Enhanced Thermoelectric Properties of Cu2ZnSnSe4 with Ga-doping

Wei, Kaya; Beauchemin, Laura; Wang, Hsin; Porter, Wallace D.; Martin, Joshua; Nolas, George S.

doi:10.1016/j.jallcom.2015.08.046

Title: Enhanced Thermoelectric Properties of Cu₂ZnSnSe₄ with Ga-doping

Abstract

Gallium doped Cu₂ZnSnSe₄ quaternary chalcogenides with and without excess Cu were synthesized by elemental reaction and densified using hot pressing in order to investigate their high temperature thermoelectric properties. The resistivity, , and Seebeck coefficient, S, for these materials decrease with increased Ga-doping while both mobility and effective mass increase with Ga doping. The power factor (S²/ρ) therefore increases with Ga-doping. The highest thermoelectric figure of merit (ZT = 0.39 at 700 K) was obtained for the composition that had the lowest thermal conductivity. Our results suggest an approach to achieving optimized thermoelectric properties and are part of the continuing effort to explore different quaternary chalcogenide compositions and structure types, as this class of materials continues to be of interest for thermoelectrics applications.

Authors:

Wei, Kaya ^[1]; Beauchemin, Laura ^[1]; Wang, Hsin ^[2]; Porter, Wallace D. ^[2]; Martin, Joshua ^[3]; Nolas, George S. ^[1]

Univ. of South Florida, Tampa, FL (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)

Publication Date:: Mon Aug 10 00:00:00 EDT 2015

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)

OSTI Identifier:: 1265657

Alternate Identifier(s):: OSTI ID: 1250202

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Alloys and Compounds

Additional Journal Information:: Journal Volume: 650; Journal ID: ISSN 0925-8388

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; quaternary chalcogenides; thermoelectric properties; gallium doping

Citation Formats


                    Wei, Kaya, Beauchemin, Laura, Wang, Hsin, Porter, Wallace D., Martin, Joshua, and Nolas, George S. Enhanced Thermoelectric Properties of Cu2ZnSnSe4 with Ga-doping.  United States: N. p., 2015. 
Web.  doi:10.1016/j.jallcom.2015.08.046.

Copy to clipboard


                    Wei, Kaya, Beauchemin, Laura, Wang, Hsin, Porter, Wallace D., Martin, Joshua, & Nolas, George S. Enhanced Thermoelectric Properties of Cu2ZnSnSe4 with Ga-doping.  United States.  https://doi.org/10.1016/j.jallcom.2015.08.046

Copy to clipboard


                    Wei, Kaya, Beauchemin, Laura, Wang, Hsin, Porter, Wallace D., Martin, Joshua, and Nolas, George S. Mon .  
"Enhanced Thermoelectric Properties of Cu2ZnSnSe4 with Ga-doping".  United States.  https://doi.org/10.1016/j.jallcom.2015.08.046.  https://www.osti.gov/servlets/purl/1265657.

Copy to clipboard


                    
@article{osti_1265657,

  title        = {Enhanced Thermoelectric Properties of Cu2ZnSnSe4 with Ga-doping},

  author       = {Wei, Kaya and Beauchemin, Laura and Wang, Hsin and Porter, Wallace D. and Martin, Joshua and Nolas, George S.},

  abstractNote = {Gallium doped Cu2ZnSnSe4 quaternary chalcogenides with and without excess Cu were synthesized by elemental reaction and densified using hot pressing in order to investigate their high temperature thermoelectric properties. The resistivity, , and Seebeck coefficient, S, for these materials decrease with increased Ga-doping while both mobility and effective mass increase with Ga doping. The power factor (S2/ρ) therefore increases with Ga-doping. The highest thermoelectric figure of merit (ZT = 0.39 at 700 K) was obtained for the composition that had the lowest thermal conductivity. Our results suggest an approach to achieving optimized thermoelectric properties and are part of the continuing effort to explore different quaternary chalcogenide compositions and structure types, as this class of materials continues to be of interest for thermoelectrics applications.},

  doi          = {10.1016/j.jallcom.2015.08.046},

  journal      = {Journal of Alloys and Compounds},

  number       = ,

  volume       = 650,

  place        = {United States},

  year         = {Mon Aug 10 00:00:00 EDT 2015},

  month        = {Mon Aug 10 00:00:00 EDT 2015}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (Publisher)

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1016/j.jallcom.2015.08.046

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 32 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Figure of merit for thermoelectrics
journal, February 1989

Mahan, G. D.
Journal of Applied Physics, Vol. 65, Issue 4
DOI: 10.1063/1.342976

Structural, thermodynamical and optical properties of Cu2-II-IV-VI4 quaternary compounds
journal, April 2005

Matsushita, H.; Ichikawa, T.; Katsui, A.
Journal of Materials Science, Vol. 40, Issue 8
DOI: 10.1007/s10853-005-1223-5

Synthesis and thermoelectric properties of Cu excess Cu ₂ ZnSnSe ₄ : Synthesis and thermoelectric properties of Cu excess Cu
journal, November 2013

Dong, Yongkwan; Wang, Hsin; Nolas, George S.
physica status solidi (RRL) - Rapid Research Letters, Vol. 8, Issue 1
DOI: 10.1002/pssr.201308274

Synthesis, Crystal Structure, and High Temperature Transport Properties of p -Type Cu ₂ Zn _{1– x} Fe _x SnSe ₄
journal, November 2013

Dong, Yongkwan; Wang, Hsin; Nolas, George S.
Inorganic Chemistry, Vol. 52, Issue 24
DOI: 10.1021/ic402455x

Cu ₂ ZnGeSe ₄ Nanocrystals: Synthesis and Thermoelectric Properties
journal, February 2012

Ibáñez, Maria; Zamani, Reza; LaLonde, Aaron
Journal of the American Chemical Society, Vol. 134, Issue 9
DOI: 10.1021/ja211952z

Phonon Scattering through a Local Anisotropic Structural Disorder in the Thermoelectric Solid Solution Cu ₂ Zn _{1– x} Fe _x GeSe ₄
journal, December 2012

Zeier, Wolfgang G.; Pei, Yanzhong; Pomrehn, Gregory
Journal of the American Chemical Society, Vol. 135, Issue 2
DOI: 10.1021/ja308627v

A wide-band-gap p-type thermoelectric material based on quaternary chalcogenides of Cu2ZnSnQ4 (Q=S,Se)
journal, May 2009

Liu, Min-Ling; Huang, Fu-Qiang; Chen, Li-Dong
Applied Physics Letters, Vol. 94, Issue 20
DOI: 10.1063/1.3130718

Composition Control and Thermoelectric Properties of Quaternary Chalcogenide Nanocrystals: The Case of Stannite Cu ₂ CdSnSe ₄
journal, December 2011

Ibáñez, Maria; Cadavid, Doris; Zamani, Reza
Chemistry of Materials, Vol. 24, Issue 3
DOI: 10.1021/cm2031812

The effect of multisubstitution on the thermoelectric properties of chalcogenide-based Cu _2.1 Zn _0.9 Sn _{1− x} In _x Se ₄ (0 ≤ x ≤ 0.1): Thermoelectric properties of chalcogenide-based Cu _2.1 Zn _0.9 Sn _{1− x} In _x Se ₄
journal, August 2013

Chetty, Raju; Falmbigl, Matthias; Rogl, Peter
physica status solidi (a), Vol. 210, Issue 11
DOI: 10.1002/pssa.201329264

Electrical conduction and mobility enhancement in p-type In-doped Cu ₂ ZnSnSe ₄ bulks
journal, February 2014

Kuo, Dong-Hau; Tsega, Moges
Japanese Journal of Applied Physics, Vol. 53, Issue 3
DOI: 10.7567/JJAP.53.035801

Thermoelectric properties of chalcogenide based Cu _2+x ZnSn _1−x Se ₄
journal, March 2013

Raju, Ch.; Falmbigl, M.; Rogl, P.
AIP Advances, Vol. 3, Issue 3
DOI: 10.1063/1.4794733

Transport Properties of Bulk Thermoelectrics: An International Round-Robin Study, Part II: Thermal Diffusivity, Specific Heat, and Thermal Conductivity
journal, March 2013

Wang, Hsin; Porter, Wallace D.; Böttner, Harald
Journal of Electronic Materials, Vol. 42, Issue 6
DOI: 10.1007/s11664-013-2516-0

The crystal structure of kesterite type compounds: A neutron and X-ray diffraction study
journal, June 2011

Schorr, Susan
Solar Energy Materials and Solar Cells, Vol. 95, Issue 6
DOI: 10.1016/j.solmat.2011.01.002

Time-resolved recombination analysis in kesterite polycrystalline thin films and photovoltaic devices with one-photon and two-photon excitation
journal, May 2015

Kuciauskas, Darius; Repins, Ingrid; Kanevce, Ana
Solar Energy Materials and Solar Cells, Vol. 136
DOI: 10.1016/j.solmat.2014.12.038

Photoelectrical properties of surfactant-free kesterite Cu2ZnSnSe4 hydrophilic nanocrystal ink and the stability in polar solvents
journal, August 2014

Kush, Priya; Deka, Sasanka
Journal of Nanoparticle Research, Vol. 16, Issue 9
DOI: 10.1007/s11051-014-2600-2

Fermi-Dirac functions of integral order
journal, December 1950

Rhodes, P.
Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 204, Issue 1078, p. 396-405
DOI: 10.1098/rspa.1950.0183

The Computation of Fermi-Dirac Functions
journal, February 1938

McDougall, J.; Stoner, E. C.
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 237, Issue 773
DOI: 10.1098/rsta.1938.0004

Works referencing / citing this record:

Quaternary chalcogenides: Promising thermoelectric material and recent progress
journal, July 2019

Wang, Teng; Huo, Taichang; Wang, Hongchao
Science China Materials, Vol. 63, Issue 1
DOI: 10.1007/s40843-019-9467-2

Enhanced thermoelectric performance through grain boundary engineering in quaternary chalcogenide Cu ₂ ZnSnSe ₄
journal, April 2018

Zhu, Yingcai; Liu, Yong; Tan, Xing
AIP Advances, Vol. 8, Issue 4
DOI: 10.1063/1.5025482

Synthesis, transport properties and electronic structure of p-type Cu _1+x Mn _2−x InTe ₄ ( x = 0, 0.2, 0.3)
journal, January 2020

Hobbis, Dean; Shi, Wencong; Popescu, Adrian
Dalton Transactions, Vol. 49, Issue 7
DOI: 10.1039/c9dt04069b

Polaronic transport in Ag-based quaternary chalcogenides
journal, September 2017

Wei, Kaya; Khabibullin, Artem R.; Stedman, Troy
Journal of Applied Physics, Vol. 122, Issue 10
DOI: 10.1063/1.5001690

Similar Records in DOE PAGES and OSTI.GOV collections:

Improved thermoelectric properties in heavily doped FeGa₃

Journal Article Ponnambalam, V. ; Morelli, Donald T. - Journal of Applied Physics

FeGa₃, a hybridization gap semiconductor, has been substituted with an n-type dopant Ge to form a series of compositions FeGa_3-xGe_x. Electrical and thermal transport properties of these compositions have been studied. Change in carrier density (n) is evident from the Hall measurements. The carrier density (n) can be as high as ~10²¹ cm^-3 in these compositions. In order to study the role of heavy doping on the thermoelectric properties of FeGa₃, an alloy series Fe_1-yCo_yGa_3-xGe_x has also been synthesized with higher concentrations of Ge (x = 0.1–0.35) and Co (y = 0.1–0.5). From resistivity and Seebeck coefficient measurements, it appearsmore »« less
Cited by 10
https://doi.org/10.1063/1.4938474

Full Text Available
Synthesis and characterization of Bi-doped Mg{sub 2}Si thermoelectric materials

Journal Article Fiameni, S., E-mail: s.fiameni@ieni.cnr.it ; Battiston, S. ; Boldrini, S. ; ... - Journal of Solid State Chemistry

The Mg{sub 2}Si-based alloys are promising candidates for thermoelectric energy conversion for the middle high range of temperature. They are very attractive as they could replace lead-based compounds due to their low cost and non toxicity. They could also result in thermoelectric generator weight reduction (a key feature for the automotive application field). The high value of thermal conductivity of the silicide-based materials could be reduced by increasing the phonon scattering in the presence of nanosized crystalline grains without heavily interfering with the electrical conductivity of the thermoelectric material. Nanostructured materials were obtained under inert atmosphere through ball milling, thermalmore »« less
https://doi.org/10.1016/J.JSSC.2012.05.004
Gallium composition dependence of crystallographic and thermoelectric properties in polycrystalline type-I Ba{sub 8}Ga{sub x}Si{sub 46-x} (nominal x=14-18) clathrates prepared by combining arc melting and spark plasma sintering methods

Journal Article Anno, Hiroaki ; JST, CREST, 5 Sanbancho, Chiyoda-ku, Tokyo 102-0075 ; Yamada, Hiroki ; ... - Journal of Solid State Chemistry

The gallium composition dependence of crystallographic and thermoelectric properties in polycrystalline n-type Ba{sub 8}Ga{sub x}Si{sub 46-x} (nominal x=14-18) compounds with the type-I clathrate structure is presented. Samples were prepared by combining arc melting and spark plasma sintering methods. Powder x-ray diffraction, Rietveld analysis, scanning electron microscopy, and energy-dispersive x-ray spectroscopy show that the solubility limit of gallium in the type-I clathrate phase is close to x=15, which is slightly higher than that for a single crystal. The carrier concentration at room temperature decreases from 2 Multiplication-Sign 10{sup 21} cm{sup -3} to 4 Multiplication-Sign 10{sup 20} cm{sup -3} as the Gamore »« less
https://doi.org/10.1016/J.JSSC.2012.03.069
First-Principles Calculations of Thermoelectric Transport Properties of Quaternary and Ternary Bulk Chalcogenide Crystals

Journal Article Hasan, Sahib ; San, Saro ; Baral, Khagendra ; ... - Materials

Chalcogenide crystals have a wide range of applications, especially as thermoelectric materials for energy conversion. Thermoelectric materials can be used to generate an electric current from a temperature gradient based on the Seebeck effect and based on the Peltier effect, and they can be used in cooling applications. Using first-principles calculations and semiclassical Boltzmann theory, we have computed the Seebeck coefficient, electrical conductivity, electronic thermal conductivity, power factor, and figure of merit of 30 chalcogenide crystals. A Quantum Espresso package is used to calculate the electronic properties and locate the Fermi level. The transport properties are then calculated using themore »« less
https://doi.org/10.3390/ma15082843

Full Text Available
Thermoelectric properties of heavily GaP- and P-doped Si{sub 0.95}Ge{sub 0.05}

Journal Article Yamashita, Osamu - Journal of Applied Physics

The Seebeck coefficient S, the electrical resistivity {rho} and the thermal conductivity {kappa} of Si{sub 0.95}Ge{sub 0.05} samples doped with 0.4 at.% P and/or 0.5{endash}2.0 mol% GaP, which were prepared by a conventional arc melting method, were measured as functions of GaP content and temperature T in the range from 323 to 1208 K. When multidoped with P and GaP, Ga tends to segregate more strongly with Ge to the grain boundaries than P, while when doped with GaP alone, both P and Ga segregate equally strongly with Ge. For multidoped samples, the S values at 323 K have amore »« less
https://doi.org/10.1063/1.1352686

Similar Records

Title: Enhanced Thermoelectric Properties of Cu2ZnSnSe4 with Ga-doping

Abstract

Citation Formats

Figure of merit for thermoelectrics journal, February 1989

Structural, thermodynamical and optical properties of Cu2-II-IV-VI4 quaternary compounds journal, April 2005

Synthesis and thermoelectric properties of Cu excess Cu 2 ZnSnSe 4 : Synthesis and thermoelectric properties of Cu excess Cu journal, November 2013

Synthesis, Crystal Structure, and High Temperature Transport Properties of p -Type Cu 2 Zn 1– x Fe x SnSe 4 journal, November 2013

Cu 2 ZnGeSe 4 Nanocrystals: Synthesis and Thermoelectric Properties journal, February 2012

Phonon Scattering through a Local Anisotropic Structural Disorder in the Thermoelectric Solid Solution Cu 2 Zn 1– x Fe x GeSe 4 journal, December 2012

A wide-band-gap p-type thermoelectric material based on quaternary chalcogenides of Cu2ZnSnQ4 (Q=S,Se) journal, May 2009

Composition Control and Thermoelectric Properties of Quaternary Chalcogenide Nanocrystals: The Case of Stannite Cu 2 CdSnSe 4 journal, December 2011

The effect of multisubstitution on the thermoelectric properties of chalcogenide-based Cu 2.1 Zn 0.9 Sn 1− x In x Se 4 (0 ≤ x ≤ 0.1): Thermoelectric properties of chalcogenide-based Cu 2.1 Zn 0.9 Sn 1− x In x Se 4 journal, August 2013

Electrical conduction and mobility enhancement in p-type In-doped Cu 2 ZnSnSe 4 bulks journal, February 2014

Thermoelectric properties of chalcogenide based Cu 2+x ZnSn 1−x Se 4 journal, March 2013

Transport Properties of Bulk Thermoelectrics: An International Round-Robin Study, Part II: Thermal Diffusivity, Specific Heat, and Thermal Conductivity journal, March 2013

The crystal structure of kesterite type compounds: A neutron and X-ray diffraction study journal, June 2011

Time-resolved recombination analysis in kesterite polycrystalline thin films and photovoltaic devices with one-photon and two-photon excitation journal, May 2015

Photoelectrical properties of surfactant-free kesterite Cu2ZnSnSe4 hydrophilic nanocrystal ink and the stability in polar solvents journal, August 2014

Fermi-Dirac functions of integral order journal, December 1950

The Computation of Fermi-Dirac Functions journal, February 1938

Quaternary chalcogenides: Promising thermoelectric material and recent progress journal, July 2019

Enhanced thermoelectric performance through grain boundary engineering in quaternary chalcogenide Cu 2 ZnSnSe 4 journal, April 2018

Synthesis, transport properties and electronic structure of p-type Cu 1+x Mn 2−x InTe 4 ( x = 0, 0.2, 0.3) journal, January 2020

Polaronic transport in Ag-based quaternary chalcogenides journal, September 2017

Title: Enhanced Thermoelectric Properties of Cu₂ZnSnSe₄ with Ga-doping

Figure of merit for thermoelectrics
journal, February 1989

Structural, thermodynamical and optical properties of Cu2-II-IV-VI4 quaternary compounds
journal, April 2005

Synthesis and thermoelectric properties of Cu excess Cu ₂ ZnSnSe ₄ : Synthesis and thermoelectric properties of Cu excess Cu
journal, November 2013

Synthesis, Crystal Structure, and High Temperature Transport Properties of p -Type Cu ₂ Zn _{1– x} Fe _x SnSe ₄
journal, November 2013

Cu ₂ ZnGeSe ₄ Nanocrystals: Synthesis and Thermoelectric Properties
journal, February 2012

Phonon Scattering through a Local Anisotropic Structural Disorder in the Thermoelectric Solid Solution Cu ₂ Zn _{1– x} Fe _x GeSe ₄
journal, December 2012

A wide-band-gap p-type thermoelectric material based on quaternary chalcogenides of Cu2ZnSnQ4 (Q=S,Se)
journal, May 2009

Composition Control and Thermoelectric Properties of Quaternary Chalcogenide Nanocrystals: The Case of Stannite Cu ₂ CdSnSe ₄
journal, December 2011

The effect of multisubstitution on the thermoelectric properties of chalcogenide-based Cu _2.1 Zn _0.9 Sn _{1− x} In _x Se ₄ (0 ≤ x ≤ 0.1): Thermoelectric properties of chalcogenide-based Cu _2.1 Zn _0.9 Sn _{1− x} In _x Se ₄
journal, August 2013

Electrical conduction and mobility enhancement in p-type In-doped Cu ₂ ZnSnSe ₄ bulks
journal, February 2014

Thermoelectric properties of chalcogenide based Cu _2+x ZnSn _1−x Se ₄
journal, March 2013

Transport Properties of Bulk Thermoelectrics: An International Round-Robin Study, Part II: Thermal Diffusivity, Specific Heat, and Thermal Conductivity
journal, March 2013

The crystal structure of kesterite type compounds: A neutron and X-ray diffraction study
journal, June 2011

Time-resolved recombination analysis in kesterite polycrystalline thin films and photovoltaic devices with one-photon and two-photon excitation
journal, May 2015

Photoelectrical properties of surfactant-free kesterite Cu2ZnSnSe4 hydrophilic nanocrystal ink and the stability in polar solvents
journal, August 2014

Fermi-Dirac functions of integral order
journal, December 1950

The Computation of Fermi-Dirac Functions
journal, February 1938

Quaternary chalcogenides: Promising thermoelectric material and recent progress
journal, July 2019

Enhanced thermoelectric performance through grain boundary engineering in quaternary chalcogenide Cu ₂ ZnSnSe ₄
journal, April 2018

Synthesis, transport properties and electronic structure of p-type Cu _1+x Mn _2−x InTe ₄ ( x = 0, 0.2, 0.3)
journal, January 2020

Polaronic transport in Ag-based quaternary chalcogenides
journal, September 2017