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.
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This content will become publicly available on June 1, 2025
Magnetotransport properties of ternary tetradymite films with high mobility
(Bi,Sb)2(Te,Se)3 tetradymite materials are among the most efficient for thermoelectric energy conversion, and most robust for topological insulator spintronic technologies, but should possess rather disparate doping properties to be useful for either technology. In this work, we report results on the molecular beam epitaxy growth of p-type (Bi0.43Sb0.57)2Te3 and n-type Bi2(Te0.95Se0.05)3 that can contribute to both technology bases, but are especially useful for topological insulators where low bulk doping is critical for devices to leverage the Dirac-like topological surface states. Comprehensive temperature, field and angular dependent magnetotransport measurements have attested to the superior quality of these ternary tetradymite films, displaying low carrier density on the order of 1018 cm–3 and a record high mobility exceeding 104 cm2 V–1 s–1 at 2 K. The remarkable manifestation of strong Shubnikov–de Haas (SdH) quantum oscillation under 9 T at liquid helium temperatures, as well as the analyses therein, has allowed direct experimental investigation of the tetradymite electronic structure with optimized ternary alloying ratio. Our effort substantiates tetradymites as a critical platform for miniaturized thermoelectric cooling and power generation in wearable consumer electronics, as well as for futuristic topological spintronics with unprecedented magnetoelectric functionalities.
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- Award ID(s):
- 2218550
- PAR ID:
- 10530563
- Publisher / Repository:
- Elsevier B.V. Publisher
- Date Published:
- Journal Name:
- Materials Today Physics
- ISSN:
- 2542-5293
- Page Range / eLocation ID:
- 101486
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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