Native Atomic Defects Manipulation for Enhancing the Electronic Transport Properties of Epitaxial SnTe Films.

P-type SnTe-based compounds have attracted extensive attention because of their high thermoelectric performance. Previous studies have made tremendous efforts to investigate native atomic defects in SnTe-based compounds, but there has been no direct experimental evidence so far. On the basis of MBE, STM, ARPES, DFT calculations, and transport measurements, this work directly visualizes the dominant native atomic defects and clarifies an alternative optimization mechanism of electronic transport properties via defect engineering in epitaxially grown SnTe (111) films. Our findings prove that positively charged Sn vacancies (VSn) and negatively charged Sn interstitials (Sni) are the leading native atomic defects that dominate electronic transport in SnTe, in contrast to previous studies that only considered VSn. Increasing the substrate temperature (Tsub) and decreasing the Te/Sn flux ratio during film growth reduces the density of VSn while increasing the density of Sni. A high Tsub results in a low hole density and high carrier mobility in SnTe films. The SnTe film grown at Tsub = 593 K and Te/Sn = 2/1 achieves its highest power factor of 1.73 mW m-1 K-2 at 673 K, which is attributed to the optimized hole density of 2.27 × 1020 cm-3 and the increased carrier mobility of 85.6 cm2 V-1 s-1. Our experimental studies on the manipulation of native atomic defects can contribute to an increased understanding of the electronic transport properties of SnTe-based compounds.

Identifying the Manipulation of Individual Atomic-Scale Defects for Boosting Thermoelectric Performances in Artificially Controlled Bi2Te3 Films.

The manipulation of individual intrinsic point defects is crucial for boosting the thermoelectric performances of n-Bi2Te3-based thermoelectric films, but was not achieved in previous studies. In this work, we realize the independent manipulation of Te vacancies VTe and antisite defects of TeBi and BiTe in molecular beam epitaxially grown n-Bi2Te3 films, which is directly monitored by a scanning tunneling microscope. By virtue of introducing dominant TeBi antisites, the n-Bi2Te3 film can achieve the state-of-the-art thermoelectric power factor of 5.05 mW m-1 K-2, significantly superior to films containing VTe and BiTe as dominant defects. Angle-resolved photoemission spectroscopy and systematic transport studies have revealed two detrimental effects regarding VTe and BiTe, which have not been discovered before: (1) The presence of BiTe antisites leads to a reduction of the carrier effective mass in the conduction band; and (2) the intrinsic transformation of VTe to BiTe during the film growth results in a built-in electric field along the film thickness direction and thus is not beneficial for the carrier mobility. This research is instructive for further engineering defects and optimizing electronic transport properties of n-Bi2Te3 and other technologically important thermoelectric materials.