Hydrogen centers and the conductivity of In2O3 single crystals

Yin, Weikai; Smithe, Kirby; Weiser, Philip; Stavola, Michael; Fowler, W. Beall; Boatner, Lynn A.; Pearton, Stephen J.; Hays, David C.; Koch, Sandro G.

doi:10.1103/PhysRevB.91.075208

Title: Hydrogen centers and the conductivity of In₂O₃ single crystals

Abstract

A series of infrared absorption experiments and complementary theory have been performed in order to determine the properties of OH and OD centers in In₂O₃ single crystals. Annealing In₂O₃ samples in H₂ or D₂ at temperatures near 450°C produces an n-type layer ≈0.06mm thick with an n-type doping of 1.6×1019 cm^-3. The resulting free-carrier absorption is correlated with an OH center with a vibrational frequency of 3306 cm^-1 that we associate with interstitial H⁺. Additional O-H (O-D) vibrational lines are assigned to metastable configurations of the interstitial H⁺(D⁺) center and complexes of H (D) with In vacancies. In addition, unlike other oxides studied recently where H trapped at an oxygen vacancy is the dominant shallow donor (ZnO and SnO₂, for example), interstitial H⁺ is found to be the dominant H-related shallow donor in In₂O₃.

Authors:

Yin, Weikai ^[1]; Smithe, Kirby ^[1]; Weiser, Philip ^[1]; Stavola, Michael ^[1]; Fowler, W. Beall ^[1]; Boatner, Lynn A. ^[2]; Pearton, Stephen J. ^[3]; Hays, David C. ^[3]; Koch, Sandro G. ^[4]

Lehigh Univ., Bethlehem, PA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
Univ. of Florida, Gainesville, FL (United States)
Dresden Univ. of Technology (Germany)

Publication Date:: Tue Feb 24 00:00:00 EST 2015

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1286842

Alternate Identifier(s):: OSTI ID: 1181179

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Physical Review B

Additional Journal Information:: Journal Volume: 91; Journal Issue: 7; Journal ID: ISSN 2469-9950

Publisher:: American Physical Society (APS)

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; In2O3; single crystals; Hydrogen

Citation Formats


                    Yin, Weikai, Smithe, Kirby, Weiser, Philip, Stavola, Michael, Fowler, W. Beall, Boatner, Lynn A., Pearton, Stephen J., Hays, David C., and Koch, Sandro G. Hydrogen centers and the conductivity of In2O3 single crystals.  United States: N. p., 2015. 
Web.  doi:10.1103/PhysRevB.91.075208.

Copy to clipboard


                    Yin, Weikai, Smithe, Kirby, Weiser, Philip, Stavola, Michael, Fowler, W. Beall, Boatner, Lynn A., Pearton, Stephen J., Hays, David C., & Koch, Sandro G. Hydrogen centers and the conductivity of In2O3 single crystals.  United States.  https://doi.org/10.1103/PhysRevB.91.075208

Copy to clipboard


                    Yin, Weikai, Smithe, Kirby, Weiser, Philip, Stavola, Michael, Fowler, W. Beall, Boatner, Lynn A., Pearton, Stephen J., Hays, David C., and Koch, Sandro G. Tue .  
"Hydrogen centers and the conductivity of In2O3 single crystals".  United States.  https://doi.org/10.1103/PhysRevB.91.075208.  https://www.osti.gov/servlets/purl/1286842.

