skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In2O3 nanowires

Abstract

We demonstrate here defect induced changes on the morphology and surface properties of indium oxide (In2O3) nanowires and further study their effects on the near-band-edge (NBE) emission, thereby showing the significant influence of surface states on In2O3 nanostructure based device characteristics for potential optoelectronic applications. In2O3 nanowires with cubic crystal structure (c-In2O3) were synthesized via carbothermal reduction technique using a gold-catalyst-assisted vapor–liquid–solid method. Onset of strong optical absorption could be observed at energies greater than 3.5 eV consistent with highly n-type characteristics due to unintentional doping from oxygen vacancy (VO) defects as confirmed using Raman spectroscopy. A combination of high resolution transmission electron microscopy, x-ray photoelectron spectroscopy and valence band analysis on the nanowire morphology and stoichiometry reveals presence of high-density of VO defects on the surface of the nanowires. As a result, chemisorbed oxygen species can be observed leading to upward band bending at the surface which corresponds to a smaller valence band offset of 2.15 eV. Temperature dependent photoluminescence (PL) spectroscopy was used to study the nature of the defect states and the influence of the surface states on the electronic band structure and NBE emission has been discussed. Lastly, our data reveals significant broadening of the NBEmore » PL peak consistent with impurity band broadening leading to band-tailing effect from heavy doping.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [2];  [2];  [1];  [1]
  1. Univ. of Illinois at Chicago, Chicago, IL (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Air Force Research Laboratory (AFRL), Air Force Office of Scientific Research (AFOSR); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1430710
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nanotechnology
Additional Journal Information:
Journal Volume: 29; Journal Issue: 17; Journal ID: ISSN 0957-4484
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; indium oxide; nanowires; vapor–liquid–solid method; defects; near-band-edge emission; degenerate; photoluminesence broadening

Citation Formats

Mukherjee, Souvik, Sarkar, Ketaki, Wiederrecht, Gary P., Schaller, Richard D., Gosztola, David J., Stroscio, Michael A., and Dutta, Mitra. Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In2O3 nanowires. United States: N. p., 2018. Web. doi:10.1088/1361-6528/aaaf34.
Mukherjee, Souvik, Sarkar, Ketaki, Wiederrecht, Gary P., Schaller, Richard D., Gosztola, David J., Stroscio, Michael A., & Dutta, Mitra. Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In2O3 nanowires. United States. doi:10.1088/1361-6528/aaaf34.
Mukherjee, Souvik, Sarkar, Ketaki, Wiederrecht, Gary P., Schaller, Richard D., Gosztola, David J., Stroscio, Michael A., and Dutta, Mitra. Thu . "Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In2O3 nanowires". United States. doi:10.1088/1361-6528/aaaf34. https://www.osti.gov/servlets/purl/1430710.
@article{osti_1430710,
title = {Defect induced structural inhomogeneity, ultraviolet light emission and near-band-edge photoluminescence broadening in degenerate In2O3 nanowires},
author = {Mukherjee, Souvik and Sarkar, Ketaki and Wiederrecht, Gary P. and Schaller, Richard D. and Gosztola, David J. and Stroscio, Michael A. and Dutta, Mitra},
abstractNote = {We demonstrate here defect induced changes on the morphology and surface properties of indium oxide (In2O3) nanowires and further study their effects on the near-band-edge (NBE) emission, thereby showing the significant influence of surface states on In2O3 nanostructure based device characteristics for potential optoelectronic applications. In2O3 nanowires with cubic crystal structure (c-In2O3) were synthesized via carbothermal reduction technique using a gold-catalyst-assisted vapor–liquid–solid method. Onset of strong optical absorption could be observed at energies greater than 3.5 eV consistent with highly n-type characteristics due to unintentional doping from oxygen vacancy (VO) defects as confirmed using Raman spectroscopy. A combination of high resolution transmission electron microscopy, x-ray photoelectron spectroscopy and valence band analysis on the nanowire morphology and stoichiometry reveals presence of high-density of VO defects on the surface of the nanowires. As a result, chemisorbed oxygen species can be observed leading to upward band bending at the surface which corresponds to a smaller valence band offset of 2.15 eV. Temperature dependent photoluminescence (PL) spectroscopy was used to study the nature of the defect states and the influence of the surface states on the electronic band structure and NBE emission has been discussed. Lastly, our data reveals significant broadening of the NBE PL peak consistent with impurity band broadening leading to band-tailing effect from heavy doping.},
doi = {10.1088/1361-6528/aaaf34},
journal = {Nanotechnology},
number = 17,
volume = 29,
place = {United States},
year = {2018},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Room-temperature ultraviolet-emitting In2O3 nanowires
journal, July 2003

  • Cao, Huaqiang; Qiu, Xianqing; Liang, Yu
  • Applied Physics Letters, Vol. 83, Issue 4
  • DOI: 10.1063/1.1596372

Band tail-induced photoluminescence broadening in heavily In-doped n-type ZnO nanowires
journal, January 2015

  • He, H. P.; Wang, Z.; Duan, H. F.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 27
  • DOI: 10.1039/c5cp02934a

The Carrier Concentration Dependence of the Debye Temperature θ in Heavily Doped n-Ge
journal, September 1972


Observation of ultraviolet emission and effect of surface states on the luminescence from tin oxide nanowires
journal, March 2009

  • Kar, Ayan; Stroscio, Michael A.; Dutta, Mitra
  • Applied Physics Letters, Vol. 94, Issue 10
  • DOI: 10.1063/1.3097011

Indium oxide—a transparent, wide-band gap semiconductor for (opto)electronic applications
journal, January 2015


Direct Optical Observation of Band-Edge Excitons, Band Gap, and Fermi Level in Degenerate Semiconducting Oxide Nanowires In 2 O 3
journal, November 2011

  • Ho, Ching-Hwa; Chan, Ching-Hsiang; Tien, Li-Chia
  • The Journal of Physical Chemistry C, Vol. 115, Issue 50
  • DOI: 10.1021/jp208789t

Thermodynamic stability, stoichiometry, and electronic structure of bcc-In 2 O 3 surfaces
journal, July 2011


Growth Mechanism and Photoluminescence Properties of In 2 O 3 Nanotowers
journal, May 2010

  • Jean, Sen-Tsun; Her, Yung-Chiun
  • Crystal Growth & Design, Vol. 10, Issue 5
  • DOI: 10.1021/cg9011839

Phase stability, electronic structure, and optical properties of indium oxide polytypes
journal, August 2007


Growth of In2O3(100) on Y-stabilized ZrO2(100) by O-plasma assisted molecular beam epitaxy
journal, March 2008

  • Bourlange, A.; Payne, D. J.; Egdell, R. G.
  • Applied Physics Letters, Vol. 92, Issue 9
  • DOI: 10.1063/1.2889500

Broadening of Impurity Bands in Heavily Doped Semiconductors
journal, July 1965


Nature of the Band Gap of In 2 O 3 Revealed by First-Principles Calculations and X-Ray Spectroscopy
journal, April 2008


Transparent conducting oxide semiconductors for transparent electrodes
journal, March 2005


Surface Treatment and Doping Dependence of In 2 O 3 Nanowires as Ammonia Sensors
journal, November 2003

  • Li, Chao; Zhang, Daihua; Lei, Bo
  • The Journal of Physical Chemistry B, Vol. 107, Issue 45
  • DOI: 10.1021/jp0361531

Selectively enhanced UV and NIR photoluminescence from a degenerate ZnO nanorod array film
journal, January 2014

  • Zhu, Qiang; Xie, Changsheng; Li, Huayao
  • Journal of Materials Chemistry C, Vol. 2, Issue 23
  • DOI: 10.1039/c4tc00011k

Oxygen Vacancy Driven Modulations in In 2 O 3 Pyramidal Beaded Nanowires
journal, September 2012

  • Hafeez, Muhammad; Zhai, Tianyou; Bhatti, Arshad S.
  • Crystal Growth & Design, Vol. 12, Issue 10
  • DOI: 10.1021/cg300870y

Doping dependent NH3 sensing of indium oxide nanowires
journal, September 2003

  • Zhang, Daihua; Li, Chao; Liu, Xiaolei
  • Applied Physics Letters, Vol. 83, Issue 9
  • DOI: 10.1063/1.1604194

Indium and tin oxide nanowires by vapor-liquid-solid growth technique
journal, February 2006

