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

Title: Antisite Pairs Suppress the Thermal Conductivity of BAs

Abstract

BAs was predicted to have an unusually high thermal conductivity with a room temperature value of 2000 W m –1 K –1, comparable to that of diamond. However, the experimentally measured thermal conductivity of BAs single crystals is still lower than this value. To identify the origin of this large inconsistency, we investigate the lattice structure and potential defects in BAs single crystals at the atomic scale using aberration-corrected scanning transmission electron microscopy (STEM). Rather than finding a large concentration of As vacancies ( V As), as widely thought to dominate the thermal resistance in BAs, our STEM results show an enhanced intensity of some B columns and a reduced intensity of some As columns, suggesting the presence of antisite defects with As B (As atom on a B site) and B As (B atom on an As site). Additional calculations show that the antisite pair with As B next to B As is preferred energetically among the different types of point defects investigated and confirm that such defects lower the thermal conductivity for B As. Using a concentration of 1.8(8)% (6.6 ± 3.0 × 10 20 cm –3 in density) for the antisite pairs estimated from STEM images, themore » thermal conductivity is estimated to be 65–100 W m –1 K –1, in reasonable agreement with our measured value. Our study suggests that As B–B As antisite pairs are the primary lattice defects suppressing thermal conductivity of B As. Possible approaches are proposed for the growth of high-quality crystals or films with high thermal conductivity. In conclusion by employing a combination of state-of-the-art synthesis, STEM characterization, theory, and physical insight, this work models a path toward identifying and understanding defect-limited material functionality.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1474871
Alternate Identifier(s):
OSTI ID: 1468867
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 121; Journal Issue: 10; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Zheng, Qiang, Polanco, Carlos A., Du, Mao -Hua, Lindsay, Lucas R., Chi, Miaofang, Yan, Jiaqiang, and Sales, Brian C. Antisite Pairs Suppress the Thermal Conductivity of BAs. United States: N. p., 2018. Web. doi:10.1103/PhysRevLett.121.105901.
Zheng, Qiang, Polanco, Carlos A., Du, Mao -Hua, Lindsay, Lucas R., Chi, Miaofang, Yan, Jiaqiang, & Sales, Brian C. Antisite Pairs Suppress the Thermal Conductivity of BAs. United States. doi:10.1103/PhysRevLett.121.105901.
Zheng, Qiang, Polanco, Carlos A., Du, Mao -Hua, Lindsay, Lucas R., Chi, Miaofang, Yan, Jiaqiang, and Sales, Brian C. Thu . "Antisite Pairs Suppress the Thermal Conductivity of BAs". United States. doi:10.1103/PhysRevLett.121.105901. https://www.osti.gov/servlets/purl/1474871.
@article{osti_1474871,
title = {Antisite Pairs Suppress the Thermal Conductivity of BAs},
author = {Zheng, Qiang and Polanco, Carlos A. and Du, Mao -Hua and Lindsay, Lucas R. and Chi, Miaofang and Yan, Jiaqiang and Sales, Brian C.},
abstractNote = {BAs was predicted to have an unusually high thermal conductivity with a room temperature value of 2000 W m–1 K–1, comparable to that of diamond. However, the experimentally measured thermal conductivity of BAs single crystals is still lower than this value. To identify the origin of this large inconsistency, we investigate the lattice structure and potential defects in BAs single crystals at the atomic scale using aberration-corrected scanning transmission electron microscopy (STEM). Rather than finding a large concentration of As vacancies (VAs), as widely thought to dominate the thermal resistance in BAs, our STEM results show an enhanced intensity of some B columns and a reduced intensity of some As columns, suggesting the presence of antisite defects with AsB (As atom on a B site) and BAs (B atom on an As site). Additional calculations show that the antisite pair with AsB next to BAs is preferred energetically among the different types of point defects investigated and confirm that such defects lower the thermal conductivity for BAs. Using a concentration of 1.8(8)% (6.6 ± 3.0 × 1020 cm–3 in density) for the antisite pairs estimated from STEM images, the thermal conductivity is estimated to be 65–100 W m–1 K–1, in reasonable agreement with our measured value. Our study suggests that AsB–BAs antisite pairs are the primary lattice defects suppressing thermal conductivity of BAs. Possible approaches are proposed for the growth of high-quality crystals or films with high thermal conductivity. In conclusion by employing a combination of state-of-the-art synthesis, STEM characterization, theory, and physical insight, this work models a path toward identifying and understanding defect-limited material functionality.},
doi = {10.1103/PhysRevLett.121.105901},
journal = {Physical Review Letters},
number = 10,
volume = 121,
place = {United States},
year = {2018},
month = {9}
}

