GaAs Nanowires Research Articles

Time-resolved open-circuit conductive atomic force microscopy for direct electromechanical characterisation

Studying nanomaterial piezoelectricity and triboelectricity is attractive for energy and sensing applications. However, quantitative characterisation of electromechanical effects in nanomaterials is challenging due to practical limitations and possible combination of effects, resulting in contradicting reports at times. When it comes to piezoelectricity at the nanoscale, piezoresponse force microscopy (PFM) is the default characterisation tool. In PFM the converse piezoelectric effect is measured - the conversion from electrical signal to mechanical response. However, there is an underlying desire to measure the direct piezoelectric effect - conversion of mechanical deformation to an electrical signal. This corresponds to energy harvesting and sensing. Here we present time-resolved open-circuit conductive atomic force microscopy (cAFM) as a new methodology to carry out direct electromechanical characterisation. We show, both theoretically and experimentally, that the standard short-circuit cAFM mode is inadequate for piezoelectric characterisation, and that resulting measurements are governed by competing mechanisms. We apply the new methodology to nanowires of GaAs, an important semiconductor, with relatively low piezoelectric coefficients. The results suggest that time-resolved operation distinguishes between triboelectric and piezoelectric signals, and that by measuring the open-circuit voltage rather than short-circuit current, the new methodology allows quantitative characterisation of the vertical piezoelectric coefficient. The result for GaAs nanowires, ∼ 1–3 pm V−1, is in good agreement with existing knowledge and theory. This method represents a significant advance in understanding the coexistence of different electromechanical effects, and in quantitative piezoelectric nanoscale characterisation. The easy implementation will enable better understanding of electromechanics at the nanoscale.

Be, Te, and Si Doping of GaAs Nanowires: Theory and Experiment

Controllable doping of III–V nanowires grown by the vapor–liquid–solid method remains a challenging task. In sharp contrast to planar layers of the same materials, dopants mainly incorporate into n...

Nondestructive Characterizations of Au-Catalyzed GaAs Nanowires on GaAs(111)B Substrates via Identifications of 1st Order Optical Phonon Modes Using μ-Raman Spectroscopy.

We report the relation between the catalyst patterning conditions and the intensity of the 1st order Raman active modes in Au-catalyzed GaAs nanowire bundles. We fabricated e-beam lithographically Au-patterned GaAs(111)B substrates by varying the patterning conditions (e-beam dose rate, dot-size and interdot-spacings), and grew GaAs nanowires via vapor-liquid-solid process using a solid-source molecular beam epitaxy. To understand the effects of the substrate preparation conditions and resulting morphologies on the optical characteristics of 1st order transverse optical and longitudinal optical phonon modes of GaAs, we characterized the nanowire bundles using complementary μ-Raman spectroscopy and scanning electron microscopy as a function of the e-beam dose rate (145-595 μC/cm²), inter-dot spacing (100 and 150 nm) and pattern size (100 and 150 nm). Ensembles of single crystalline GaAs nanowires covered with different Au-thickness exhibit a downshift and asymmetric broadening of the 1st order transverse optical and longitudinal optical phonon peaks relative to GaAs bulk modes. We also showed that the sensitivity of a downshift and broadening of Raman spectra are directly related to morphological and surface coverage variations in as-grown nanowires. We observed clear increases of the transverse optical and longitudinal optical intensity as well as the relatively higher peak shift and broadening of Raman spectra from the 100 nm patterning in response to the dose rate change. Strong dependence of Raman spectra of the nanowire bundles on the e-beam dose rate changes are attributed to the variations in spatial density, size, shape and random growth orientation of the wires. We have shown that the identification of the changes in GaAs longitudinal optical and Arsenic anti-site peaks is good indicators to characterize the quality of as-grown GaAs nanowires. Our finding confirms the utilization of Raman spectroscopy as a powerful tool for characterizing chemical, structural, and morphological information of as-grown nanowires within the supporting substrate.

Facet-driven formation of axial and radial In(Ga)As clusters in GaAs nanowires

Embedding quantum dots in nanowires (NWs) constitutes one promising building block for quantum photonic technologies. Earlier attempts to grow InAs quantum dots on GaAs nanowires were based on the Stranski–Krastanov growth mechanism. Here, we propose a novel strain-driven mechanism to form 3D In-rich clusters on the NW sidewalls and also on the NW top facets. The focus is on ternary InGaAs nanowire quantum dots which are particularly attractive for producing single photons at telecommunication wavelengths. In(Ga)As clusters were realized on the inclined top facets and also on the {11-2} corner facets of GaAs NW arrays by depositing InAs at a high growth temperature (630 °C). High-angle annular dark-field scanning transmission electron microscopy combined with energy-dispersive x-ray spectroscopy confirms that the observed 3D clusters are indeed In-rich. The optical functionality of the as-grown samples was verified using optical technique of cathodoluminescence. Emission maps close to the NW tip shows the presence of optically active emission centers along the NW sidewalls. Our work illustrates how facets can be used to engineer the growth of localized emitters in semiconducting NWs.

Effects of Density and Diameter on Surface Optical Phonon Modes in GaAs Nanowire Bundles.

We report the systematic investigation of the surface optical phonon modes in Au-catalyzed GaAs nanowires grown on an Au pre-patterned GaAs(111)B substrate using μ-Raman spectroscopy. We employed electron-beam dose rate as a control parameter during the substrate patterning step for adjusting the nanowire base diameter and coverage, which are independent from the nanowire growth conditions. We have experimentally studied the effect of the fill factor and average diameter on the surface optical phonon modes and explained the red-shift and broadening of the surface optical phonon frequencies by employing the dielectric continuum model. The surface optical phonon mode shift is exhibited to be sensitive to fill factor, rather than base diameter. The decrease in the average diameter from 280 nm to 180 nm results in the asymmetric broadening and red-shift of the surface optical phonon frequency (~1.83 cm-1) but the theoretical calculation from the isolated single nanowire-based dielectric continuum model cannot solely explain the behaviors of the surface optical phonon mode. In contrast, the change in the fill factor from 0.01 to 0.83 results in a shift of the surface optical phonon frequency (~6.5 cm-1) from the GaAs bulk value. The red-shift and asymmetric broadening of the surface optical phonons, in an agreement with the Maxwell-Garnett approximation, are consequences of dipolar interaction of randomly aligned neighboring nanowires and the polar nature of GaAs nanowire bundles. This work suggests the pre-patterning parameter dependent surface optical phonon characteristics of GaAs nanowire bundles which are of great importance in the nondestructive characterization of low-dimensional opto-electronic materials and devices.

Comparison of GaAs nanowire growth seeded by Ag and Au colloidal nanoparticles on silicon

We present a comparative study of GaAs nanowire growth on Si(111) substrates by molecular beam epitaxy with the assistance of Au and Ag colloidal nanoparticles. Our approach allows the synthesis of nanowires with different catalyst materials in separate sectors of the same substrate within the same epitaxial process. We match the experimental results to the modeling of chemical potentials and nanowire length distributions to analyze the impact of silicon incorporation into the catalyst droplets on the growth rates and size homogeneity in ensembles of Au- and Ag-catalyzed GaAs nanowires.

Electrochemical nanostructuring of (111) oriented GaAs crystals: from porous structures to nanowires.

A comparative study of the anodization processes occurring at the GaAs(111)A and GaAs(111)B surfaces exposed to electrochemical etching in neutral NaCl and acidic HNO3 aqueous electrolytes is performed in galvanostatic and potentiostatic anodization modes. Anodization in NaCl electrolytes was found to result in the formation of porous structures with porosity controlled either by current under the galvanostatic anodization, or by the potential under the potentiostatic anodization. Possibilities to produce multilayer porous structures are demonstrated. At the same time, one-step anodization in a HNO3 electrolyte is shown to lead to the formation of GaAs triangular shape nanowires with high aspect ratio (400 nm in diameter and 100 µm in length). The new data are compared to those previously obtained through anodizing GaAs(100) wafers in alkaline KOH electrolyte. An IR photodetector based on the GaAs nanowires is demonstrated.

Effect of the Uniaxial Compression on the GaAs Nanowire Solar Cell.

