Mechanism of self-assembled growth of ordered GaAs nanowire arrays by metalorganic vapor phase epitaxy on GaAs vicinal substrates

We report the self-catalyzed growth of GaAs nanowire arrays by metalorganic vapor phase epitaxy (MOVPE) on GaAs vicinal substrates. The effect of substrate misorientation on the nanowire growth and the influence of growth parameters such as temperature and input V/III ratio have been studied in detail. Variation in the nanowire growth mechanism and consequential changes in the nanowire growth morphology were observed. A VLS growth mechanism with negligible effect of the vicinal surface gave rise to randomly distributed droplet-terminated GaAs nanowires at 400?°C and multiprong root-grown GaAs nanowire clusters at 500?°C with low V/III ratio. The substrate misorientation effect was dominant at 500?°C with higher V/III ratio, in which case the combined effect of the vicinal surface and the self-catalyzed Ga droplets assisted the realization of self-assembled and crystallographically oriented epitaxial nanowire arrays through the vapor-solid mechanism.     

van der Waals epitaxy of InAs nanowires vertically aligned on single-layer graphene

Semiconductor nanowire arrays integrated vertically on graphene films offer significant advantages for many sophisticated device applications. We report on van der Waals (VDW) epitaxy of InAs nanowires vertically aligned on graphene substrates using metal-organic chemical vapor deposition. The strong correlation between the growth direction of InAs nanowires and surface roughness of graphene substrates was investigated using various graphene films with different numbers of stacked layers. Notably, vertically well-aligned InAs nanowire arrays were obtained easily on single-layer graphene substrates with sufficiently strong VDW attraction. This study presents a considerable advance toward the VDW heteroepitaxy of inorganic nanostructures on chemical vapor-deposited large-area graphenes. More importantly, this work demonstrates the thinnest epitaxial substrate material that yields vertical nanowire arrays by the VDW epitaxy method.     

Temperature conditions for GaAs nanowire formation by Au-assisted molecular beam epitaxy

Molecular beam epitaxial growth of GaAs nanowires using Au particles as a catalyst was investigated. Prior to the growth during annealing, Au alloyed with Ga coming from the GaAs substrate, and melted. Phase transitions of the resulting particles were observed in?situ by reflection high-energy electron diffraction (RHEED). The temperature domain in which GaAs nanowire growth is possible was determined. The lower limit of this domain (320?°C) is close to the observed catalyst solidification temperature. Below this temperature, the catalyst is buried by GaAs growth. Above the higher limit (620?°C), the catalyst segregates on the surface with no significant nanowire formation. Inside this domain, the influence of growth temperature on the nanowire morphology and crystalline structure was investigated in detail by scanning electron microscopy and transmission electron microscopy. The correlation of the nanowire morphology with the RHEED patterns observed during the growth was established. Wurtzite GaAs was found to be the dominant crystal structure of the wires.     

Direct imaging of the atomic structure inside a nanowire by scanning tunnelling microscopy

Semiconductor nanowires are expected to be important components in future nano-electronics and photonics. Already a wide range of applications has been realized, such as high-performance field-effect transistors, bio/chemical sensors, diode logics and single-nanowire lasers. As nanowires have small cross-sections and large surface-to-bulk ratios, their properties can be significantly influenced by individual atomic-scale structural features, and they can have properties or even atomic arrangements with no bulk counterparts. Hence, experimental methods capable of directly addressing the atomic-scale structure of nanowires are highly desirable. One such method is scanning tunnelling microscopy (STM), which, by direct imaging of the atomic and electronic structure of surfaces has revolutionized the perception of nanoscale objects and low-dimensional systems. Here we demonstrate how combining STM with an embedding scheme allows us to image the interior of semiconductor nanowires with atomic resolution. Defect structures such as planar twin segments and single-atom impurities are imaged inside a GaAs nanowire. Further, we image an intriguing GaAs nanowire that is separated into two distinct nanocrystallites along the growth direction of the wire.     

In-situ TEM observation of repeating events of nucleation in epitaxial growth of nano CoSi2 in nanowires of Si

The formation of CoSi and CoSi2 in Si nanowires at 700 and 800 degrees C, respectively, by point contact reactions between nanodots of Co and nanowires of Si have been investigated in situ in a ultrahigh vacuum high-resolution transmission electron microscope. The CoSi2 has undergone an axial epitaxial growth in the Si nanowire and a stepwise growth mode was found. We observed that the stepwise growth occurs repeatedly in the form of an atomic step sweeping across the CoSi2/Si interface. It appears that the growth of a new step or a new silicide layer requires an independent event of nucleation. We are able to resolve the nucleation stage and the growth stage of each layer of the epitaxial growth in video images. In the nucleation stage, the incubation period is measured, which is much longer than the period needed to grow the layer across the silicide/Si interface. So the epitaxial growth consists of a repeating nucleation and a rapid stepwise growth across the epitaxial interface. This is a general behavior of epitaxial growth in nanowires. The axial heterostructure of CoSi2/Si/CoSi2 with sharp epitaxial interfaces has been obtained. A discussion of the kinetics of supply limited and source-limited reaction in nanowire case by point contact reaction is given. The heterostructures are promising as high performance transistors based on intrinsic Si nanowires.     

