Role of point defects in the electrical and optical properties of In2O3

Chatratin, Intuon; Sabino, Fernando P.; Reunchan, Pakpoom; Limpijumnong, Sukit; Varley, Joel B.; Van de Walle, Chris G.; Janotti, Anderson

doi:10.1103/PhysRevMaterials.3.074604

Title: Role of point defects in the electrical and optical properties of ${In}_{2} O_{3}$

Journal Article · 29 July 2019 · Physical Review Materials

DOI: https://doi.org/10.1103/PhysRevMaterials.3.074604 · OSTI ID:1577946

Chatratin, Intuon ^[1]; Sabino, Fernando P. ^[2];

^[3]; Limpijumnong, Sukit ^[4]; Varley, Joel B. ^[5]; Van de Walle, Chris G. ^[6]; Janotti, Anderson ^[2]

Univ. of Delaware, Newark, DE (United States); Kasetsart Univ., Bangkok (Thailand)
Univ. of Delaware, Newark, DE (United States)
Kasetsart Univ., Bangkok (Thailand); Thailand Center of Excellence in Physics (ThEP Center), Bangkok (Thailand)
The Inst. for the Promotion of Teaching Science and Technology, Bangkok (Thailand)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Univ. of California, Santa Barbara, CA (United States)

Using hybrid density-functional calculations we investigate the effects of native point defects on the electrical and optical properties of In₂O₃. We analyze formation energies, transition levels, and local lattice relaxations for all native point defects. We find that donor defects are in general more energetically favorable than acceptor defects, except near O-rich conditions, where oxygen interstitials and indium vacancies have low formation energy in n-type In₂O₃. The oxygen vacancy is the lowest-energy donor defect with transition level (2+/+) slightly below and (+/0) slightly above the conduction-band minimum (CBM), with a predicted luminescence peak at 2.3 eV associated with the transition $$V$$ $$^{0}_{O}$$ → $$V$$ $$^{+}_{O}$$. Despite being a shallow donor, the oxygen vacancy becomes electrically inactive for Fermi levels at or higher than ~0.1 eV above the CBM. As a result, this indicates that conductivity due to oxygen vacancies will saturate at rather low carrier concentrations when compared to typical carrier concentrations required for transparent conducting oxides in many device applications.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1577946

Report Number(s):: LLNL-JRNL--792281; 990446

Journal Information:: Physical Review Materials, Journal Name: Physical Review Materials Journal Issue: 7 Vol. 3; ISSN PRMHAR; ISSN 2475-9953

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

References (61)

