Highly charged interface trap states in PbS1–x govern electro-thermal transport
Abstract
This work describes our discovery of the dominant role of highly charged interfaces on the electrothermal transport properties of PbS, along with a method to reduce the barrier potential for charge carriers by an order of magnitude. High temperature thermoelectrics such as PbS are inevitably exposed to elevated temperatures during postsynthesis treatment as well as operation. However, we observed that as the material was heated, large concentrations of sulfur vacancy (V$$\ddot{S}$$) sites were formed at temperatures as low as 266 °C. This loss of sulfur doped the PbS n-type and increased the carrier concentration, where these excess electrons were trapped and immobilized at interfacial defect sites in polycrystalline PbS with an abundance of grain boundaries. Sulfur deficient PbS0.81 exhibited a large barrier potential for charge carriers of 0.352 eV, whereas annealing the material under a sulfur-rich environment prevented V$$\ddot{S}$$ formation and lowered the barrier by an order of magnitude to 0.046 eV. Through ab initio calculations, the formation of V$$\ddot{S}$$ was found to be more favorable on the surface compared to the bulk of the material with a 1.72 times lower formation energy barrier. Furthermore, these observations underline the importance of controlling interface-vacancy effects in the preparation of bulk materials comprised of nanoscale constituents.
- Authors:
-
- Univ. of Connecticut, Storrs, CT (United States)
- Univ. of Connecticut, Storrs, CT (United States); Georgia Inst. of Technology, Atlanta, GA (United States)
- Clemson Univ., SC (United States)
- Univ. of Connecticut, Storrs, CT (United States); Univ. of Arizona, Tucson, AZ (United States)
- Univ. of Connecticut, Storrs, CT (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Center for Integrated Nanotechnologies (CINT)
- Publication Date:
- Research Org.:
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); UConn Research Foundation
- OSTI Identifier:
- 1570619
- Alternate Identifier(s):
- OSTI ID: 1542685
- Report Number(s):
- LA-UR-18-31330
Journal ID: ISSN 2166-532X
- Grant/Contract Number:
- 89233218CNA000001; CAREER-1553987; REU-1560098; PD17-0137; TG-DMR170031
- Resource Type:
- Accepted Manuscript
- Journal Name:
- APL Materials
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 7; Journal ID: ISSN 2166-532X
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Material Science; Semiconductors; Polycrystalline material; Interfaces; Thermoelectrics; Potential energy barrier; Transport properties; Crystallographic defects; Thermal transport; Ab-initio methods
Citation Formats
Yazdani, Sajad, Huan, Tran Doan, Liu, Yufei, Kashfi-Sadabad, Raana, Montaño, Raul David, He, Jian, and Pettes, Michael Thompson. Highly charged interface trap states in PbS1–x govern electro-thermal transport. United States: N. p., 2019.
Web. doi:10.1063/1.5096786.
Yazdani, Sajad, Huan, Tran Doan, Liu, Yufei, Kashfi-Sadabad, Raana, Montaño, Raul David, He, Jian, & Pettes, Michael Thompson. Highly charged interface trap states in PbS1–x govern electro-thermal transport. United States. https://doi.org/10.1063/1.5096786
Yazdani, Sajad, Huan, Tran Doan, Liu, Yufei, Kashfi-Sadabad, Raana, Montaño, Raul David, He, Jian, and Pettes, Michael Thompson. Tue .
"Highly charged interface trap states in PbS1–x govern electro-thermal transport". United States. https://doi.org/10.1063/1.5096786. https://www.osti.gov/servlets/purl/1570619.
@article{osti_1570619,
title = {Highly charged interface trap states in PbS1–x govern electro-thermal transport},
author = {Yazdani, Sajad and Huan, Tran Doan and Liu, Yufei and Kashfi-Sadabad, Raana and Montaño, Raul David and He, Jian and Pettes, Michael Thompson},
abstractNote = {This work describes our discovery of the dominant role of highly charged interfaces on the electrothermal transport properties of PbS, along with a method to reduce the barrier potential for charge carriers by an order of magnitude. High temperature thermoelectrics such as PbS are inevitably exposed to elevated temperatures during postsynthesis treatment as well as operation. However, we observed that as the material was heated, large concentrations of sulfur vacancy (V$\ddot{S}$) sites were formed at temperatures as low as 266 °C. This loss of sulfur doped the PbS n-type and increased the carrier concentration, where these excess electrons were trapped and immobilized at interfacial defect sites in polycrystalline PbS with an abundance of grain boundaries. Sulfur deficient PbS0.81 exhibited a large barrier potential for charge carriers of 0.352 eV, whereas annealing the material under a sulfur-rich environment prevented V$\ddot{S}$ formation and lowered the barrier by an order of magnitude to 0.046 eV. Through ab initio calculations, the formation of V$\ddot{S}$ was found to be more favorable on the surface compared to the bulk of the material with a 1.72 times lower formation energy barrier. Furthermore, these observations underline the importance of controlling interface-vacancy effects in the preparation of bulk materials comprised of nanoscale constituents.},
doi = {10.1063/1.5096786},
journal = {APL Materials},
number = 7,
volume = 7,
place = {United States},
year = {2019},
month = {7}
}
Figures / Tables:

Works referenced in this record:
Colloidal Quantum Dot Solar Cells
journal, June 2015
- Carey, Graham H.; Abdelhady, Ahmed L.; Ning, Zhijun
- Chemical Reviews, Vol. 115, Issue 23
Electron Doping in Bottom-Up Engineered Thermoelectric Nanomaterials through HCl-Mediated Ligand Displacement
journal, March 2015
- Ibáñez, Maria; Korkosz, Rachel J.; Luo, Zhishan
- Journal of the American Chemical Society, Vol. 137, Issue 12
Model of transport properties of thermoelectric nanocomposite materials
journal, May 2009
- Popescu, A.; Woods, L. M.; Martin, J.