Copy to clipboard


                    
@article{osti_1286842,

  title        = {Hydrogen centers and the conductivity of In2O3 single crystals},

  author       = {Yin, Weikai and Smithe, Kirby and Weiser, Philip and Stavola, Michael and Fowler, W. Beall and Boatner, Lynn A. and Pearton, Stephen J. and Hays, David C. and Koch, Sandro G.},

  abstractNote = {A series of infrared absorption experiments and complementary theory have been performed in order to determine the properties of OH and OD centers in In2O3 single crystals. Annealing In2O3 samples in H2 or D2 at temperatures near 450°C produces an n-type layer ≈0.06mm thick with an n-type doping of 1.6×1019 cm-3. The resulting free-carrier absorption is correlated with an OH center with a vibrational frequency of 3306 cm-1 that we associate with interstitial H+. Additional O-H (O-D) vibrational lines are assigned to metastable configurations of the interstitial H+(D+) center and complexes of H (D) with In vacancies. In addition, unlike other oxides studied recently where H trapped at an oxygen vacancy is the dominant shallow donor (ZnO and SnO2, for example), interstitial H+ is found to be the dominant H-related shallow donor in In2O3.},

  doi          = {10.1103/PhysRevB.91.075208},

  journal      = {Physical Review B},

  number       = 7,

  volume       = 91,

  place        = {United States},

  year         = {Tue Feb 24 00:00:00 EST 2015},

  month        = {Tue Feb 24 00:00:00 EST 2015}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (Publisher)

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1103/PhysRevB.91.075208

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 32 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Hydrogen multicentre bonds
journal, December 2006

Janotti, Anderson; Van de Walle, Chris G.
Nature Materials, Vol. 6, Issue 1
DOI: 10.1038/nmat1795

Hydrogenated cation vacancies in semiconducting oxides
journal, August 2011

Varley, J. B.; Peelaers, H.; Janotti, A.
Journal of Physics: Condensed Matter, Vol. 23, Issue 33
DOI: 10.1088/0953-8984/23/33/334212

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

Becke, Axel D.
The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
DOI: 10.1063/1.464913

Conductivity in transparent oxide semiconductors
journal, August 2011

King, P. D. C.; Veal, T. D.
Journal of Physics: Condensed Matter, Vol. 23, Issue 33
DOI: 10.1088/0953-8984/23/33/334214

Hartree-Fock study of phase changes in ZnO at high pressure
journal, September 1993

Jaffe, J. E.; Hess, A. C.
Physical Review B, Vol. 48, Issue 11
DOI: 10.1103/PhysRevB.48.7903

Photoconductive Detection of Tetrahedrally Coordinated Hydrogen in ZnO
journal, April 2012

Koch, S. G.; Lavrov, E. V.; Weber, J.
Physical Review Letters, Vol. 108, Issue 16
DOI: 10.1103/PhysRevLett.108.165501

Hydrogen-doped In₂O₃ as High-mobility Transparent Conductive Oxide
July 2007

Koida, Takashi; Fujiwara, Hiroyuki; Kondo, Michio
DOI: 10.1143/JJAP.46.L685

Behaviour of hydrogen in wide band gap oxides
journal, May 2014

Li, H.; Robertson, J.
Journal of Applied Physics, Vol. 115, Issue 20
DOI: 10.1063/1.4878415

Evaporated Sn‐doped In ₂ O ₃ films: Basic optical properties and applications to energy‐efficient windows
journal, December 1986

Hamberg, I.; Granqvist, C. G.
Journal of Applied Physics, Vol. 60, Issue 11
DOI: 10.1063/1.337534

Special points for Brillouin-zone integrations
journal, June 1976

Monkhorst, Hendrik J.; Pack, James D.
Physical Review B, Vol. 13, Issue 12, p. 5188-5192
DOI: 10.1103/PhysRevB.13.5188

Hydrogen in oxide semiconductors
journal, May 2012

McCluskey, Matthew D.; Tarun, Marianne C.; Teklemichael, Samuel T.
Journal of Materials Research, Vol. 27, Issue 17
DOI: 10.1557/jmr.2012.137

A theoretical method to determine atomic pseudopotentials for electronic structure calculations of molecules and solids
journal, January 1975

Durand, Philippe; Barthelat, Jean-Claude
Theoretica Chimica Acta, Vol. 38, Issue 4
DOI: 10.1007/BF00963468

Semiconducting oxides
journal, August 2011

Catlow, Richard; Walsh, Aron
Journal of Physics: Condensed Matter, Vol. 23, Issue 33
DOI: 10.1088/0953-8984/23/33/330301