Twin-free uniform epitaxial GaAs nanowires grown by a two-temperature process

We demonstrate vertically aligned epitaxial GaAs nanowires of excellent crystallographic quality and optimal shape, grown by Au nanoparticle-catalyzed metalorganic chemical vapor deposition. This is achieved by a two-temperature growth procedure, consisting of a brief initial high-temperature growth step followed by prolonged growth at a lower temperature. The initial high-temperature step is essential for obtaining straight, vertically aligned epitaxial nanowires on the (111)B GaAs substrate. The lower temperature employed for subsequent growth imparts superior nanowire morphology and crystallographic quality by minimizing radial growth and eliminating twinning defects. Photoluminescence measurements confirm the excellent optical quality of these two-temperature grown nanowires. Two mechanisms are proposed to explain the success of this two-temperature growth process, one involving Au nanoparticle-GaAs interface conditions and the other involving melting-solidification temperature hysteresis of the Au-Ga nanoparticle alloy.     

Heteroepitaxial growth of vertical GaAs nanowires on Si(111) substrates by metal-organic chemical vapor deposition

Epitaxial growth of vertical GaAs nanowires on Si(111) substrates is demonstrated by metal-organic chemical vapor deposition via a vapor-liquid-solid growth mechanism. Systematic experiments indicate that substrate pretreatment, pregrowth alloying temperature, and growth temperature are all crucial to vertical epitaxial growth. Nanowire growth rate and morphology can be well controlled by the growth temperature, the metal-organic precursor molar fraction, and the molar V/III ratio. The as-grown GaAs nanowires have a predominantly zinc-blende crystal structure along a <111> direction. Crystallographic {111} stacking faults found perpendicular to the growth axis could be almost eliminated via growth at high V/III ratio and low temperature. Single nanowire field effect transistors based on unintentionally doped GaAs nanowires were fabricated and found to display a strong effect of surface states on their transport properties.     

The morphology of axial and branched nanowire heterostructures

We present an extensive investigation of the epitaxial growth of Au-assisted axial heterostructure nanowires composed of group IV and III-V materials and derive a model to explain the overall morphology of such wires. By analogy with 2D epitaxial growth, this model relates the wire morphology (i.e., whether it is kinked or straight) to the relationship of the interface energies between the two materials and the particle. This model suggests that, for any pair of materials, it should be easier to form a straight wire with one interface direction than the other, and we demonstrate this for the material combinations presented here. However, such factors as kinetics and the use of surfactants may permit the growth of straight double heterostructure nanowires. Finally, we demonstrate that branched nanowire heterostructures, also known as nanotrees, can be successfully explained by the same model.     

New mode of vapor-liquid-solid nanowire growth

We report on the new mode of the vapor-liquid-solid nanowire growth with a droplet wetting the sidewalls and surrounding the nanowire rather than resting on its top. It is shown theoretically that such an unusual configuration happens when the growth is catalyzed by a lower surface energy metal. A model of a nonspherical elongated droplet shape in the wetting case is developed. Theoretical predictions are compared to the experimental data on the Ga-catalyzed growth of GaAs nanowires by molecular beam epitaxy. In particular, it is demonstrated that the experimentally observed droplet shape is indeed nonspherical. The new VLS mode has a major impact on the crystal structure of GaAs nanowires, helping to avoid the uncontrolled zinc blende-wurtzite polytylism under optimized growth conditions. Since the triple phase line nucleation is suppressed on surface energetic grounds, all nanowires acquire pure zinc blende phase along the entire length, as demonstrated by the structural studies of our GaAs nanowires.     

Uniform and position-controlled InAs nanowires on 2" Si substrates for transistor applications

This study presents a novel approach for indirect integration of InAs nanowires on 2' Si substrates. We have investigated and developed epitaxial growth of InAs nanowires on 2' Si substrates via the introduction of a thin yet high-quality InAs epitaxial layer grown by metalorganic vapor phase epitaxy. We demonstrate well-aligned nanowire growth including precise position and diameter control across the full wafer using very thin epitaxial layers (<300 nm). Statistical analysis results performed on the grown nanowires across the 2' wafer size verifies our full control on the grown nanowire with 100% growth yield. From the crystallographic viewpoint, these InAs nanowires are predominantly of wurtzite structure. Furthermore, we show one possible device application of the aforementioned structure in vertical wrap-gated field-effect transistor geometry. The vertically aligned InAs nanowires are utilized as transistor channels and the InAs epitaxial layer is employed as the source contact. A high uniformity of the device characteristics for numerous transistors is further presented and RF characterization of these devices demonstrates an f(t) of 9.8 GHz.     

