Density Functional Studies of Stoichiometric Surfaces of Orthorhombic Hybrid Perovskite CH3NH3PbI3
Abstract
Organic/inorganic hybrid perovskite materials are highly attractive for dye-sensitized solar cells as demonstrated by their rapid advances in energy conversion efficiency. In this work, the structures, energetics, and electronic properties for a range of stoichiometric surfaces of the orthorhombic perovskite CH3NH3PbI3 are theoretically studied using density functional theory. Various possible spatially and constitutionally isomeric surfaces are considered by diversifying the spatial orientations and connectivities of surface Pb-I bonds. The comparison of the surface energies for the most stable configurations identified for various surfaces shows that the stabilities of stoichiometric surfaces are mainly dictated by the coordination numbers of surface atoms, which are directly correlated with the numbers of broken bonds. Additionally, Coulombic interactions between I anions and organic countercations on the surface also contribute to the stabilization. Electronic properties are compared between the most stable (100) surface and the bulk phase, showing generally similar features except for the lifted band degeneracy and the enhanced bandgap energy for the surface. These studies on the stoichiometric surfaces serve as the first step toward gaining a fundamental understanding of the interfacial properties in the current structural design of perovskite based solar cells, in order to achieve further breakthroughs in solar conversion efficiencies.
- Authors:
-
- Griffith Univ., Nathan, Queensland (Australia)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1185779
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 119; Journal Issue: 2; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Perovskite solar cells; CH3NH3PbI3; Density functional theory; Stoichiometric surfaces.
Citation Formats
Wang, Yun, Huang, Jingsong, Sumpter, Bobby G., Zhang, Haimin, Liu, Porun, Yang, Huagui, and Zhao, Huijun. Density Functional Studies of Stoichiometric Surfaces of Orthorhombic Hybrid Perovskite CH3NH3PbI3. United States: N. p., 2014.
Web. doi:10.1021/jp511123s.
Wang, Yun, Huang, Jingsong, Sumpter, Bobby G., Zhang, Haimin, Liu, Porun, Yang, Huagui, & Zhao, Huijun. Density Functional Studies of Stoichiometric Surfaces of Orthorhombic Hybrid Perovskite CH3NH3PbI3. United States. https://doi.org/10.1021/jp511123s
Wang, Yun, Huang, Jingsong, Sumpter, Bobby G., Zhang, Haimin, Liu, Porun, Yang, Huagui, and Zhao, Huijun. 2014.
"Density Functional Studies of Stoichiometric Surfaces of Orthorhombic Hybrid Perovskite CH3NH3PbI3". United States. https://doi.org/10.1021/jp511123s. https://www.osti.gov/servlets/purl/1185779.
@article{osti_1185779,
title = {Density Functional Studies of Stoichiometric Surfaces of Orthorhombic Hybrid Perovskite CH3NH3PbI3},
author = {Wang, Yun and Huang, Jingsong and Sumpter, Bobby G. and Zhang, Haimin and Liu, Porun and Yang, Huagui and Zhao, Huijun},
abstractNote = {Organic/inorganic hybrid perovskite materials are highly attractive for dye-sensitized solar cells as demonstrated by their rapid advances in energy conversion efficiency. In this work, the structures, energetics, and electronic properties for a range of stoichiometric surfaces of the orthorhombic perovskite CH3NH3PbI3 are theoretically studied using density functional theory. Various possible spatially and constitutionally isomeric surfaces are considered by diversifying the spatial orientations and connectivities of surface Pb-I bonds. The comparison of the surface energies for the most stable configurations identified for various surfaces shows that the stabilities of stoichiometric surfaces are mainly dictated by the coordination numbers of surface atoms, which are directly correlated with the numbers of broken bonds. Additionally, Coulombic interactions between I anions and organic countercations on the surface also contribute to the stabilization. Electronic properties are compared between the most stable (100) surface and the bulk phase, showing generally similar features except for the lifted band degeneracy and the enhanced bandgap energy for the surface. These studies on the stoichiometric surfaces serve as the first step toward gaining a fundamental understanding of the interfacial properties in the current structural design of perovskite based solar cells, in order to achieve further breakthroughs in solar conversion efficiencies.},
doi = {10.1021/jp511123s},
url = {https://www.osti.gov/biblio/1185779},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 2,
volume = 119,
place = {United States},
year = {Fri Dec 19 00:00:00 EST 2014},
month = {Fri Dec 19 00:00:00 EST 2014}
}
Web of Science
Works referenced in this record:
Dye-Sensitized Solar Cells
journal, November 2010
- Hagfeldt, Anders; Boschloo, Gerrit; Sun, Licheng
- Chemical Reviews, Vol. 110, Issue 11
Solid-state dye-sensitized mesoporous TiO2 solar cells with high photon-to-electron conversion efficiencies
journal, October 1998
- Bach, U.; Lupo, D.; Comte, P.
- Nature, Vol. 395, Issue 6702
Porphyrin-Sensitized Solar Cells with Cobalt (II/III)-Based Redox Electrolyte Exceed 12 Percent Efficiency
journal, November 2011
- Yella, A.; Lee, H. -W.; Tsao, H. N.
- Science, Vol. 334, Issue 6056
The Swift Surge of Perovskite Photovoltaics
journal, July 2013
- Bisquert, Juan
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 15
Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9%
journal, August 2012
- Kim, Hui-Seon; Lee, Chang-Ryul; Im, Jeong-Hyeok
- Scientific Reports, Vol. 2, Issue 1
Mechanism of carrier accumulation in perovskite thin-absorber solar cells
journal, July 2013
- Kim, Hui-Seon; Mora-Sero, Ivan; Gonzalez-Pedro, Victoria
- Nature Communications, Vol. 4, Issue 1
Efficient planar heterojunction perovskite solar cells by vapour deposition
journal, September 2013
- Liu, Mingzhen; Johnston, Michael B.; Snaith, Henry J.
- Nature, Vol. 501, Issue 7467, p. 395-398
Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites
journal, October 2012
- Lee, M. M.; Teuscher, J.; Miyasaka, T.
- Science, Vol. 338, Issue 6107, p. 643-647
Chemical Management for Colorful, Efficient, and Stable Inorganic–Organic Hybrid Nanostructured Solar Cells
journal, March 2013
- Noh, Jun Hong; Im, Sang Hyuk; Heo, Jin Hyuck
- Nano Letters, Vol. 13, Issue 4, p. 1764-1769
Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber
journal, October 2013
- Stranks, S. D.; Eperon, G. E.; Grancini, G.
- Science, Vol. 342, Issue 6156, p. 341-344
Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH3NH3PbI3
journal, October 2013
- Xing, G.; Mathews, N.; Sun, S.
- Science, Vol. 342, Issue 6156, p. 344-347
Enhancement of Perovskite-Based Solar Cells Employing Core–Shell Metal Nanoparticles
journal, August 2013
- Zhang, Wei; Saliba, Michael; Stranks, Samuel D.
- Nano Letters, Vol. 13, Issue 9
Organometal Perovskite Light Absorbers Toward a 20% Efficiency Low-Cost Solid-State Mesoscopic Solar Cell
journal, July 2013
- Park, Nam-Gyu
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 15, p. 2423-2429
Perovskite Solar Cells Keep On Surging
journal, May 2014
- Service, R. F.
- Science, Vol. 344, Issue 6183, Article No. 458
Interface engineering of highly efficient perovskite solar cells
journal, July 2014
- Zhou, H.; Chen, Q.; Li, G.
- Science, Vol. 345, Issue 6196
A hole-conductor-free, fully printable mesoscopic perovskite solar cell with high stability
journal, July 2014
- Mei, A.; Li, X.; Liu, L.
- Science, Vol. 345, Issue 6194, p. 295-298
Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells
journal, May 2009
- Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo
- Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051
Mesoscopic CH3NH3PbI3/TiO2 Heterojunction Solar Cells
journal, October 2012
- Etgar, Lioz; Gao, Peng; Xue, Zhaosheng
- Journal of the American Chemical Society, Vol. 134, Issue 42, p. 17396-17399
Materials interface engineering for solution-processed photovoltaics
journal, August 2012
- Graetzel, Michael; Janssen, René A. J.; Mitzi, David B.
- Nature, Vol. 488, Issue 7411
Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications
journal, January 2013
- Baikie, Tom; Fang, Yanan; Kadro, Jeannette M.
- Journal of Materials Chemistry A, Vol. 1, Issue 18
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990
- Vanderbilt, David
- Physical Review B, Vol. 41, Issue 11, p. 7892-7895
Density functional theory analysis of structural and electronic properties of orthorhombic perovskite CH 3 NH 3 PbI 3
journal, January 2014
- Wang, Yun; Gould, Tim; Dobson, John F.
- Phys. Chem. Chem. Phys., Vol. 16, Issue 4
Van der Waals Density Functional for General Geometries
journal, June 2004
- Dion, M.; Rydberg, H.; Schröder, E.
- Physical Review Letters, Vol. 92, Issue 24
Van der Waals density functionals applied to solids
journal, May 2011
- Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos
- Physical Review B, Vol. 83, Issue 19
Importance of Spin–Orbit Coupling in Hybrid Organic/Inorganic Perovskites for Photovoltaic Applications
journal, August 2013
- Even, Jacky; Pedesseau, Laurent; Jancu, Jean-Marc
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 17
CH3NH3PbX3, ein Pb(II)-System mit kubischer Perowskitstruktur / CH3NH3PbX3, a Pb(II)-System with Cubic Perovskite Structure
journal, December 1978
- Weber, Dieter
- Zeitschrift für Naturforschung B, Vol. 33, Issue 12
Cation rotation in methylammonium lead halides
journal, November 1985
- Wasylishen, R. E.; Knop, Osvald; Macdonald, J. B.
- Solid State Communications, Vol. 56, Issue 7
Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter‐wave spectroscopy
journal, December 1987
- Poglitsch, A.; Weber, D.
