapping of energy dissipation on the nanoscale Jesse, Stephen; Kalinin, Sergei V.; Proksch, Roger Nanotechnology, Vol. 18, Issue 43 https://doi.org/10.1088/0957-4484/18/43/435503	journal	September 2007
Nanoscale electromechanics of paraelectric materials with mobile charges: Size effects and nonlinearity of electromechanical response of SrTiO $_{3}$ films Morozovska, A. N.; Eliseev, E. A.; Svechnikov, G. S. Physical Review B, Vol. 84, Issue 4 https://doi.org/10.1103/PhysRevB.84.045402	journal	July 2011
Exploring Anomalous Polarization Dynamics in Organometallic Halide Perovskites Ahmadi, Mahshid; Collins, Liam; Puretzky, Alexander Advanced Materials, Vol. 30, Issue 11 https://doi.org/10.1002/adma.201705298	journal	January 2018
Trap States, Electric Fields, and Phase Segregation in Mixed‐Halide Perovskite Photovoltaic Devices Knight, Alexander J.; Patel, Jay B.; Snaith, Henry J. Advanced Energy Materials, Vol. 10, Issue 9 https://doi.org/10.1002/aenm.201903488	journal	January 2020
Thermodynamics of electromechanically coupled mixed ionic-electronic conductors: Deformation potential, Vegard strains, and flexoelectric effect Morozovska, A. N.; Eliseev, E. A.; Tagantsev, A. K. Physical Review B, Vol. 83, Issue 19 https://doi.org/10.1103/PhysRevB.83.195313	journal	May 2011
Understanding the relationship between ion migration and the anomalous hysteresis in high-efficiency perovskite solar cells: A fresh perspective from halide substitution Zhang, Teng; Chen, Haining; Bai, Yang Nano Energy, Vol. 26 https://doi.org/10.1016/j.nanoen.2016.05.052	journal	August 2016
Resistive Switching Behavior in Organic-Inorganic Hybrid CH ₃ NH ₃ PbI _{3 −x} Cl _x Perovskite for Resistive Random Access Memory Devices Yoo, Eun Ji; Lyu, Miaoqiang; Yun, Jung-Ho Advanced Materials, Vol. 27, Issue 40 https://doi.org/10.1002/adma.201502889	journal	August 2015
Domain nucleation and hysteresis loop shape in piezoresponse force spectroscopy Morozovska, Anna N.; Eliseev, Eugene A.; Kalinin, Sergei V. Applied Physics Letters, Vol. 89, Issue 19 https://doi.org/10.1063/1.2378526	journal	November 2006
First-Order Reversal Curve Probing of Spatially Resolved Polarization Switching Dynamics in Ferroelectric Nanocapacitors Kim, Yunseok; Kumar, Amit; Ovchinnikov, Oleg ACS Nano, Vol. 6, Issue 1 https://doi.org/10.1021/nn203831h	journal	December 2011
Unusual defect physics in CH ₃ NH ₃ PbI ₃ perovskite solar cell absorber Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa Applied Physics Letters, Vol. 104, Issue 6 https://doi.org/10.1063/1.4864778	journal	February 2014
Frequency dependent dynamical electromechanical response of mixed ionic-electronic conductors Morozovska, A. N.; Eliseev, E. A.; Bravina, S. L. Journal of Applied Physics, Vol. 111, Issue 1 https://doi.org/10.1063/1.3673868	journal	January 2012
Quantification of light-enhanced ionic transport in lead iodide perovskite thin films and its solar cell applications Zhao, Yi-Cheng; Zhou, Wen-Ke; Zhou, Xu Light: Science & Applications, Vol. 6, Issue 5 https://doi.org/10.1038/lsa.2016.243	journal	October 2016
Band excitation in scanning probe microscopy: sines of change Jesse, Stephen; Kalinin, Sergei V. Journal of Physics D: Applied Physics, Vol. 44, Issue 46 https://doi.org/10.1088/0022-3727/44/46/464006	journal	November 2011
From Ultrafast to Ultraslow: Charge-Carrier Dynamics of Perovskite Solar Cells Shi, Jiangjian; Li, Yiming; Li, Yusheng Joule, Vol. 2, Issue 5 https://doi.org/10.1016/j.joule.2018.04.010	journal	May 2018
Ferroelectric Poling of Methylammonium Lead Iodide Thin Films Röhm, Holger; Leonhard, Tobias; Hoffmann, Michael J. Advanced Functional Materials, Vol. 30, Issue 5 https://doi.org/10.1002/adfm.201908657	journal	November 2019
Impact of microstructure on local carrier lifetime in perovskite solar cells de Quilettes, D. W.; Vorpahl, S. M.; Stranks, S. D. Science, Vol. 348, Issue 6235 https://doi.org/10.1126/science.aaa5333	journal	April 2015