- Physical Review B, Vol. 79, Issue 20
Raising the Thermoelectric Performance of p-Type PbS with Endotaxial Nanostructuring and Valence-Band Offset Engineering Using CdS and ZnS
journal, September 2012
- Zhao, Li-Dong; He, Jiaqing; Hao, Shiqiang
- Journal of the American Chemical Society, Vol. 134, Issue 39
A new class of doped nanobulk high-figure-of-merit thermoelectrics by scalable bottom-up assembly
journal, January 2012
- Mehta, Rutvik J.; Zhang, Yanliang; Karthik, Chinnathambi
- Nature Materials, Vol. 11, Issue 3
Thermoelectric alloys between PbSe and PbS with effective thermal conductivity reduction and high figure of merit
journal, January 2014
- Wang, Heng; Wang, Jianli; Cao, Xianlong
- Journal of Materials Chemistry A, Vol. 2, Issue 9
Thermoelectrics with Earth Abundant Elements: High Performance p-type PbS Nanostructured with SrS and CaS
journal, April 2012
- Zhao, Li-Dong; He, Jiaqing; Wu, Chun-I
- Journal of the American Chemical Society, Vol. 134, Issue 18
Nanoscale self-assembly of thermoelectric materials: a review of chemistry-based approaches
journal, August 2018
- Yazdani, Sajad; Pettes, Michael Thompson
- Nanotechnology, Vol. 29, Issue 43
A Reexamination of Phonon Transport Through a Nanoscale Point Contact in Vacuum
journal, November 2013
- Thompson Pettes, Michael; Shi, Li
- Journal of Heat Transfer, Vol. 136, Issue 3
Nanostructured materials for thermoelectric applications
journal, January 2010
- Bux, Sabah K.; Fleurial, Jean-Pierre; Kaner, Richard B.
- Chemical Communications, Vol. 46, Issue 44
Thermoelectric transport in surface- and antimony-doped bismuth telluride nanoplates
journal, October 2016
- Pettes, Michael Thompson; Kim, Jaehyun; Wu, Wei
- APL Materials, Vol. 4, Issue 10
Characterization of Lorenz number with Seebeck coefficient measurement
journal, April 2015
- Kim, Hyun-Sik; Gibbs, Zachary M.; Tang, Yinglu
- APL Materials, Vol. 3, Issue 4
Polyelectrolyte-Assisted Oxygen Vacancies: A New Route to Defect Engineering in Molybdenum Oxide
journal, May 2018
- Yazdani, Sajad; Kashfi-Sadabad, Raana; Huan, Tran Doan
- Langmuir, Vol. 34, Issue 21
Principles of heat flow in Porous Insulators
journal, December 1935
- Russell, H. W.
- Journal of the American Ceramic Society, Vol. 18, Issue 1-12
Heat Transfer in Thermoelectric Materials and Devices
journal, May 2013
- Tian, Zhiting; Lee, Sangyeop; Chen, Gang
- Journal of Heat Transfer, Vol. 135, Issue 6
Thermophysical properties of polycrystalline PbS, PbSe, and PbTe in the temperature range 300?700 K
journal, September 1983
- El-Sharkawy, A. A.; Abou El-Azm, A. M.; Kenawy, M. I.
- International Journal of Thermophysics, Vol. 4, Issue 3
Core–Shell Nanoparticles As Building Blocks for the Bottom-Up Production of Functional Nanocomposites: PbTe–PbS Thermoelectric Properties
journal, March 2013
- Ibáñez, Maria; Zamani, Reza; Gorsse, Stéphane
- ACS Nano, Vol. 7, Issue 3
Application of Zinc Oxide Varistors
journal, July 1990
- Gupta, Tapan K.
- Journal of the American Ceramic Society, Vol. 73, Issue 7
The electrical properties of polycrystalline silicon films
journal, December 1975
- Seto, John Y. W.
- Journal of Applied Physics, Vol. 46, Issue 12
Growth and Characterization of Polycrystalline Silicon
journal, January 1973
- Rai-Choudhury, P.; Hower, P. L.
- Journal of The Electrochemical Society, Vol. 120, Issue 12
First-principles study of anisotropic thermoelectric transport properties of IV-VI semiconductor compounds SnSe and SnS
journal, September 2015
- Guo, Ruiqiang; Wang, Xinjiang; Kuang, Youdi
- Physical Review B, Vol. 92, Issue 11
Hall Mobility in Chemically Deposited Polycrystalline Silicon
journal, October 1971
- Kamins, T. I.
- Journal of Applied Physics, Vol. 42, Issue 11
High Performance Thermoelectrics from Earth-Abundant Materials: Enhanced Figure of Merit in PbS by Second Phase Nanostructures
journal, December 2011
- Zhao, Li-Dong; Lo, Shih-Han; He, Jiaqing
- Journal of the American Chemical Society, Vol. 133, Issue 50
Enhanced Seebeck coefficient through energy-barrier scattering in PbTe nanocomposites
journal, March 2009
- Martin, J.; Wang, Li; Chen, Lidong
- Physical Review B, Vol. 79, Issue 11
Low-cost, abundant binary sulfides as promising thermoelectric materials
journal, May 2016
- Ge, Zhen-Hua; Zhao, Li-Dong; Wu, Di
- Materials Today, Vol. 19, Issue 4
Abundance of chemical elements in the continental crust: a new table
journal, August 1964
- Taylor, S. R.
- Geochimica et Cosmochimica Acta, Vol. 28, Issue 8
Thermoelectric Properties of Lead Chalcogenide Core–Shell Nanostructures
journal, October 2011
- Scheele, Marcus; Oeschler, Niels; Veremchuk, Igor
- ACS Nano, Vol. 5, Issue 11
Nanostructures Boost the Thermoelectric Performance of PbS
journal, March 2011
- Johnsen, Simon; He, Jiaqing; Androulakis, John
- Journal of the American Chemical Society, Vol. 133, Issue 10
High-performance thermoelectric nanocomposites from nanocrystal building blocks
journal, March 2016
- Ibáñez, Maria; Luo, Zhishan; Genç, Aziz
- Nature Communications, Vol. 7, Issue 1
Phonon conduction in PbSe, PbTe, and PbTe Se from first-principles calculations
journal, May 2012
- Tian, Zhiting; Garg, Jivtesh; Esfarjani, Keivan
- Physical Review B, Vol. 85, Issue 18
Figure of merit for thermoelectrics
journal, February 1989
- Mahan, G. D.
- Journal of Applied Physics, Vol. 65, Issue 4
Inversion of conductivity type in Bi2Te3−xSx crystals
journal, September 1985
- Horák, J.; Lošťák, P.; Koudelka, L.
- Solid State Communications, Vol. 55, Issue 11
Synthesis and property evaluation of CuFeS2−x as earth-abundant and environmentally-friendly thermoelectric materials
journal, February 2013
- Li, Jianhui; Tan, Qing; Li, Jing-Feng
- Journal of Alloys and Compounds, Vol. 551
Strong enhancement of phonon scattering through nanoscale grains in lead sulfide thermoelectrics
journal, June 2014
- Wu, Haijun; Carrete, Jesús; Zhang, Zhiyun
- NPG Asia Materials, Vol. 6, Issue 6
Interpretation of Hall Effect and Resistivity Data in PbS and Similar Binary Compound Semiconductors
journal, December 1953
- Scanlon, Wayne W.
- Physical Review, Vol. 92, Issue 6
Recent advances in the optical and electronic properties of PbS, PbSe, PbTe and their alloys
journal, January 1959
- Scanlon, W. W.
- Journal of Physics and Chemistry of Solids, Vol. 8
Dynamics of Photoexcited Carriers in Polycrystalline PbS and at PbS/ZnO Heterojunctions: Influence of Grain Boundaries and Interfaces
journal, May 2018
- Kushnir, Kateryna; Chen, Kefan; Zhou, Lite
- The Journal of Physical Chemistry C, Vol. 122, Issue 22
High-performance thermoelectric nanocomposites from nanocrystal building blocks
text, January 2016
- Ibáñez, María; Luo, Zhishan; Genç, Aziz
- ETH Zurich
Thermoelectric properties of lead chalcogenide core-shell nanostructures
text, January 2012
- Scheele, Marcus; Oeschler, Niels; Veremchuk, Igor
- arXiv
First-principles study of anisotropic thermoelectric transport properties of IV-VI semiconductor compounds SnSe and SnS
text, January 2015
- Guo, Ruiqiang; Wang, Xinjiang; Kuang, Youdi
- arXiv
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