- The Journal of Chemical Physics, Vol. 87, Issue 11, p. 6373-6378
Dielectric study of CH3NH3PbX3 (X = Cl, Br, I)
journal, July 1992
- Onoda-Yamamuro, Noriko; Matsuo, Takasuke; Suga, Hiroshi
- Journal of Physics and Chemistry of Solids, Vol. 53, Issue 7
A negative surface energy for alumina
journal, April 2004
- Łodziana, Zbigniew; Topsøe, Nan-Yu; Nørskov, Jens K.
- Nature Materials, Vol. 3, Issue 5
Effect of a humid environment on the surface structure of
journal, May 2003
- Sun, Qiang; Reuter, Karsten; Scheffler, Matthias
- Physical Review B, Vol. 67, Issue 20
Surface Structure and Reactivity of Anatase TiO 2 Crystals with Dominant {001} Facets
journal, March 2013
- Selçuk, Sencer; Selloni, Annabella
- The Journal of Physical Chemistry C, Vol. 117, Issue 12
New software tools for the calculation and display of isolated and attached interfacial-energy minimizing particle shapes
journal, August 2012
- Zucker, Rachel V.; Chatain, Dominique; Dahmen, Ulrich
- Journal of Materials Science, Vol. 47, Issue 24
Role of Dispersive Interactions in Determining Structural Properties of Organic–Inorganic Halide Perovskites: Insights from First-Principles Calculations
journal, July 2014
- Egger, David A.; Kronik, Leeor
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 15
Colloidal nanoplatelets with two-dimensional electronic structure
journal, October 2011
- Ithurria, S.; Tessier, M. D.; Mahler, B.
- Nature Materials, Vol. 10, Issue 12
Works referencing / citing this record:
Glimpses of the modification of perovskite with graphene-analogous materials in photocatalytic applications
journal, January 2015
- Acharya, Saumyaprava; Martha, Satyabadi; Sahoo, Prakash Chandra
- Inorganic Chemistry Frontiers, Vol. 2, Issue 9
Progress in Theoretical Study of Metal Halide Perovskite Solar Cell Materials
journal, August 2017
- Xiao, Zewen; Yan, Yanfa
- Advanced Energy Materials, Vol. 7, Issue 22
Impact of iodine antisite (I Pb ) defects on the electronic properties of the (110) CH 3 NH 3 PbI 3 surface
journal, October 2018
- Taufique, M. F. N.; Khanal, Rabi; Choudhury, Samrat
- The Journal of Chemical Physics, Vol. 149, Issue 16
Computational screening of methylammonium based halide perovskites with bandgaps suitable for perovskite-perovskite tandem solar cells
journal, December 2018
- Kar, M.; Körzdörfer, T.
- The Journal of Chemical Physics, Vol. 149, Issue 21
Atomic structure and electronic properties of lead and tin based hybrid halide perovskite surface for photovoltaic applications
journal, August 2019
- Khanal, Rabi; Ayers, Nicholas; Banerjee, Soumik
- AIP Advances, Vol. 9, Issue 8
Understanding interactions between halide perovskite surfaces and atmospheric/VOC gas molecules: an ab initio investigation
journal, July 2018
- Zhang, Lei; Yu, Fengxi; Li, Qingfang
- Journal of Physics D: Applied Physics, Vol. 51, Issue 31
Density Functional Theory Investigation of Carbon Dots as Hole-transport Material in Perovskite Solar Cells
journal, October 2018
- Kasi Matta, Sri; Zhang, Chunmei; O'Mullane, Anthony P.
- ChemPhysChem, Vol. 19, Issue 22
Bulk and surface DFT investigations of inorganic halide perovskites screened using machine learning and materials property databases
journal, January 2019
- Jain, Deepak; Chaube, Suryanaman; Khullar, Prerna
- Physical Chemistry Chemical Physics, Vol. 21, Issue 35
Materials Discovery of Stable and Nontoxic Halide Perovskite Materials for High‐Efficiency Solar Cells
journal, April 2019
- Jacobs, Ryan; Luo, Guangfu; Morgan, Dane
- Advanced Functional Materials, Vol. 29, Issue 23
Progress of Surface Science Studies on ABX 3 ‐Based Metal Halide Perovskite Solar Cells
journal, April 2020
- Qiu, Longbin; He, Sisi; Ono, Luis K.
- Advanced Energy Materials, Vol. 10, Issue 13
Photostriction of CH 3 NH 3 PbBr 3 Perovskite Crystals
journal, July 2017
- Wei, Tzu-Chiao; Wang, Hsin-Ping; Li, Ting-You
- Advanced Materials, Vol. 29, Issue 35
Functionalization of perovskite thin films with moisture-tolerant molecules
journal, January 2016
- Yang, Shuang; Wang, Yun; Liu, Porun
- Nature Energy, Vol. 1, Issue 2
A close examination of the structure and dynamics of HC(NH 2 ) 2 PbI 3 by MD simulations and group theory
journal, January 2016
- Carignano, M. A.; Saeed, Y.; Aravindh, S. Assa
- Physical Chemistry Chemical Physics, Vol. 18, Issue 39
Materials Discovery of Stable and Nontoxic Halide Perovskite Materials for High-Efficiency Solar Cells
text, January 2019
- Jacobs, Ryan; Luo, Guangfu; Morgan, Dane
- arXiv