Anomalously large interface charge in polarity-switchable photovoltaic devices: an indication of mobile ions in organic–inorganic halide perovskites Zhao, Yong; Liang, Chunjun; Zhang, Huimin Energy & Environmental Science, Vol. 8, Issue 4 https://doi.org/10.1039/C4EE04064C	journal	January 2015
Performance-limiting nanoscale trap clusters at grain junctions in halide perovskites Doherty, Tiarnan A. S.; Winchester, Andrew J.; Macpherson, Stuart Nature, Vol. 580, Issue 7803 https://doi.org/10.1038/s41586-020-2184-1	journal	April 2020
Lattice strain causes non-radiative losses in halide perovskites Jones, Timothy W.; Osherov, Anna; Alsari, Mejd Energy & Environmental Science, Vol. 12, Issue 2 https://doi.org/10.1039/C8EE02751J	journal	January 2019
Dynamic behaviour in piezoresponse force microscopy Jesse, Stephen; Baddorf, Arthur P.; Kalinin, Sergei V. Nanotechnology, Vol. 17, Issue 6 https://doi.org/10.1088/0957-4484/17/6/014	journal	February 2006
Hysteretic Ion Migration and Remanent Field in Metal Halide Perovskites Liu, Yongtao; Borodinov, Nikolay; Lorenz, Matthias Advanced Science, Vol. 7, Issue 19 https://doi.org/10.1002/advs.202001176	journal	August 2020
Ferroelastic Fingerprints in Methylammonium Lead Iodide Perovskite Hermes, Ilka M.; Bretschneider, Simon A.; Bergmann, Victor W. The Journal of Physical Chemistry C, Vol. 120, Issue 10 https://doi.org/10.1021/acs.jpcc.5b11469	journal	January 2016
Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency Saliba, Michael; Matsui, Taisuke; Seo, Ji-Youn Energy & Environmental Science, Vol. 9, Issue 6 https://doi.org/10.1039/C5EE03874J	journal	January 2016
Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber Stranks, S. D.; Eperon, G. E.; Grancini, G. Science, Vol. 342, Issue 6156, p. 341-344 https://doi.org/10.1126/science.1243982	journal	October 2013
The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells Leguy, Aurelien M. A.; Frost, Jarvist Moore; McMahon, Andrew P. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8124	journal	May 2015
Facet-dependent photovoltaic efficiency variations in single grains of hybrid halide perovskite Leblebici, Sibel Y.; Leppert, Linn; Li, Yanbo Nature Energy, Vol. 1, Issue 8 https://doi.org/10.1038/nenergy.2016.93	journal	July 2016
Chemical nature of ferroelastic twin domains in CH3NH3PbI3 perovskite Liu, Yongtao; Collins, Liam; Proksch, Roger Nature Materials, Vol. 17, Issue 11 https://doi.org/10.1038/s41563-018-0152-z	journal	August 2018
Progress and Opportunities for Cs Incorporated Perovskite Photovoltaics Tang, Shi; Huang, Shujuan; Wilson, Gregory J. Trends in Chemistry, Vol. 2, Issue 7 https://doi.org/10.1016/j.trechm.2020.04.002	journal	July 2020
A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells McMeekin, D. P.; Sadoughi, G.; Rehman, W. Science, Vol. 351, Issue 6269 https://doi.org/10.1126/science.aad5845	journal	January 2016
Anisotropic carrier diffusion in single MAPbI ₃ grains correlates to their twin domains Hermes, Ilka M.; Best, Andreas; Winkelmann, Leonard Energy & Environmental Science, Vol. 13, Issue 11 https://doi.org/10.1039/D0EE01016B	journal	January 2020
CH ₃ NH ₃ PbI ₃ perovskites: Ferroelasticity revealed Strelcov, Evgheni; Dong, Qingfeng; Li, Tao Science Advances, Vol. 3, Issue 4 https://doi.org/10.1126/sciadv.1602165	journal	April 2017
Imaging mechanism of piezoresponse force microscopy of ferroelectric surfaces Kalinin, Sergei V.; Bonnell, Dawn A. Physical Review B, Vol. 65, Issue 12 https://doi.org/10.1103/PhysRevB.65.125408	journal	March 2002
Thiocyanate-Treated Perovskite-Nanocrystal-Based Light-Emitting Diodes with Insight in Efficiency Roll-Off Chen, Fang; Boopathi, Karunakara Moorthy; Imran, Muhammad Materials, Vol. 13, Issue 2 https://doi.org/10.3390/ma13020367	journal	January 2020

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