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.

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Silicon has several advantages when compared to other thermoelectric materials, but until recently it was not used for thermoelectric applications due to its high thermal conductivity, 156 W K(-1) m(-1) at room temperature. Nanostructuration as means to decrease thermal transport through enhanced phonon scattering has been a subject of many studies. In this work we have evaluated the effects of nanostructuration on the lattice dynamics of bulk nanocrystalline doped silicon. The samples were prepared by gas phase synthesis, followed by current and pressure assisted sintering. The heat capacity, density of phonons states, and elastic constants were measured, which all reveal a significant, ≈25%, reduction in the speed of sound. The samples present a significantly decreased lattice thermal conductivity, ≈25 W K(-1) m(-1), which, combined with a very high carrier mobility, results in a dimensionless figure of merit with a competitive value that peaks at ZT≈ 0.57 at 973 °C. Due to its easily scalable and extremely low-cost production process, nanocrystalline Si prepared by gas phase synthesis followed by sintering could become the material of choice for high temperature thermoelectric generators.

Abstract

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

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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.

Hybrid organic-inorganic solar cells from poly(3-hexylthiophene) (P3HT) and freestanding silicon nanocrystals (Si-ncs) combine the advantages of siliconbased photovoltaics with the cost-efficient solution processing technique. At present, the microwave-plasma synthesis of Si-ncs that allows for a future upscaling to industrial demands is at the expense of the Si-nc surface quality and the number of charge-trapping defects. Here, we present an enhancement of the solar cell performance by identifying the major factors which are limiting the device efficiency. With the help of low-cost post-growth treatments of the Si-ncs and the optimization of various device parameters, P3HT:Si-ncs bulk heterojunction solar cells with an efficiency up to 1.1 % are achieved. In particular, etching of the Si-ncs with hydrofluoric acid to remove the surface oxide shells and surface defects has a strong impact on the solar cell performance. An intermediate Si weight ratio of around 60 % is found to lead to the highest current densities. For Si-ncs with very small diameters, an additional enhancement of the open circuit voltage was observed. Moreover, we show that the structural order of P3HT has a strong influence on the efficiency, which can be explained by an improved charge carrier separation at the P3HT/Si-ncs interface in combination with an enhanced charge transport in the P3HT phase.