On the nature and temperature dependence of the fundamental band gap of In ₂ O ₃ : Nature and temperature dependence of the fundamental band gap of In Irmscher, K.; Naumann, M.; Pietsch, M. physica status solidi (a), Vol. 211, Issue 1 https://doi.org/10.1002/pssa.201330184	journal	September 2013
Plasma-assisted molecular beam epitaxy of Sn-doped In ₂ O ₃ : Sn incorporation, structural changes, doping limits, and compensation : Plasma-assisted molecular beam epitaxy of Sn-doped In Bierwagen, Oliver; Speck, James S. physica status solidi (a), Vol. 211, Issue 1 https://doi.org/10.1002/pssa.201330224	journal	October 2013
Electrical and Optical Properties of Sputtered In2O3 films. I. Electrical Properties and Intrinsic Absorption Müller, H. K. Physica Status Solidi (b), Vol. 27, Issue 2 https://doi.org/10.1002/pssb.19680270229	journal	January 1968
Electron concentration and mobility in In2O3 De Wit, J. H. W.; Van Unen, G.; Lahey, M. Journal of Physics and Chemistry of Solids, Vol. 38, Issue 8 https://doi.org/10.1016/0022-3697(77)90117-2	journal	January 1977
Electrical properties of In2O3 De Wit, J. H. W. Journal of Solid State Chemistry, Vol. 8, Issue 2 https://doi.org/10.1016/0022-4596(73)90007-8	journal	October 1973
Electron concentration and mobility in In2O3 de Wit, J. H. W.; van Unen, G.; Lahey, M. Solid State Communications, Vol. 21, Issue 12 https://doi.org/10.1016/0038-1098(77)90346-5	journal	March 1977
Transparent conductors—A status review Chopra, K. L.; Major, S.; Pandya, D. K. Thin Solid Films, Vol. 102, Issue 1 https://doi.org/10.1016/0040-6090(83)90256-0	journal	April 1983
Study of the effect of the oxygen partial pressure on the properties of rf reactive magnetron sputtered tin-doped indium oxide films Meng, Li-jian; dos Santos, M. P. Applied Surface Science, Vol. 120, Issue 3-4 https://doi.org/10.1016/S0169-4332(97)00224-9	journal	December 1997
Vacancy defects in indium oxide: An ab-initio study Reunchan, Pakpoom; Zhou, Xin; Limpijumnong, Sukit Current Applied Physics, Vol. 11, Issue 3 https://doi.org/10.1016/j.cap.2011.03.051	journal	May 2011
Dopant chemical potential modulation on oxygen vacancies formation in In2O3: A comparative density functional study Yu, Zhi Gen; Sun, Jian; Sullivan, Michael B. Chemical Physics Letters, Vol. 621 https://doi.org/10.1016/j.cplett.2015.01.008	journal	February 2015
Effect of nitrogen annealing on the structural, optical and photoluminescence properties of In2O3 thin films Beji, Nasreddine; Reghima, Meriem; Souli, Mehdi Journal of Alloys and Compounds, Vol. 675 https://doi.org/10.1016/j.jallcom.2016.03.115	journal	August 2016
Melt growth, characterization and properties of bulk In2O3 single crystals Galazka, Z.; Uecker, R.; Irmscher, K. Journal of Crystal Growth, Vol. 362 https://doi.org/10.1016/j.jcrysgro.2011.10.029	journal	January 2013
A novel crystal growth technique from the melt: Levitation-Assisted Self-Seeding Crystal Growth Method Galazka, Zbigniew; Uecker, Reinhard; Fornari, Roberto Journal of Crystal Growth, Vol. 388 https://doi.org/10.1016/j.jcrysgro.2013.11.049	journal	February 2014
Epitaxial Sb-doped SnO2 and Sn-doped In2O3 transparent conducting oxide contacts on GaN-based light emitting diodes Tsai, Min-Ying; Bierwagen, Oliver; Speck, James S. Thin Solid Films, Vol. 605 https://doi.org/10.1016/j.tsf.2015.09.022	journal	April 2016
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets Chen, Ruyi; Cui, Qirui; Liao, Liyang Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23414-3	journal	May 2021
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-58835-5	journal	February 2020
Thermodynamics of native defects in In ₂ O ₃ crystals using a first-principles method Liu, Jian; Liu, Tingyu; Liu, Fengming RSC Adv., Vol. 4, Issue 70 https://doi.org/10.1039/C4RA07046A	journal	January 2014
Defect formation in In ₂ O ₃ and SnO ₂ : a new atomistic approach based on accurate lattice energies Hou, Qing; Buckeridge, John; Lazauskas, Tomas Journal of Materials Chemistry C, Vol. 6, Issue 45 https://doi.org/10.1039/C8TC04760J	journal	January 2018
Precise measurements of oxygen content: Oxygen vacancies in transparent conducting indium oxide films Bellingham, J. R.; Mackenzie, A. P.; Phillips, W. A. Applied Physics Letters, Vol. 58, Issue 22 https://doi.org/10.1063/1.104858	journal	June 1991
