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.

Compositional analysis of oxide-embedded III-V nanostructures.

Nanowire growth enables creation of embedded heterostructures, where one material is completely surrounded by another. Through materials-selective post-growth oxidation it is also possible to combine amorphous oxides and crystalline, e.g. III-V materials. Such oxide-embedded structures pose a challenge for compositional characterization through transmission electron microscopy since the materials will overlap in projection. Furthermore, materials electrically isolated by an embedding oxide are more sensitive to electron beam-induced alterations. Methods that can directly isolate the embedded material, preferably at reduced electron doses, will be required in this situation. Here, we analyse the performance of two such techniques-local lattice parameter measurements from high resolution micrographs and bulk plasmon energy measurements from electron energy loss spectra-by applying them to analyse InP-AlInP segments embedded in amorphous aluminium oxide. We demonstrate the complementarity of the two methods, which show an overall excellent agreement. However, in regions with residual strain, which we analyse through molecular dynamics simulations, the two techniques diverge from the true value in opposite directions.

Characterisation of worn WC tool using STEM-EDS aided by principal component analysis.

Interdiffusion and chemical reactions contribute to tool wear in metal machining. Increased understanding of these processes, through characterisation of worn tools, can facilitate design of more resilient materials through chemical and diffusional passivation. However, the unknown reaction conditions, the large number of elements, and the formation of interspersed phases makes for a complex analysis. Here, we demonstrate the use of scanning transmission electron microscopy and energy dispersive X-ray spectroscopy for characterising the interaction layer between a titanium alloy and a cemented carbide tool. Principal component analysis is used to find chemical correlations and help separate signals from embedded phases. Crucially, we evaluate the required X-ray count statistics from simulated spectrum images and theory prior to the experiment. We find no indications of intermediate phases between the original WC and the metallic W interaction layer. Furthermore, we find enrichment of minor constituents in the titanium alloy closest to the tool which alter the solubility of out-diffusing species, suggesting strong interrelations between the diffusion processes.

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.

Atomic-Scale Choreography of Vapor-Liquid-Solid Nanowire Growth.

Functional materials and devices require nanoscale control of morphology, crystal structure, and composition. Vapor-liquid-solid (VLS) crystal growth and its related growth modes enable the synthesis of 1D nanostructures, commonly called "nanowires", where the necessary nanoscale heterogeneity can be encoded axially. During the VLS process, a seed particle collects atoms and directs the nucleation of crystalline material. Modulating the delivery of growth species or conditions permits compositional and/or structural encoding. A range of materials and devices (e.g., for electronics, photonics, thermal transport, and bioprobes) have been produced by VLS growth, but plenty of challenges remain: many desirable structures cannot currently be made, and even for those structures that can be made, the parameter window-in terms of, e.g., temperatures and pressures-is often narrow. Moreover, we are quite far from ab initio determination of which growth conditions should be used or even if a desired structure is fundamentally achievable within the VLS framework. To fully understand the challenges and promises of VLS growth, the governing physicochemical processes must be explored and understood at the atomic scale. This final level of detail is being unraveled with the help of in situ characterization techniques. The picture that is emerging is of a highly dynamical process with several deeply interconnected and highly fundamental components that are difficult to detect with postgrowth ex situ interrogation. For example, recent in situ microscopy and spectroscopy studies have shown that the growth front can undergo cyclical reshaping involving dissolution as well as crystallization and that the state of the nanowire surface, which changes with growth conditions as a result of a competition between adsorption and desorption of passivating species, plays a crucial role in determining the transport to/from and the stability of the seed particle. The available in situ observations currently constitute a somewhat disparate list, but if they can be connected to each other and to the outstanding challenges, they promise meaningful advances in our understanding of VLS growth. In this Account, we review the state of the art regarding the atomic-scale thermodynamic and kinetic phenomena that control VLS growth. Rather than cataloging all of the outstanding contributions to the field, we give priority to in situ observations that have revealed unexpected effects as well as those that hint at incongruities in our current knowledge. As such, our discussion should be viewed as an opportunity to gain deeper understanding and control of the fundamental processes at play, which will be crucial in future scale-up efforts and expansion to completely new materials systems and application areas.

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.

In situ etching for control over axial and radial III-V nanowire growth rates using HBr.

We report on the influence of hydrogen bromide (HBr) in situ etching on the growth of InP, GaP and GaAs nanowires. We find that HBr can be used to impede undesired radial growth during axial growth for all three material systems. The use of HBr opens a window for optimizing the growth parameters with respect to the materials' quality rather than only their morphology. Transmission electron microscopy (TEM) characterization reveals a partial transition from a wurtzite crystal structure to a zincblende upon the use of HBr during growth. For InP, defect-related luminescence due to parasitic radial growth is removed by use of HBr. For GaP, the etching with HBr reduced the defect-related luminescence, but no change in peak emission energy was observed. For GaAs, the HBr etching resulted in a shift to lower photon emission energies due to a shift in the crystal structure, which reduced the wurtzite segments.

FIB plan and side view cross-sectional TEM sample preparation of nanostructures.

Focused ion beam is a powerful method for cross-sectional transmission electron microscope sample preparation due to being site specific and not limited to certain materials. It has, however, been difficult to apply to many nanostructured materials as they are prone to damage due to extending from the surface. Here we show methods for focused ion beam sample preparation for transmission electron microscopy analysis of such materials, demonstrated on GaAs-GaInP core shell nanowires. We use polymer resin as support and protection and are able to produce cross-sections both perpendicular to and parallel with the substrate surface with minimal damage. Consequently, nanowires grown perpendicular to the substrates could be imaged both in plan and side view, including the nanowire-substrate interface in the latter case. Using the methods presented here we could analyze the faceting and homogeneity of hundreds of adjacent nanowires in a single lamella.

Combining axial and radial nanowire heterostructures: radial Esaki diodes and tunnel field-effect transistors.

The ever-growing demand on high-performance electronics has generated transistors with very impressive figures of merit (Radosavljevic et al., IEEE Int. Devices Meeting 2009, 1-4 and Cho et al., IEEE Int. Devices Meeting 2011, 15.1.1-15.1.4). The continued scaling of the supply voltage of field-effect transistors, such as tunnel field-effect transistors (TFETs), requires the implementation of advanced transistor architectures including FinFETs and nanowire devices. Moreover, integration of novel materials with high electron mobilities, such as III-V semiconductors and graphene, are also being considered to further enhance the device properties (del Alamo, Nature 2011, 479, 317-323, and Liao et al., Nature 2010, 467, 305-308). In nanowire devices, boosting the drive current at a fixed supply voltage or maintaining a constant drive current at a reduced supply voltage may be achieved by increasing the cross-sectional area of a device, however at the cost of deteriorated electrostatics. A gate-all-around nanowire device architecture is the most favorable electrostatic configuration to suppress short channel effects; however, the arrangement of arrays of parallel vertical nanowires to address the drive current predicament will require additional chip area. The use of a core-shell nanowire with a radial heterojunction in a transistor architecture provides an attractive means to address the drive current issue without compromising neither chip area nor device electrostatics. In addition to design advantages of a radial transistor architecture, we in this work illustrate the benefit in terms of drive current per unit chip area and compare the experimental data for axial GaSb/InAs Esaki diodes and TFETs to their radial counterparts and normalize the electrical data to the largest cross-sectional area of the nanowire, i.e. the occupied chip area, assuming a vertical device geometry. Our data on lateral devices show that radial Esaki diodes deliver almost 7 times higher peak current, Jpeak = 2310 kA/cm(2), than the maximum peak current of axial GaSb/InAs(Sb) Esaki diodes per unit chip area. The radial TFETs also deliver high peak current densities Jpeak = 1210 kA/cm(2), while their axial counterparts at most carry Jpeak = 77 kA/cm(2), normalized to the largest cross-sectional area of the nanowire.

Semiconductor-oxide heterostructured nanowires using postgrowth oxidation.

Semiconductor-oxide heterointerfaces have several electron volts high-charge carrier potential barriers, which may enable devices utilizing quantum confinement at room temperature. While a single heterointerface is easily formed by oxide deposition on a crystalline semiconductor, as in MOS transistors, the amorphous structure of most oxides inhibits epitaxy of a second semiconductor layer. Here, we overcome this limitation by separating epitaxy from oxidation, using postgrowth oxidation of AlP segments to create axial and core-shell semiconductor-oxide heterostructured nanowires. Complete epitaxial AlP-InP nanowire structures were first grown in an oxygen-free environment. Subsequent exposure to air converted the AlP segments into amorphous aluminum oxide segments, leaving isolated InP segments in an oxide matrix. InP quantum dots formed on the nanowire sidewalls exhibit room temperature photoluminescence with small line widths (down to 15 meV) and high intensity. This optical performance, together with the control of heterostructure segment length, diameter, and position, opens up for optoelectrical applications at room temperature.

Electron trapping in InP nanowire FETs with stacking faults.

Semiconductor III-V nanowires are promising components of future electronic and optoelectronic devices, but they typically show a mixed wurtzite-zinc blende crystal structure. Here we show, theoretically and experimentally, that the crystal structure dominates the conductivity in such InP nanowires. Undoped devices show very low conductivities and mobilities. The zincblende segments are quantum wells orthogonal to the current path and our calculations indicate that an electron concentration of up to 4.6 × 10(18) cm(-3) can be trapped in these. The calculations also show that the room temperature conductivity is controlled by the longest zincblende segment, and that stochastic variations in this length lead to an order of magnitude variation in conductivity. The mobility shows an unexpected decrease for low doping levels, as well as an unusual temperature dependence that bear resemblance with polycrystalline semiconductors.

Single InAs/GaSb nanowire low-power CMOS inverter.

III-V semiconductors have so far predominately been employed for n-type transistors in high-frequency applications. This development is based on the advantageous transport properties and the large variety of heterostructure combinations in the family of III-V semiconductors. In contrast, reports on p-type devices with high hole mobility suitable for complementary metal-oxide-semiconductor (CMOS) circuits for low-power operation are scarce. In addition, the difficulty to integrate both n- and p-type devices on the same substrate without the use of complex buffer layers has hampered the development of III-V based digital logic. Here, inverters fabricated from single n-InAs/p-GaSb heterostructure nanowires are demonstrated in a simple processing scheme. Using undoped segments and aggressively scaled high-κ dielectric, enhancement mode operation suitable for digital logic is obtained for both types of transistors. State-of-the-art on- and off-state characteristics are obtained and the individual long-channel n- and p-type transistors exhibit minimum subthreshold swings of SS = 98 mV/dec and SS = 400 mV/dec, respectively, at V(ds) = 0.5 V. Inverter characteristics display a full signal swing and maximum gain of 10.5 with a small device-to-device variability. Complete inversion is measured at low frequencies although large parasitic capacitances deform the waveform at higher frequencies.

Demonstration of defect-free and composition tunable GaxIn1-xSb nanowires.

The Ga(x)In(1-x)Sb ternary system has many interesting material properties, such as high carrier mobilities and a tunable range of bandgaps in the infrared. Here we present the first report on the growth and compositional control of Ga(x)In(1-x)Sb material grown in the form of nanowires from Au seeded nanoparticles by metalorganic vapor phase epitaxy. The composition of the grown Ga(x)In(1-x)Sb nanowires is precisely controlled by tuning the growth parameters where x varies from 1 to ∼0.3. Interestingly, the growth rate of the Ga(x)In(1-x)Sb nanowires increases with diameter, which we model based on the Gibbs-Thomson effect. Nanowire morphology can be tuned from high to very low aspect ratios, with perfect zinc blende crystal structure regardless of composition. Finally, electrical characterization on nanowire material with a composition of Ga(0.6)In(0.4)Sb showed clear p-type behavior.

Mo3Ni2N Nanoparticle Generation by Spark Discharge.

Spark ablation is an advantageous method for the generation of metallic nanoparticles with defined particle sizes and compositions. The reaction of the metal particles with the carrier gas during the synthesis and, therefore, the incorporation of those light elements into structural voids or even compound formation was confirmed for hydrides and oxides but has only been suspected to occur for nitrides. In this study, dispersed nanoparticles of Mo3Ni2N and Mo with Janus morphology, and defined particle sizes were obtained by spark discharge generation as a result of carrier gas ionization and characterized using transmission electron microscopy and powder X-ray diffraction. Metal nitrides possess beneficial catalytic and thermoelectric properties, as well as high hardness and wear resistance. Therefore, this method offers the possibility of controlled synthesis of materials which are interesting for numerous applications.

Redox dynamics of 2D crystalline vanadium oxide phases on high-index anatase facets.

Vanadium oxides exist in a multitude of phases with varying structure and stoichiometry. This abundance of phases can be extended through the use of other oxides as supports, and through redox treatments. However, the combined effects of different supports and redox treatments can be difficult to identify, particularly when present as different terminating facets on nanoparticles. Here, we examine structural dynamics of 2D vanadium oxides supported on anatase TiO2 nanoparticles, correlated with changes in oxidation state, using in situ transmission electron microscopy imaging and electron energy loss spectroscopy. As the average oxidation state is reduced below V(IV), an ordered cubic V(II) phase is observed exclusively at the high-index {10l} facets of the support. This local accommodation of highly reduced states is necessary for explaining the observed range of average oxidation states. In turn, the findings show that oxidation states extending from V(V)-V(IV) to V(II) can be simultaneously stabilized by different supporting oxide surfaces during exposure to atmospheres with controlled redox potential.

Probing the wurtzite conduction band structure using state filling in highly doped InP nanowires.

We have grown InP nanowires doped with hydrogen sulfide, which exhibit sulfur concentrations of up to 1.4%. The highest doped nanowires show a pure wurtzite crystal structure, in contrast to bulk InP which has the zinc blende structure. The nanowires display photoluminescence which is strongly blue shifted compared with the band gap, well into the visible range. We find evidence of a second conduction band minimum at the gamma point about 0.23 eV above the band edge, in excellent agreement with recent theoretical predictions. Electrical measurements show high conductivity and breakdown currents of 10(7) A/cm(2).

High current density Esaki tunnel diodes based on GaSb-InAsSb heterostructure nanowires.

We present electrical characterization of broken gap GaSb-InAsSb nanowire heterojunctions. Esaki diode characteristics with maximum reverse current of 1750 kA/cm(2) at 0.50 V, maximum peak current of 67 kA/cm(2) at 0.11 V, and peak-to-valley ratio (PVR) of 2.1 are obtained at room temperature. The reverse current density is comparable to that of state-of-the-art tunnel diodes based on heavily doped p-n junctions. However, the GaSb-InAsSb diodes investigated in this work do not rely on heavy doping, which permits studies of transport mechanisms in simple transistor structures processed with high-κ gate dielectrics and top-gates. Such processing results in devices with improved PVR (3.5) and stability of the electrical properties.

Electron image series reconstruction of twin interfaces in InP superlattice nanowires.

The twin interface structure in twinning superlattice InP nanowires with zincblende structure has been investigated using electron exit wavefunction restoration from focal series images recorded on an aberration-corrected transmission electron microscope. By comparing the exit wavefunction phase with simulations from model structures, it was possible to determine the twin structure to be the ortho type with preserved In-P bonding order across the interface. The bending of the thin nanowires away from the intended 110 axis could be estimated locally from the calculated diffraction pattern, and this parameter was successfully taken into account in the simulations.

Changes in contact angle of seed particle correlated with increased zincblende formation in doped InP nanowires.

Nanowires grown with the vapor-liquid-solid method commonly exhibit polytypism, showing both zincblende and wurtzite crystal structure. We have grown p-type InP nanowires using DEZn as a dopant precursor and studied the wetting of the seed particle and the nanowire crystal structure. The nanowires grown with high DEZn molar fractions exhibit deformed seed particles after growth. We observe 20% smaller nanowire diameter at the highest DEZn molar fraction, indicating a significant increase in contact angle of the seed particle during growth. The decrease in diameter correlates with an increase in zincblende segment length as measured by TEM. We explain the results with a modified nucleation model.

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.