Nils Petermann

Plasma synthesis of nanostructures for improved thermoelectric properties

The utilization of silicon-based materials for thermoelectrics is studied with respect to the synthesis and processing of doped silicon nanoparticles from gas phase plasma synthesis. It is found that plasma synthesis enables 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. Small particles a few tens of nanometres and below that are easily achievable from plasma synthesis, and a weak surface oxidation, both lead to a pronounced sinter activity about 350 K below the temperature usually needed for the successful densification of silicon. The thermoelectric properties of our sintered materials are comparable to the best results found for nanocrystalline silicon prepared by methods other than plasma synthesis.

Role of oxygen on microstructure and thermoelectric properties of silicon nanocomposites

Phosphorus-doped silicon nanopowder from a gas phase process was compacted by DC-current sintering in order to obtain thermoelectrically active, nanocrystalline bulk silicon. A density between 95% and 96% compared to the density of single crystalline silicon was achieved, while preserving the nanocrystalline character with an average crystallite size of best 25 nm. As a native surface oxidation of the nanopowder usually occurs during nanopowder handling, a focus of this work is on the role of oxygen on microstructure and transport properties of the nanocomposite. A characterization with transmission electron microscopy (TEM) showed that the original core/shell structure of the nanoparticles was not found within the sintered nanocomposites. Two different types of oxide precipitates could be identified by energy filtered imaging technique. For a detailed analysis, 3-dimensional tomography with reconstruction was done using a needle-shaped sample prepared by focused ion beam (FIB). The 3-dimensional distribu...

From nanoparticles to nanocrystalline bulk: percolation effects in field assisted sintering of silicon nanoparticles

Nanocrystalline bulk materials are desirable for many applications as they combine mechanical strength and specific electronic transport properties. Our bottom-up approach starts with tailored nanoparticles. Compaction and thermal treatment are crucial, but usually the final stage sintering is accompanied by rapid grain growth which spoils nanocrystallinity. For electrically conducting nanoparticles, field activated sintering techniques overcome this problem. Small grain sizes have been maintained in spite of consolidation. Nevertheless, the underlying principles, which are of high practical importance, have not been fully elucidated yet. In this combined experimental and theoretical work, we show how the developing microstructure during sintering correlates with the percolation paths of the current through the powder using highly doped silicon nanoparticles as a model system. It is possible to achieve a nanocrystalline bulk material and a homogeneous microstructure. For this, not only the generation of current paths due to compaction, but also the disintegration due to Joule heating is required. The observed density fluctuations on the micrometer scale are attributed to the heat profile of the simulated powder networks.

Laser-sintered thin films of doped SiGe nanoparticles

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.

Thermal conductivity of mesoporous films measured by Raman spectroscopy

We measure the in-plane thermal conductance of mesoporous Ge and SiGe thin films using the Raman-shift method and, based on a finite differences simulation accounting for the geometry of the sample, extract the in-plane thermal conductivity. For a suspended thin film of laser-sintered SiGe nanoparticles doped with phosphorus, we find an effective in-plane thermal conductivity of 0.05 W/m K in vacuum for a temperature difference of 400 K and a mean temperature of 500 K. Under similar conditions, the effective in-plane thermal conductivity of a laser-sintered undoped Ge nanoparticle film is 0.5 W/m K. Accounting for a porosity of approximately 50%, the normalized thermal conductivities are 0.1 W/m K and 1 W/m K, respectively. The thermoelectric performance is discussed, considering that the electrical in-plane conductivity is also affected by the mesoporosity.

Efficiency Enhancement in Hybrid P3HT/Silicon Nanocrystal Solar Cells

Abstract Hybrid organic-inorganic solar cells from poly(3-hexylthiophene) (P3HT) and freestanding silicon nanocrystals (Si-ncs) combine the advantages of silicon-based 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.

Nanocrystalline silicon: Lattice dynamics and enhanced thermoelectric properties

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.

Spatially resolved determination of thermal conductivity by Raman spectroscopy

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 Si78Ge22 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 bulk-nanocrystalline 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.

A sintered nanoparticle p-n junction observed by a Seebeck microscan

A nanoparticular p-n junction was realized by a field-assisted sintering process, using p-type and n-type doped silicon nanoparticles. A spatially resolved Seebeck microscan showed a broad transition from the positively doped to the negatively doped range. Overshoots on both sides are characteristic for the transition. Despite the tip size being much larger than the mean particle size, information about the dopant distribution between the particles is deduced from modeling the measured data under different assumptions, including the limited spatial resolution of the tip. The best match between measured and modeled data is achieved by the idea of doping compensation, due to the sintering process. Due to a short time at high temperature during the field-assisted sintering process, solid state diffusion is too slow to be solely responsible for the observed compensation of donors and acceptors over a wide range. Therefore, these measurements support a densification mechanism based on (partial) melting and rec...

A Thermoelectric Generator Concept Using a p – n Junction: Experimental Proof of Principle

Conventional thermoelectric generators (TEGs) use single p- and n-doped legs for thermoelectric energy harvesting. We explore a concept using thermoelectric p–n junctions made from densified silicon nanoparticles. The nanoparticle powder was synthesized in a microwave plasma reactor using silane, diborane, and phosphine as precursors. To achieve a bulk sample with a p–n junction, a layer of boron-doped nanoparticle powder was stacked on a layer of phosphorus-doped powder and compacted by current-activated pressure- assisted densification. To use the p–n structure as a TEG, a temperature gradient was applied along the p–n junction. It is expected that this temperature gradient leads to electron–hole pair generation and separation in the junction, and diffusion of the charge carriers. A reference method was used to characterize the open-circuit voltage of the p–n junction TEG.