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

Title: Metastable rocksalt ZnO is p -type dopable

Abstract

Despite decades of efforts, achieving p-type conductivity in the wide band gap ZnO in its ground-state wurtzite structure continues to be a challenge. Here we detail how p-type ZnO can be realized in a known metastable, high-pressure rocksalt phase (also wide-gap) with Li as an external dopant. Using modern defect theory, we predict Li to dope the rocksalt phase p-type by preferentially substituting for Zn and introducing shallow acceptor levels, resulting in predicted hole concentrations to exceed 1019cm-3. Formation of compensating donors like interstitial Li and unintentional hydrogen, ubiquitous in wurtzite phase, is inhibited by the close-packed nature of the rocksalt polymorph. Also, relatively high absolute valence band edge of rocksalt ZnO benefits low hole effective masses and hole delocalization. In addition to the technological significance, our results reveal polymorphism as a promising route to overcome strong doping asymmetry of wide band gap oxides.

Authors:
 [1];  [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1476978
Alternate Identifier(s):
OSTI ID: 1465234
Report Number(s):
NREL/JA-5K00-72568
Journal ID: ISSN 2475-9953; PRMHAR
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 8; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; defects; electronic structure; first-principles calculations; semiconductors; structural properties

Citation Formats

Goyal, Anuj, and Stevanović, Vladan. Metastable rocksalt ZnO is p -type dopable. United States: N. p., 2018. Web. doi:10.1103/PhysRevMaterials.2.084603.
Goyal, Anuj, & Stevanović, Vladan. Metastable rocksalt ZnO is p -type dopable. United States. doi:10.1103/PhysRevMaterials.2.084603.
Goyal, Anuj, and Stevanović, Vladan. Mon . "Metastable rocksalt ZnO is p -type dopable". United States. doi:10.1103/PhysRevMaterials.2.084603. https://www.osti.gov/servlets/purl/1476978.
@article{osti_1476978,
title = {Metastable rocksalt ZnO is p -type dopable},
author = {Goyal, Anuj and Stevanović, Vladan},
abstractNote = {Despite decades of efforts, achieving p-type conductivity in the wide band gap ZnO in its ground-state wurtzite structure continues to be a challenge. Here we detail how p-type ZnO can be realized in a known metastable, high-pressure rocksalt phase (also wide-gap) with Li as an external dopant. Using modern defect theory, we predict Li to dope the rocksalt phase p-type by preferentially substituting for Zn and introducing shallow acceptor levels, resulting in predicted hole concentrations to exceed 1019cm-3. Formation of compensating donors like interstitial Li and unintentional hydrogen, ubiquitous in wurtzite phase, is inhibited by the close-packed nature of the rocksalt polymorph. Also, relatively high absolute valence band edge of rocksalt ZnO benefits low hole effective masses and hole delocalization. In addition to the technological significance, our results reveal polymorphism as a promising route to overcome strong doping asymmetry of wide band gap oxides.},
doi = {10.1103/PhysRevMaterials.2.084603},
journal = {Physical Review Materials},
issn = {2475-9953},
number = 8,
volume = 2,
place = {United States},
year = {2018},
month = {8}
}

Works referenced in this record:

Trapping of cubic ZnO nanocrystallites at ambient conditions
journal, December 2002

  • Decremps, F.; Pellicer-Porres, J.; Datchi, F.
  • Applied Physics Letters, Vol. 81, Issue 25
  • DOI: 10.1063/1.1527696

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

A computational framework for automation of point defect calculations
journal, April 2017


Carbon nanomaterials for electronics, optoelectronics, photovoltaics, and sensing
journal, January 2013

  • Jariwala, Deep; Sangwan, Vinod K.; Lauhon, Lincoln J.
  • Chem. Soc. Rev., Vol. 42, Issue 7
  • DOI: 10.1039/C2CS35335K

A phenomenological model for systematization and prediction of doping limits in II–VI and I–III–VI2 compounds
journal, March 1998

  • Zhang, S. B.; Wei, Su-Huai; Zunger, Alex
  • Journal of Applied Physics, Vol. 83, Issue 6
  • DOI: 10.1063/1.367120

Non-equilibrium origin of high electrical conductivity in gallium zinc oxide thin films
journal, December 2013

  • Zakutayev, Andriy; Perry, Nicola H.; Mason, Thomas O.
  • Applied Physics Letters, Vol. 103, Issue 23
  • DOI: 10.1063/1.4841355

Surprising stability of neutral interstitial hydrogen in diamond and cubic BN
journal, January 2016


