The utilization of silicon-based materials for thermoelectrics is studied with respect to synthesis and processing of doped silicon nanoparticles from gas phase plasma synthesis. It is found that plasma synthesis enables for the formation of spherical, highly crystalline and soft-agglomerated materials. We discuss the requirements for the formation of dense sintered bodies while keeping the crystallite size small. Both, small particles sizing a few ten nanometer and below that are easily achievable from plasma synthesis, and a weak surface oxidation lead to a pronounced sinter activity about 350 K below the temperature usually needed for successful densification of silicon. The thermoelectric properties of our sintered materials are comparable with the best results found for nanocrystalline silicon prepared by other methods than plasma synthesis.

We present a study of the morphology and the thermoelectric properties of short-pulse laser-sintered (LS) nanoparticle (NP) thin films, consisting of SiGe alloy NPs or composites of Si and Ge NPs. Laser-sintering of spin-coated NP films in vacuum results in a macroporous percolating network with a typical thickness of 300 nm. The Seebeck coefficient is independent of the sintering process and typical for degenerate doping. The electrical conductivity of LS films rises with increasing temperature, best described by a power-law and influenced by two-dimensional percolation effects.Comment: 4 pages, 4 figure

We review the Raman shift method as a non-destructive optical tool to investigate the thermal conductivity and demonstrate the possibility to map this quantity with a micrometer resolution by studying thin film and bulk materials for thermoelectric applications. In this method, a focused laser beam both thermally excites a sample and undergoes Raman scattering at the excitation spot. The temperature dependence of the phonon energies measured is used as a local thermometer. We discuss that the temperature measured is an effective one and describe how the thermal conductivity is deduced from single temperature measurements to full temperature maps, with the help of analytical or numerical treatments of heat diffusion. We validate the method and its analysis on 3-and 2-dimensional single crystalline samples before applying it to more complex Si-based materials. A suspended thin mesoporous film of phosphorus-doped laser-sintered Si 78 Ge 22 nanoparticles is investigated to extract the in-plane thermal conductivity from the effective temperatures, measured as a function of the distance to the heat sink. Using an iterative multigrid Gauss-Seidel algorithm the experimental data can be modelled yielding a thermal conductivity of 0.1 W/m K after normalizing by the porosity. As a second application we map the surface of a phosphorus-doped 3-dimensional bulknanocrystalline Si sample which exhibits anisotropic and oxygen-rich precipitates. Thermal conductivities as low as 11 W/m K are found in the regions of the precipitates, significantly lower than the 17 W/m K in the surrounding matrix. The present work serves as a basis to more routinely use the Raman shift method as a versatile tool for thermal conductivity investigations, both for samples with high and low thermal conductivity and in a variety of geometries.

Porous, highly doped semiconductors are potential candidates for thermoelectric energy conversion elements. We report on the fabrication of thin films of Ge via short-pulse laser-sintering of Ge nanoparticles (NPs) in vacuum and study the macroporous morphology of the samples by secondary electron microscopy (SEM) imaging. The temperature dependence of the electrical conductivity and the Seebeck coefficient of undoped Ge is discussed in conjunction with the formation of a defect band near the valence band. We further introduce a versatile method of doping the resulting films with a variety of common dopant elements in group-IV semiconductors by using a liquid containing the dopant atoms. This method is fully compatible with laser-direct writing and suited to fabricate small scale thermoelectric generators. The incorporation of the dopants is verified by X-ray photoelectron spectroscopy (XPS) and their electrical activation is studied by conductivity and thermopower measurements.