Structural and Chemical Features Giving Rise to Defect Tolerance of Binary Semiconductors

Kurchin, Rachel C.; Gorai, Prashun; Buonassisi, Tonio; Stevanović, Vladan

doi:10.1021/acs.chemmater.8b01505

Title: Structural and Chemical Features Giving Rise to Defect Tolerance of Binary Semiconductors

Journal Article · Thu Jul 26 00:00:00 EDT 2018 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.8b01505· OSTI ID:1476979

^[1];

^[2]; Buonassisi, Tonio ^[1]; Stevanović, Vladan ^[2]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)

Defect tolerance, or the resilience of electronic transport properties of a crystalline material to the presence of defects, has emerged as a critical factor in the success of hybrid lead halide perovskites as photovoltaic absorbers. A key aspect of defect tolerance is the shallow character of dominant intrinsic defects. However, while qualitative heuristics to identify other defect-tolerant materials have been proposed, in particular, the presence of a partially oxidized ns² cation such as Pb, no compelling comprehensive understanding of how these shallow defects arise has yet emerged. Using modern defect theory and defect calculations, we conduct a detailed investigation of the mechanisms and identify specific features related to the chemical composition and crystal structure that give rise to defect tolerance. We find that an ns² cation is necessary but not sufficient to guarantee shallow cation vacancies in an s-p system, and that a compound's crystal structure can ensure shallow anion vacancies in a variety of ways. Specifically, the crystal site symmetry can enforce weak interactions between the orbitals that form the defect states, thus ensuring that those defect states are shallow. We substantiate our findings by computing defect formation energies in several known as well as hypothetical materials and conclude by discussing prospects for identifying semiconductors that satisfy these criteria.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1476979

Report Number(s):: NREL/JA-5K00-72569

Journal Information:: Chemistry of Materials, Vol. 30, Issue 16; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 26 works

Citation information provided by
Web of Science

References (69)

