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

Title: Impurity-derived p-type conductivity in cubic boron arsenide

Abstract

Cubic boron arsenide (c-BAs) exhibits an ultrahigh thermal conductivity (κ) approaching 1300 Wm-1 K-1 at room temperature. However, c-BAs is believed to incorporate high concentrations of crystal imperfections that can both quench κ and act as sources of unintentional p-type conductivity. Although this behavior has been attributed to native defects, we show here, using optical and magnetic resonance spectroscopies together with first-principles calculations, that unintentional acceptor impurities such as silicon and/or carbon are more likely candidates for causing the observed conductivity. These results also clarify that the true low-temperature bandgap of c-BAs is 0.3 eV higher than the widely reported value of ~1.5 eV. Low-temperature photoluminescence measurements of c-BAs crystals reveal impurity-related recombination processes (including donor-acceptor pair recombination), and electron paramagnetic resonance experiments show evidence for effective mass-like shallow acceptors. Our hybrid density functional calculations indicate that native defects are incapable of giving rise to such signals. Instead, we find that group-IV impurities readily incorporate on the As site and act as shallow acceptors. Finally, such impurities can dominate the electrical properties of c-BAs, and their influence on phonon scattering must be considered when optimizing thermal conductivity.

Authors:
 [1];  [2];  [1];  [1];  [1]; ORCiD logo [3];  [3];  [3];  [3];  [3]
  1. Naval Research Lab. (NRL), Washington, DC (United States)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  3. Univ. of Houston, Houston, TX (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); US Department of the Navy, Office of Naval Research (ONR); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1545270
Alternate Identifier(s):
OSTI ID: 1577944
Report Number(s):
LLNL-JRNL-792285
Journal ID: ISSN 0003-6951
Grant/Contract Number:  
AC52-07NA27344; N00014-16-1-2436
Resource Type:
Accepted Manuscript
Journal Name:
Applied Physics Letters
Additional Journal Information:
Journal Volume: 113; Journal Issue: 25; Journal ID: ISSN 0003-6951
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; Materials science

Citation Formats

Lyons, John L., Varley, Joel B., Glaser, Evan R., Freitas, Jaime A., Culbertson, James C., Tian, Fei, Gamage, Geethal Amila, Sun, Haoran, Ziyaee, Hamidreza, and Ren, Zhifeng. Impurity-derived p-type conductivity in cubic boron arsenide. United States: N. p., 2018. Web. doi:10.1063/1.5058134.
Lyons, John L., Varley, Joel B., Glaser, Evan R., Freitas, Jaime A., Culbertson, James C., Tian, Fei, Gamage, Geethal Amila, Sun, Haoran, Ziyaee, Hamidreza, & Ren, Zhifeng. Impurity-derived p-type conductivity in cubic boron arsenide. United States. doi:10.1063/1.5058134.
Lyons, John L., Varley, Joel B., Glaser, Evan R., Freitas, Jaime A., Culbertson, James C., Tian, Fei, Gamage, Geethal Amila, Sun, Haoran, Ziyaee, Hamidreza, and Ren, Zhifeng. Thu . "Impurity-derived p-type conductivity in cubic boron arsenide". United States. doi:10.1063/1.5058134. https://www.osti.gov/servlets/purl/1545270.
@article{osti_1545270,
title = {Impurity-derived p-type conductivity in cubic boron arsenide},
author = {Lyons, John L. and Varley, Joel B. and Glaser, Evan R. and Freitas, Jaime A. and Culbertson, James C. and Tian, Fei and Gamage, Geethal Amila and Sun, Haoran and Ziyaee, Hamidreza and Ren, Zhifeng},
abstractNote = {Cubic boron arsenide (c-BAs) exhibits an ultrahigh thermal conductivity (κ) approaching 1300 Wm-1 K-1 at room temperature. However, c-BAs is believed to incorporate high concentrations of crystal imperfections that can both quench κ and act as sources of unintentional p-type conductivity. Although this behavior has been attributed to native defects, we show here, using optical and magnetic resonance spectroscopies together with first-principles calculations, that unintentional acceptor impurities such as silicon and/or carbon are more likely candidates for causing the observed conductivity. These results also clarify that the true low-temperature bandgap of c-BAs is 0.3 eV higher than the widely reported value of ~1.5 eV. Low-temperature photoluminescence measurements of c-BAs crystals reveal impurity-related recombination processes (including donor-acceptor pair recombination), and electron paramagnetic resonance experiments show evidence for effective mass-like shallow acceptors. Our hybrid density functional calculations indicate that native defects are incapable of giving rise to such signals. Instead, we find that group-IV impurities readily incorporate on the As site and act as shallow acceptors. Finally, such impurities can dominate the electrical properties of c-BAs, and their influence on phonon scattering must be considered when optimizing thermal conductivity.},
doi = {10.1063/1.5058134},
journal = {Applied Physics Letters},
number = 25,
volume = 113,
place = {United States},
year = {2018},
month = {12}
}

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

Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Unusual high thermal conductivity in boron arsenide bulk crystals
journal, July 2018


Paramagnetic Resonance Absorption from Acceptors in Silicon
journal, October 1960


Simultaneously high electron and hole mobilities in cubic boron-V compounds: BP, BAs, and BSb
journal, August 2018