  • Nguyen, Pho; Vaddiraju, Sreeram; Meyyappan, M.
  • Journal of Electronic Materials, Vol. 35, Issue 2
  • DOI: 10.1007/bf02692436

Broadening of near-band-gap photoluminescence in n-GaN films
journal, July 1998

  • Iliopoulos, E.; Doppalapudi, D.; Ng, H. M.
  • Applied Physics Letters, Vol. 73, Issue 3
  • DOI: 10.1063/1.121839

Surface versus bulk electronic/defect structures of transparent conducting oxides: I. Indium oxide and ITO
journal, September 2006

  • Harvey, S. P.; Mason, T. O.; Gassenbauer, Y.
  • Journal of Physics D: Applied Physics, Vol. 39, Issue 18
  • DOI: 10.1088/0022-3727/39/18/006

Enhanced optical properties due to indium incorporation in zinc oxide nanowires
journal, January 2016

  • Farid, S.; Mukherjee, S.; Sarkar, K.
  • Applied Physics Letters, Vol. 108, Issue 2
  • DOI: 10.1063/1.4939454

Zinc‐indium‐oxide: A high conductivity transparent conducting oxide
journal, October 1995

  • Phillips, Julia M.; Cava, R. J.; Thomas, G. A.
  • Applied Physics Letters, Vol. 67, Issue 15
  • DOI: 10.1063/1.115118

Band-gap renormalization and band filling in Si-doped GaN films studied by photoluminescence spectroscopy
journal, October 1999

  • Yoshikawa, M.; Kunzer, M.; Wagner, J.
  • Journal of Applied Physics, Vol. 86, Issue 8
  • DOI: 10.1063/1.371377

The stability of ionic crystal surfaces
journal, November 1979


Band gap, electronic structure, and surface electron accumulation of cubic and rhombohedral In 2 O 3
journal, May 2009


Ultraviolet light emission and excitonic fine structures in ultrathin single-crystalline indium oxide nanowires
journal, January 2010

  • Wei, Z. P.; Guo, D. L.; Liu, B.
  • Applied Physics Letters, Vol. 96, Issue 3
  • DOI: 10.1063/1.3284654

In 2 O 3 Nanotowers:  Controlled Synthesis and Mechanism Analysis
journal, May 2007

  • Yan, You-Guo; Zhang, Ye; Zeng, Hai-Bo
  • Crystal Growth & Design, Vol. 7, Issue 5
  • DOI: 10.1021/cg0607194

Experimental determination of valence band maxima for SrTiO[sub 3], TiO[sub 2], and SrO and the associated valence band offsets with Si(001)
journal, January 2004

  • Chambers, S. A.; Droubay, T.; Kaspar, T. C.
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 22, Issue 4
  • DOI: 10.1116/1.1768525

Controlled Synthesis of In 2 O 3 Octahedrons and Nanowires
journal, July 2005

  • Hao, Yufeng; Meng, Guowen; Ye, Changhui
  • Crystal Growth & Design, Vol. 5, Issue 4
  • DOI: 10.1021/cg050103z

Temperature dependence of the energy gap in semiconductors
journal, January 1967


Thermodynamic stability, stoichiometry, and electronic structure of bcc-In 2 O 3 surfaces
journal, July 2011


Band gap, electronic structure, and surface electron accumulation of cubic and rhombohedral In 2 O 3
journal, May 2009


Nature of the Band Gap of In 2 O 3 Revealed by First-Principles Calculations and X-Ray Spectroscopy
journal, April 2008


Phase stability, electronic structure, and optical properties of indium oxide polytypes
journal, August 2007


Indium and tin oxide nanowires by vapor-liquid-solid growth technique
journal, February 2006

  • Nguyen, Pho; Vaddiraju, Sreeram; Meyyappan, M.
  • Journal of Electronic Materials, Vol. 35, Issue 2
  • DOI: 10.1007/BF02692436

Band tail-induced photoluminescence broadening in heavily In-doped n-type ZnO nanowires
journal, January 2015

  • He, H. P.; Wang, Z.; Duan, H. F.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 27
  • DOI: 10.1039/C5CP02934A

Broadening of Impurity Bands in Heavily Doped Semiconductors
journal, July 1965