Hartmut Wiggers

Silicon nanoparticles : Absorption, emission, and the nature of the electronic bandgap

Silicon nanoparticles synthesized in the gas phase are studied. From time-resolved photoluminescence measurements we determine, quantitatively, the size-dependence of the oscillator strength of the nanoparticles. We investigate experimentally the absorption and photoluminescence emission of nanoparticle ensembles with a broad size distribution. Using a model which accounts for size-effects in both oscillator strength and quantum-confinement, we are able to calculate absorption and emission spectra of ensemble samples. From these results we have determined, whether silicon nanoparticles should be regarded as indirect or direct semiconductors. Moreover, we systematically study the influence of the particle size-distribution on the optical spectra.

Formation and properties of ZnO nano-particles from gas phase synthesis processes

ZnO nano-particles have been synthesized in low pressure flow reactors utilizing Zn(CH3)2 as precursor. Two different synthesis routes have been employed. A low pressure flame reactor and a microwave reactor were used for synthesis of ZnO particle in Zn(CH3)2 doped H2/O2/Ar flames and Zn(CH3)2 doped Ar/O2 plasmas, respectively. The particle formation process has been investigated in situ by a particle mass spectrometer. Also, sampled powders have been investigated ex situ by means of FT-IR, XRD, TEM, and UV-VIS. For both synthesis routes nanometer sized ZnO particles were found with particle diameters in the range between 4 to 8 nm. In cases of the flame reactor the results suggest a strong influence of water on the particle formation process.

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.

Electronic properties of doped silicon nanocrystal films

The structural and electrical properties before and after laser annealing of spin-coated films of doped silicon nanocrystals (ncs) produced from the gas phase are presented. While the as-deposited films form a porous network of ncs and show only weak electrical conductivity independent of the doping level, a laser annealing step leads to sintering and melting of the particles and tremendously increases the lateral conductivity. By controlled doping of the initial particles, the conductivity can be further enhanced by seven orders of magnitude reaching values of up to 5 Ω−1 cm−1. The conductivity is found to increase with the doping concentration for highly doped samples while it is independent of the doping level below a critical concentration of 1019 cm−3. The results are discussed within a compensational model taking into account the defect concentration from electron paramagnetic resonance measurements and the activation energies of the electrical conductivity. Surface segregation of phosphorus during ...

Silicon Particle Formation by Pyrolysis of Silane in a Hot Wall Gasphase Reactor

The formation of silicon powder by pyrolysis of silane diluted in argon at different concentrations has been studied. A hot wall gas-phase reactor was used for the thermal decomposition of SiH 4 at 1000°C and atmospheric pressure. The composition, morphology, size, and shape of the particles produced has been studied utilizing electron microscopy, X-ray diffraction, infrared spectroscopy, and BET gas adsorption. Depending on the experimental conditions, agglomerates of polycrystalline, sintered particles have been obtained, which are composed of nanocrystallites of about 25 nm in size.

Electrical properties of aluminum-doped zinc oxide (AZO) nanoparticles synthesized by chemical vapor synthesis.

Aluminum-doped zinc oxide nanoparticles have been prepared by chemical vapor synthesis, which facilitates the incorporation of a higher percentage of dopant atoms, far above the thermodynamic solubility limit of aluminum. The electrical properties of aluminum-doped and undoped zinc oxide nanoparticles were investigated by impedance spectroscopy. The impedance is measured under hydrogen and synthetic air between 323 and 673 K. The measurements under hydrogen as well as under synthetic air show transport properties depending on temperature and doping level. Under hydrogen atmosphere, a decreasing conductivity with increasing dopant content is observed, which can be explained by enhanced scattering processes due to an increasing disorder in the nanocrystalline material. The temperature coefficient for the doped samples switches from positive temperature coefficient behavior to negative temperature coefficient behavior with increasing dopant concentration. In the presence of synthetic air, the conductivity firstly increases with increasing dopant content by six orders of magnitude. The origin of the increasing conductivity is the generation of free charge carriers upon dopant incorporation. It reaches its maximum at a concentration of 7.7% of aluminum, and drops for higher doping levels. In all cases, the conductivity under hydrogen is higher than under synthetic air and can be changed reversibly by changing the atmosphere.

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...

Microcrystalline silicon formation by silicon nanoparticles

Thin silicon films are of great importance for large-area electronic applications, for example, as the basis for switching electronics in flat-panel display devices or as the active layer of solar cells. In this paper, we show that silicon nanoparticles have the potential to be used as raw material for further processing toward a microcrystalline silicon film. This can be done by thermal treatment with a reduced thermal budget because the melting point of the nanoparticles is much lower with only 60% of the equilibrium melting temperature of silicon. Coagulation processes of liquid droplets then lead to the growth of microcrystalline silicon in agglomerated nanoparticles. We demonstrate by in situ transmission electron microscopy (TEM) and differential thermal analysis that silicon nanoparticles with a size of approximately 20nm start melting at around 1000K; furthermore, the TEM observations directly demonstrate the details of the coagulation process leading to microcrystalline silicon.

Comparison of Micro- and Nanoscale Fe+3–Containing (Hematite) Particles for Their Toxicological Properties in Human Lung Cells In Vitro

The specific properties of nanoscale particles, large surface-to-mass ratios and highly reactive surfaces, have increased their commercial application in many fields. However, the same properties are also important for the interaction and bioaccumulation of the nonbiodegradable nanoscale particles in a biological system and are a cause for concern. Hematite (α-Fe₂O₃), being a mineral form of Fe(III) oxide, is one of the most used iron oxides besides magnetite. The aim of our study was the characterization and comparison of biophysical reactivity and toxicological effects of α-Fe₂O₃ nano- (d < 100 nm) and microscale (d < 5 μm) particles in human lung cells. Our study demonstrates that the surface reactivity of nanoscale α-Fe₂O₃ differs from that of microscale particles with respect to the state of agglomeration, radical formation potential, and cellular toxicity. The presence of proteins in culture medium and agglomeration were found to affect the catalytic properties of the hematite nano- and microscale particles. Both the nano- and microscale α-Fe₂O₃ particles were actively taken up by human lung cells in vitro, although they were not found in the nuclei and mitochondria. Significant genotoxic effects were only found at very high particle concentrations (> 50 μg/ml). The nanoscale particles were slightly more potent in causing cyto- and genotoxicity as compared with their microscale counterparts. Both types of particles induced intracellular generation of reactive oxygen species. This study underlines that α-Fe₂O₃ nanoscale particles trigger different toxicological reaction pathways than microscale particles. However, the immediate environment of the particles (biomolecules, physiological properties of medium) modulates their toxicity on the basis of agglomeration rather than their actual size.

Freestanding silicon quantum dots: origin of red and blue luminescence

In this paper, we studied the behavior of silicon quantum dots (Si-QDs) after etching and surface oxidation by means of photoluminescence (PL) measurements, Fourier transform infrared spectroscopy (FTIR) and electron paramagnetic resonance spectroscopy (EPR). We observed that etching of red luminescing Si-QDs with HF acid drastically reduces the concentration of defects and significantly enhances their PL intensity together with a small shift in the emission spectrum. Additionally, we observed the emergence of blue luminescence from Si-QDs during the re-oxidation of freshly etched particles. Our results indicate that the red emission is related to the quantum confinement effect, while the blue emission from Si-QDs is related to defect states at the newly formed silicon oxide surface.