Research regarding ways to increase solar cell efficiency is in high demand. Mechanical deformation of a nanowire (NW) solar cell can improve its efficiency. Here, the effect of uniaxial compression on GaAs nanowire solar cells was studied via conductive atomic force microscopy (C-AFM) supported by numerical simulation. C-AFM I–V curves were measured for wurtzite p-GaAs NW grown on p-Si substrate. Numerical simulations were performed considering piezoresistance and piezoelectric effects. Solar cell efficiency reduction of 50% under a −0.5% strain was observed. The analysis demonstrated the presence of an additional fixed electrical charge at the NW/substrate interface, which was induced due to mismatch between the crystal lattices, thereby affecting the efficiency. Additionally, numerical simulations regarding the p-n GaAs NW solar cell under uniaxial compression were performed, showing that solar efficiency could be controlled by mechanical deformation and configuration of the wurtzite and zinc blende p-n segments in the NW. The relative solar efficiency was shown to be increased by 6.3% under −0.75% uniaxial compression. These findings demonstrate a way to increase efficiency of GaAs NW-based solar cells via uniaxial mechanical compression.

Interatomic potential for atomistic simulation of self-catalyzed GaAs nanowires growth

Semiconductor nanowires are long time candidates for numerous applications. Complete understanding of their most common growth process (vapour-liquid-solid), however, is essential in order to achieve the crystalline quality that applications demand. To date, most of the information gathered to understand vapour-liquid-solid growth comes from ex situ and in situ electron microscopy images. Still, those approaches might miss some important features due to time and length scales involved. In this sense, computational simulations can provide additional insights into the process. Yet, so far, no computational simulation was able to consistently reproduce the growth of more than one monolayer of a semiconductor nanowire through the vapour-liquid-solid method. By using a force matching software (PotFit), we developed a new GaAs interatomic potential for molecular dynamics simulations. Our potential can reproduce several features of the growth of self-catalyzed GaAs nanowires, including: formation of zinc blende and wurtzite layers, layer-by-layer formation of the solid phase, b-polar surface growth preference and the dependency between growth rate and precursor flow.

(Invited) Gap Nanowires with Twinning Superlattices: Structure, Optical Properties and Applications

Semiconductor nanowires (NWs) are a good candidate for future optoelectronic devices. However, the control of the essential parameters that determine the electronic and optical quality of NWs, such as crystal structure and incorporation of impurity dopants, are still challenging problems. Most III-V NWs exhibit crystal defects, which are typically randomly distributed zincblende twinning segments and stacking faults that can affect the optical and electrical properties of NW devices. The incorporation of intentional impurity dopants in NWs is important for the fabrication of p-n junctions and control of the electrical conductivity of NWs. The effect of Te and Be impurity dopant concentration on the crystal structure, surface roughness and optical properties of GaAs NWs will be presented. Four identical GaAs NW arrays were grown: an undoped sample (as a reference) and 6 samples with different Te and Be doping concentration. High resolution transmission electron microscopy (HRTEM) revealed an unusual superlattice twinning, with periodicity that became wider and more regular as the doping level increased. Twin boundaries in GaP are shown to act as an atomically narrow plane of wurtzite phase with a type-I homostructure band alignment. Twin boundaries and stacking faults (wider regions of the wurtzite phase) lead to the introduction of shallow trap states observed in photoluminescence studies. Controlling the surface roughness, the periodicity, and the width of twinning planes with doping concentration might open new possibilities for high efficiency NW-based thermoelectric devices, but also has wide implications for all NW devices.

Wafer-scale nanofabrication of sub-100 nm arrays by deep-UV displacement Talbot lithography

In this manuscript, we demonstrate the potential of replacing the standard bottom anti-reflective coating (BARC) with a polymethylglutarimide (PMGI) layer for wafer-scale nanofabrication by means of deep-UV displacement talbot lithography (DTL). PMGI is functioning as a developable non-UV sensitive bottom anti-reflective coating (DBARC). After introducing the fabrication process using a standard BARC-based coating and the novel PMGI-based one, the DTL nanopatterning capabilities for both coatings are compared by means of the fabrication of etched nanoholes in a dielectric layer and metal nanodots made by lift-off. Improvement of DTL capabilities are attributed to a reduction of process complexity by avoiding the use of O2 plasma etching of the BARC layer. We show the capacity of this approach to produce nanoholes or nanodots with diameters ranging from 95 to 200 nm at a wafer-scale using only one mask and a proper exposing dose. The minimum diameter of the nanoholes is reduced from 118 to 95 nm when using the PMGI-based coating instead of the BARC-based one. The possibilities opened by the PMGI-based coating are illustrated by the successful fabrication of an array of nanoholes with sub-100 nm diameter for GaAs nanowire growth on a 2″ GaAs wafer, a 2″ nanoimprint lithography (NIL) master stamp, and an array of Au nanodots made by lift-off on a 4″ silica wafer. Therefore, DTL possess the potential for wafer-scale manufacturing of nano-engineered materials.