Hydrogen impurities and shallow donors in SnO $_{2}$ studied by infrared spectroscopy
journal, July 2011

Bekisli, Figen; Stavola, Michael; Fowler, W. Beall
Physical Review B, Vol. 84, Issue 3
DOI: 10.1103/PhysRevB.84.035213

Electron concentration and mobility in In2O3
journal, January 1977

De Wit, J. H. W.; Van Unen, G.; Lahey, M.
Journal of Physics and Chemistry of Solids, Vol. 38, Issue 8
DOI: 10.1016/0022-3697(77)90117-2

Identification of two hydrogen donors in ZnO
journal, April 2009

Lavrov, E. V.; Herklotz, F.; Weber, J.
Physical Review B, Vol. 79, Issue 16
DOI: 10.1103/PhysRevB.79.165210

Hydrogen as a Cause of Doping in Zinc Oxide
journal, July 2000

Van de Walle, Chris G.
Physical Review Letters, Vol. 85, Issue 5
DOI: 10.1103/PhysRevLett.85.1012

Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980

Krishnan, R.; Binkley, J. S.; Seeger, R.
The Journal of Chemical Physics, Vol. 72, Issue 1
DOI: 10.1063/1.438955

OH ⁻ ions in Oxide Crystals
journal, January 2001

Wöhlecke, M.; Kovács, L.
Critical Reviews in Solid State and Materials Sciences, Vol. 26, Issue 1
DOI: 10.1080/20014091104161

Pseudopotential Hartree-Fock study of seventeen III-V and IV-IV semiconductors
journal, May 1991

Causà, M.; Dovesi, R.; Roetti, C.
Physical Review B, Vol. 43, Issue 14
DOI: 10.1103/PhysRevB.43.11937

Hydrogen donors in ${SnO}_{2}$ studied by infrared spectroscopy and first-principles calculations
journal, November 2010

Hlaing Oo, W. M.; Tabatabaei, S.; McCluskey, M. D.
Physical Review B, Vol. 82, Issue 19
DOI: 10.1103/PhysRevB.82.193201

Electrical Conductivity and Growth of Single‐Crystal Indium Sesquioxide
journal, October 1964

Remeika, J. P.; Spencer, E. G.
Journal of Applied Physics, Vol. 35, Issue 10
DOI: 10.1063/1.1713110

The In‐P‐O Phase Diagram: Construction and Applications
journal, June 1982

Schwartz, G. P.; Sunder, W. A.; Griffiths, J. E.
Journal of The Electrochemical Society, Vol. 129, Issue 6
DOI: 10.1149/1.2124151

Shallow donor state of hydrogen in ${In}_{2} O_{3}$ and ${SnO}_{2}$ : Implications for conductivity in transparent conducting oxides
journal, August 2009

King, P. D. C.; Lichti, R. L.; Celebi, Y. G.
Physical Review B, Vol. 80, Issue 8
DOI: 10.1103/PhysRevB.80.081201

The high temperature behavior of In2O3
journal, March 1975

de Wit, J. H. W.
Journal of Solid State Chemistry, Vol. 13, Issue 3
DOI: 10.1016/0022-4596(75)90118-8

Identification of the native defect doping mechanism in amorphous indium zinc oxide thin films studied using ultra high pressure oxidation
journal, February 2013

Lee, Sunghwan; Paine, David C.
Applied Physics Letters, Vol. 102, Issue 5
DOI: 10.1063/1.4790187

Hydrogen doping in indium oxide: An ab initio study
journal, November 2009

Limpijumnong, Sukit; Reunchan, Pakpoom; Janotti, Anderson
Physical Review B, Vol. 80, Issue 19
DOI: 10.1103/PhysRevB.80.193202

Fundamentals of Semiconductors
book, January 2010

Yu, Peter Y.; Cardona, Manuel
Graduate Texts in Physics
DOI: 10.1007/978-3-642-00710-1

