First-Principles Characterization of Surface Phonons of Halide Perovskite CsPbI3 and Their Role in Stabilization

Yang, Ruo Xi; Tan, Liang Z.

doi:10.1021/acs.jpclett.1c02515

First-Principles Characterization of Surface Phonons of Halide Perovskite CsPbI₃ and Their Role in Stabilization

Journal Article · Fri Sep 17 00:00:00 EDT 2021 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.1c02515· OSTI ID:1829062

^[1]; ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

The stability of halide perovskites has been a long-standing issue for their real-world application. Approaches to improve stability include nanostructuring, dimensionality reduction, and strain engineering, where surfaces play an important role in the formation of a stable structure. To understand the mechanism we compute the lattice dynamics of the surface of CsPbI₃ using density functional theory. We demonstrate, for the first time, that CsPbI₃ crystals exhibit surface phonons that are localized on the outermost layers of the slabs, and we perform a complete symmetry characterization including an identification of the Raman/IR active modes. These surface phonons are present in the optically active cubic phase but are absent in the optically inactive "yellow" phase. Furthermore, we show that the surface suppresses bulk instabilities by hardening soft modes of the bulk cubic phase, resulting in phase stabilization and quenching of dynamical disorder. Finally, this study is fundamental for understanding the structural behavior of halide perovskite materials with high surface area-to-volume ratios, and for guiding stabilization strategies.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

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

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1829062

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 38 Vol. 12; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (55)

Efficient and Stable CsPbI 3 Solar Cells via Regulating Lattice Distortion with Surface Organic Terminal Groups Wu, Tianhao; Wang, Yanbo; Dai, Zhensheng Advanced Materials https://doi.org/10.1002/adma.201900605	journal	April 2019
Phase-Stable CsPbI ₃ Nanocrystals: The Reaction Temperature Matters Dutta, Anirban; Dutta, Sumit K.; Das Adhikari, Samrat Angewandte Chemie International Edition, Vol. 57, Issue 29 https://doi.org/10.1002/anie.201803701	journal	June 2018
The one phonon Raman spectrum in microcrystalline silicon Richter, H.; Wang, Z. P.; Ley, L. Solid State Communications, Vol. 39, Issue 5 https://doi.org/10.1016/0038-1098(81)90337-9	journal	August 1981
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Raman spectra and vibrational analysis of CsPbI3: A fast and reliable technique to identify lead halide perovskite polymorphs Satta, Jessica; Melis, Claudio; Carbonaro, Carlo Maria Journal of Materiomics, Vol. 7, Issue 1 https://doi.org/10.1016/j.jmat.2020.08.004	journal	January 2021
Toward Eco-friendly and Stable Perovskite Materials for Photovoltaics Ju, Ming-Gang; Chen, Min; Zhou, Yuanyuan Joule, Vol. 2, Issue 7 https://doi.org/10.1016/j.joule.2018.04.026	journal	July 2018
First principles phonon calculations in materials science Togo, Atsushi; Tanaka, Isao Scripta Materialia, Vol. 108 https://doi.org/10.1016/j.scriptamat.2015.07.021	journal	November 2015
Ruddlesden–Popper Hybrid Lead Iodide Perovskite 2D Homologous Semiconductors Stoumpos, Constantinos C.; Cao, Duyen H.; Clark, Daniel J. Chemistry of Materials, Vol. 28, Issue 8, p. 2852-2867 https://doi.org/10.1021/acs.chemmater.6b00847	journal	April 2016
Halide Perovskites: Is It All about the Interfaces? Schulz, Philip; Cahen, David; Kahn, Antoine Chemical Reviews, Vol. 119, Issue 5 https://doi.org/10.1021/acs.chemrev.8b00558	journal	March 2019
Light-Induced Degradation of CH ₃ NH ₃ PbI ₃ Hybrid Perovskite Thin Film Li, Youzhen; Xu, Xuemei; Wang, Congcong The Journal of Physical Chemistry C, Vol. 121, Issue 7 https://doi.org/10.1021/acs.jpcc.6b11853	journal	February 2017
Degradation of Methylammonium Lead Iodide Perovskite Structures through Light and Electron Beam Driven Ion Migration Yuan, Haifeng; Debroye, Elke; Janssen, Kris The Journal of Physical Chemistry Letters, Vol. 7, Issue 3 https://doi.org/10.1021/acs.jpclett.5b02828	journal	January 2016
Structural Instabilities Related to Highly Anharmonic Phonons in Halide Perovskites Marronnier, Arthur; Lee, Heejae; Geffroy, Bernard The Journal of Physical Chemistry Letters, Vol. 8, Issue 12 https://doi.org/10.1021/acs.jpclett.7b00807	journal	June 2017
Spontaneous Octahedral Tilting in the Cubic Inorganic Cesium Halide Perovskites CsSnX ₃ and CsPbX ₃ (X = F, Cl, Br, I) Yang, Ruo Xi; Skelton, Jonathan M.; da Silva, E. Lora The Journal of Physical Chemistry Letters, Vol. 8, Issue 19 https://doi.org/10.1021/acs.jpclett.7b02423	journal	September 2017
Lattice Dynamics and Thermal Stability of Cubic-Phase CsPbI ₃ Quantum Dots Zhou, Wei; Sui, Fan; Zhong, Guohua The Journal of Physical Chemistry Letters, Vol. 9, Issue 17 https://doi.org/10.1021/acs.jpclett.8b02036	journal	August 2018
In Situ Raman Spectroscopic Studies of Thermal Stability of All-Inorganic Cesium Lead Halide (CsPbX ₃ , X = Cl, Br, I) Perovskite Nanocrystals Liao, Mengling; Shan, Beibei; Li, Ming The Journal of Physical Chemistry Letters, Vol. 10, Issue 6 https://doi.org/10.1021/acs.jpclett.9b00344	journal	February 2019
Layer Edge States Stabilized by Internal Electric Fields in Two-Dimensional Hybrid Perovskites Hong, Jisook; Prendergast, David; Tan, Liang Z. Nano Letters, Vol. 21, Issue 1 https://doi.org/10.1021/acs.nanolett.0c03468	journal	October 2020
Complete Suppression of Detrimental Polymorph Transitions in All-Inorganic Perovskites via Nanoconfinement Kong, Xiaoqing; Shayan, Kamran; Hua, Sophia ACS Applied Energy Materials, Vol. 2, Issue 4 https://doi.org/10.1021/acsaem.9b00322	journal	March 2019
Direct Observation of Dynamic Symmetry Breaking above Room Temperature in Methylammonium Lead Iodide Perovskite Beecher, Alexander N.; Semonin, Octavi E.; Skelton, Jonathan M. ACS Energy Letters, Vol. 1, Issue 4 https://doi.org/10.1021/acsenergylett.6b00381	journal	October 2016
Cubic or Orthorhombic? Revealing the Crystal Structure of Metastable Black-Phase CsPbI ₃ by Theory and Experiment Sutton, Rebecca J.; Filip, Marina R.; Haghighirad, Amir A. ACS Energy Letters, Vol. 3, Issue 8 https://doi.org/10.1021/acsenergylett.8b00672	journal	June 2018
Coherent Nanotwins and Dynamic Disorder in Cesium Lead Halide Perovskite Nanocrystals Bertolotti, Federica; Protesescu, Loredana; Kovalenko, Maksym V. ACS Nano, Vol. 11, Issue 4 https://doi.org/10.1021/acsnano.7b00017	journal	April 2017
Anharmonicity and Disorder in the Black Phases of Cesium Lead Iodide Used for Stable Inorganic Perovskite Solar Cells Marronnier, Arthur; Roma, Guido; Boyer-Richard, Soline ACS Nano, Vol. 12, Issue 4 https://doi.org/10.1021/acsnano.8b00267	journal	March 2018
The inorganic crystal structure data base Bergerhoff, G.; Hundt, R.; Sievers, R. Journal of Chemical Information and Modeling, Vol. 23, Issue 2 https://doi.org/10.1021/ci00038a003	journal	May 1983
Semiconducting Tin and Lead Iodide Perovskites with Organic Cations: Phase Transitions, High Mobilities, and Near-Infrared Photoluminescent Properties Stoumpos, Constantinos C.; Malliakas, Christos D.; Kanatzidis, Mercouri G. Inorganic Chemistry, Vol. 52, Issue 15, p. 9019-9038 https://doi.org/10.1021/ic401215x	journal	July 2013
Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051 https://doi.org/10.1021/ja809598r	journal	May 2009
2D Homologous Perovskites as Light-Absorbing Materials for Solar Cell Applications Cao, Duyen H.; Stoumpos, Constantinos C.; Farha, Omar K. Journal of the American Chemical Society, Vol. 137, Issue 24 https://doi.org/10.1021/jacs.5b03796	journal	June 2015
Termination Dependence of Tetragonal CH ₃ NH ₃ PbI ₃ Surfaces for Perovskite Solar Cells Haruyama, Jun; Sodeyama, Keitaro; Han, Liyuan The Journal of Physical Chemistry Letters, Vol. 5, Issue 16 https://doi.org/10.1021/jz501510v	journal	August 2014
Nanocrystals of Cesium Lead Halide Perovskites (CsPbX ₃ , X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I. Nano Letters, Vol. 15, Issue 6 https://doi.org/10.1021/nl5048779	journal	February 2015
High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe Nature, Vol. 536, Issue 7616 https://doi.org/10.1038/nature18306	journal	July 2016
Mapping vibrational surface and bulk modes in a single nanocube Lagos, Maureen J.; Trügler, Andreas; Hohenester, Ulrich Nature, Vol. 543, Issue 7646 https://doi.org/10.1038/nature21699	journal	March 2017
Light-activated photocurrent degradation and self-healing in perovskite solar cells Nie, Wanyi; Blancon, Jean-Christophe; Neukirch, Amanda J. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11574	journal	May 2016
Lattice anchoring stabilizes solution-processed semiconductors Liu, Mengxia; Chen, Yuelang; Tan, Chih-Shan Nature, Vol. 570, Issue 7759 https://doi.org/10.1038/s41586-019-1239-7	journal	May 2019
Light and oxygen induced degradation limits the operational stability of methylammonium lead triiodide perovskite solar cells Bryant, Daniel; Aristidou, Nicholas; Pont, Sebastian Energy & Environmental Science, Vol. 9, Issue 5 https://doi.org/10.1039/C6EE00409A	journal	January 2016
Structural and chemical evolution of methylammonium lead halide perovskites during thermal processing from solution Nenon, David P.; Christians, Jeffrey A.; Wheeler, Lance M. Energy & Environmental Science, Vol. 9, Issue 6 https://doi.org/10.1039/C6EE01047D	journal	January 2016
Scaling behavior of moisture-induced grain degradation in polycrystalline hybrid perovskite thin films Wang, Qi; Chen, Bo; Liu, Ye Energy & Environmental Science, Vol. 10, Issue 2 https://doi.org/10.1039/C6EE02941H	journal	January 2017
Exploring the surface chemistry of cesium lead halide perovskite nanocrystals Grisorio, Roberto; Di Clemente, Milvia Elena; Fanizza, Elisabetta Nanoscale, Vol. 11, Issue 3 https://doi.org/10.1039/C8NR08011A	journal	January 2019
Photoluminescence signatures of thermal expansion, electron–phonon coupling and phase transitions in cesium lead bromide perovskite nanosheets Lao, Xiangzhou; Zhou, Wei; Bao, Yitian Nanoscale, Vol. 12, Issue 13 https://doi.org/10.1039/D0NR00025F	journal	January 2020
Probing lattice vibrations of stabilized CsPbI ₃ polymorphs via low-frequency Raman spectroscopy Yang, Yi; Robbins, Jason P.; Ezeonu, Lotanna Journal of Materials Chemistry C, Vol. 8, Issue 26 https://doi.org/10.1039/D0TC02123G	journal	January 2020
Understanding size dependence of phase stability and band gap in CsPbI ₃ perovskite nanocrystals Yang, Ruo Xi; Tan, Liang Z. The Journal of Chemical Physics, Vol. 152, Issue 3 https://doi.org/10.1063/1.5128016	journal	January 2020