Controlling the abruptness of axial heterojunctions in III-V nanowires: beyond the reservoir effect

Heterostructure nanowires have many potential applications due to the avoidance of interface defects by lateral strain relaxation. However, most heterostructure semiconductor nanowires suffer from persistent interface compositional grading, normally attributed to the dissolution of growth species in the common alloy seed particles. Although progress has been made for some material systems, most binary material combinations remain problematic due to the interaction of growth species in the alloy. In this work we investigate the formation of interfaces in InAs-GaAs heterostructures experimentally and theoretically and demonstrate a technique to attain substantially sharper interfaces. We show that by pulsing the Ga source during heterojunction formation, In is pushed out before GaAs growth initiates, greatly reducing In carry-over. This procedure will be directly applicable to any nanowire system with finite nonideal solubility of growth species in the alloy seed particle and greatly improve the applicability of these structures in future devices.     

Suitability of Au- and self-assisted GaAs nanowires for optoelectronic applications

The incorporation of Au during vapor-liquid-solid nanowire growth might inherently limit the performance of nanowire-based devices. Here, we assess the material quality of Au-assisted and Au-free grown GaAs/(Al,Ga)As core-shell nanowires using photoluminescence spectroscopy. We show that at room temperature, the internal quantum efficiency is systematically much lower for the Au-assisted nanowires than for the Au-free ones. In contrast, the optoelectronic material quality of the latter is comparable to that of state-of-the-art planar double heterostructures.     

A study of the growth mechanism of CVD-grown ZnO nanowires

ZnO nanowires were grown by CVD process using both pure Zn powder and a mixture of ZnO and graphite powders as the Zn source, and the key factors controlling nanowire growth were identified. In both processes, the partial pressure of zinc vapor determines the prevailing growth morphology and is sensitive to the growth conditions. In the case of Zn powder as the source, the predominant growth mechanism is driven by self-catalyzed growth on the Si substrate, and in the case of a mixture of ZnO and graphite used as the source, the formation of ZnO nanowires is controlled by the vapor–liquid-solid mechanism, where the gold particles serve as catalyst.     

GaAs/AlGaAs heterostructure nanowires studied by cathodoluminescence

In this report we explore the structural and optical properties of GaAs/A1GaAs heterostructure nanowires grown by metalorganic vapour phase epitaxy using gold seed-particles. The optical studies were done by low-temperature cathodo- luminescence （CL） in a scanning electron microscope （SEM）. We perform a systematic investigation of how the nanowire growth-temperature affects the total photon emission, and variations in the emission energy and intensity along the length of the nanowires. The morphology and crystal structures of the nanowires were investigated using SEM and transmission electron microscopy （TEM）. In order to correlate specific photon emission characteristics with variations in the nanowire crystal structure directly, TEM and spatially resolved CL measurements were performed on the same individual nanowires. We found that the main emission energy was located at around 1.48 eV, and that the emission intensity was greatly enhanced when increasing the GaAs nanowire core growth temperature. The data strongly suggests that this emission energy is related to rotational twins in the GaAs nanowire core. Our measurements also show that radial overgrowth by GaAs on the GaAs nanowire core can have a deteriorating effect on the optical quality of the nanowires. Finally, we conclude that an in situ pre-growth annealing step at a sufficiently high temperature significantly improves the optical quality of the nanowires.     

Self-organized Ce(1-x)Gd(x)O(2-y) nanowire networks with very fast coarsening driven by attractive elastic interactions

Assembling arrays of ordered nanowires is a key objective for many of their potential applications. However, a lack of understanding and control of the nanowires' growth mechanisms limits their thorough development. In this work, an appealing new path towards self-organized epitaxial nanowire networks produced by high-throughput solution methods is reported. Two requisites are identified to generate the nanowires: a thermodynamic driving force for an unrestricted elongated equilibrium island shape, and a very fast effective coarsening rate. These requirements are met in anisotropically strained Ce(1-x)Gd(x)O(2-y) nanowires with the (011) orientation grown on the (001) surface of LaAlO(3) substrates. Nanowires with aspect ratios above ≈100 oriented along two mutually orthogonal axes are obtained leading to labyrinthine networks. A very fast effective nanowire growth rate (≈60 nm min(-1)) for ex-situ thermally annealed nanostructures derives from simultaneous kinetic processes occurring in a branched network. Ostwald ripening and anisotropic dynamic coalescence, both promoted by strain-driven attractive nanowire interaction, and rapid recrystallization, enabled by fast atomic diffusion associated with a high concentration of oxygen vacancies, contribute to such an effective growth rate. This bottom-up approach to self-organized nanowire growth has a wide potential for many materials and functionalities.     

