Nanowire Sidewalls Research Articles

Alloy-assisted deposition of three-dimensional arrays of atomic gold catalyst for crystal growth studies

Large-scale assembly of individual atoms over smooth surfaces is difficult to achieve. A configuration of an atom reservoir, in which individual atoms can be readily extracted, may successfully address this challenge. In this work, we demonstrate that a liquid gold–silicon alloy established in classical vapor–liquid–solid growth can deposit ordered and three-dimensional rings of isolated gold atoms over silicon nanowire sidewalls. We perform ab initio molecular dynamics simulation and unveil a surprising single atomic gold-catalyzed chemical etching of silicon. Experimental verification of this catalytic process in silicon nanowires yields dopant-dependent, massive and ordered 3D grooves with spacing down to ~5 nm. Finally, we use these grooves as self-labeled and ex situ markers to resolve several complex silicon growths, including the formation of nodes, kinks, scale-like interfaces, and curved backbones.

Length distributions of Au-catalyzed III-V nanowires in different regimes of the diffusion-induced growth

We present a model for kinetic broadening effects on the length distributions of Au-catalyzed III-V nanowires obtained in the growth regime with adatom diffusion from the substrate and the nanowire sidewalls to the top. We observe three different regimes for the length distribution evolution with time. For short growth times, the length distribution is sub-Poissonian, converting to broader than Poissonian with increasing the mean length above a certain threshold value. After the diffusion flux from the nanowire sidewalls has stabilized, the length distribution variance increases linearly with the mean length, as in the Poissonian process.

Pure wurtzite GaP nanowires grown on zincblende GaP substrates by selective area vapor liquid solid epitaxy

We report on the growth of single phase wurtzite (WZ) GaP nanowires (NWs) on GaP (111) B substrates by metal organic molecular beam epitaxy following the selective area vapor–liquid–solid (SA-VLS) approach. During the SA-VLS process, precursors are supplied directly to the NW sidewalls, and the short diffusion length of gallium (or its precursors) does not significantly limit axial growth. Transmission electron microscopy (TEM) images reveal that no stacking faults are present along a 600 nm long NW. The lattice constants of the pure WZ GaP obtained from the TEM images agree with values determined previously by x-ray diffraction from non-pure NW ensembles.

Anisotropic phase coherence in GaAs/InAs core/shell nanowires

Low-temperature transport in nanowires is accompanied by phase-coherent effects, which are observed as modulation of the conductance in an external magnetic field. In the GaAs/InAs core/shell nanowires investigated here, these are h/e flux periodic oscillations in a magnetic field aligned parallel to the nanowire axis and aperiodic universal conductance fluctuations in a field aligned perpendicularly to the nanowire axis. Both electron interference effects are used to analyse the phase coherence of the system. Temperature-dependent measurements are carried out, in order to derive the phase coherence lengths in the cross-sectional plane as well as along the nanowire sidewalls. It is found that these values show a strong anisotropy, which can be explained by the crystal structure of the GaAs/InAs core/shell nanowire. For nanowires with a radius as low as 45 nm, flux periodic oscillations were observed up to a temperature of 55 K.

Field Emission from Self-Catalyzed GaAs Nanowires.

We report observations of field emission from self-catalyzed GaAs nanowires grown on Si (111). The measurements were taken inside a scanning electron microscope chamber with a nano-controlled tungsten tip functioning as anode. Experimental data were analyzed in the framework of the Fowler-Nordheim theory. We demonstrate stable current up to 10−7 A emitted from the tip of single nanowire, with a field enhancement factor β of up to 112 at anode-cathode distance d = 350 nm. A linear dependence of β on the anode-cathode distance was found. We also show that the presence of a Ga catalyst droplet suppresses the emission of current from the nanowire tip. This allowed for the detection of field emission from the nanowire sidewalls, which occurred with a reduced field enhancement factor and stability. This study further extends GaAs technology to vacuum electronics applications.