Assessment of dynamic structural instabilities across 24 cubic inorganic halide perovskites Yang, Ruo Xi; Skelton, Jonathan M.; da Silva, Estelina L. The Journal of Chemical Physics, Vol. 152, Issue 2 https://doi.org/10.1063/1.5131575	journal	January 2020
Pressure dependence of the Raman modes for orthorhombic and monoclinic phases of CsPbI ₃ at room temperature Kurt, Arzu Journal of Applied Physics, Vol. 128, Issue 7 https://doi.org/10.1063/5.0012355	journal	August 2020
Modeling the contribution of point defects to the Raman spectrum of crystalline materials Roma, Guido Modelling and Simulation in Materials Science and Engineering, Vol. 27, Issue 7 https://doi.org/10.1088/1361-651X/ab2962	journal	July 2019
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Size-dependent surface phonon mode of CdSe quantum dots Hwang, Young-Nam; Park, Seung-Han; Kim, Dongho Physical Review B, Vol. 59, Issue 11 https://doi.org/10.1103/PhysRevB.59.7285	journal	March 1999
Recovering hidden Bloch character: Unfolding electrons, phonons, and slabs Allen, P. B.; Berlijn, T.; Casavant, D. A. Physical Review B, Vol. 87, Issue 8 https://doi.org/10.1103/PhysRevB.87.085322	journal	February 2013
Modeling energy-loss spectra due to phonon excitation Forbes, B. D.; Allen, L. J. Physical Review B, Vol. 94, Issue 1 https://doi.org/10.1103/PhysRevB.94.014110	journal	July 2016
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 100, Issue 13 https://doi.org/10.1103/PhysRevLett.100.136406	journal	April 2008
Erratum: Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces [Phys. Rev. Lett. 100 , 136406 (2008)] Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 102, Issue 3 https://doi.org/10.1103/PhysRevLett.102.039902	journal	January 2009
First-Principles Study of Confinement Effects on the Raman Spectra of Si Nanocrystals Khoo, K. H.; Zayak, A. T.; Kwak, H. Physical Review Letters, Vol. 105, Issue 11 https://doi.org/10.1103/PhysRevLett.105.115504	journal	September 2010
Local Polar Fluctuations in Lead Halide Perovskite Crystals Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z. Physical Review Letters, Vol. 118, Issue 13 https://doi.org/10.1103/PhysRevLett.118.136001	journal	March 2017
Vibrational Surface Electron-Energy-Loss Spectroscopy Probes Confined Surface-Phonon Modes Lourenço-Martins, Hugo; Kociak, Mathieu Physical Review X, Vol. 7, Issue 4 https://doi.org/10.1103/PhysRevX.7.041059	journal	December 2017
Bilbao Crystallographic Server. II. Representations of crystallographic point groups and space groups Aroyo, Mois I.; Kirov, Asen; Capillas, Cesar Acta Crystallographica Section A Foundations of Crystallography, Vol. 62, Issue 2 https://doi.org/10.1107/S0108767305040286	journal	March 2006
Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites Lee, M. M.; Teuscher, J.; Miyasaka, T. Science, Vol. 338, Issue 6107, p. 643-647 https://doi.org/10.1126/science.1228604	journal	October 2012
Interface engineering of highly efficient perovskite solar cells Zhou, H.; Chen, Q.; Li, G. Science, Vol. 345, Issue 6196 https://doi.org/10.1126/science.1254050	journal	July 2014
High-performance photovoltaic perovskite layers fabricated through intramolecular exchange Yang, W. S.; Noh, J. H.; Jeon, N. J. Science, Vol. 348, Issue 6240 https://doi.org/10.1126/science.aaa9272	journal	May 2015
Quantum dot-induced phase stabilization of -CsPbI3 perovskite for high-efficiency photovoltaics Swarnkar, A.; Marshall, A. R.; Sanehira, E. M. Science, Vol. 354, Issue 6308 https://doi.org/10.1126/science.aag2700	journal	October 2016

Similar Records

Understanding size dependence of phase stability and band gap in CsPbI₃ perovskite nanocrystals

Journal Article · Wed Jan 15 23:00:00 EST 2020 · Journal of Chemical Physics · OSTI ID:1604722

Understanding the Instability of the Halide Perovskite CsPbI₃ through Temperature-Dependent Structural Analysis

Journal Article · Tue Jul 07 00:00:00 EDT 2020 · Advanced Materials · OSTI ID:1649994

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
band structure
colloids
layers
perovskites
phonons

First-Principles Characterization of Surface Phonons of Halide Perovskite CsPbI3 and Their Role in Stabilization

Citation Formats

References (55)

Similar Records

Related Subjects

First-Principles Characterization of Surface Phonons of Halide Perovskite CsPbI₃ and Their Role in Stabilization