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
6.5% efficient perovskite quantum-dot-sensitized solar cell Im, Jeong-Hyeok; Lee, Chang-Ryul; Lee, Jin-Wook Nanoscale, Vol. 3, Issue 10, p. 4088-4093 https://doi.org/10.1039/c1nr10867k	journal	January 2011
Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9% Kim, Hui-Seon; Lee, Chang-Ryul; Im, Jeong-Hyeok Scientific Reports, Vol. 2, Issue 1 https://doi.org/10.1038/srep00591	journal	August 2012
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
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
Sequential deposition as a route to high-performance perovskite-sensitized solar cells Burschka, Julian; Pellet, Norman; Moon, Soo-Jin Nature, Vol. 499, Issue 7458, p. 316-319 https://doi.org/10.1038/nature12340	journal	July 2013
Efficient planar heterojunction perovskite solar cells by vapour deposition Liu, Mingzhen; Johnston, Michael B.; Snaith, Henry J. Nature, Vol. 501, Issue 7467, p. 395-398 https://doi.org/10.1038/nature12509	journal	September 2013
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
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
Perovskite solar cells: Danger from within Wilks, Regan G.; Bär, Marcus Nature Energy, Vol. 2, Issue 1 https://doi.org/10.1038/nenergy.2016.204	journal	January 2017
Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells Yang, Woon Seok; Park, Byung-Wook; Jung, Eui Hyuk Science, Vol. 356, Issue 6345 https://doi.org/10.1126/science.aan2301	journal	June 2017
Promises and challenges of perovskite solar cells Correa-Baena, Juan-Pablo; Saliba, Michael; Buonassisi, Tonio Science, Vol. 358, Issue 6364 https://doi.org/10.1126/science.aam6323	journal	November 2017
Assessment of Hybrid Organic–Inorganic Antimony Sulfides for Earth-Abundant Photovoltaic Applications Yang, Ruo Xi; Butler, Keith T.; Walsh, Aron The Journal of Physical Chemistry Letters, Vol. 6, Issue 24 https://doi.org/10.1021/acs.jpclett.5b02555	journal	December 2015
Identifying defect-tolerant semiconductors with high minority-carrier lifetimes: beyond hybrid lead halide perovskites Brandt, Riley E.; Stevanović, Vladan; Ginley, David S. MRS Communications, Vol. 5, Issue 2 https://doi.org/10.1557/mrc.2015.26	journal	May 2015
Relativistic electronic structure and band alignment of BiSI and BiSeI: candidate photovoltaic materials Ganose, Alex M.; Butler, Keith T.; Walsh, Aron Journal of Materials Chemistry A, Vol. 4, Issue 6 https://doi.org/10.1039/C5TA09612J	journal	January 2016
Searching for promising new perovskite-based photovoltaic absorbers: the importance of electronic dimensionality Xiao, Zewen; Meng, Weiwei; Wang, Jianbo Materials Horizons, Vol. 4, Issue 2 https://doi.org/10.1039/C6MH00519E	journal	January 2017
Design of nitride semiconductors for solar energy conversion Zakutayev, Andriy Journal of Materials Chemistry A, Vol. 4, Issue 18 https://doi.org/10.1039/C5TA09446A	journal	January 2016
Functionality-Directed Screening of Pb-Free Hybrid Organic–Inorganic Perovskites with Desired Intrinsic Photovoltaic Functionalities Yang, Dongwen; Lv, Jian; Zhao, Xingang Chemistry of Materials, Vol. 29, Issue 2 https://doi.org/10.1021/acs.chemmater.6b03221	journal	January 2017
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
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
Halide-Dependent Electronic Structure of Organolead Perovskite Materials Buin, Andrei; Comin, Riccardo; Xu, Jixian Chemistry of Materials, Vol. 27, Issue 12 https://doi.org/10.1021/acs.chemmater.5b01909	journal	June 2015
High Defect Tolerance in Lead Halide Perovskite CsPbBr ₃ Kang, Jun; Wang, Lin-Wang The Journal of Physical Chemistry Letters, Vol. 8, Issue 2 https://doi.org/10.1021/acs.jpclett.6b02800	journal	January 2017
Defect Tolerant Semiconductors for Solar Energy Conversion Zakutayev, Andriy; Caskey, Christopher M.; Fioretti, Angela N. The Journal of Physical Chemistry Letters, Vol. 5, Issue 7 https://doi.org/10.1021/jz5001787	journal	March 2014
Chemical trends of defect formation and doping limit in II-VI semiconductors: The case of CdTe Wei, Su-Huai; Zhang, S. B. Physical Review B, Vol. 66, Issue 15 https://doi.org/10.1103/PhysRevB.66.155211	journal	October 2002
First-principles calculations for defects and impurities: Applications to III-nitrides Van de Walle, Chris G.; Neugebauer, Jörg Journal of Applied Physics, Vol. 95, Issue 8 https://doi.org/10.1063/1.1682673	journal	April 2004
First principles study of native defects in InI Biswas, Koushik; Du, Mao-Hua Journal of Applied Physics, Vol. 109, Issue 11 https://doi.org/10.1063/1.3592231	journal	June 2011
First principles study of point defects in SnS Malone, Brad D.; Gali, Adam; Kaxiras, Efthimios Phys. Chem. Chem. Phys., Vol. 16, Issue 47 https://doi.org/10.1039/C4CP03010A	journal	January 2014