Lattice diffusion and vapor solid growths forming nanoarchitectures on ZnO nanowires

We report hierarchical nanoarchitectures formed on the tips and sidewalls of ZnO nanowires which is formed on the top of microtubes. The whole growth process of these micro/nanostructures during thermal oxidation combines lattice/grain/surface ionic diffusion along with vapor solid mechanism. All the process takes place along with the presence of an electric current, which plays an important role forming the ZnO molecules due to Zn metal evaporation and attracting them to condense into nanostructures of several morphologies. The observation of a very long needle-like nanowire reveals the stack nature of the growth. These nanoarchitectures are rarely observed experimentally. Raman scattering confirms phonon confinement in the nanostructures. Photoluminescence measurements indicate a route for engineering defects on the surface of ZnO microtubes after the complete coalescence of the nanostructures through heat treatment. This experiment would be useful for improving nanostructure organization which could provide an impact in the manufacturability of nanostructure-based systems.

Self-Assembly of InAs Nanostructures on the Sidewalls of GaAs Nanowires Directed by a Bi Surfactant.

Surface energies play a dominant role in the self-assembly of three-dimensional (3D) nanostructures. In this Letter, we show that using surfactants to modify surface energies can provide a means to externally control nanostructure self-assembly, enabling the synthesis of novel hierarchical nanostructures. We explore Bi as a surfactant in the growth of InAs on the {11̅0} sidewall facets of GaAs nanowires. The presence of surface Bi induces the formation of InAs 3D islands by a process resembling the Stranski-Krastanov mechanism, which does not occur in the absence of Bi on these surfaces. The InAs 3D islands nucleate at the corners of the {11̅0} facets above a critical shell thickness and then elongate along ⟨110⟩ directions in the plane of the nanowire sidewalls. Exploiting this growth mechanism, we realize a series of novel hierarchical nanostructures, ranging from InAs quantum dots on single {11̅0} nanowire facets to zigzag-shaped nanorings completely encircling nanowire cores. Photoluminescence spectroscopy and cathodoluminescence spectral line scans reveal that small surfactant-induced InAs 3D islands behave as optically active quantum dots. This work illustrates how surfactants can provide an unprecedented level of external control over nanostructure self-assembly.

Designing Morphology in Epitaxial Silicon Nanowires: The Role of Gold, Surface Chemistry, and Phosphorus Doping.

Vertically aligned semiconductor nanowires (NWs) have many potential applications for NW-based technologies, ranging from solar cells to intracellular sensors. Aligned NWs can be fabricated by top-down etching of planar wafers or synthesized from the bottom up using the vapor-liquid-solid (VLS) mechanism to induce epitaxial growth on lattice-matched substrates. The VLS process permits the modulation of dopants along the NW growth axis, which if combined with dopant-dependent wet-chemical etching, can be used to encode precise morphology. However, the synthesis of vertical and linear NWs with complex morphology is nontrivial, requiring control over multiple interdependent aspects of the VLS process. Here, we demonstrate sub-10 nm morphology in ⟨111⟩ epitaxial silicon (Si) NWs grown by the VLS mechanism on (111) Si substrates with gold (Au) catalysts. Using silane (SiH4), phosphine (PH3), and hydrochloric acid (HCl) precursor gases at 480 °C, precise morphology is encoded through abrupt phosphorus (P) dopant transitions, which are found to be less than 5 nm in width. The results highlight three mechanistic attributes of the process. First, NW growth in the ⟨111⟩ direction is found to be unstable at high SiH4 partial pressures and growth rates unless using HCl, which stabilizes NW growth through chlorination of the NW sidewall. Second, aggregated Au deposited on the NW surface by the VLS catalyst is found to be immobile on the chlorinated surface and to impede selective wet-chemical etching by potassium hydroxide (KOH) solution, preventing the design of precise morphology. Third, the aggregation of Au is found to be strongly dependent on the SiH4 partial pressure and NW growth rate, and values exceeding ∼100 mTorr and ∼150 nm/min, respectively, are required to minimize Au and thereby enable selective wet-chemical etching. Under optimized growth conditions, we find that abrupt, complex, and arbitrary dopant profiles and morphologies can be encoded in vertical Si NWs, and we expect that a variety of electronic and photonic applications can be realized with these designed nanostructures.