Projector augmented-wave method
journal, December 1994


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

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


A New Carbon Allotrope with Six-Fold Helical Chains in all-sp2 Bonding Networks
journal, March 2014

  • Wang, Jian-Tao; Chen, Changfeng; Wang, Enge
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep04339

APPLIED PHYSICS: Transparent Electronics
journal, May 2003


Fundamentals of zinc oxide as a semiconductor
journal, October 2009


Solids, liquids, and gases under high pressure
journal, March 2018


Nobel Lecture: Background story of the invention of efficient blue InGaN light emitting diodes
journal, October 2015


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

Acceptors in ZnO
journal, March 2015

  • McCluskey, Matthew D.; Corolewski, Caleb D.; Lv, Jinpeng
  • Journal of Applied Physics, Vol. 117, Issue 11
  • DOI: 10.1063/1.4913827

Momentum-space formalism for the total energy of solids
journal, November 1979


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

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


Origin of p -type doping difficulty in ZnO: The impurity perspective
journal, August 2002


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

p -type semiconducting properties in lithium-doped MgO single crystals
journal, October 2002


Effects of hole localization on limiting p -type conductivity in oxide and nitride semiconductors
journal, January 2014

  • Lyons, J. L.; Janotti, A.; Van de Walle, C. G.
  • Journal of Applied Physics, Vol. 115, Issue 1
  • DOI: 10.1063/1.4838075

Perspective: Oxide molecular-beam epitaxy rocks!
journal, June 2015


Synthesis and thermal stability of cubic ZnO in the salt nanocomposites
journal, February 2010

  • Sokolov, P. S.; Baranov, A. N.; Dobrokhotov, Zh. V.
  • Russian Chemical Bulletin, Vol. 59, Issue 2
  • DOI: 10.1007/s11172-010-0082-7

Growth and stability of rocksalt Zn 1−x Mg x O epilayers and ZnO/MgO superlattice on MgO (100) substrate by molecular beam epitaxy
journal, June 2016

  • Lu, C. -Y. James; Tu, Y. -T.; Yan, T.
  • The Journal of Chemical Physics, Vol. 144, Issue 21
  • DOI: 10.1063/1.4950885

High-pressure zinc oxide phase as visible-light-active photocatalyst with narrow band gap
journal, January 2017

  • Razavi-Khosroshahi, Hadi; Edalati, Kaveh; Wu, Ji
  • Journal of Materials Chemistry A, Vol. 5, Issue 38
  • DOI: 10.1039/C7TA05262F

Assessing capability of semiconductors to split water using ionization potentials and electron affinities only
journal, January 2014

  • Stevanović, Vladan; Lany, Stephan; Ginley, David S.
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 8
  • DOI: 10.1039/c3cp54589j

Polaronic hole localization and multiple hole binding of acceptors in oxide wide-gap semiconductors
journal, August 2009


A hybrid density functional study of lithium in ZnO: Stability, ionization levels, and diffusion
journal, November 2009


The formation of a rock-salt type ZnO thin film by low-level alloying with MgO
journal, May 2004


Correcting density functional theory for accurate predictions of compound enthalpies of formation: Fitted elemental-phase reference energies
journal, March 2012


P-type electrical conduction in transparent thin films of CuAlO2
journal, October 1997

  • Kawazoe, Hiroshi; Yasukawa, Masahiro; Hyodo, Hiroyuki
  • Nature, Vol. 389, Issue 6654
  • DOI: 10.1038/40087

A comprehensive review of ZnO materials and devices
journal, August 2005

  • Özgür, Ü.; Alivov, Ya. I.; Liu, C.
  • Journal of Applied Physics, Vol. 98, Issue 4
  • DOI: 10.1063/1.1992666

Identifying defect-tolerant semiconductors with high minority-carrier lifetimes: beyond hybrid lead halide perovskites
journal, May 2015

  • Brandt, Riley E.; Stevanović, Vladan; Ginley, David S.
  • MRS Communications, Vol. 5, Issue 2
  • DOI: 10.1557/mrc.2015.26

Invisible circuits
journal, October 1997


First-principles calculation of intrinsic defect chemistry and self-doping in PbTe
journal, October 2017


Universal alignment of hydrogen levels in semiconductors, insulators and solutions
journal, June 2003


Energetics of quaternary III-V alloys described by incorporation and clustering of impurities
journal, September 2009


Dual nature of acceptors in GaN and ZnO: The curious case of the shallow MgGa deep state
journal, April 2010

  • Lany, Stephan; Zunger, Alex
  • Applied Physics Letters, Vol. 96, Issue 14
  • DOI: 10.1063/1.3383236