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

Title: Oxidation-Induced Polymerization of InP Surface and Implications for Optoelectronic Applications

Abstract

InP is among the most studied materials for energy-conversion applications including optoelectronics and photoelectrochemical devices. One of the long-standing challenges with this material, and III–V semiconductors more generally, is to understand and control surface oxide formation, which critically impacts device functionality, performance, and durability. In this work, we integrate advanced in situ ambient pressure X-ray photoelectron spectroscopy (APXPS) and ab initio simulations to reveal the mechanism of the oxidation process on the InP(001) surface. By interpreting the APXPS results through direct ab initio spectroscopic calculations of surface models, and by comparing calculated and measured work functions, we provide an unbiased picture of the chemical evolution of the thermal oxide. Furthermore, at low temperatures (<573 K), O2 exposure leads to predominant formation of cross-linked POx units dispersed with submonolayer thickness, which grow into an amorphous two-dimensional (2D) film that is kinetically limited to the surface layer. Increased temperature (>573 K) leads to the polymerization of POx units and the formation of a complex, inhomogeneous 3D network of surface oxide that is progressively indium rich and phosphorus poor toward the surface. Finally, accelerated phosphorus loss via a hitherto unreported coupled charge-transfer isomer transformation mechanism leads to the formation of a thick, amorphousmore » In2O3-like oxide at 773 K with very different optoelectronic and hot carrier transportation properties. In addition to unraveling complex mechanisms of surface oxidation, our results suggest the possibility of deliberately tuning oxide composition by leveraging competition between thermodynamic and kinetic factors.« less

Authors:
ORCiD logo [1];  [2];  [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Notre Dame, IN (United States). Notre Dame Radiation Lab. (NDRL); Univ. of Notre Dame, IN (United States)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1662033
Report Number(s):
LLNL-JRNL-806782
Journal ID: ISSN 1932-7447; 1010884
Grant/Contract Number:  
AC52-07NA27344; FC02-04ER15533
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 51; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; work function; oxides; phosphorus; oxygen; oxidation

Citation Formats

Zhang, Xueqiang, Ogitsu, Tadashi, Wood, Brandon C., Pham, Tuan Anh, and Ptasinska, Sylwia. Oxidation-Induced Polymerization of InP Surface and Implications for Optoelectronic Applications. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.jpcc.9b07260.
Zhang, Xueqiang, Ogitsu, Tadashi, Wood, Brandon C., Pham, Tuan Anh, & Ptasinska, Sylwia. Oxidation-Induced Polymerization of InP Surface and Implications for Optoelectronic Applications. United States. https://doi.org/10.1021/acs.jpcc.9b07260
Zhang, Xueqiang, Ogitsu, Tadashi, Wood, Brandon C., Pham, Tuan Anh, and Ptasinska, Sylwia. Thu . "Oxidation-Induced Polymerization of InP Surface and Implications for Optoelectronic Applications". United States. https://doi.org/10.1021/acs.jpcc.9b07260. https://www.osti.gov/servlets/purl/1662033.
@article{osti_1662033,
title = {Oxidation-Induced Polymerization of InP Surface and Implications for Optoelectronic Applications},
author = {Zhang, Xueqiang and Ogitsu, Tadashi and Wood, Brandon C. and Pham, Tuan Anh and Ptasinska, Sylwia},
abstractNote = {InP is among the most studied materials for energy-conversion applications including optoelectronics and photoelectrochemical devices. One of the long-standing challenges with this material, and III–V semiconductors more generally, is to understand and control surface oxide formation, which critically impacts device functionality, performance, and durability. In this work, we integrate advanced in situ ambient pressure X-ray photoelectron spectroscopy (APXPS) and ab initio simulations to reveal the mechanism of the oxidation process on the InP(001) surface. By interpreting the APXPS results through direct ab initio spectroscopic calculations of surface models, and by comparing calculated and measured work functions, we provide an unbiased picture of the chemical evolution of the thermal oxide. Furthermore, at low temperatures (<573 K), O2 exposure leads to predominant formation of cross-linked POx units dispersed with submonolayer thickness, which grow into an amorphous two-dimensional (2D) film that is kinetically limited to the surface layer. Increased temperature (>573 K) leads to the polymerization of POx units and the formation of a complex, inhomogeneous 3D network of surface oxide that is progressively indium rich and phosphorus poor toward the surface. Finally, accelerated phosphorus loss via a hitherto unreported coupled charge-transfer isomer transformation mechanism leads to the formation of a thick, amorphous In2O3-like oxide at 773 K with very different optoelectronic and hot carrier transportation properties. In addition to unraveling complex mechanisms of surface oxidation, our results suggest the possibility of deliberately tuning oxide composition by leveraging competition between thermodynamic and kinetic factors.},
doi = {10.1021/acs.jpcc.9b07260},
journal = {Journal of Physical Chemistry. C},
number = 51,
volume = 123,
place = {United States},
year = {2019},
month = {11}
}

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

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share: