Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Understanding Cu incorporation in the Cu2xHg2-xGeTe4 structure using resonant x-ray diffraction

Abstract

The ability to control carrier concentration based on the extent of Cu solubility in the Cu2x Hg2-x GeTe4 alloy compound (where 0 ≤ x ≤ 1) makes Cu2x Hg2-x GeTe4 an interesting case study in the field of thermoelectrics. While Cu clearly plays a role in this process, it is unknown exactly how Cu incorporates into the Cu2x Hg2-x GeTe4 crystal structure and how this affects the carrier concentration. In this work, we use a combination of resonant energy x-ray diffraction (REXD) experiments and density functional theory (DFT) calculations to elucidate the nature of Cu incorporation into the Cu2x Hg2-x GeTe4 structure. REXD across the Cuk edge facilitates the characterization of Cu incorporation in the Cu2x Hg2-x GeTe 4 alloy and enables direct quantification of antisite defects. Here, we find that Cu substitutes for Hg at a 2:1 ratio, wherein Cu annihilates a vacancy and swaps with a Hg atom. DFT calculations confirm this result and further indicate that the incorporation of Cu occurs preferentially on one of the z = 1/4 or z = 3/4 planes before filling the other plane. Furthermore, the amount of CuHg antisite defects quantified by REXD was found to be directly proportional to themore » experimentally measured hole concentration, indicating that the CuHg defects are the driving force for tuning carrier concentration in the Cu2x Hg2-x GeTe4 alloy. The link uncovered here between crystal structure, or more specifically antisite defects, and carrier concentration can be extended to similar cation-disordered material systems and will aid the development of improved thermoelectric and other functional materials through defect engineering.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [5];  [6]; ORCiD logo [7]
+ Show Author Affiliations
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., CA (United States)
  2. Colorado School of Mines, Golden, CO (United States); Univ. of California, Santa Barbara, CA (United States)
  3. Univ. of Illinois at Urbana-Champaign, IL (United States); National Center for Supercomputing Applications, Urbana, IL (United States); São Paulo State Univ. (UNESP), São Paulo (Brazil). Inst. de Física Teórica
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Univ. of Illinois at Urbana-Champaign, IL (United States); National Center for Supercomputing Applications, Urbana, IL (United States)
  6. Colorado School of Mines, Golden, CO (United States)
  7. SLAC National Accelerator Lab., Menlo Park, CA (United States); Univ. of Colorado, Boulder, CO (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1768226
Grant/Contract Number:  
1729149; DGE-114747; 1729594; OCI-0725070; ACI-1238993; AC02-76SF00515; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 5; Journal Issue: 1; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Levy-Wendt, Ben L., Ortiz, Brenden R., Gomes, Lídia C., Stone, Kevin H., Passarello, Donata, Ertekin, Elif, Toberer, Eric S., and Toney, Michael F. Understanding Cu incorporation in the Cu2xHg2-xGeTe4 structure using resonant x-ray diffraction. United States: N. p., 2021. Web. doi:10.1103/physrevmaterials.5.015402.
Copy to clipboard
Levy-Wendt, Ben L., Ortiz, Brenden R., Gomes, Lídia C., Stone, Kevin H., Passarello, Donata, Ertekin, Elif, Toberer, Eric S., & Toney, Michael F. Understanding Cu incorporation in the Cu2xHg2-xGeTe4 structure using resonant x-ray diffraction. United States. https://doi.org/10.1103/physrevmaterials.5.015402
Copy to clipboard
Levy-Wendt, Ben L., Ortiz, Brenden R., Gomes, Lídia C., Stone, Kevin H., Passarello, Donata, Ertekin, Elif, Toberer, Eric S., and Toney, Michael F. Fri . "Understanding Cu incorporation in the Cu2xHg2-xGeTe4 structure using resonant x-ray diffraction". United States. https://doi.org/10.1103/physrevmaterials.5.015402. https://www.osti.gov/servlets/purl/1768226.
Copy to clipboard
@article{osti_1768226,
title = {Understanding Cu incorporation in the Cu2xHg2-xGeTe4 structure using resonant x-ray diffraction},
author = {Levy-Wendt, Ben L. and Ortiz, Brenden R. and Gomes, Lídia C. and Stone, Kevin H. and Passarello, Donata and Ertekin, Elif and Toberer, Eric S. and Toney, Michael F.},
abstractNote = {The ability to control carrier concentration based on the extent of Cu solubility in the Cu2x Hg2-x GeTe4 alloy compound (where 0 ≤ x ≤ 1) makes Cu2x Hg2-x GeTe4 an interesting case study in the field of thermoelectrics. While Cu clearly plays a role in this process, it is unknown exactly how Cu incorporates into the Cu2x Hg2-x GeTe4 crystal structure and how this affects the carrier concentration. In this work, we use a combination of resonant energy x-ray diffraction (REXD) experiments and density functional theory (DFT) calculations to elucidate the nature of Cu incorporation into the Cu2x Hg2-x GeTe4 structure. REXD across the Cuk edge facilitates the characterization of Cu incorporation in the Cu2x Hg2-x GeTe 4 alloy and enables direct quantification of antisite defects. Here, we find that Cu substitutes for Hg at a 2:1 ratio, wherein Cu annihilates a vacancy and swaps with a Hg atom. DFT calculations confirm this result and further indicate that the incorporation of Cu occurs preferentially on one of the z = 1/4 or z = 3/4 planes before filling the other plane. Furthermore, the amount of CuHg antisite defects quantified by REXD was found to be directly proportional to the experimentally measured hole concentration, indicating that the CuHg defects are the driving force for tuning carrier concentration in the Cu2x Hg2-x GeTe4 alloy. The link uncovered here between crystal structure, or more specifically antisite defects, and carrier concentration can be extended to similar cation-disordered material systems and will aid the development of improved thermoelectric and other functional materials through defect engineering.},
doi = {10.1103/physrevmaterials.5.015402},
journal = {Physical Review Materials},
number = 1,
volume = 5,
place = {United States},
year = {Fri Jan 15 00:00:00 EST 2021},
month = {Fri Jan 15 00:00:00 EST 2021}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1103/physrevmaterials.5.015402
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