Bulk and surface characterization of In $_{2}$ O $_{3}$ (001) single crystals
journal, March 2012

Hagleitner, Daniel R.; Menhart, Manfred; Jacobson, Peter
Physical Review B, Vol. 85, Issue 11
DOI: 10.1103/PhysRevB.85.115441

n -type doping of oxides by hydrogen
journal, July 2002

Kılıç, Çetin; Zunger, Alex
Applied Physics Letters, Vol. 81, Issue 1
DOI: 10.1063/1.1482783

Works referencing / citing this record:

Diffusivity of the interstitial hydrogen shallow donor in In ₂ O ₃
journal, April 2018

Qin, Ying; Weiser, Philip; Villalta, Karla
Journal of Applied Physics, Vol. 123, Issue 16
DOI: 10.1063/1.4995593

A review of Ga ₂ O ₃ materials, processing, and devices
journal, March 2018

Pearton, S. J.; Yang, Jiancheng; Cary, Patrick H.
Applied Physics Reviews, Vol. 5, Issue 1
DOI: 10.1063/1.5006941

Tutorial: Novel properties of defects in semiconductors revealed by their vibrational spectra
journal, April 2018

Stavola, Michael; Fowler, W. Beall
Journal of Applied Physics, Vol. 123, Issue 16
DOI: 10.1063/1.5011036

Structure and vibrational properties of the dominant O-H center in β-Ga ₂ O ₃
journal, June 2018

Weiser, Philip; Stavola, Michael; Fowler, W. Beall
Applied Physics Letters, Vol. 112, Issue 23
DOI: 10.1063/1.5029921

Similar Records in DOE PAGES and OSTI.GOV collections:

Contrasting the experimental properties of hydrogen in SnO{sub 2}, In{sub 2}O{sub 3}, and TiO{sub 2}

Journal Article Stavola, Michael ; Bekisli, Figen ; Yin, Weikai ; ... - Journal of Applied Physics

IR spectroscopy has been used to investigate the properties of H and D in single crystals of the transparent conducting oxides, SnO{sub 2}, and In{sub 2}O{sub 3}. H introduces several O-H stretching lines and also the broad absorption arising from free carriers. IR spectroscopy has been used to identify the sources of n-type conductivity, its thermal stability, and the reactions of H-containing defects. The properties of OH and OD centers in TiO{sub 2}, while studied for decades, reveal new surprises and properties that are in sharp contrast to the shallow, H-related donors seen in SnO{sub 2} and In{sub 2}O{sub 3}.more »« less
https://doi.org/10.1063/1.4837955
Symmetry and diffusivity of the interstitial hydrogen shallow-donor center in In₂O₃

Journal Article Weiser, Philip ; Qin, Ying ; Yin, Weikai ; ... - Applied Physics Letters

Uniaxial stress experiments performed for the 3306 cm^-1 vibrational line assigned to the interstitial-hydrogen, shallow-donor center in In₂O₃ reveal its symmetry and transition- moment direction. The defect alignment that can be produced by a [001] stress applied at 165 K is due to a process that is also a hydrogen- diffusion jump, providing a microscopic determination of the diffusion constant for H in In₂O₃ and its mechanism. Lastly, our experimental results strongly complement theoretical predictions for the structure and diffusion of the interstitial hydrogen donor center in In₂O₃.
Cited by 11
https://doi.org/10.1063/1.4967943

Full Text Available
Strongly hydrogen-bonded molecular solid, isonicotinic acid: Raman spectra of the -C/sup 16/O/sub 2/H and -C/sup 16/O/sub 2/D species and infrared and Raman spectra of the -C/sup 18/O/sub 2/H acid

Journal Article Spinner, E - J. Phys. Chem.; (United States)