Formation of Single Tiers of Bridging Silicon Nanowires for Transistor Applications Using Vapor–Liquid–Solid Growth from Short Silicon‐on‐Insulator Sidewalls

Single tiers of silicon nanowires that bridge the gap between the short sidewalls of silicon‐on‐insulator (SOI) source/drain pads are formed. The formation of a single tier of bridging nanowires is enabled by the attachment of a single tier of Au catalyst nanoparticles to short SOI sidewalls and the subsequent growth of epitaxial nanowires via the vapor–liquid–solid (VLS) process. The growth of unobstructed nanowire material occurs due to the attachment of catalyst nanoparticles on silicon surfaces and the removal of catalyst nanoparticles from the SOI‐buried oxide (BOX). Three‐terminal current–voltage measurements of the structure using the substrate as a planar backgate after VLS nanowire growth reveal transistor behaviour characteristics.     

A cathodoluminescence study of the influence of the seed particle preparation method on the optical properties of GaAs nanowires

Cathodoluminescence at 8?K is used to compare the optical properties of AlGaAs-capped GaAs nanowires, grown by metal-organic vapour phase epitaxy and seeded by gold particles prepared by different methods. Six different methods were used to fabricate and deposit gold seed particles onto GaAs substrates: colloid particles, aerosol particles and particles defined by electron beam lithography. The nanowires were grown with and without an in?situ annealing step prior to the nanowire growth. The morphology showed no significant differences between the nanowires. The emissions from ensembles of nanowires have the same peak position, irrespective of seed particle type. Without the in?situ annealing step prior to the nanowire growth, there are significant differences in the emission intensity and emission patterns from nanowires grown from different seed particles. When an in?situ annealing step is included, all the resulting nanowires show identical optical emission intensity and emission patterns. This shows the importance of using an in?situ annealing step prior to growth. This study demonstrates that different preparation methods for gold seed particles can be used to produce GaAs nanowires with highly similar optical properties. The choice of particle preparation method to be used can therefore be based on availability and cost.     

In Situ Grown Epitaxial Heterojunction Exhibits High‐Performance Electrocatalytic Water Splitting

Electrocatalytic performance can be enhanced by engineering a purposely designed nanoheterojunction and fine‐tuning the interface electronic structure. Herein a new approach of developing atomic epitaxial in‐growth in Co‐Ni₃N nanowires array is devised, where a nanoconfinement effect is reinforced at the interface. The Co‐Ni₃N heterostructure array is formed by thermal annealing NiCo₂O₄ precursor nanowires under an optimized condition, during which the nanowire morphology is retained. The epitaxial in‐growth structure of Co‐Ni₃N at nanometer scale facilitates the electron transfer between the two different domains at the epitaxial interface, leading to a significant enhancement in catalytic activities for both hydrogen and oxygen evolution reactions (10 and 16 times higher in the respective turn‐over frequency compared to Ni₃N‐alone nanorods). The interface transfer effect is verified by electronic binding energy shift and density functional theory (DFT) calculations. This nanoconfinement effect occurring during in situ atomic epitaxial in‐growth of the two compatible materials shows an effective pathway toward high‐performance electrocatalysis and energy storages.     

Vertically standing Ge nanowires on GaAs(110) substrates

The growth of epitaxial Ge nanowires is investigated on (100), (111) B and (110) GaAs substrates in the growth temperature range from 300 to 380?°C. Unlike epitaxial Ge nanowires on Ge or Si substrates, Ge nanowires on GaAs substrates grow predominantly along the [Formula: see text] direction. Using this unique property, vertical [Formula: see text] Ge nanowires epitaxially grown on GaAs(110) surface are realized. In addition, these Ge nanowires exhibit minimal tapering and uniform diameters, regardless of growth temperatures, which is an advantageous property for device applications. Ge nanowires growing along the [Formula: see text] directions are particularly attractive candidates for forming nanobridge devices on conventional (100) surfaces.     

Measurement of Local Si‐Nanowire Growth Kinetics Using In situ Transmission Electron Microscopy of Heated Cantilevers

A technique to study nanowire growth processes on locally heated microcantilevers in situ in a transmission electron microscope has been developed. The in situ observations allow the characterization of the nucleation process of silicon wires, as well as the measurement of growth rates of individual nanowires and the ability to observe the formation of nanowire bridges between separate cantilevers to form a complete nanowire device. How well the nanowires can be nucleated controllably on typical cantilever sidewalls is examined, and the measurements of nanowire growth rates are used to calibrate the cantilever‐heater parameters used in finite‐element models of cantilever heating profiles, useful for optimization of the design of devices requiring local growth.