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Title: 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:
 [1];  [2];  [2];  [1];  [1];  [1];  [1]
  1. Griffith Univ., Nathan, Queensland (Australia)
  2. 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}
}

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Cited by: 63 works
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Works referenced in this record:

Dye-Sensitized Solar Cells
journal, November 2010


Photoelectrochemical cells
journal, November 2001


The Swift Surge of Perovskite Photovoltaics
journal, July 2013


Perovskite-Based Solar Cells
journal, October 2013


Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9%
journal, August 2012


Mechanism of carrier accumulation in perovskite thin-absorber solar cells
journal, July 2013


Efficient planar heterojunction perovskite solar cells by vapour deposition
journal, September 2013


Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites
journal, October 2012


Chemical Management for Colorful, Efficient, and Stable Inorganic–Organic Hybrid Nanostructured Solar Cells
journal, March 2013


Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber
journal, October 2013


Long-Range Balanced Electron- and Hole-Transport Lengths in Organic-Inorganic CH3NH3PbI3
journal, October 2013


Enhancement of Perovskite-Based Solar Cells Employing Core–Shell Metal Nanoparticles
journal, August 2013


Organometal Perovskite Light Absorbers Toward a 20% Efficiency Low-Cost Solid-State Mesoscopic Solar Cell
journal, July 2013


Perovskite Solar Cells Keep On Surging
journal, May 2014


Interface engineering of highly efficient perovskite solar cells
journal, July 2014


A hole-conductor-free, fully printable mesoscopic perovskite solar cell with high stability
journal, July 2014


Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells
journal, May 2009


Mesoscopic CH3NH3PbI3/TiO2 Heterojunction Solar Cells
journal, October 2012


Materials interface engineering for solution-processed photovoltaics
journal, August 2012


Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitised solar cell applications
journal, January 2013


Ab initiomolecular dynamics for liquid metals
journal, January 1993


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990


Density functional theory analysis of structural and electronic properties of orthorhombic perovskite CH 3 NH 3 PbI 3
journal, January 2014


Van der Waals Density Functional for General Geometries
journal, June 2004


Van der Waals density functionals applied to solids
journal, May 2011


Importance of Spin–Orbit Coupling in Hybrid Organic/Inorganic Perovskites for Photovoltaic Applications
journal, August 2013


Cation rotation in methylammonium lead halides
journal, November 1985


Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeter‐wave spectroscopy
journal, December 1987


Dielectric study of CH3NH3PbX3 (X = Cl, Br, I)
journal, July 1992


A negative surface energy for alumina
journal, April 2004


Effect of a humid environment on the surface structure of RuO 2 ( 110 )
journal, May 2003


Surface Structure and Reactivity of Anatase TiO 2 Crystals with Dominant {001} Facets
journal, March 2013


New software tools for the calculation and display of isolated and attached interfacial-energy minimizing particle shapes
journal, August 2012


Colloidal nanoplatelets with two-dimensional electronic structure
journal, October 2011


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Progress in Theoretical Study of Metal Halide Perovskite Solar Cell Materials
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Impact of iodine antisite (I Pb ) defects on the electronic properties of the (110) CH 3 NH 3 PbI 3 surface
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Understanding interactions between halide perovskite surfaces and atmospheric/VOC gas molecules: an ab initio investigation
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Density Functional Theory Investigation of Carbon Dots as Hole-transport Material in Perovskite Solar Cells
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Bulk and surface DFT investigations of inorganic halide perovskites screened using machine learning and materials property databases
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Materials Discovery of Stable and Nontoxic Halide Perovskite Materials for High‐Efficiency Solar Cells
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