While the infrared spectrum of solid isonicotinic OD acid differs from that of the OH acid by far more than one might expect, that of the /sup 18/OH acid is very similar to that of the /sup 16/OH acid in regard to the broad O-H stretching absorption plateau from ca. 1340 to 660 cm/sup -1/. The /sup 18/O labeling results permit extensive vibrational assignment and show which of the inverted bands (transmission window) are due to intramolecular vibrational coupling and which to coupling across the H...N bond. The Raman spectra mostly do not differ from one another by more thanmore »« less
https://doi.org/10.1021/j100323a014
Hydrogen-related complexes in Li-diffused ZnO single crystals

Journal Article Corolewski, Caleb D. ; Parmar, Narendra S. ; Lynn, Kelvin G. ; ... - Journal of Applied Physics

Zinc oxide (ZnO) is a wide band gap semiconductor and a potential candidate for next generation white solid state lighting applications. In this work, hydrogen-related complexes in lithium diffused ZnO single crystals were studied. In addition to the well-known Li-OH complex, several other hydrogen defects were observed. When a mixture of Li2O and ZnO is used as the dopant source, zinc vacancies are suppressed and the bulk Li concentration is very high (>1019 cm-3). In that case, the predominant hydrogen complex has a vibrational frequency of 3677 cm-1, attributed to surface O-H species. When Li2CO3 is used, a structured bluemore »« less
Cited by 13
https://doi.org/10.1063/1.4959106

Full Text Available
Vibrationally enhanced charge transfer and mode/bond-specific H{sup +} and D{sup +} transfer in the reaction of HOD{sup +} with N{sub 2}O

Journal Article Bell, David M. ; Anderson, Scott L. - Journal of Chemical Physics

The reaction of HOD{sup +} with N{sub 2}O was studied over the collision energy (E{sub col}) range from 0.20 eV to 2.88 eV, for HOD{sup +} in its ground state and in each of its fundamental vibrational states: bend (010), OD stretch (100), and OH stretch (001). The dominant reaction at low E{sub col} is H{sup +} and D{sup +} transfer, but charge transfer becomes dominant for E{sub col} > 0.5 eV. Increasing E{sub col} enhances charge transfer only in the threshold region (E{sub col} < 1 eV), but all modes of HOD{sup +} vibrational excitation enhance this channel overmore »« less
https://doi.org/10.1063/1.4820955

Similar Records

Title: Hydrogen centers and the conductivity of In2O3 single crystals

Abstract

Citation Formats

Hydrogen multicentre bonds journal, December 2006

Hydrogenated cation vacancies in semiconducting oxides journal, August 2011

Density‐functional thermochemistry. III. The role of exact exchange journal, April 1993

Conductivity in transparent oxide semiconductors journal, August 2011

Hartree-Fock study of phase changes in ZnO at high pressure journal, September 1993

Photoconductive Detection of Tetrahedrally Coordinated Hydrogen in ZnO journal, April 2012

Hydrogen-doped In2O3 as High-mobility Transparent Conductive Oxide July 2007

Behaviour of hydrogen in wide band gap oxides journal, May 2014

Evaporated Sn‐doped In 2 O 3 films: Basic optical properties and applications to energy‐efficient windows journal, December 1986

Special points for Brillouin-zone integrations journal, June 1976

Hydrogen in oxide semiconductors journal, May 2012

A theoretical method to determine atomic pseudopotentials for electronic structure calculations of molecules and solids journal, January 1975

Semiconducting oxides journal, August 2011

Hydrogen impurities and shallow donors in SnO 2 studied by infrared spectroscopy journal, July 2011

Electron concentration and mobility in In2O3 journal, January 1977

Identification of two hydrogen donors in ZnO journal, April 2009

Hydrogen as a Cause of Doping in Zinc Oxide journal, July 2000

Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions journal, January 1980

OH − ions in Oxide Crystals journal, January 2001

Pseudopotential Hartree-Fock study of seventeen III-V and IV-IV semiconductors journal, May 1991

Hydrogen donors in SnO 2 studied by infrared spectroscopy and first-principles calculations journal, November 2010

Electrical Conductivity and Growth of Single‐Crystal Indium Sesquioxide journal, October 1964

