From plasma to nanoparticles: optical and particle emission of a spark discharge generator.

The increased demand for high purity nanoparticles (NPs) of defined geometry necessitates the continuous development of generation routes. One of the most promising physical techniques for producing metal, semiconductor or alloy NPs in the gas phase is spark discharge NP generation. The technique has a great potential for up-scaling without altering the particles. Despite the simplicity of the setup, the formation of NPs in a spark discharge takes place via complex multi-scale processes, which greatly hinders the investigation via conventional NP measurement techniques. In the present work, time-resolved optical emission spectroscopy (OES) was used to provide information on the species present in the spark from as early as approximately 100 ns after the initiation of the discharge. We demonstrate that operando emission spectroscopy can deliver valuable insights into NP formation. The emission spectra of the spark are used to identify, among others, the main stages of material erosion and to calculate the quenching rate of the generated metal vapour. We demonstrate that the alteration of key control parameters, that are typically used to optimize NP generation, clearly affect the emission spectra. We report for Cu and Au NPs that the intensity of spectral lines emitted by metal atoms levels off when spark energy is increased above an energy threshold, suggesting that the maximum concentration of metal vapour produced in the generator is limited. This explains the size variation of the generated NPs. We report a strong correlation between the optical and particle emission of the spark discharge generator, which demonstrate the suitability of OES as a valuable characterization tool that will allow for the more deliberate optimization of spark-based NP generation.

Structural investigation of GaInP nanowires using X-ray diffraction.

In this work the structure of ternary Ga x In1 - x P nanowires is investigated with respect to the chemical composition and homogeneity. The nanowires were grown by metal-organic vapor-phase epitaxy. For the investigation of ensemble fluctuations on several lateral length scales, X-ray diffraction reciprocal space maps have been analyzed. The data reveal a complicated varying materials composition across the sample and in the nanowires on the order of 20%. The use of modern synchrotron sources, where beam-sizes in the order of several 10 µm are available, enables us to investigate compositional gradients along the sample by recording diffraction patterns at different positions. In addition, compositional variations were found also within single nanowires in X-ray energy dispersive spectroscopy measurements.

Particle-assisted Ga(x)In(1-x)P nanowire growth for designed bandgap structures.

Non-tapered vertically straight Ga(x)In(1-x)P nanowires were grown in a compositional range from Ga(0.2)In(0.8)P to pure GaP in particle-assisted mode by controlling the trimethylindium, trimethylgallium and hydrogen chloride flows in metal-organic vapor phase epitaxy. X-ray energy dispersive spectroscopy in transmission electron microscopy revealed homogeneous radial material composition in single nanowires, whereas variations in the material composition were found along the nanowires. High-resolution x-ray diffraction indicates a variation of the material composition on the order of about 19% measuring an entire sample area, i.e., including edge effects during growth. The non-capped nanowires emit room temperature photoluminescence strongly in the energy range of 1.43-2.16 eV, correlated with the bandgap expected from the material composition.

Synthesis and magnetic characterization of MnAs nanoparticles via nanoparticle conversion.

We report on the synthesis of ferromagnetic manganese arsenide (MnAs) nanoparticles via the conversion of primary Mn particles which are generated in an aerosol process in a spark discharge generator. After sintering and size selection in an aerosol setup, the particles are deposited on GaAs(100)B and Si(111) substrates. Subsequent conversion to MnAs particles takes place in an annealing process under a hydrogen atmosphere with an arsine background pressure. The magnetic properties are studied using a SQUID magnetometer. The annealed MnAs particles exhibit hexagonal facets and show anisotropic magnetic behaviour on GaAs(100)B substrates, whereas on Si(111) they remain spherical and show isotropic magnetic behaviour. Scanning transmission electron microscopy studies are used to confirm the conversion from Mn to MnAs.

Controlled polytypic and twin-plane superlattices in iii-v nanowires.

Semiconductor nanowires show promise for use in nanoelectronics, fundamental electron transport studies, quantum optics and biological sensing. Such applications require a high degree of nanowire growth control, right down to the atomic level. However, many binary semiconductor nanowires exhibit a high density of randomly distributed twin defects and stacking faults, which results in an uncontrolled, or polytypic, crystal structure. Here, we demonstrate full control of the crystal structure of InAs nanowires by varying nanowire diameter and growth temperature. By selectively tuning the crystal structure, we fabricate highly reproducible polytypic and twin-plane superlattices within single nanowires. In addition to reducing defect densities, this level of control could lead to bandgap engineering and novel electronic behaviour.

Precursor evaluation for in situ InP nanowire doping.

The use of tetraethyltin (TESn) and dimethylzinc (DMZn) as in situ n- and p-dopant precursors during particle-assisted growth of InP nanowires is reported. Gate voltage dependent transport measurements demonstrate that the nanowires can be predictably synthesized as either n- or p-type. These doped nanowires can be characterized based on their electric field response and we find that n-type doping scales over a range from 10(17) to 10(19) cm(-3) with increasing input TESn dopant molar fraction. On the other hand, the p-type doping using DMZn saturates at low levels, probably related to a strong increase in nanowire growth rate with increasing DMZn molar fractions. By optimizing growth conditions with respect to tapering, axial pn-junctions exhibiting rectifying behavior were fabricated. The pn-junctions can be operated as light emitting diodes.

Core-shell InP-CdS nanowires: fabrication and study.

InP nanowires are fabricated by organo-metallic vapour phase epitaxy and studied via photoluminescence measurements performed on single nanowires, finding evidence of state filling with increasing excitation power density. To increase flexibility in fabrication technology we developed a wet chemical procedure to grow a CdS shell on these wires. In these InP-CdS wires the luminescence efficiency was decreased with respect to the bare wires. The CdS capping procedure needs further investigations to improve the emission properties of nanowires, in order to become technically useful. We suggest as possible improvements of this technique to increase the bath temperature and/or illuminate the sample with UV radiation during the capping procedure.

Aerosol phase generation of In-Se nanoparticles.

Results on the generation and heat treatment of In-Se nanoparticles, made by heterogeneous condensation of selenium on indium nanoparticles synthesised via the evaporation/condensation route are reported. In-situ aerosol measurements are complemented with ex-situ analysis, to provide structural, morphological, and compositional information on the In-Se nanoparticles. Our results indicate that prior to heat treatment In-Se nanoparticles have a shape in the aerosol phase, similar to an asymmetric dumbbell. The bigger particle of the dumbbell structure is made up of amorphous Se, while the overall composition of the polycrystalline smaller particle is around InSe. The smaller particle has an intrinsic structure, and consists of different InSe-compounds, with a decreasing In content towards the shell. The shape of the In-Se nanoparticles is different in the aerosol phase and on the surface of the samples. The observed variety of particle sizes and shapes on the sample surface is shown to be partly due to the agglomeration of the aerosol phase binaries (i.e., dumbbells) via coalescence on the surface of the sample and wetting of the sample surface by the Se nanoparticles. These processes make the bigger particle of the dumbbell structure appear almost perfectly hemispherical on the sample surfaces. During heat treatment at lower temperatures mainly the evaporative removal of the big Se particle of the dumbbell structure will take place. Annealing of the smaller particles starts to dominate at temperatures above 240 degrees C and makes the composition of the small particles closer to that of the thermodynamically most favoured In2Se3.