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Title: The importance of phase equilibrium for doping efficiency: iodine doped PbTe

Abstract

Semiconductor engineering relies heavily on doping efficiency and dopability. Low doping efficiency may cause low mobility and failure to reach target carrier concentrations or even the desired carrier type. Semiconducting thermoelectric materials perform best with degenerate carrier concentrations, meaning high performance in new materials might not be realized experimentally without a route to optimal doping. Doping in the classic PbTe thermoelectric system has been largely successful but reported doping efficiencies can vary, raising concerns about reproducibility. Here, we stress the importance of phase equilibria considerations during synthesis to avoid undesired intrinsic defects leading to sub-optimal doping. By saturation annealing at 973 K, we decidedly fix the composition in single crystal iodine-doped PbTe samples to be Pb-rich or Te-rich without introducing impurity phases. We show that, regardless of iodine concentration, degenerate n-type carrier concentrations with ideal doping efficiency require Pb-rich compositions. Electrons in Te-rich samples are heavily compensated by charged intrinsic Pb vacancy defects. From Hall effect measurements and a simple defect model supported by modern defect calculations, we map out the 973 K ternary Pb–Te–I phase diagram to explicitly link carrier concentration and composition. Furthermore, we discuss unintentional composition changes due to loss of volatile Te during synthesis and measurements.more » The methods and concepts applied here may guide doping studies on other lead chalcogenide systems as well as any doped, complex semiconductor.« less

Authors:
 [1];  [1]; ORCiD logo [2];  [1];  [1];  [3];  [1]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
  2. National Renewable Energy Laboratory (NREL), Golden, CO (United States); Colorado School of Mines, Golden, CO (United States)
  3. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); National Science Foundation (NSF)
OSTI Identifier:
1559781
Report Number(s):
NREL/JA-5K00-74711
Journal ID: ISSN 2051-6347; MHAOAL
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Materials Horizons
Additional Journal Information:
Journal Volume: 6; Journal Issue: 7; Journal ID: ISSN 2051-6347
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; semiconductors; phase equilibrium; doping

Citation Formats

Male, James, Agne, Matthias T., Goyal, Anuj, Anand, Shashwat, Witting, Ian T., Stevanovic, Vladan, and Snyder, G. Jeffrey. The importance of phase equilibrium for doping efficiency: iodine doped PbTe. United States: N. p., 2019. Web. doi:10.1039/C9MH00294D.
Male, James, Agne, Matthias T., Goyal, Anuj, Anand, Shashwat, Witting, Ian T., Stevanovic, Vladan, & Snyder, G. Jeffrey. The importance of phase equilibrium for doping efficiency: iodine doped PbTe. United States. doi:10.1039/C9MH00294D.
Male, James, Agne, Matthias T., Goyal, Anuj, Anand, Shashwat, Witting, Ian T., Stevanovic, Vladan, and Snyder, G. Jeffrey. Wed . "The importance of phase equilibrium for doping efficiency: iodine doped PbTe". United States. doi:10.1039/C9MH00294D.
@article{osti_1559781,
title = {The importance of phase equilibrium for doping efficiency: iodine doped PbTe},
author = {Male, James and Agne, Matthias T. and Goyal, Anuj and Anand, Shashwat and Witting, Ian T. and Stevanovic, Vladan and Snyder, G. Jeffrey},
abstractNote = {Semiconductor engineering relies heavily on doping efficiency and dopability. Low doping efficiency may cause low mobility and failure to reach target carrier concentrations or even the desired carrier type. Semiconducting thermoelectric materials perform best with degenerate carrier concentrations, meaning high performance in new materials might not be realized experimentally without a route to optimal doping. Doping in the classic PbTe thermoelectric system has been largely successful but reported doping efficiencies can vary, raising concerns about reproducibility. Here, we stress the importance of phase equilibria considerations during synthesis to avoid undesired intrinsic defects leading to sub-optimal doping. By saturation annealing at 973 K, we decidedly fix the composition in single crystal iodine-doped PbTe samples to be Pb-rich or Te-rich without introducing impurity phases. We show that, regardless of iodine concentration, degenerate n-type carrier concentrations with ideal doping efficiency require Pb-rich compositions. Electrons in Te-rich samples are heavily compensated by charged intrinsic Pb vacancy defects. From Hall effect measurements and a simple defect model supported by modern defect calculations, we map out the 973 K ternary Pb–Te–I phase diagram to explicitly link carrier concentration and composition. Furthermore, we discuss unintentional composition changes due to loss of volatile Te during synthesis and measurements. The methods and concepts applied here may guide doping studies on other lead chalcogenide systems as well as any doped, complex semiconductor.},
doi = {10.1039/C9MH00294D},
journal = {Materials Horizons},
number = 7,
volume = 6,
place = {United States},
year = {2019},
month = {4}
}

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