The In‐P‐O Phase Diagram: Construction and Applications journal, June 1982

Shallow donor state of hydrogen in In 2 O 3 and SnO 2 : Implications for conductivity in transparent conducting oxides journal, August 2009

The high temperature behavior of In2O3 journal, March 1975

Identification of the native defect doping mechanism in amorphous indium zinc oxide thin films studied using ultra high pressure oxidation journal, February 2013

Hydrogen doping in indium oxide: An ab initio study journal, November 2009

Fundamentals of Semiconductors book, January 2010

Bulk and surface characterization of In 2 O 3 (001) single crystals journal, March 2012

n -type doping of oxides by hydrogen journal, July 2002

Diffusivity of the interstitial hydrogen shallow donor in In 2 O 3 journal, April 2018

A review of Ga 2 O 3 materials, processing, and devices journal, March 2018

Tutorial: Novel properties of defects in semiconductors revealed by their vibrational spectra journal, April 2018

Structure and vibrational properties of the dominant O-H center in β-Ga 2 O 3 journal, June 2018

Title: Hydrogen centers and the conductivity of In₂O₃ single crystals

Hydrogen multicentre bonds
journal, December 2006

Hydrogenated cation vacancies in semiconducting oxides
journal, August 2011

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

Conductivity in transparent oxide semiconductors
journal, August 2011

Hartree-Fock study of phase changes in ZnO at high pressure
journal, September 1993

Photoconductive Detection of Tetrahedrally Coordinated Hydrogen in ZnO
journal, April 2012

Hydrogen-doped In₂O₃ as High-mobility Transparent Conductive Oxide
July 2007

Behaviour of hydrogen in wide band gap oxides
journal, May 2014

Evaporated Sn‐doped In ₂ O ₃ films: Basic optical properties and applications to energy‐efficient windows
journal, December 1986

Special points for Brillouin-zone integrations
journal, June 1976

Hydrogen in oxide semiconductors
journal, May 2012

A theoretical method to determine atomic pseudopotentials for electronic structure calculations of molecules and solids
journal, January 1975

Semiconducting oxides
journal, August 2011

Hydrogen impurities and shallow donors in SnO $_{2}$ studied by infrared spectroscopy
journal, July 2011

Electron concentration and mobility in In2O3
journal, January 1977

Identification of two hydrogen donors in ZnO
journal, April 2009

Hydrogen as a Cause of Doping in Zinc Oxide
journal, July 2000

Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980

OH ⁻ ions in Oxide Crystals
journal, January 2001

Pseudopotential Hartree-Fock study of seventeen III-V and IV-IV semiconductors
journal, May 1991

Hydrogen donors in ${SnO}_{2}$ studied by infrared spectroscopy and first-principles calculations
journal, November 2010

Electrical Conductivity and Growth of Single‐Crystal Indium Sesquioxide
journal, October 1964

The In‐P‐O Phase Diagram: Construction and Applications
journal, June 1982

Shallow donor state of hydrogen in ${In}_{2} O_{3}$ and ${SnO}_{2}$ : Implications for conductivity in transparent conducting oxides
journal, August 2009

The high temperature behavior of In2O3
journal, March 1975

Identification of the native defect doping mechanism in amorphous indium zinc oxide thin films studied using ultra high pressure oxidation
journal, February 2013

Hydrogen doping in indium oxide: An ab initio study
journal, November 2009

Fundamentals of Semiconductors
book, January 2010

Bulk and surface characterization of In $_{2}$ O $_{3}$ (001) single crystals
journal, March 2012

n -type doping of oxides by hydrogen
journal, July 2002

Diffusivity of the interstitial hydrogen shallow donor in In ₂ O ₃
journal, April 2018

A review of Ga ₂ O ₃ materials, processing, and devices
journal, March 2018

Tutorial: Novel properties of defects in semiconductors revealed by their vibrational spectra
journal, April 2018

Structure and vibrational properties of the dominant O-H center in β-Ga ₂ O ₃
journal, June 2018