Formation of GeO 2 complex composed nanostructures by the vapor liquid solid method

In this work, we presented the synthesized results of GeO2 complex composed nanostructures (nanobubbles (NBs) on sidewall of nanowires (NWs)) via the vapor liquid solid (VLS) method. By using a 20 nm of Au nano–film (AuNF) catalyst, prepared by the conventional direct current (DC) magnetron sputtering deposition method, the GeO2 NBs were randomly synthesized along the sidewall of GeO2 NW based two thermal annealing modes in vacuum–furnaces (~10−3 torr) with the diameter in the region conformed from 150 to 450 nm. Transmission electron microscopy (TEM) images indicated the different crystalline phases of NB depended on annealing temperature (T2 = 600 and 650 °C for (102) & (110) plane, respectively). Energy–dispersive x–ray (EDX) analysis results only showed oxygen (69.08%) and germanium (30.92%) of GeO2 nanobubble. Also, bright blue emission peak at wavelength of 438 nm was observed from GeO2 NB–NW–like structure at room temperature. This leads to applications of optoelectronic nanodevices. The detailed of NBs formation mechanism on NW was also discussed.

Tunable Morphology and Doping of ZnO Nanowires by Chemical Bath Deposition Using Aluminum Nitrate

Mastering the properties of ZnO nanowires grown by the low temperature chemical bath deposition (CBD) is of crucial importance but is still challenging. We show that the shape, dimensions, and doping of ZnO nanowires can simultaneously be tuned by the addition of aluminum nitrate in the standard chemical system using zinc nitrate, hexamethylenetetramine, and ammonia in aqueous solution. The formation and doping mechanisms of ZnO nanowires are thoroughly investigated by combining chemical, structural, and optical analyses with in situ pH measurements correlated with thermodynamic simulations. We reveal that the electrostatic interactions of Al(OH)4– complexes with the positive m-plane sidewalls of ZnO nanowires at a given pH favor their adsorption as capping agents, reducing the radial growth and promoting the elongation, while favoring the aluminum uniform incorporation. Importantly, the aluminum doping is found to be thermally activated above the low temperature of 200 °C under oxygen atmosphere, as indicated by the occurrence of six related additional modes in the range of 200–900 cm–1 in temperature-dependent Raman spectroscopy. These findings show that CBD using aluminum nitrate is of high potential for tuning both the morphology of ZnO nanowires and their physical properties via the aluminum doping, which paves the way for their more efficient use into sensing, electronic, and optoelectronic devices on both flexible and rigid substrates.

Broad Band Light Absorption and High Photocurrent of (In,Ga)N Nanowire Photoanodes Resulting from a Radial Stark Effect.

The photoelectrochemical properties of (In,Ga)N nanowire photoanodes are investigated using H2O2 as a hole scavenger to prevent photocorrosion. Under simulated solar illumination, In0.16Ga0.84N nanowires grown by plasma-assisted molecular beam epitaxy show a high photocurrent of 2.7 mA/cm2 at 1.2 V vs reversible hydrogen electrode. This value is almost the theoretical maximum expected from the corresponding band gap (2.8 eV) for homogeneous bulk material without taking into account surface effects. These nanowires exhibit a higher incident photon-to-current conversion efficiency over a broader wavelength range and a higher photocurrent than a compact layer with higher In content of 28%. These results are explained by the combination of built-in electric fields at the nanowire sidewall surfaces and compositional fluctuations in (In,Ga)N, which gives rise to a radial Stark effect. This effect enables spatially indirect transitions at energies much lower than the band gap. The resulting broad band light absorption leads to high photocurrents. This benefit of the radial Stark effect in (In,Ga)N nanowires for solar harvesting applications opens up the perspective to break the theoretical limit for photocurrents.

Ultrafast, Polarized, Single-Photon Emission from m-Plane InGaN Quantum Dots on GaN Nanowires.

We demonstrate single-photon emission from self-assembled m-plane InGaN quantum dots (QDs) embedded on the side-walls of GaN nanowires. A combination of electron microscopy, cathodoluminescence, time-resolved microphotoluminescence (μPL), and photon autocorrelation experiments give a thorough evaluation of the QD structural and optical properties. The QD exhibits antibunched emission up to 100 K, with a measured autocorrelation function of g(2)(0) = 0.28(0.03) at 5 K. Studies on a statistically significant number of QDs show that these m-plane QDs exhibit very fast radiative lifetimes (260 ± 55 ps) suggesting smaller internal fields than any of the previously reported c-plane and a-plane QDs. Moreover, the observed single photons are almost completely linearly polarized aligned perpendicular to the crystallographic c-axis with a degree of linear polarization of 0.84 ± 0.12. Such InGaN QDs incorporated in a nanowire system meet many of the requirements for implementation into quantum information systems and could potentially open the door to wholly new device concepts.

Step Flow Model of Radial Growth and Shape Evolution of Semiconductor Nanowires

A model of radial growth of vertically aligned nanowires (NW) via formation and propagation of monoatomic steps at nanowire sidewalls is developed. The model allows to describe self-consistently the step dynamics and the axial growth of the NW. It is shown that formation of NWs with an abrupt change of wire diameter and a non-tapered section at the top might be explained by the bunching of sidewall steps due to the presence of a strong sink for adatoms at the NW top. The Ehrlich–Schwoebel barrier for the attachment of adatoms to the descending step favors the step bunching at the beginning of the radial growth and promotes the decay of the bunch at a later time of the NW growth.

Growth of isolated InAs quantum dots on core-shell GaAs/InP nanowire sidewalls by MOCVD

We demonstrate the growth of isolated InAs quantum dots on the sidewalls of core-shell GaAs/InP nanowires based on the vapor-liquid-solid MOCVD method. The quantum dots are grown under the Stranski-Krastanov mode and exhibit defect-free zinc blende structure. Discrete sharp emission peaks are observed in the range of 1.37–1.39eV, with linewidths ranging from several hundred μeV to 1meV or more. Excitonic and biexcitonic emissions are observed, exhibiting different power-dependent intensity and linewidth behavior. This work may open a way for the fabrication of single photon devices based on the vapor-liquid-solid MOCVD method.

Quenching of the luminescence intensity of GaN nanowires under electron beam exposure: impact of C adsorption on the exciton lifetime

Electron irradiation of GaN nanowires in a scanning electron microscope strongly reduces their luminous efficiency as shown by cathodoluminescence imaging and spectroscopy. We demonstrate that this luminescence quenching originates from a combination of charge trapping at already existing surface states and the formation of new surface states induced by the adsorption of C on the nanowire sidewalls. The interplay of these effects leads to a complex temporal evolution of the quenching, which strongly depends on the incident electron dose per area. Time-resolved photoluminescence measurements on electron-irradiated samples reveal that the carbonaceous adlayer affects both the nonradiative and the radiative recombination dynamics.

Optical Properties of Silicon Nanowires Fabricated by Environment-Friendly Chemistry.

Silicon nanowires (SiNWs) were fabricated by metal-assisted chemical etching (MACE) where hydrofluoric acid (HF), which is typically used in this method, was changed into ammonium fluoride (NH4F). The structure and optical properties of the obtained SiNWs were investigated in details. The length of the SiNW arrays is about 2 μm for 5 min of etching, and the mean diameter of the SiNWs is between 50 and 200 nm. The formed SiNWs demonstrate a strong decrease of the total reflectance near 5–15 % in the spectral region λ < 1 μm in comparison to crystalline silicon (c-Si) substrate. The interband photoluminescence (PL) and Raman scattering intensities increase strongly for SiNWs in comparison with the corresponding values of the c-Si substrate. These effects can be interpreted as an increase of the excitation intensity of SiNWs due to the strong light scattering and the partial light localization in an inhomogeneous optical medium. Along with the interband PL was also detected the PL of SiNWs in the spectral region of 500–1100 nm with a maximum at 750 nm, which can be explained by the radiative recombination of excitons in small Si nanocrystals at nanowire sidewalls in terms of a quantum confinement model. So SiNWs, which are fabricated by environment-friendly chemistry, have a great potential for use in photovoltaic and photonics applications.

Top-down, in-plane GaAs nanowire MOSFETs on an Al2O3 buffer with a trigate oxide from focused ion-beam milling and chemical oxidation

The top-down fabrication of an in-plane nanowire (NW) GaAs metal–oxide–semiconductor field-effect transistor (MOSFET) with a trigate oxide implemented by liquid-phase chemical-enhanced oxidation (LPCEO) is reported. A 2 μm long channel having an effective cross section ∼70 × 220 nm2 is directly fabricated into an epitaxial n+-GaAs layer. This in-plane NW structure is achieved by focused ion beam (FIB) milling and hydrolyzation oxidation resulting in electronic isolation from the substrate through a semiconductor-on-insulator structure with an n+-GaAs/Al2O3 layer stack. The channel is epitaxially connected to the μm-scale source and drain within a single layer for a planar MOSFET to avoid any issues of ohmic contact and LPCEO to the NW. To fabricate a MOSFET, the top and the two sidewalls of the in-plane NW are oxidized by LPCEO to relieve the surface damage from FIB as well as to transform these surfaces to a ∼15 nm thick gate oxide. This trigate device has threshold voltage ∼0.14 V and peak transconductance ∼35 μS μm−1 with a subthreshold swing ∼150 mV/decade and on/off ratio of drain current ∼103, comparable to the performance of bottom-up NW devices.

The Synergic Effect of Atomic Hydrogen Adsorption and Catalyst Spreading on Ge Nanowire Growth Orientation and Kinking

Hydride precursors are commonly used for semiconductor nanowire growth from the vapor phase and hydrogen is quite often used as a carrier gas. Here, we used in situ scanning electron microscopy and spatially resolved Auger spectroscopy to reveal the essential role of atomic hydrogen in determining the growth direction of Ge nanowires with an Au catalyst. With hydrogen passivating nanowire sidewalls the formation of inclined facets is suppressed, which stabilizes the growth in the ⟨111⟩ direction. By contrast, without hydrogen gold diffuses out of the catalyst and decorates the nanowire sidewalls, which strongly affects the surface free energy of the system and results in the ⟨110⟩ oriented growth. The experiments with intentional nanowire kinking reveal the existence of an energetic barrier, which originates from the kinetic force needed to drive the droplet out of its optimum configuration on top of a nanowire. Our results stress the role of the catalyst material and surface chemistry in determining the nanowire growth direction and provide additional insights into a kinking mechanism, thus allowing to inhibit or to intentionally initiate spontaneous kinking.

Insights into gold-catalyzed plasma-assisted CVD growth of silicon nanowires

Understanding and controlling effectively the behavior of metal catalyst droplets during the Vapor-Liquid-Solid growth of nanowires are crucial for their applications. In this work, silicon nanowires are produced by plasma-assisted Chemical Vapor Deposition using gold as a catalyst. The influence of hydrogen plasma on nanowire growth is investigated experimentally and theoretically. Interestingly, in contrast to conventional chemical vapor deposition, the growth rate of silicon nanowires shows a decrease as a function of their diameters, which is consistent with the incorporation of silicon via sidewall diffusion. We show that Ostwald ripening of catalyst droplets during nanowire growth is inhibited in the presence of a hydrogen plasma. However, when the plasma is off, the diffusion of Au atoms on the nanowire sidewall can take place. Based on this observation, we have developed a convenient method to grow silicon nanotrees.

Surface Hydrogen Enables Subeutectic Vapor-Liquid-Solid Semiconductor Nanowire Growth.

Vapor-liquid-solid nanowire growth below the bulk metal-semiconductor eutectic temperature is known for several systems; however, the fundamental processes that govern this behavior are poorly understood. Here, we show that hydrogen atoms adsorbed on the Ge nanowire sidewall enable AuGe catalyst supercooling and control Au transport. Our approach combines in situ infrared spectroscopy to directly and quantitatively determine hydrogen atom coverage with a "regrowth" step that allows catalyst phase to be determined with ex situ electron microscopy. Maintenance of a supercooled catalyst with only hydrogen radical delivery confirms the centrality of sidewall chemistry. This work underscores the importance of the nanowire sidewall and its chemistry on catalyst state, identifies new methods to regulate catalyst composition, and provides synthetic strategies for subeutectic growth in other nanowire systems.