Low‐resistivity transparent In ₂ O ₃ films prepared by reactive ion plating Jeong, J. I.; Moon, J. H.; Hong, J. H. Applied Physics Letters, Vol. 64, Issue 10 https://doi.org/10.1063/1.110893	journal	March 1994
Hybrid functionals based on a screened Coulomb potential Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 118, Issue 18 https://doi.org/10.1063/1.1564060	journal	May 2003
Electrical Properties of Single Crystals of Indium Oxide Weiher, R. L. Journal of Applied Physics, Vol. 33, Issue 9 https://doi.org/10.1063/1.1702560	journal	September 1962
Optical Properties of Indium Oxide Weiher, R. L.; Ley, R. P. Journal of Applied Physics, Vol. 37, Issue 1 https://doi.org/10.1063/1.1707830	journal	January 1966
Substitutional diatomic molecules NO, NC, CO, N2, and O2: Their vibrational frequencies and effects on p doping of ZnO Limpijumnong, Sukit; Li, Xiaonan; Wei, Su-Huai Applied Physics Letters, Vol. 86, Issue 21 https://doi.org/10.1063/1.1931823	journal	May 2005
The origin of n-type conductivity in undoped In2O3 Tomita, Takumi; Yamashita, Kazuyoshi; Hayafuji, Yoshinori Applied Physics Letters, Vol. 87, Issue 5 https://doi.org/10.1063/1.2001741	journal	August 2005
Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)] Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 124, Issue 21 https://doi.org/10.1063/1.2204597	journal	June 2006
Growth of In2O3(100) on Y-stabilized ZrO2(100) by O-plasma assisted molecular beam epitaxy Bourlange, A.; Payne, D. J.; Egdell, R. G. Applied Physics Letters, Vol. 92, Issue 9 https://doi.org/10.1063/1.2889500	journal	March 2008
Evaporated Sn‐doped In ₂ O ₃ films: Basic optical properties and applications to energy‐efficient windows Hamberg, I.; Granqvist, C. G. Journal of Applied Physics, Vol. 60, Issue 11 https://doi.org/10.1063/1.337534	journal	December 1986
Limits for n-type doping in In2O3 and SnO2: A theoretical approach by first-principles calculations using hybrid-functional methodology Ágoston, Péter; Körber, Christoph; Klein, Andreas Journal of Applied Physics, Vol. 108, Issue 5 https://doi.org/10.1063/1.3467780	journal	September 2010
High electron mobility In2O3(001) and (111) thin films with nondegenerate electron concentration Bierwagen, Oliver; Speck, James S. Applied Physics Letters, Vol. 97, Issue 7 https://doi.org/10.1063/1.3480416	journal	August 2010
Transport and angular resolved photoemission measurements of the electronic properties of In ₂ O ₃ bulk single crystals Scherer, V.; Janowitz, C.; Krapf, A. Applied Physics Letters, Vol. 100, Issue 21 https://doi.org/10.1063/1.4719665	journal	May 2012
Indium oxide—a transparent, wide-band gap semiconductor for (opto)electronic applications Bierwagen, Oliver Semiconductor Science and Technology, Vol. 30, Issue 2 https://doi.org/10.1088/0268-1242/30/2/024001	journal	January 2015
Geometry, electronic structure and thermodynamic stability of intrinsic point defects in indium oxide Ágoston, Péter; Erhart, Paul; Klein, Andreas Journal of Physics: Condensed Matter, Vol. 21, Issue 45 https://doi.org/10.1088/0953-8984/21/45/455801	journal	October 2009
Hydrogenated cation vacancies in semiconducting oxides Varley, J. B.; Peelaers, H.; Janotti, A. Journal of Physics: Condensed Matter, Vol. 23, Issue 33 https://doi.org/10.1088/0953-8984/23/33/334212	journal	August 2011
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
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
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Effects of cation d states on the structural and electronic properties of III-nitride and II-oxide wide-band-gap semiconductors Janotti, Anderson; Segev, David; Van de Walle, Chris G. Physical Review B, Vol. 74, Issue 4 https://doi.org/10.1103/PhysRevB.74.045202	journal	July 2006
Native point defects in ZnO Janotti, Anderson; Van de Walle, Chris G. Physical Review B, Vol. 76, Issue 16 https://doi.org/10.1103/PhysRevB.76.165202	journal	October 2007
Defect energetics in ZnO: A hybrid Hartree-Fock density functional study Oba, Fumiyasu; Togo, Atsushi; Tanaka, Isao Physical Review B, Vol. 77, Issue 24 https://doi.org/10.1103/PhysRevB.77.245202	journal	June 2008
Band gap, electronic structure, and surface electron accumulation of cubic and rhombohedral In 2 O 3 King, P. D. C.; Veal, T. D.; Fuchs, F. Physical Review B, Vol. 79, Issue 20 https://doi.org/10.1103/PhysRevB.79.205211	journal	May 2009
Hydrogen doping in indium oxide: An ab initio study Limpijumnong, Sukit; Reunchan, Pakpoom; Janotti, Anderson Physical Review B, Vol. 80, Issue 19 https://doi.org/10.1103/PhysRevB.80.193202	journal	November 2009
Ab initio modeling of diffusion in indium oxide Ágoston, Péter; Albe, Karsten Physical Review B, Vol. 81, Issue 19 https://doi.org/10.1103/PhysRevB.81.195205	journal	May 2010
Role of self-trapping in luminescence and p -type conductivity of wide-band-gap oxides Varley, J. B.; Janotti, A.; Franchini, C. Physical Review B, Vol. 85, Issue 8 https://doi.org/10.1103/PhysRevB.85.081109	journal	February 2012
Comparative study of defect transition energy calculation methods: The case of oxygen vacancy in In 2 O 3 and ZnO Yin, Wan-Jian; Ma, Jie; Wei, Su-Huai Physical Review B, Vol. 86, Issue 4 https://doi.org/10.1103/PhysRevB.86.045211	journal	July 2012
Electrical transport, electrothermal transport, and effective electron mass in single-crystalline In 2 O 3 films Preissler, Natalie; Bierwagen, Oliver; Ramu, Ashok T. Physical Review B, Vol. 88, Issue 8 https://doi.org/10.1103/PhysRevB.88.085305	journal	August 2013
Polymorphism of indium oxide: Materials physics of orthorhombic In 2 O 3 Walsh, Aron; Scanlon, David O. Physical Review B, Vol. 88, Issue 16 https://doi.org/10.1103/PhysRevB.88.161201	journal	October 2013
Compensating vacancy defects in Sn- and Mg-doped In 2 O 3 Korhonen, E.; Tuomisto, F.; Bierwagen, O. Physical Review B, Vol. 90, Issue 24 https://doi.org/10.1103/PhysRevB.90.245307	journal	December 2014
Origin of and tuning the optical and fundamental band gaps in transparent conducting oxides: The case of M 2 O 3 ( M = Al , Ga , In ) Sabino, Fernando P.; Besse, Rafael; Oliveira, Luiz Nunes Physical Review B, Vol. 92, Issue 20 https://doi.org/10.1103/PhysRevB.92.205308	journal	November 2015
Many-electron effects on the dielectric function of cubic In 2 O 3 : Effective electron mass, band nonparabolicity, band gap renormalization, and Burstein-Moss shift Feneberg, Martin; Nixdorf, Jakob; Lidig, Christian Physical Review B, Vol. 93, Issue 4 https://doi.org/10.1103/PhysRevB.93.045203	journal	January 2016
Nature of the Band Gap of In 2 O 3 Revealed by First-Principles Calculations and X-Ray Spectroscopy Walsh, Aron; Da Silva, Juarez L. F.; Wei, Su-Huai Physical Review Letters, Vol. 100, Issue 16 https://doi.org/10.1103/PhysRevLett.100.167402	journal	April 2008
Sources of Electrical Conductivity in SnO 2 Singh, Abhishek Kumar; Janotti, Anderson; Scheffler, Matthias Physical Review Letters, Vol. 101, Issue 5 https://doi.org/10.1103/PhysRevLett.101.055502	journal	July 2008
Fully Ab Initio Finite-Size Corrections for Charged-Defect Supercell Calculations Freysoldt, Christoph; Neugebauer, Jörg; Van de Walle, Chris G. Physical Review Letters, Vol. 102, Issue 1 https://doi.org/10.1103/PhysRevLett.102.016402	journal	January 2009
Intrinsic n -Type Behavior in Transparent Conducting Oxides: A Comparative Hybrid-Functional Study of In 2 O 3 , SnO 2 , and ZnO Ágoston, Péter; Albe, Karsten; Nieminen, Risto M. Physical Review Letters, Vol. 103, Issue 24 https://doi.org/10.1103/PhysRevLett.103.245501	journal	December 2009
Dopability, Intrinsic Conductivity, and Nonstoichiometry of Transparent Conducting Oxides Lany, Stephan; Zunger, Alex Physical Review Letters, Vol. 98, Issue 4 https://doi.org/10.1103/PhysRevLett.98.045501	journal	January 2007
Deep vs shallow nature of oxygen vacancies and consequent n -type carrier concentrations in transparent conducting oxides Buckeridge, J.; Catlow, C. R. A.; Farrow, M. R. Physical Review Materials, Vol. 2, Issue 5 https://doi.org/10.1103/PhysRevMaterials.2.054604	journal	May 2018
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
Refinement of the crystal structure of In ₂ O ₃ at two wavelengths Marezio, M. Acta Crystallographica, Vol. 20, Issue 6 https://doi.org/10.1107/S0365110X66001749	journal	November 1966
First-Principles Calculations of Anion Vacancies in Oxides and Nitrides Tanaka, Isao; Tatsumi, Kazuyoshi; Nakano, Masanobu Journal of the American Ceramic Society, Vol. 85, Issue 1 https://doi.org/10.1111/j.1151-2916.2002.tb00041.x	journal	January 2002
Transparent Conducting Oxides Ginley, David S.; Bright, Clark MRS Bulletin, Vol. 25, Issue 8 https://doi.org/10.1557/mrs2000.256	journal	August 2000

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