Sub-Picosecond Carrier Dynamics Explored using Automated High-Throughput Studies of Doping Inhomogeneity within a Bayesian Framework.

Bottom-up production of semiconductor nanomaterials is often accompanied by inhomogeneity resulting in a spread in electronic properties which may be influenced by the nanoparticle geometry, crystal quality, stoichiometry, or doping. Using photoluminescence spectroscopy of a population of more than 11 000 individual zinc-doped gallium arsenide nanowires, inhomogeneity is revealed in, and correlation between doping and nanowire diameter by use of a Bayesian statistical approach. Recombination of hot-carriers is shown to be responsible for the photoluminescence lineshape; by exploiting lifetime variation across the population, hot-carrier dynamics is revealed at the sub-picosecond timescale showing interband electronic dynamics. High-throughput spectroscopy together with a Bayesian approach are shown to provide unique insight in an inhomogeneous nanomaterial population, and can reveal electronic dynamics otherwise requiring complex pump-probe experiments in highly non-equilibrium conditions.

Aerotaxy: gas-phase epitaxy of quasi 1D nanostructures.

Cost- and resource-efficient growth is necessary for many applications of semiconductor nanowires. We here present the design, operational details and theory behind Aerotaxy, a scalable alternative technology for producing quality crystalline nanowires at a remarkably high growth rate and throughput. Using size-controlled Au seed particles and organometallic precursors, Aerotaxy can produce nanowires with perfect crystallinity and controllable dimensions, and the method is suitable to meet industrial production requirements. In this report, we explain why Aerotaxy is an efficient method for fabricating semiconductor nanowires and explain the technical aspects of our custom-built Aerotaxy system. Investigations using SEM (scanning electron microscope), TEM (transmission electron microscope) and other characterization methods are used to support the claim that Aerotaxy is indeed a scalable method capable of producing nanowires with reproducible properties. We have investigated both binary and ternary III-V semiconductor material systems like GaAs and GaAsP. In addition, common aspects of Aerotaxy nanowires deduced from experimental observations are used to validate the Aerotaxy growth model, based on a computational flow dynamics (CFD) approach. We compare the experimental results with the model behaviour to better understand Aerotaxy growth.

Optical far-field extinction of a single GaAs nanowire towards in situ size control of aerotaxy nanowire growth.

A substrate-free approach of semiconductor nanowire growth has been achieved by the aerotaxy technique previously. In this work, we propose an in situ method to monitor the size of nanowires through non-destructive optical-extinction measurements. Our work aims to build a theoretical look-up database of extinction spectra for a single nanowire of varying dimensions. We describe the origin of possible peaks in the spectra, for example due to nanowire-length dependent Fabry-Perot resonances and nanowire-diameter dependent TM and TE mode resonances. Furthermore, we show that the Au catalyst on top of the nanowire can be ignored in the simulations when the volume of the nanowire is an order of magnitude larger than that of the Au catalyst and the diameter is small compared to the incident wavelength. For the calculation of the extinction spectra, we use the finite element method, the discrete dipole approximation and the Mie theory. To compare with experimental measurements of randomly oriented nanowires, we perform an averaging over nanowire orientation for the modeled results. However, in the experiments, nanowires are accumulating on the quartz window of the measurement setup, which leads to increasing uncertainty in the comparison with the experimental extinction spectra. This uncertainty can be eliminated by considering both a sparse and a dense collection of nanowires on the quartz window in the optical simulations. Finally, we create a database of extinction spectra for a GaAs nanowire of varying diameters and lengths. This database can be used to estimate the diameter and the length of the nanowires by comparing the position of a peak and the peak-to-shoulder difference in the extinction spectrum. Possible tapering of nanowires can be monitored through the appearance of an additional peak at a wavelength of 700-800 nm.

Electron Tomography Reveals the Droplet Covered Surface Structure of Nanowires Grown by Aerotaxy.

For the purpose of functionalizing III-V semiconductor nanowires using n-doping, Sn-doped GaAs zincblende nanowires are produced, using the growth method of Aerotaxy. The growth conditions used are such that Ga droplets, formed on the nanowire surface, increase in number and concentrations when the Sn-precursor concentration is increased. Droplet-covered wires grown with varying Sn concentrations are analyzed by transmission electron microscopy and electron tomography, which together establish the positioning of the droplets to be preferentially on {-111}B facets. These facets have the same polarity as the main wire growth direction, [-1-1-1]B. This means that the generated Ga particles can form nucleation sites for possible nanowire branch growth. The concept of azimuthal mapping is introduced as a useful tool for nanowire surface visualization and evaluation. It is demonstrated here that electron tomography is useful in revealing both the surface and internal morphologies of the nanowires, opening up for applications in the analysis of more structurally complicated systems like radially asymmetrical nanowires. The analysis also gives a further understanding of the limits of the dopants which can be used for Aerotaxy nanowires.

n-type doping and morphology of GaAs nanowires in Aerotaxy.

Controlled doping in semiconductor nanowires modifies their electrical and optical properties, which are important for high efficiency optoelectronic devices. We have grown n-type (Sn) doped GaAs nanowires in Aerotaxy, a new continuous gas phase mass production technique. The morphology of Sn doped nanowires is found to be a strong function of dopant, tetraethyltin to trimethylgallium flow ratio, Au-Ga-Sn alloying, and nanowire growth temperatures. High temperature and high flow ratios result in low morphological quality nanowires and in parasitic growth on the wire base and surface. Alloying and growth temperatures of 400 °C and 530 °C, respectively, resulted in good morphological quality nanowires for a flow ratio of TESn to TMGa up to 2.25 × 10-3. The wires are pure zinc-blende for all investigated growth conditions, whereas nanowires grown by metal-organic vapor phase epitaxy with the same growth conditions are usually mainly Wurtzite. The growth rate of the doped wires is found to be dependent more on the TESn flow fraction than on alloying and nanowire growth temperatures. Our photoluminescence measurements, supported by four-point probe resistivity measurements, reveal that the carrier concentration in the doped wires varies only slightly (1-3) × 1019 cm-3 with TESn flow fraction and both alloying and growth temperatures, indicating that good morphological quality wires with high carrier density can be grown with low TESn flow. Carrier concentrations lower than 1019 cm-3 can be grown by further reducing the flow fraction of TESn, which may give better morphology wires.

Enhanced Optical Biosensing by Aerotaxy Ga(As)P Nanowire Platforms Suitable for Scalable Production.

Sensitive detection of low-abundance biomolecules is central for diagnostic applications. Semiconductor nanowires can be designed to enhance the fluorescence signal from surface-bound molecules, prospectively improving the limit of optical detection. However, to achieve the desired control of physical dimensions and material properties, one currently uses relatively expensive substrates and slow epitaxy techniques. An alternative approach is aerotaxy, a high-throughput and substrate-free production technique for high-quality semiconductor nanowires. Here, we compare the optical sensing performance of custom-grown aerotaxy-produced Ga(As)P nanowires vertically aligned on a polymer substrate to GaP nanowires batch-produced by epitaxy on GaP substrates. We find that signal enhancement by individual aerotaxy nanowires is comparable to that from epitaxy nanowires and present evidence of single-molecule detection. Platforms based on both types of nanowires show substantially higher normalized-to-blank signal intensity than planar glass surfaces, with the epitaxy platforms performing somewhat better, owing to a higher density of nanowires. With further optimization, aerotaxy nanowires thus offer a pathway to scalable, low-cost production of highly sensitive nanowire-based platforms for optical biosensing applications.

Dual topography of laminin corona on gallium arsenide nanowires.

Nanowires (NWs) are novel nanomaterials with applications in everything from medical implants to solar cells. With increasing number of applications, it is increasingly likely that organisms are exposed to these materials either intentionally or by accident. It is, therefore, important to study their interactions with biological systems and biomolecules. Upon exposure to biological fluids, nanostructure surfaces are quickly covered by a biomolecule corona. The composition of the corona determines the nanostructure's biological fate. Furthermore, upon adsorption, the protein structure can be affected. In order to study the corona morphology, we used two model proteins, laminin of the extracellular matrix and the immune system enzyme myeloperoxidase. We image the protein corona directly by cryo-TEM and enhance resolution by labeling the corona with activated gold nanoparticles. Three-dimensional imaging of the protein corona further increases the resolution and reveals irregularities in corona topography. By doing so, we identified bimodal distribution of spacing between gold nanoparticles and the NW surface for laminin corona at 58 and 85 nm distance from the NWs' surface. The dual topography of the corona is adding a new complexity of the protein corona surface and its interactions with the surrounding biology.

Calculation of Hole Concentrations in Zn Doped GaAs Nanowires.

We have previously demonstrated that we can grow p-type GaAs nanowires using Zn doping during gold catalyzed growth with aerotaxy. In this investigation, we show how to calculate the hole concentrations in such nanowires. We base the calculations on the Zhang-Northrup defect formation energy. Using density functional theory, we calculate the energy of the defect, a Zn atom on a Ga site, using a supercell approach. The chemical potentials of Zn and Ga in the liquid catalyst particle are calculated from a thermodynamically assessed database including Au, Zn, Ga, and As. These quantities together with the chemical potential of the carriers enable us to calculate the hole concentration in the nanowires self-consistently. We validate our theoretical results against aerotaxy grown GaAs nanowires where we have varied the hole concentration by varying the Zn/Ga ratio in the aerotaxy growth.

Workplace Emissions and Exposures During Semiconductor Nanowire Production, Post-production, and Maintenance Work.

BACKGROUND: Nanowires are a high-aspect-ratio material of increasing interest for a wide range of applications. A new and promising method to produce nanowires is by aerotaxy, where the wires are grown in a continuous stream of gas. The aerotaxy method can grow nanowires much faster than by more conventional methods. Nanowires have important properties in common with asbestos fibers, which indicate that there can be potential health effects if exposure occurs. No conclusive exposure (or emission) data from aerotaxy-production of nanowires has so far been published. METHODS: Different work tasks during semiconductor nanowire production, post-production, and maintenance were studied. A combination of direct-reading instruments for number concentration (0.007-20 µm) and filter sampling was used to assess the emissions (a couple of centimeter from the emission sources), the exposure in the personal breathing zone (max 30 cm from nose-mouth), and the concentrations in the background zone (at least 3 m from any emission source). The filters were analyzed for metal dust composition and number concentration of nanowires. Various surfaces were sampled for nanowire contamination. RESULTS: The particle concentrations in the emission zone (measured with direct-reading instruments) were elevated during cleaning of arc discharge, manual reactor cleaning, exchange of nanowire outflow filters, and sonication of substrates with nanowires. In the case of cleaning of the arc discharge and manual reactor cleaning, the emissions affected the concentrations in the personal breathing zone and were high enough to also affect the concentrations in the background. Filter analysis with electron microscopy could confirm the presence of nanowires in some of the air samples. CONCLUSIONS: Our results show that a major part of the potential for exposure occurs not during the actual manufacturing, but during the cleaning and maintenance procedures. The exposures and emissions were evaluated pre- and post-upscaling the production and showed that some work tasks (e.g. exchange of nanowire outflow filters and sonication of substrates with nanowires) increased the emissions post-upscaling.