Oscillations of As Concentration and Electron-to-Hole Ratio in Si-Doped GaAs Nanowires

III–V nanowires grown by the vapor–liquid–solid method often show self-regulated oscillations of group V concentration in a catalyst droplet over the monolayer growth cycle. We investigate theoretically how this effect influences the electron-to-hole ratio in Si-doped GaAs nanowires. Several factors influencing the As depletion in the vapor–liquid–solid nanowire growth are considered, including the time-scale separation between the steps of island growth and refill, the “stopping effect” at very low As concentrations, and the maximum As concentration at nucleation and desorption. It is shown that the As depletion effect is stronger for slower nanowire elongation rates and faster for island growth relative to refill. Larger concentration oscillations suppress the electron-to-hole ratio and substantially enhance the tendency for the p-type Si doping of GaAs nanowires, which is a typical picture in molecular beam epitaxy. The oscillations become weaker and may finally disappear in vapor deposition techniques such as hydride vapor phase epitaxy, where the n-type Si doping of GaAs nanowires is more easily achievable.

Optical property and lasing of GaAs-based nanowires

GaAs-based nanowire (NW) lasers working in the infrared region is critical in integrated optoelectronics. In the past few decades, the field of NW lasers has developed rapidly. Compared with materials working in the ultraviolet and visible ranges, GaAs-based infrared NW lasers, however, are more difficult to achieve because of their specific properties. In this review, we focus on the recent developments of GaAs-based NWs, more especially, the optical property and lasing of GaAs-based NWs. The growth mechanism of GaAs NWs is introduced in detail, including the crystal phase control and the growth of complex structures. Subsequently, the influence and improvement of the optical properties of GaAs-based NWs are introduced and discussed. Finally, the design and latest progress of GaAs-based NW lasers are put forward.

Effect of Arsenic Depletion on the Silicon Doping of Vapor–Liquid–Solid GaAs Nanowires

It is well known that chemical potential driving the vapor–liquid–solid growth of nanowires oscillates in synchronization with the monolayer growth. In III–V nanowires, this occurs due to depletion of group V atoms in a catalyst droplet. The amphoteric behavior of silicon doping, which often changes from n‐type in planar GaAs layers to p‐type in nanowires, is attributed to low arsenic concentrations. Herein, we present an analytical model which quantifies the doping oscillations over the monolayer formation cycle, and its impact on the electron‐to‐hole ratio for the silicon doping of GaAs nanowires. It is shown that arsenic depletion can easily double the amphoteric effect and strongly favor the tendency for p‐type doping. On a more general ground, the nanowire doping process appears highly sensitive to the chemical potential oscillations related to a restricted amount of material in a nanoscale catalyst.

Formation Mechanism of Twinning Superlattices in Doped GaAs Nanowires.

Recent investigations of III-V semiconductor nanowires have revealed periodic zinc-blende twins, known as twinning superlattices, that are often induced by a high-impurity dopant concentration. In the present study, the relationship between the nanowire morphology, crystal structure, and impurity dopant concentration (Te and Be) of twinning superlattices has been studied in GaAs nanowires grown by molecular beam epitaxy using the self-assisted (with a Ga droplet) vapor-liquid-solid process. The contact angle between the Ga droplet and the nanowire top facet decreased linearly with the dopant concentration, whereas the period of the twinning superlattices increased with the doping concentration and was proportional to the nanowire radius. Our model, which is based entirely on surface energetics, is able to explain a unified formation mechanism of twinning superlattices in doped semiconductor nanowires.

Kinetics of Nucleus Growth from a Nanophase

The kinetics of nucleus growth from a parent nanophase medium with a limited stock of material has been theoretically studied in the presence of possible growth arrest caused by destruction of the source of supersaturation. This regime is characteristic of the island growth of GaAs nanowires (NWs) from a Ga nanodroplet via the vapor–liquid–solid (VLS) mechanism as observed during in situ diagnostics of NW growth inside a transmission electron microscope. A fundamentally new hierarchy of time scales is established, according to which the entire cycle of monocentric nucleation and growth can be divided into three stages: (i) fast growth of nucleus until the growth arrest, (ii) slow growth at a rate of material supply to the nanophase, and (iii) nanophase pumping up to the initial state. The criterion of growth arrest is formulated as dependent on the nanophase size.