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

Improving Thermoelectric Performance of Chalcogenide Cu 2–2 x CdSnSe 4 by Cu Vacancy
journal, October 2017

  • Zhou, Yun; Chen, Qiufan; Dong, Lihua
  • Nanoscience and Nanotechnology Letters, Vol. 9, Issue 10
  • DOI: 10.1166/nnl.2017.2518

Perfect short-range ordered alloy with line-compound-like properties in the ZnSnN2:ZnO system
journal, May 2020

  • Pan, Jie; Cordell, Jacob J.; Tucker, Garritt J.
  • npj Computational Materials, Vol. 6, Issue 1
  • DOI: 10.1038/s41524-020-0331-8

Projector augmented-wave method
journal, December 1994

Thermoelectric properties of indium doped Cu2CdSnSe4
journal, May 2016

Utilizing Site Disorder in the Development of New Energy-Relevant Semiconductors
journal, June 2020

Thermoelectric properties of Ag 1− x GaTe 2 with chalcopyrite structure
journal, August 2011

  • Yusufu, Aikebaier; Kurosaki, Ken; Kosuga, Atsuko
  • Applied Physics Letters, Vol. 99, Issue 6
  • DOI: 10.1063/1.3617458

Bootstrap Methods for Standard Errors, Confidence Intervals, and Other Measures of Statistical Accuracy
journal, February 1986

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

Quantifying point defects in Cu 2 ZnSn(S,Se) 4 thin films using resonant x-ray diffraction
journal, October 2016

  • Stone, Kevin H.; Christensen, Steven T.; Harvey, Steven P.
  • Applied Physics Letters, Vol. 109, Issue 16
  • DOI: 10.1063/1.4964738

Enhanced thermoelectric performance in Cd doped CuInTe 2 compounds
journal, April 2014

  • Cheng, N.; Liu, R.; Bai, S.
  • Journal of Applied Physics, Vol. 115, Issue 16
  • DOI: 10.1063/1.4872250