Projector augmented-wave method
journal, December 1994


Seeded growth of boron arsenide single crystals with high thermal conductivity
journal, January 2018

  • Tian, Fei; Song, Bai; Lv, Bing
  • Applied Physics Letters, Vol. 112, Issue 3
  • DOI: 10.1063/1.5004200

Four-phonon scattering significantly reduces intrinsic thermal conductivity of solids
journal, October 2017


Thermal and thermoelectric transport measurements of an individual boron arsenide microstructure
journal, May 2016

  • Kim, Jaehyun; Evans, Daniel A.; Sellan, Daniel P.
  • Applied Physics Letters, Vol. 108, Issue 20
  • DOI: 10.1063/1.4950970

Electrostatic interactions between charged defects in supercells
journal, December 2010

  • Freysoldt, Christoph; Neugebauer, Jörg; Van de Walle, Chris G.
  • physica status solidi (b), Vol. 248, Issue 5
  • DOI: 10.1002/pssb.201046289

Electronic structure of BAs and boride III-V alloys
journal, November 2000


Fully Ab Initio Finite-Size Corrections for Charged-Defect Supercell Calculations
journal, January 2009


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


The bond ionicity in ANB8−N compounds from maximally localized Wannier functions
journal, July 2015


First-principles calculations for point defects in solids
journal, March 2014

  • Freysoldt, Christoph; Grabowski, Blazej; Hickel, Tilmann
  • Reviews of Modern Physics, Vol. 86, Issue 1
  • DOI: 10.1103/RevModPhys.86.253

Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013

  • Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy
  • APL Materials, Vol. 1, Issue 1
  • DOI: 10.1063/1.4812323

Ab initio study of the effect of vacancies on the thermal conductivity of boron arsenide
journal, July 2016


Preparation and Properties of Boron Arsenide Films
journal, January 1974

  • Chu, T. L.; Hyslop, A. E.
  • Journal of The Electrochemical Society, Vol. 121, Issue 3
  • DOI: 10.1149/1.2401826

First-Principles Determination of Ultrahigh Thermal Conductivity of Boron Arsenide: A Competitor for Diamond?
journal, July 2013


Antisite Pairs Suppress the Thermal Conductivity of BAs
journal, September 2018


Experimental observation of high thermal conductivity in boron arsenide
journal, July 2018


Electron paramagnetic resonance of boron acceptors in isotopically purified silicon
journal, April 2010


The chips are down for Moore’s law
journal, February 2016


Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
journal, June 2006

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 124, Issue 21
  • DOI: 10.1063/1.2204597

Descriptor-Based Approach for the Prediction of Cation Vacancy Formation Energies and Transition Levels
journal, October 2017

  • Varley, Joel B.; Samanta, Amit; Lordi, Vincenzo
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 20
  • DOI: 10.1021/acs.jpclett.7b02333

Point defects and dopants of boron arsenide from first-principles calculations: Donor compensation and doping asymmetry
journal, November 2018

  • Chae, S.; Mengle, K.; Heron, J. T.
  • Applied Physics Letters, Vol. 113, Issue 21
  • DOI: 10.1063/1.5062267

Experimental study of the proposed super-thermal-conductor: BAs
journal, February 2015

  • Lv, Bing; Lan, Yucheng; Wang, Xiqu
  • Applied Physics Letters, Vol. 106, Issue 7
  • DOI: 10.1063/1.4913441

Synthesis and Characterization of a p-Type Boron Arsenide Photoelectrode
journal, June 2012

  • Wang, Shijun; Swingle, Sarah F.; Ye, Heechang
  • Journal of the American Chemical Society, Vol. 134, Issue 27
  • DOI: 10.1021/ja301765v

Gas-pressure chemical vapor transport growth of millimeter-sized c-BAs single crystals with moderate thermal conductivity
journal, June 2018

  • Xing, Jie; Glaser, Evan R.; Song, Bai
  • Applied Physics Letters, Vol. 112, Issue 24
  • DOI: 10.1063/1.5034787

Boron arsenide phonon dispersion from inelastic x-ray scattering: Potential for ultrahigh thermal conductivity
journal, December 2016


Pair Spectra and "Edge" Emission in Gallium Phosphide
journal, January 1964


Multimillimeter-sized cubic boron arsenide grown by chemical vapor transport via a tellurium tetraiodide transport agent
journal, June 2018

  • Xing, Jie; Chen, Xi; Zhou, Yuanyuan
  • Applied Physics Letters, Vol. 112, Issue 26
  • DOI: 10.1063/1.5038025

Thermal conductivity of isotopically modified single crystal diamond
journal, June 1993


High thermal conductivity in cubic boron arsenide crystals
journal, July 2018


Calculated electronic, transport, and related properties of zinc blende boron arsenide (zb-BAs)
journal, October 2016

  • Nwigboji, Ifeanyi H.; Malozovsky, Yuriy; Franklin, Lashounda
  • Journal of Applied Physics, Vol. 120, Issue 14
  • DOI: 10.1063/1.4964421

Inter-impurity recombinations in semiconductors
journal, January 1973


    Works referencing / citing this record:

    Electronic band structure and optical properties of boron arsenide
    journal, May 2019