Shallow halogen vacancies in halide optoelectronic materials Shi, Hongliang; Du, Mao-Hua Physical Review B, Vol. 90, Issue 17 https://doi.org/10.1103/PhysRevB.90.174103	journal	November 2014
Investigation of Bismuth Triiodide (BiI ₃ ) for Photovoltaic Applications Brandt, Riley E.; Kurchin, Rachel C.; Hoye, Robert L. Z. The Journal of Physical Chemistry Letters, Vol. 6, Issue 21 https://doi.org/10.1021/acs.jpclett.5b02022	journal	October 2015
Methylammonium Bismuth Iodide as a Lead-Free, Stable Hybrid Organic-Inorganic Solar Absorber Hoye, Robert L. Z.; Brandt, Riley E.; Osherov, Anna Chemistry - A European Journal, Vol. 22, Issue 8 https://doi.org/10.1002/chem.201505055	journal	January 2016
Searching for “Defect-Tolerant” Photovoltaic Materials: Combined Theoretical and Experimental Screening Brandt, Riley E.; Poindexter, Jeremy R.; Gorai, Prashun Chemistry of Materials, Vol. 29, Issue 11 https://doi.org/10.1021/acs.chemmater.6b05496	journal	May 2017
Strongly Enhanced Photovoltaic Performance and Defect Physics of Air-Stable Bismuth Oxyiodide (BiOI) Hoye, Robert L. Z.; Lee, Lana C.; Kurchin, Rachel C. Advanced Materials, Vol. 29, Issue 36 https://doi.org/10.1002/adma.201702176	journal	July 2017
Erratum: “Transient terahertz photoconductivity measurements of minority-carrier lifetime in tin sulfide thin films: Advanced metrology for an early stage photovoltaic material” [J. Appl. Phys. 119 , 035101 (2016)] Jaramillo, R.; Sher, Meng-Ju; Ofori-Okai, Benjamin K. Journal of Applied Physics, Vol. 119, Issue 24 https://doi.org/10.1063/1.4954931	journal	June 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
High Charge Carrier Mobilities and Lifetimes in Organolead Trihalide Perovskites Wehrenfennig, Christian; Eperon, Giles E.; Johnston, Michael B. Advanced Materials, Vol. 26, Issue 10 https://doi.org/10.1002/adma.201305172	journal	December 2013
Rashba Spin–Orbit Coupling Enhanced Carrier Lifetime in CH ₃ NH ₃ PbI ₃ Zheng, Fan; Tan, Liang Z.; Liu, Shi Nano Letters, Vol. 15, Issue 12 https://doi.org/10.1021/acs.nanolett.5b01854	journal	November 2015
Research Update: Relativistic origin of slow electron-hole recombination in hybrid halide perovskite solar cells Azarhoosh, Pooya; McKechnie, Scott; Frost, Jarvist M. APL Materials, Vol. 4, Issue 9 https://doi.org/10.1063/1.4955028	journal	September 2016
Statistics of the Recombinations of Holes and Electrons Shockley, W.; Read, W. T. Physical Review, Vol. 87, Issue 5 https://doi.org/10.1103/PhysRev.87.835	journal	September 1952
Electron-Hole Recombination in Germanium Hall, R. N. Physical Review, Vol. 87, Issue 2 https://doi.org/10.1103/PhysRev.87.387	journal	July 1952
Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: Case studies for ZnO and GaAs Lany, Stephan; Zunger, Alex Physical Review B, Vol. 78, Issue 23, Article No. 235104 https://doi.org/10.1103/PhysRevB.78.235104	journal	December 2008
First-principles calculations for point defects in solids Freysoldt, Christoph; Grabowski, Blazej; Hickel, Tilmann Reviews of Modern Physics, Vol. 86, Issue 1 https://doi.org/10.1103/RevModPhys.86.253	journal	March 2014
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
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
Correcting density functional theory for accurate predictions of compound enthalpies of formation: Fitted elemental-phase reference energies Stevanović, Vladan; Lany, Stephan; Zhang, Xiuwen Physical Review B, Vol. 85, Issue 11 https://doi.org/10.1103/PhysRevB.85.115104	journal	March 2012
Thermoelectric Performance and Defect Chemistry in n-Type Zintl KGaSb ₄ Ortiz, Brenden R.; Gorai, Prashun; Stevanović, Vladan Chemistry of Materials, Vol. 29, Issue 10 https://doi.org/10.1021/acs.chemmater.7b01217	journal	May 2017
Phase Boundary Mapping to Obtain n-type Mg3Sb2-Based Thermoelectrics Ohno, Saneyuki; Imasato, Kazuki; Anand, Shashwat Joule, Vol. 2, Issue 1 https://doi.org/10.1016/j.joule.2017.11.005	journal	January 2018
First-principles calculation of intrinsic defect chemistry and self-doping in PbTe Goyal, Anuj; Gorai, Prashun; Toberer, Eric S. npj Computational Materials, Vol. 3, Issue 1 https://doi.org/10.1038/s41524-017-0047-6	journal	October 2017
A computational framework for automation of point defect calculations Goyal, Anuj; Gorai, Prashun; Peng, Haowei Computational Materials Science, Vol. 130 https://doi.org/10.1016/j.commatsci.2016.12.040	journal	April 2017
Polaronic hole localization and multiple hole binding of acceptors in oxide wide-gap semiconductors Lany, Stephan; Zunger, Alex Physical Review B, Vol. 80, Issue 8 https://doi.org/10.1103/PhysRevB.80.085202	journal	August 2009
Variations of ionization potential and electron affinity as a function of surface orientation: The case of orthorhombic SnS Stevanović, Vladan; Hartman, Katy; Jaramillo, R. Applied Physics Letters, Vol. 104, Issue 21 https://doi.org/10.1063/1.4879558	journal	May 2014
Defect Engineering of BiI ₃ Single Crystals: Enhanced Electrical and Radiation Performance for Room Temperature Gamma-Ray Detection Han, HyukSu; Hong, Minki; Gokhale, Sasmit S. The Journal of Physical Chemistry C, Vol. 118, Issue 6 https://doi.org/10.1021/jp411201k	journal	January 2014
Vacancies in CdTe: experiment and theory Lany, S.; Ostheimer, V.; Wolf, H. Physica B: Condensed Matter, Vol. 308-310 https://doi.org/10.1016/S0921-4526(01)00841-9	journal	December 2001
Origins of the $p$ -type nature and cation deficiency in ${Cu}_{2} O$ and related materials Raebiger, Hannes; Lany, Stephan; Zunger, Alex Physical Review B, Vol. 76, Issue 4 https://doi.org/10.1103/PhysRevB.76.045209	journal	July 2007
Polymorphism, compressibility and thermal expansion of thallous iodide Samara, G. A.; Walters, L. C.; Northrop, David A. Journal of Physics and Chemistry of Solids, Vol. 28, Issue 10 https://doi.org/10.1016/0022-3697(67)90164-3	journal	October 1967
Stereochemistry of post-transition metal oxides: revision of the classical lone pair model Walsh, Aron; Payne, David J.; Egdell, Russell G. Chemical Society Reviews, Vol. 40, Issue 9 https://doi.org/10.1039/c1cs15098g	journal	January 2011
The Role of Intrinsic Defects in Methylammonium Lead Iodide Perovskite Kim, Jongseob; Lee, Sung-Hoon; Lee, Jung Hoon The Journal of Physical Chemistry Letters, Vol. 5, Issue 8 https://doi.org/10.1021/jz500370k	journal	March 2014
Bismuth chalcohalides and oxyhalides as optoelectronic materials Shi, Hongliang; Ming, Wenmei; Du, Mao-Hua Physical Review B, Vol. 93, Issue 10 https://doi.org/10.1103/PhysRevB.93.104108	journal	March 2016
Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells Frost, Jarvist M.; Butler, Keith T.; Brivio, Federico Nano Letters, Vol. 14, Issue 5 https://doi.org/10.1021/nl500390f	journal	April 2014
Instilling defect tolerance in new compounds Walsh, Aron; Zunger, Alex Nature Materials, Vol. 16, Issue 10 https://doi.org/10.1038/nmat4973	journal	September 2017
An assessment of silver copper sulfides for photovoltaic applications: theoretical and experimental insights Savory, Christopher N.; Ganose, Alex M.; Travis, Will Journal of Materials Chemistry A, Vol. 4, Issue 32 https://doi.org/10.1039/C6TA03376H	journal	January 2016
Identification and design principles of low hole effective mass p-type transparent conducting oxides Hautier, Geoffroy; Miglio, Anna; Ceder, Gerbrand Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3292	journal	August 2013
High-Mobility Bismuth-based Transparent p -Type Oxide from High-Throughput Material Screening Bhatia, Amit; Hautier, Geoffroy; Nilgianskul, Tan Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b03794	journal	December 2015
Structural design principles for low hole effective mass s-orbital-based p-type oxides Ha, Viet-Anh; Ricci, Francesco; Rignanese, Gian-Marco Journal of Materials Chemistry C, Vol. 5, Issue 23 https://doi.org/10.1039/C7TC00528H	journal	January 2017
Intrinsic Instability of Cs ₂ In(I)M(III)X ₆ (M = Bi, Sb; X = Halogen) Double Perovskites: A Combined Density Functional Theory and Experimental Study Xiao, Zewen; Du, Ke-Zhao; Meng, Weiwei Journal of the American Chemical Society, Vol. 139, Issue 17 https://doi.org/10.1021/jacs.7b02227	journal	April 2017
Roles of Pseudo-Closed s ² Orbitals for Different Intrinsic Hole Generation between Tl–Bi and In–Bi Bromide Double Perovskites Xiao, Zewen; Yan, Yanfa; Hosono, Hideo The Journal of Physical Chemistry Letters, Vol. 9, Issue 1 https://doi.org/10.1021/acs.jpclett.7b02949	journal	December 2017
Rational Design: A High-Throughput Computational Screening and Experimental Validation Methodology for Lead-Free and Emergent Hybrid Perovskites Chakraborty, Sudip; Xie, Wei; Mathews, Nripan ACS Energy Letters, Vol. 2, Issue 4 https://doi.org/10.1021/acsenergylett.7b00035	journal	March 2017
Lead-Free Halide Perovskite Solar Cells with High Photocurrents Realized Through Vacancy Modulation Kumar, Mulmudi Hemant; Dharani, Sabba; Leong, Wei Lin Advanced Materials, Vol. 26, Issue 41 https://doi.org/10.1002/adma.201401991	journal	September 2014
Lead-free organic–inorganic tin halide perovskites for photovoltaic applications Noel, Nakita K.; Stranks, Samuel D.; Abate, Antonio Energy Environ. Sci., Vol. 7, Issue 9 https://doi.org/10.1039/C4EE01076K	journal	January 2014
Structure–Band Gap Relationships in Hexagonal Polytypes and Low-Dimensional Structures of Hybrid Tin Iodide Perovskites Stoumpos, Constantinos C.; Mao, Lingling; Malliakas, Christos D. Inorganic Chemistry, Vol. 56, Issue 1 https://doi.org/10.1021/acs.inorgchem.6b02764	journal	December 2016