Impact of gas adsorption on the stability and electronic properties of negative electron affinity GaAs nanowire photocathodes

The influence of CO, CO2, H2O, H2 and CH4 adsorption on the stability and electronic properties of negative electron affinity (NEA) GaAs nanowire surfaces activated by Cs/O and Cs/NF3 are systematically investigated via first-principles. The calculations indicated that GaAs nanowires activated with 3Cs/O are more susceptible to the surface contamination. After residual gas molecule adsorption, 3Cs/O activated surfaces exhibit direct bandgap character, while 3Cs/NF3 activated surfaces are inversely indirect bandgap. In addition, residual gas adsorption results in a notable increase of band gap, work function and electron affinity of GaAs nanowire surfaces. The incoporation of residual gas molecules also induces a new electric dipole [Cs-gas] with a direction from Cs to gas molecule. From the perspective of theoretical calculation, it is predicted that GaAs nanowires activated through Cs/NF3 has a stronger stability compared with Cs/O in the aspect of gas exposure.

Single GaAs nanowire based photodetector fabricated by dielectrophoresis

Mechanical manipulation of nanowires (NWs) for their integration in electronics is still problematic because of their reduced dimensions, risking to produce mechanical damage to the NW structure and electronic properties during the assembly process. In this regard, contactless NW manipulation based methods using non-uniform electric fields, like dielectrophoresis (DEP) are usually much softer than mechanical methods, offering a less destructive alternative for integrating nanostructures in electronic devices. Here, we report a feasible and reproducible dielectrophoretic method to assemble single GaAs NWs (with radius 35–50 nm, and lengths 3–5 μm) on conductive electrodes layout with assembly yields above 90% per site, and alignment yields of 95%. The electrical characteristics of the dielectrophoretic contact formed between a GaAs NW and conductive electrodes have been measured, observing Schottky barrier like contacts. Our results also show the fast fabrication of diodes with rectifying characteristics due to the formation of a low-resistance contact between the Ga catalytic droplet at the tip of the NW when using Al doped ZnO as electrode. The current-voltage characteristics of a single Ga-terminated GaAs NW measured in dark and under illumination exhibit a strong sensitivity to visible light under forward bias conditions (around two orders of magnitude), mainly produced by a change on the series resistance of the device.

Spatially-resolved luminescence and crystal structure of single core–shell nanowires measured in the as-grown geometry

We report on the direct correlation between the structural and optical properties of single, as-grown core-multi-shell GaAs/In0.15Ga0.85As/GaAs/AlAs/GaAs nanowires. Fabricated by molecular beam epitaxy on a pre-patterned Si(111) substrate, on a row of well separated nucleation sites, it was possible to access individual nanowires in the as-grown geometry. The polytype distribution along the growth axis of the nanowires was revealed by synchrotron-based nanoprobe x-ray diffraction techniques monitoring the axial 111 Bragg reflection. For the same nanowires, the spatially-resolved emission properties were obtained by cathodoluminescence hyperspectral linescans in a scanning electron microscope. Correlating both measurements, we reveal a blueshift of the shell quantum well emission energy combined with an increased emission intensity for segments exhibiting a mixed structure of alternating wurtzite and zincblende stacking compared with the pure crystal polytypes. The presence of this mixed structure was independently confirmed by cross-sectional transmission electron microscopy.

Influence of gallium and arsenic deposition rates on the GaAs planar nanowire morphology

Using the Monte Carlo simulation, the dependence of GaAs nanowire morphology on Ga and As2 flux intensities was analyzed. The self-catalyzed growth of planar GaAs nanowires on GaAs(111)A substrates was considered. Depending on the arsenic and gallium fluxes, three possible scenarios of the GaAs nanowire formation were shown. The regions of gallium and arsenic deposition rates necessary for obtaining a stable planar growth of GaAs nanowires were revealed. The reasons for the transition of planar GaAs nanowire growth to the nonplanar one were analyzed.