We report the room-temperature, cross-plane thermal conductivities, and longitudinal speeds of sound of multilayer films [(TiTe2)(3)(Bi2Te3)(x)(TiTe2)(3)(Sb2Te3)(y)](i) (x=1-5, y=1-5) and misfit-layer dichalcogenide films [(PbSe)(m)(TSe2)(n)](i) (T=W or Mo, m=1-5, and n=1-5) synthesized by the modulated elemental reactants method. The thermal conductivities of these nanoscale layered materials fall below the predicted minimum thermal conductivity of the component compounds: two times lower than the minimum thermal conductivity of Bi2Te3 for multilayer [(TiTe2)(3)(Bi2Te3)(x)(TiTe2)(3)(Sb2Te3)(y)](i) films and five to six times lower than the minimum thermal conductivity of PbSe for misfit-layer dichalcogenides [(PbSe)(m)(TSe2)(n)](i). We attribute the low thermal conductivities to the anisotropic bonding of the layered crystals and orientational disorder in the stacking of layered crystals along the direction perpendicular to the surface

We investigate the lower limit to the lattice thermal conductivity of Bi2Te3 and related materials using thin films synthesized by the method of elemental reactants. The thermal conductivities of single layer films of (Bi0.5Sb0.5)2Te3 and multilayer films of (Bi2Te3)m(TiTe2)n and [(BixSb1−x)2Te3]m(TiTe2)n are measured by time-domain thermoreflectance; the thermal conductivity data are compared to our prior work on nanocrystalline Bi2Te3 and a Debye–Callaway model of heat transport by acoustic phonons. The homogeneous nanocrystalline films have average grain sizes 30<d<100 nm as measured by the width of the (003) x-ray diffraction peak. Multilayer films incorporating turbostratic TiTe2 enable studies of the effective thermal conductivity of Bi2Te3 layers as thin as 2 nm. In the limit of small grain size or layer thickness, the thermal conductivity of Bi2Te3 approaches the predicted minimum thermal conductivity of 0.31 W/m K. The dependence of the thermal conductivity on grain size is in good agreement with our Debye–Callaway model. The use of alloy (Bi,Sb)2Te3 layers further reduces the thermal conductivity of the nanoscale layers to as low as 0.20 W/m K.

We review a synthetic strategy for investigating the various effects of thermal conductivity reducing mechanisms in thermoelectric materials. Elemental nanolaminate precursors are used to selfassemble [(Bi 1−x Sb x 2 Te 3 ] m [(TiTe 2 1 36 ] n intergrowth thin films with controlled and well-defined composition and nanostructure, allowing the influence of alloying, effective grain size, and turbostratic disorder on the cross-plane thermal conductivity to be independently and collectively assessed. By combining all three features, thermal conductivity values well below the predicted minimum thermal conductivity of the components are obtained. These approaches, potentially combined with temperature dependent measurements, can offer a useful way to study phonon scattering mechanisms in thermoelectric materials.

Abstract

This article demonstrates that carrier concentrations in bismuth telluride films can be controlled through annealing in controlled vapor pressures of tellurium. For the bismuth telluride source with a small excess of tellurium, all the films reached a steady state carrier concentration of 4 9 10 19 carriers/cm 3 with Seebeck coefficients of À170 lV K À1 . For temperatures below 300°C and for film thicknesses of 0.4 lm or less, the rate-limiting step in reaching a steady state for the carrier concentration appeared to be the mass transport of tellurium through the gas phase. At higher temperatures, with the resulting higher pressures of tellurium or for thicker films, it was expected that mass transport through the solid would become rate limiting. The mobility also changed with annealing, but at a rate different from that of the carrier concentration, perhaps as a consequence of the non-equilibrium concentration of defects trapped in the films studied by the low temperature synthesis approach.

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Sb 2 Te 3 ) x (TiTe 2 ) y superlattices with varying values of x and fixed y were prepared using modulated elemental reactants. A procedure to calibrate the ratio of the elements and the absolute amount deposited is discussed. The structure of a reactant designed to form a (Sb 2 Te 3 ) 3 (TiTe 2 ) 3 superlattice is followed as a function of annealing temperature. The annealing conditions obtained from this study enabled us to prepare a series of (Sb 2 Te 3 ) x (TiTe 2 ) y superlattices. The samples were characterized using x-ray reflectivity, x-ray diffraction, and electron probe microanalysis (EPMA)