Cited By (4)

Fast and interpretable classification of small X-ray diffraction datasets using data augmentation and deep neural networks Oviedo, Felipe; Ren, Zekun; Sun, Shijing npj Computational Materials, Vol. 5, Issue 1 https://doi.org/10.1038/s41524-019-0196-x	journal	May 2019
Electronic Structure and Optoelectronic Properties of Bismuth Oxyiodide Robust against Percent‐Level Iodine‐, Oxygen‐, and Bismuth‐Related Surface Defects Huq, Tahmida N.; Lee, Lana C.; Eyre, Lissa Advanced Functional Materials, Vol. 30, Issue 13 https://doi.org/10.1002/adfm.201909983	journal	March 2020
The complex defect chemistry of antimony selenide Savory, Christopher N.; Scanlon, David O. Journal of Materials Chemistry A, Vol. 7, Issue 17 https://doi.org/10.1039/c9ta02022e	journal	January 2019
Fast and interpretable classification of small X-ray diffraction datasets using data augmentation and deep neural networks Oviedo, Felipe; Ren, Zekun; Sun, Shijing arXiv https://doi.org/10.48550/arxiv.1811.08425	preprint	January 2018

Figures / Tables (7)

Similar Records

Shallow halogen vacancies in halide optoelectronic materials

Journal Article · Wed Nov 05 00:00:00 EST 2014 · Physical Review. B, Condensed Matter and Materials Physics · OSTI ID:1476979

Shi, Hongliang; Du, Mao -Hua

Defect Tolerance to Intolerance in the Vacancy-Ordered Double Perovskite Semiconductors Cs₂SnI₆ and Cs₂TeI₆

Journal Article · Tue Jun 28 00:00:00 EDT 2016 · Journal of the American Chemical Society · OSTI ID:1476979

Maughan, Annalise E.; Ganose, Alex M.; Bordelon, Mitchell M.; +3 more

Large dielectric constant, high acceptor density, and deep electron traps in perovskite solar cell material CsGeI₃

Journal Article · Fri Jan 01 00:00:00 EST 2016 · Journal of Materials Chemistry. A · OSTI ID:1476979

Ming, Wenmei; Shi, Hongliang; Du, Mao-Hua

Related Subjects

36 MATERIALS SCIENCE
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
defects
electronic strucutre
semiconductors
halide perovskites