Effects of porosity and surface roughness on the X-ray intensity reflected from a powder specimen
journal, October 1972

Improved Thermoelectric Properties of Cu-Doped Quaternary Chalcogenides of Cu 2 CdSnSe 4
journal, October 2009

  • Liu, Min-Ling; Chen, I-Wei; Huang, Fu-Qiang
  • Advanced Materials, Vol. 21, Issue 37
  • DOI: 10.1002/adma.200900409

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

High-temperature thermoelectric properties of Cu 1– x InTe 2 with a chalcopyrite structure
journal, January 2012

  • Kosuga, Atsuko; Plirdpring, Theerayuth; Higashine, Ryosuke
  • Applied Physics Letters, Vol. 100, Issue 4
  • DOI: 10.1063/1.3678044

Phenomenological model of anisotropic peak broadening in powder diffraction
journal, April 1999

Inhomogeneous Electron Gas
journal, November 1964

Resonant X-ray diffraction: `forbidden' Bragg reflections induced by thermal vibrations and point defects
journal, July 2000

  • Dmitrienko, V. E.; Ovchinnikova, E. N.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 56, Issue 4
  • DOI: 10.1107/S0108767300003421

Effects of the Defects on the Thermoelectric Properties of Cu–In–Te Chalcopyrite-Related Compounds
journal, November 2012

  • Kosuga, Atsuko; Higashine, Ryosuke; Plirdpring, Theerayuth
  • Japanese Journal of Applied Physics, Vol. 51
  • DOI: 10.1143/JJAP.51.121803

Carrier density control in Cu 2 HgGeTe 4 and discovery of Hg 2 GeTe 4 via phase boundary mapping
journal, January 2019

  • Ortiz, Brenden R.; Gordiz, Kiarash; Gomes, Lídia C.
  • Journal of Materials Chemistry A, Vol. 7, Issue 2
  • DOI: 10.1039/C8TA10332A

Ultralow Thermal Conductivity in Diamond-Like Semiconductors: Selective Scattering of Phonons from Antisite Defects
journal, May 2018

Bootstrap confidence intervalsCommentCommentCommentCommentRejoinder
journal, September 1996

  • DiCiccio, Thomas J.; Efron, Bradley; Hall, Peter
  • Statistical Science, Vol. 11, Issue 3
  • DOI: 10.1214/ss/1032280214

Thermoelectric transport properties of diamond-like Cu 1−x Fe 1+x S 2 tetrahedral compounds
journal, November 2014

  • Li, Yulong; Zhang, Tiansong; Qin, Yuting
  • Journal of Applied Physics, Vol. 116, Issue 20
  • DOI: 10.1063/1.4902849

The Role of Zn in Chalcopyrite CuFeS 2 : Enhanced Thermoelectric Properties of Cu 1- x Zn x FeS 2 with In Situ Nanoprecipitates
journal, October 2016

  • Xie, Hongyao; Su, Xianli; Zheng, Gang
  • Advanced Energy Materials, Vol. 7, Issue 3
  • DOI: 10.1002/aenm.201601299

Efficiency Enhancement of Cu 2 ZnSn(S,Se) 4 Solar Cells via Alkali Metals Doping
journal, January 2016

  • Hsieh, Yao-Tsung; Han, Qifeng; Jiang, Chengyang
  • Advanced Energy Materials, Vol. 6, Issue 7
  • DOI: 10.1002/aenm.201502386

Point defects in Cu 2 ZnSnSe 4 (CZTSe): Resonant X-ray diffraction study of the low-temperature order/disorder transition : Point defects in Cu
journal, July 2017

  • Schelhas, L. T.; Stone, K. H.; Harvey, S. P.
  • physica status solidi (b), Vol. 254, Issue 9
  • DOI: 10.1002/pssb.201700156

Thermoelectric properties of tetrahedrally bonded wide-gap stannite compounds Cu2ZnSn1−xInxSe4
journal, March 2009

  • Shi, X. Y.; Huang, F. Q.; Liu, M. L.
  • Applied Physics Letters, Vol. 94, Issue 12
  • DOI: 10.1063/1.3103604

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: