Insights into the Synthesis Mechanisms of Ag-Cu3P-GaP Multicomponent Nanoparticles.

Metal-semiconductor nanoparticle heterostructures are exciting materials for photocatalytic applications. Phase and facet engineering are critical for designing highly efficient catalysts. Therefore, understanding processes occurring during the nanostructure synthesis is crucial to gain control over properties such as the surface and interface facets' orientations, morphology, and crystal structure. However, the characterization of nanostructures after the synthesis makes clarifying their formation mechanisms nontrivial and sometimes even impossible. In this study, we used an environmental transmission electron microscope with an integrated metal-organic chemical vapor deposition system to enlighten fundamental dynamic processes during the Ag-Cu3P-GaP nanoparticle synthesis using Ag-Cu3P seed particles. Our results reveal that the GaP phase nucleated at the Cu3P surface, and growth proceeded via a topotactic reaction involving counter-diffusion of Cu+ and Ga3+ cations. After the initial GaP growth steps, the Ag and Cu3P phases formed specific interfaces with the GaP growth front. GaP growth proceeded by a similar mechanism observed for the nucleation involving the diffusion of Cu atoms through/along the Ag phase toward other regions, followed by the redeposition of Cu3P at a specific Cu3P crystal facet, not in contact with the GaP phase. The Ag phase was essential for this process by acting as a medium enabling the efficient transport of Cu atoms away from and, simultaneously, Ga atoms toward the GaP-Cu3P interface. This study shows that enlightening fundamental processes is critical for progress in synthesizing phase- and facet-engineered multicomponent nanoparticles with tailored properties for specific applications, including catalysis.

Interface Dynamics in Ag-Cu3P Nanoparticle Heterostructures.

Earth-abundant transition metal phosphides are promising materials for energy-related applications. Specifically, copper(I) phosphide is such a material and shows excellent photocatalytic activity. Currently, there are substantial research efforts to synthesize well-defined metal-semiconductor nanoparticle heterostructures to enhance the photocatalytic performance by an efficient separation of charge carriers. The involved crystal facets and heterointerfaces have a major impact on the efficiency of a heterostructured photocatalyst, which points out the importance of synthesizing potential photocatalysts in a controlled manner and characterizing their structural and morphological properties in detail. In this study, we investigated the interface dynamics occurring around the synthesis of Ag-Cu3P nanoparticle heterostructures by a chemical reaction between Ag-Cu nanoparticle heterostructures and phosphine in an environmental transmission electron microscope. The major product of the Cu-Cu3P phase transformation using Ag-Cu nanoparticle heterostructures with a defined interface as a template preserved the initially present Ag{111} facet of the heterointerface. After the complete transformation, corner truncation of the faceted Cu3P phase led to a physical transformation of the nanoparticle heterostructure. In some cases, the structural rearrangement toward an energetically more favorable heterointerface has been observed and analyzed in detail at the atomic level. The herein-reported results will help better understand dynamic processes in Ag-Cu3P nanoparticle heterostructures and enable facet-engineered surface and heterointerface design to tailor their physical properties.

Airborne Gold Nanoparticle Detection Using Photoluminescence Excited with a Continuous Wave Laser.

We report the observation of photoluminescence emission from airborne gold, silver, and copper nanoparticles. A continuous wave 532 nm laser was employed for excitation. Photoluminescence from gold nanoparticles carried in a nitrogen gas flow was both spectrally resolved and directly imaged in situ using an intensified charge-coupled device camera. The simultaneously detected Raman signal from the nitrogen molecules enables quantitative estimation of the photoluminescence quantum yield of the gold nanoparticles. Photoluminescence from metal nanoparticles carried in a gas flow provides a potential tool for operando imaging of plasmonic metal nanoparticles in aerosol reactions.

General Trends in Core-Shell Preferences for Bimetallic Nanoparticles.

Surface segregation phenomena dictate core-shell preference of bimetallic nanoparticles and thus play a crucial role in the nanoparticle synthesis and applications. Although it is generally agreed that surface segregation depends on the constituent materials' physical properties, a comprehensive picture of the phenomena on the nanoscale is not yet complete. Here we use a combination of molecular dynamics (MD) and Monte Carlo (MC) simulations on 45 bimetallic combinations to determine the general trend on the core-shell preference and the effects of size and composition. From the extensive studies over sizes and compositions, we find that the surface segregation and degree of the core-shell tendency of the bimetallic combinations depend on the sufficiency or scarcity of the surface-preferring material. Principal component analysis (PCA) and linear discriminant analysis (LDA) on the molecular dynamics simulations results reveal that cohesive energy and Wigner-Seitz radius are the two primary factors that have an "additive" effect on the segregation level and core-shell preference in the bimetallic nanoparticles studied. When the element with the higher cohesive energy also has the larger Wigner-Seitz radius, its core preference decreases, and thus this combination forms less segregated structures than what one would expect from the cohesive energy difference alone. Highly segregated structures (highly segregated core-shell or Janus-like) are expected to form when both the relative cohesive energy difference is greater than ∼20%, and the relative Wigner-Seitz radius difference is greater than ∼4%. Practical guides for predicting core-shell preference and degree of segregation level are presented.

Nanoparticle-Assisted Pool Boiling Heat Transfer on Micro-Pin-Fin Surfaces.

Boiling heat transfer intensification is of significant relevance to energy conversion and various cooling processes. This study aimed to enhance the saturated pool boiling of FC-72 (a dielectric liquid) by surface modifications and explore mechanisms of the enhancement. Specifically, circular and square micro pin fins were fabricated on silicon surfaces by dry etching and then copper nanoparticles were deposited on the micro-pin-fin surfaces by electrostatic deposition. Experimental results indicated that compared with a smooth surface, the micro pin fins increased the heat transfer coefficient and the critical heat flux by more than 200 and 65-83%, respectively, which were further enhanced by the nanoparticles up to 24% and more than 20%, respectively. Correspondingly, the enhancement mechanism was carefully explored by high-speed bubble visualizations, surface wickability measurements, and model analysis. It was quantitatively found that small bubble departure diameters with high bubble departure frequencies promoted high heat transfer coefficients. The wickability, which characterizes the ability of a liquid to rewet a surface, played an important role in determining the critical heat flux, but further analyses indicated that evaporation beneath bubbles was also essential and competition between the wicking and the evaporation finally triggered the critical heat flux.

Continuous gas-phase synthesis of core-shell nanoparticles via surface segregation.

Synthesis methods of highly functional core@shell nanoparticles with high throughput and high purity are in great demand for applications, including catalysis and optoelectronics. Traditionally chemical synthesis has been widely explored, but recently, gas-phase methods have attracted attention since such methods can provide a more flexible choice of materials and altogether avoid solvents. Here, we demonstrate that Cu@Ag core-shell nanoparticles with well-controlled size and compositional variance can be generated via surface segregation using spark ablation with an additional heating step, which is a continuous gas-phase process. The characterization of the nanoparticles reveals that the Cu-Ag agglomerates generated by spark ablation adopt core-shell or quasi-Janus structures depending on the compaction temperature used to transform the agglomerates into spherical particles. Molecular dynamics (MD) simulations verify that the structural evolution is caused by heat-induced surface segregation. With the incorporated heat treatment that acts as an annealing and equilibrium cooling step after the initial nucleation and growth processes in the spark ablation, the presented method is suitable for creating nanoparticles with both uniform size and composition and uniform bimetallic configuration. We confirm the compositional uniformity between particles by analyzing compositional variance of individual particles rather than presenting an ensemble-average of many particles. This gas-phase synthesis method can be employed for generating other bi- or multi-metallic nanoparticles with the predicted configuration of the structure from the surface energy and atomic size of the elements.

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.

Simultaneous Growth of Pure Wurtzite and Zinc Blende Nanowires.

The opportunity to engineer III-V nanowires in wurtzite and zinc blende crystal structure allows for exploring properties not conventionally available in the bulk form as well as opening the opportunity for use of additional degrees of freedom in device fabrication. However, the fundamental understanding of the nature of polytypism in III-V nanowire growth is still lacking key ingredients to be able to connect the results of modeling and experiments. Here we show InP nanowires of both pure wurtzite and pure zinc blende grown simultaneously on the same InP [100]-oriented substrate. We find wurtzite nanowires to grow along [Formula: see text] and zinc blende counterparts along [Formula: see text]. Further, we discuss the nucleation, growth, and polytypism of our nanowires against the background of existing theory. Our results demonstrate, first, that the crystal growth conditions for wurtzite and zinc blende nanowire growth are not mutually exclusive and, second, that the interface energies predominantly determine the crystal structure of the 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.

Self-Seeded Axio-Radial InAs-InAs1-xPx Nanowire Heterostructures beyond "Common" VLS Growth.

Semiconductors are essential for modern electronic and optoelectronic devices. To further advance the functionality of such devices, the ability to fabricate increasingly complex semiconductor nanostructures is of utmost importance. Nanowires offer excellent opportunities for new device concepts; heterostructures have been grown in either the radial or axial direction of the core nanowire but never along both directions at the same time. This is a consequence of the common use of a foreign metal seed particle with fixed size for nanowire heterostructure growth. In this work, we present for the first time a growth method to control heterostructure growth in both the axial and the radial directions simultaneously while maintaining an untapered self-seeded growth. This is demonstrated for the InAs/InAs1-xPx material system. We show how the dimensions and composition of such axio-radial nanowire heterostructures can be designed including the formation of a "pseudo-superlattice" consisting of five separate InAs1-xPx segments with varying length. The growth of axio-radial nanowire heterostructures offers an exciting platform for novel nanowire structures applicable for fundamental studies as well as nanowire devices. The growth concept for axio-radial nanowire heterostructures is expected to be fully compatible with Si substrates.

Recombination dynamics in aerotaxy-grown Zn-doped GaAs nanowires.

In this paper we have investigated the dynamics of photo-generated charge carriers in a series of aerotaxy-grown GaAs nanowires (NWs) with different levels of Zn doping. Time-resolved photo-induced luminescence and transient absorption have been employed to investigate radiative (band edge transition) and non-radiative charge recombination processes, respectively. We find that the photo-luminescence (PL) lifetime of intrinsic GaAs NWs is significantly increased after growing an AlGaAs shell over them, indicating that an AlGaAs shell can effectively passivate the surface of aerotaxy-grown GaAs NWs. We observe that PL decay time as well as PL intensity decrease with increasing Zn doping, which can be attributed to thermally activated electron trapping with the trap density increased due to the Zn doping level.

GaAsP Nanowires Grown by Aerotaxy.

We have grown GaAsP nanowires with high optical and structural quality by Aerotaxy, a new continuous gas phase mass production process to grow III-V semiconductor based nanowires. By varying the PH3/AsH3 ratio and growth temperature, size selected GaAs1-xPx nanowires (80 nm diameter) with pure zinc-blende structure and with direct band gap energies ranging from 1.42 to 1.90 eV (at 300 K), (i.e., 0 ≤ x ≤ 0.43) were grown, which is the energy range needed for creating tandem III-V solar cells on silicon. The phosphorus content in the NWs is shown to be controlled by both growth temperature and input gas phase ratio. The distribution of P in the wires is uniform over the length of the wires and among the wires. This proves the feasibility of growing GaAsP nanowires by Aerotaxy and results indicate that it is a generic process that can be applied to the growth of other III-V semiconductor based ternary nanowires.

Surface morphology of Au-free grown nanowires after native oxide removal.

Using scanning tunneling microscopy, we evaluate the surface structure and morphology down to the atomic scale for micrometers along Au-free grown InAs nanowires (NWs) free from native oxide. We find that removal of the native oxide (which covers the NWs upon exposure to the ambient air) using atomic hydrogen does not alter the underlying step structure. Imaging with sub-nanometer resolution along the NWs, we find an extremely low tapering (diameter change along the NW) of 1.7 ± 0.5 ŵm(-1). A surface morphology with monolayer high islands, whose shape was influenced by stacking faults, was found to cover the NWs and was attributed to the decomposed native oxide. The appearance of point defects in the form of As-vacancies at the surface is analyzed and we set limits to the amount of carbon impurities in the NWs.

X-ray diffraction strain analysis of a single axial InAs 1-x Px nanowire segment.

The spatial strain distribution in and around a single axial InAs 1-x Px hetero-segment in an InAs nanowire was analyzed using nano-focused X-ray diffraction. In connection with finite-element-method simulations a detailed quantitative picture of the nanowire's inhomogeneous strain state was achieved. This allows for a detailed understanding of how the variation of the nanowire's and hetero-segment's dimensions affect the strain in its core region and in the region close to the nanowire's side facets. Moreover, ensemble-averaging high-resolution diffraction experiments were used to determine statistical information on the distribution of wurtzite and zinc-blende crystal polytypes in the nanowires.

Direct deposition of gas phase generated aerosol gold nanoparticles into biological fluids--corona formation and particle size shifts.

An ongoing discussion whether traditional toxicological methods are sufficient to evaluate the risks associated with nanoparticle inhalation has led to the emergence of Air-Liquid interface toxicology. As a step in this process, this study explores the evolution of particle characteristics as they move from the airborne state into physiological solution. Airborne gold nanoparticles (AuNP) are generated using an evaporation-condensation technique. Spherical and agglomerate AuNPs are deposited into physiological solutions of increasing biological complexity. The AuNP size is characterized in air as mobility diameter and in liquid as hydrodynamic diameter. AuNP:Protein aggregation in physiological solutions is determined using dynamic light scattering, particle tracking analysis, and UV absorption spectroscopy. AuNPs deposited into homocysteine buffer form large gold-aggregates. Spherical AuNPs deposited in solutions of albumin were trapped at the Air-Liquid interface but was readily suspended in the solutions with a size close to that of the airborne particles, indicating that AuNP:Protein complex formation is promoted. Deposition into serum and lung fluid resulted in larger complexes, reflecting the formation of a more complex protein corona. UV absorption spectroscopy indicated no further aggregation of the AuNPs after deposition in solution. The corona of the deposited AuNPs shows differences compared to AuNPs generated in suspension. Deposition of AuNPs from the aerosol phase into biological fluids offers a method to study the protein corona formed, upon inhalation and deposition in the lungs in a more realistic way compared to particle liquid suspensions. This is important since the protein corona together with key particle properties (e.g. size, shape and surface reactivity) to a large extent may determine the nanoparticle effects and possible translocation to other organs.

Solid-liquid-vapor metal-catalyzed etching of lateral and vertical nanopores.

Etching is an essential tool for the creation of nanostructures, where patterned metal structures can be used as masks. Here, we investigate HCl gas etching of InP substrates decorated with Au nanoparticles, and find that the etch rate is strongly increased at the Au-InP interfaces. The {111}A facets of the InP are preferentially etched. The metal nanoparticles follow in the etch direction, thereby creating nanopores. The size and position of the pores is controlled by the Au nanoparticles, and we measure nanopores as thin as 20 nm with an aspect ratio of 25:1. The direction of the nanopores is influenced by the temperature and the substrate orientation, which we use to demonstrate lateral, vertical and inclined nanopores. We explain the process by a solid-liquid-vapor model, in which the liquid metal particle catalyzes the dissolution of the solid InP.

A general approach for sharp crystal phase switching in InAs, GaAs, InP, and GaP nanowires using only group V flow.

III-V-based nanowires usually exhibit random mixtures of wurtzite (WZ) and zinc blende (ZB) crystal structure, and pure crystal phase wires represent the exception rather than the rule. In this work, the effective group V hydride flow was the only growth parameter which was changed during MOVPE growth to promote transitions from WZ to ZB and from ZB to WZ. Our technique works in the same way for all investigated III-Vs (GaP, GaAs, InP, and InAs), with low group V flow for WZ and high group V flow for ZB conditions. This strongly suggests a common underlying mechanism. It displays to our best knowledge the simplest changes of the growth condition to control the nanowire crystal structure. The inherent reduction of growth variables is a crucial requirement for the interpretation in the frame of existing understanding of polytypism in III-V nanowires. We show that the change in surface energetics of the vapor-liquid-solid system at the vapor-liquid and liquid-solid interface is likely to control the crystal structure in our nanowires.

InP nanowire array solar cells achieving 13.8% efficiency by exceeding the ray optics limit.

Photovoltaics based on nanowire arrays could reduce cost and materials consumption compared with planar devices but have exhibited low efficiency of light absorption and carrier collection. We fabricated a variety of millimeter-sized arrays of p-type/intrinsic/n-type (p-i-n) doped InP nanowires and found that the nanowire diameter and the length of the top n-segment were critical for cell performance. Efficiencies up to 13.8% (comparable to the record planar InP cell) were achieved by using resonant light trapping in 180-nanometer-diameter nanowires that only covered 12% of the surface. The share of sunlight converted into photocurrent (71%) was six times the limit in a simple ray optics description. Furthermore, the highest open-circuit voltage of 0.906 volt exceeds that of its planar counterpart, despite about 30 times higher surface-to-volume ratio of the nanowire cell.

Gas-borne particles with tunable and highly controlled characteristics for nanotoxicology studies.

For nanotoxicology investigations of air-borne particles to provide relevant results it is ever so important that the particle exposure of, for example cells, closely resembles the "real" exposure situation, that the dosimetry is well defined, and that the characteristics of the deposited nanoparticles are known in detail. By synthesizing the particles in the gas-phase and directly depositing them on lung cells the particle deposition conditions in the lung is closely mimicked. In this work we present a setup for generation of gas-borne nanoparticles of a variety of different materials with highly controlled and tunable particle characteristics, and demonstrate the method by generation of gold particles. Particle size, number concentration and mass of individual particles of the population are measured on-line by means of differential mobility analyzers (DMA) and an aerosol particle mass analyzer (APM), whereas primary particle size and internal structure are investigated by transmission electron microscopy. A method for estimating the surface area dose from the DMA-APM measurements is applied and we further demonstrate that for the setup used, a deposition time of around 1 h is needed for deposition onto cells in an air-liquid interface chamber, using electrostatic deposition, to reach a toxicological relevant surface area dose.

Continuous gas-phase synthesis of nanowires with tunable properties.

Semiconductor nanowires are key building blocks for the next generation of light-emitting diodes, solar cells and batteries. To fabricate functional nanowire-based devices on an industrial scale requires an efficient methodology that enables the mass production of nanowires with perfect crystallinity, reproducible and controlled dimensions and material composition, and low cost. So far there have been no reports of reliable methods that can satisfy all of these requirements. Here we show how aerotaxy, an aerosol-based growth method, can be used to grow nanowires continuously with controlled nanoscale dimensions, a high degree of crystallinity and at a remarkable growth rate. In our aerotaxy approach, catalytic size-selected Au aerosol particles induce nucleation and growth of GaAs nanowires with a growth rate of about 1 micrometre per second, which is 20 to 1,000 times higher than previously reported for traditional, substrate-based growth of nanowires made of group III-V materials. We demonstrate that the method allows sensitive and reproducible control of the nanowire dimensions and shape--and, thus, controlled optical and electronic properties--through the variation of growth temperature, time and Au particle size. Photoluminescence measurements reveal that even as-grown nanowires have good optical properties and excellent spectral uniformity. Detailed transmission electron microscopy investigations show that our aerotaxy-grown nanowires form along one of the four equivalent〈111〉B crystallographic directions in the zincblende unit cell, which is also the preferred growth direction for III-V nanowires seeded by Au particles on a single-crystal substrate. The reported continuous and potentially high-throughput method can be expected substantially to reduce the cost of producing high-quality nanowires and may enable the low-cost fabrication of nanowire-based devices on an industrial scale.