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

Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

Figures / Tables:

FIG. 1 FIG. 1: (a) The crystal structure of BAs in the projection of [001]. Note that each atomic column along this direction is constructed of atoms of a single type. (b) A HAADF image along [001] for a region with thickness of 1.7 nm (∼3.6 unit cells). The thickness for thismore » region was calculated from its EEL spectrum in (c). The intensity profile for the dashed rectangular region in (b) is displayed in (d), revealing AsB antisite defects and intensity weakening for their neighboring As columns. The intensities of the two B columns marked by red asterisks in (d) are 0.38 and 0.19, respectively, revealing 1AsB in each of them, and the intensity difference between them is due to the probe channeling (see details in Fig. S3 in Supplementary Materials [9]).« less

Save / Share:

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Thermal diffusivity of isotopically enriched C 12 diamond
journal, July 1990


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


Ab initio thermal transport in compound semiconductors
journal, April 2013


Effect of nitrogen and vacancy defects on the thermal conductivity of diamond: An ab initio Green's function approach
journal, September 2014


Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

Electronic structure and defect properties of Tl 6 SeI 4 : Density functional calculations
journal, October 2012


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

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


EELS log-ratio technique for specimen-thickness measurement in the TEM
journal, February 1988

  • Malis, T.; Cheng, S. C.; Egerton, R. F.
  • Journal of Electron Microscopy Technique, Vol. 8, Issue 2
  • DOI: 10.1002/jemt.1060080206

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

New group III-group V compounds: BP and BAs
journal, April 1958


Influence of the exchange screening parameter on the performance of screened hybrid functionals
journal, December 2006

  • Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F.
  • The Journal of Chemical Physics, Vol. 125, Issue 22
  • DOI: 10.1063/1.2404663

Ab initio phonon point defect scattering and thermal transport in graphene
journal, January 2018


First-principles prediction of stabilities and instabilities of compounds and alloys in the ternary B-As-P system
journal, July 2017


The B-Li (Boron-Lithium) system
journal, December 2003


QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Phase diagram of the system nickel-boron
journal, February 1967

  • Portnoi, K. I.; Romashov, V. M.; Chubarov, V. M.
  • Soviet Powder Metallurgy and Metal Ceramics, Vol. 6, Issue 2
  • DOI: 10.1007/BF00775639

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


Cluster scattering effects on phonon conduction in graphene
journal, January 2010


Method to extract anharmonic force constants from first principles calculations
journal, April 2008


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


Exceptionally Strong Phonon Scattering by B Substitution in Cubic SiC
journal, August 2017


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


Thermal conductivity of isotopically modified graphene
journal, January 2012

  • Chen, Shanshan; Wu, Qingzhi; Mishra, Columbia
  • Nature Materials, Vol. 11, Issue 3
  • DOI: 10.1038/nmat3207

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


Semiconducting icosahedral boron arsenide crystal growth for neutron detection
journal, March 2011


Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: Case studies for ZnO and GaAs
journal, December 2008


Three-Dimensional Imaging of Individual Dopant Atoms in SrTiO 3
journal, December 2013


Ab initio study of the unusual thermal transport properties of boron arsenide and related materials
journal, December 2013


Crystal Growth and Properties of Boron Monoarsenide
journal, February 1972

  • Chu, T. L.; Hyslop, A. E.
  • Journal of Applied Physics, Vol. 43, Issue 2
  • DOI: 10.1063/1.1661106

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

Emerging challenges and materials for thermal management of electronics
journal, May 2014


An electron microscope for the aberration-corrected era
journal, February 2008


Quantitative STEM Imaging of Order-Disorder Phenomena in Double Perovskite Thin Films
journal, October 2016


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


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


The crystal structure of the ф phase in the boron-sodium system
journal, January 1970


Effects of electron channeling in HAADF-STEM intensity in La2CuSnO6
journal, March 2009


    Works referencing / citing this record:

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


      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.