Thermal and Electrical Transport Study on Thermoelectric Materials Through Nanostructuring and Magnetic Field

Abstract

Thermoelectric (TE) materials are of great interest to contemporary scientists because of their ability to directly convert temperature differences into electricity, and are regarded as a promising mode of alternative energy. The TE conversion efficiency is determined by the Carnot efficiency, η_C and is relevant to a commonly used figure of merit ZT of a material. Improving the value of ZT is presently a core mission within the TE field. In order to advance our understanding of thermoelectric materials and improve their efficiency, this dissertation investigates the low-temperature behavior of the p-type thermoelectric Cu2Se through chemical doping and nanostructuring. It demonstrates a method to separate the electronic and lattice thermal conductivities in single crystal Bi2Te3, Cu, Al, Zn, and probes the electrical transport of quasi 2D bismuth textured thin films. Cu2Se is a good high temperature TE material due to its phonon-liquid electron-crystal (PLEC) properties. It shows a discontinuity in transport coefficients and ZT around a structural transition. The present work on Cu2Se at low temperatures shows that it is a promising p-type TE material in the low temperature regime and investigates the Peierls transition and charge-density wave (CDW) response to doping [1]. After entering the CDW ground state, an oscillation (wave-like fluctuation) was observed in the dc I-V curve near 50 K; this exhibits a periodic negative differential resistivity in an applied electric field due to the current. An investigation into the doping effect of Zn, Ni, and Te on the CDW ground state shows that Zn and Ni-doped Cu2Se produces an increased semiconducting energy gap and electron-phonon coupling constant, while the Te doping suppresses the Peierls transition. A similar fluctuating wave-like dc I-V curve was observed in Cu1.98Zn0.02Se near 40 K. This oscillatory behavior in the dc I-V curve was found to be insensitive to magnetic field but temperature dependent [2]. Understanding reducing thermal conductivity in TE materials is an important facet of increasing TE efficiency and potential applications. In this dissertation, a magnetothermal (MTR) resistance method is used to measure the lattice thermal conductivity, κ_ph of single crystal Bi2Te3 from 5 to 60 K. A large transverse magnetic field is applied to suppress the electronic thermal conduction while measuring thermal conductivity and electrical resistivity. The lattice thermal conductivity is then calculated by extrapolating the thermal conductivity versus electrical conductivity curve to a zero electrical conductivity value. The results show that the measured phonon thermal conductivity follows the e^(Δ_min⁄T) temperature dependence and the Lorenz ratio corresponds to the modified Sommerfeld value in the intermediate temperature range. These low-temperature experimental data and analysis on Bi2Te3 are important compliments to previous measurements and theoretical calculations at higher temperatures, 100 – 300 K. The MTR method on Bi2Te3 provides data necessary for first-principles calculations [4]. A parallel study on single crystal Cu, Al and Zn shows the applicability of the MTR method for separating κ_e and κ_ph in metals and indicates a significant deviation of the Lorenz ratio between 5 K and 60 K [3]. Elemental bismuth is a component of many TE compounds and in this dissertation magnetoresistance measurements are used investigate the effect of texturing in polycrystalline bismuth thin films. Electrical current in bismuth films with texturing such that all grains are oriented with the trigonal axis normal to the film plane is found to flow in an isotropic manner. By contrast, bismuth films with no texture such that not all grains have the same crystallographic orientation exhibit anisotropic current flow, giving rise to preferential current flow pathways in each grain depending on its orientation. Textured and non-textured bismuth thin films are examined by measuring their angle-dependent magnetoresistance at different temperatures (3 – 300 K) and applied magnetic fields (0 – 90 kOe). Experimental evidence shows that the anisotropic conduction is due to the large mass anisotropy of bismuth and is confirmed by a parallel study on an antimony thin film [5]. [1] Mengliang Yao, Weishu Liu, Xiang Chen, Zhensong Ren, Stephen Wilson, Zhifeng Ren, and Cyril Opeil, J. Alloys Compd. 699, 718 (2017). [2] Mengliang Yao, Weishu Liu, Xiang Chen, Zhensong Ren, Stephen Wilson, Zhifeng Ren, and Cyril P. Opeil, J. Materiomics 3, 150 (2017). [3] Experimental determination of phonon thermal conductivity and Lorenz ratio of single crystal metals: Al, Cu and Zn, Mengliang Yao, Mona Zebarjadi, and Cyril P. Opeil, under review. [4] Experimental determination of phonon thermal conductivity and Lorenz ratio of single crystal bismuth telluride, Mengliang Yao, Stephen Wilson, Mona Zebarjadi, and Cyril Opeil, under review. [5] Albert D. Liao, Mengliang Yao, Ferhat Katmis, Mingda Li, Shuang Tang, Jagadeesh S. Moodera, Cyril Opeil, Mildred S. Dresselhaus, Appl. Phys. Lett. 105, 063114 (2014).