Growth Of GaN Nanorods Research Articles

Mg incorporation induced microstructural evolution of reactively sputtered GaN epitaxial films to Mg-doped GaN nanorods

Mg-doped GaN films/nanorods were grown epitaxially on c-sapphire by reactive co-sputtering of GaAs and Mg at different N2 percentages in Ar–N2 sputtering atmosphere. Energy dispersive x-ray spectroscopy revealed that the Mg incorporation increases with increase of Mg area coverage of GaAs target, but does not depend on N2 percentage. In comparison to undoped GaN films, Mg-doped GaN displayed substantial decrease of lateral conductivity and electron concentration with the initial incorporation of Mg, indicating p-type doping, but revealed insulating behaviour at larger Mg content. Morphological investigations by scanning electron microscopy have shown that the films grown with 2%–4% Mg area coverages displayed substantially improved columnar structure, compared to undoped GaN films, along with rough and voided surface features at lower N2 percentages. With increase of Mg area coverage to 6%, the growth of vertically aligned and well-separated nanorods, terminating with smooth hexagonal faces was observed in the range of 50%–75% N2 in sputtering atmosphere. High-resolution x-ray diffraction studies confirmed the epitaxial character of Mg-doped GaN films and nanorods, which displayed complete c-axis orientation of crystallites and a mosaic structure, aligned laterally with the c-sapphire lattice. The catalyst-free growth of self-assembled Mg-doped GaN nanorods is attributed to increase of surface energy anisotropy due to the incorporation of Mg. However, with further increase of Mg area coverage to 8%, the nanorods revealed lateral merger, suggesting enhanced radial growth at larger Mg content.

Role of Surface Chemistry of Ta Metal Foil on the Growth of GaN Nanorods by Laser Molecular Beam Epitaxy and Their Field Emission Characteristics.

This study investigates the influence of surface nitridation of Ta metal foil substrates on the growth of GaN nanorods using the laser molecular beam epitaxy (LMBE) technique and the field emission characteristics of the grown GaN nanorod ensemble. Surface morphology examinations underscore the pivotal role of Ta foil nitridation in shaping the dimensions and densities of GaN nanorods. Bare Ta foil fosters the formation of high-density, vertically self-aligned GaN nanorods at a growth temperature of 700 °C. Furthermore, the density of these nanorods is directly related to the duration of Ta foil nitridation, with increased duration leading to a reduced nanorod density. X-ray Photoelectron Spectroscopy (XPS) studies reveal that the transition of the Ta foil surface from tantalum oxide to tantalum nitride during nitridation emerges as a crucial factor influencing GaN nanorod growth. Photoluminescence (PL) spectroscopy at ambient temperature reveals a strong near-band-edge (NBE) emission peak with negligible defect-related peaks, displaying the high optical quality of the GaN nanorods. The highly dense vertically aligned GaN nanorod ensemble growth without Ta prenitridation exhibits the most favorable field emission performance, featuring a turn-on field of 2.1 V/μm, a field enhancement factor of 2480, and a stable long-term operation at the emission current density of 2.26 mA/cm2. This study advances the understanding of the role of the surface chemistry of metal foil in determining GaN nanorod growth and opens up exciting possibilities for tailoring advanced optoelectronic devices for specific application requirements.

Achieving Ultra-long GaN Nanorod Growth by Lowering Nucleation Energy Via Surface Modification for Optical Sensors

We introduce a pit-formation method on a GaN substrate to obtain ultra-long GaN nanorods (NRs) grown homoepitaxially through hydride vapor phase epitaxy (HVPE) without an additional catalyst or a c...

Self-induced growth of GaN nanorod assembly on flexible niobium metal foil using laser molecular beam epitaxy

Self-induced GaN nanorod (NR) growth on flexible niobium (Nb) metal foil has been reported using laser assisted molecular beam epitaxy (LMBE) technique. The role of growth temperature (600, 650 and 700 °C), laser repetition rate (10–30 Hz) and Nb foil pre-nitridation condition on the formation and properties of GaN NRs have been studied systematically. The dense (~2.42 × 109 cm−2) GaN NRs were grown on pre-nitridated Nb metal foil at growth temperature of 700 °C with length and diameter of ~550–640 nm and ~60–130 nm, respectively. The low growth temperature of 650 °C or the high laser repetition rate of 30 Hz increases the radial growth rate of GaN NRs on Nb foil which results the coalescence of NRs. The size and density of GaN NRs on Nb metal foil could be controlled with tuning of LMBE growth parameters. The GaN NRs obtained on bare and nitridated Nb foil have excellent optical properties with an intense near band emission peak position at ~3.40 eV and a narrow linewidth of 90–100 meV. The controlled growth of GaN NRs with excellent optical quality on Nb foil offers the possibility of realization of futuristic high efficient flexible III-nitride nanostructure-based optoelectronic devices.

Highly regular rosette-shaped cathodoluminescence in GaN self-assembled nanodisks and nanorods

Self-assembled GaN nanorods were grown by metal-organic chemical vapor deposition. A highly regular rosette-shaped cathodoluminescence pattern in the GaN nanorods is observed, where its origin is helpful to deepen the understanding of GaN nanorod growth. The pattern forms at the very early stages of nanorod growth, which consists of yellow luminescence at the edges and the non-luminous region at six vertices of the hexagon. To clarify its origin, we carried out detailed cathodoluminescence studies, electron microscopy studies and nanoscale secondary ion mass spectrometry at both the nanorod surface and cross-section. We found the pattern is not related to optical resonance modes or polarity inversion, which are commonly reported in GaN nanostructures. After chemical composition and strain analysis, we found higher carbon and nitrogen cluster concentration and large compressive strain at the pattern area. The pattern formation may relate to facet preferential distribution of non-radiative recombination centers related to excess carbon/nitrogen. This work provides an insight into strain distribution and defect-related emission in GaN nanorod, which is critical for future optoelectronic applications.

Controlled growth of GaN nanorods directly on flexible Mo metal foil by laser molecular beam epitaxy

Direct growth of one-dimensional (1D) GaN nanostructures on metal foils is perceived as a promising approach for the realization of futuristic flexible opto-electronic devices. Optimization of growth process to achieve 1D GaN nanostructures on metal foils is a challenging task as the growth is sensitive to the nature of individual metals. Here, we report the laser molecular beam epitaxy growth of GaN nanorods by investigating the role of growth temperature, laser energy density and laser repetition rate in the range of 500–700 °C, 3–5 J/cm2and 10–30 Hz, respectively. A higher growth temperature is noticed to be very crucial in determining the formation of 1D GaN nanorod while the laser energy and repetition rate mostly control the nanorod density. GaN nanorod ensemble with the density, length and top cross-sectional width, respectively,~1.41 × 109 cm−2, 430–620 nm and 70–160 nm is achieved at 700 °C using laser energy density of ~5 J/cm2 and repetition rate of 10 Hz. The shape of GaN nanorods is nearly same for different laser repetition rates (20–30 Hz) and the density of GaN nanorods increases with the laser repetition rate (~3.42 × 109 cm−2 for 20 Hz and ~3.51 × 109 cm−2 for 30 Hz). X-ray diffraction, Raman spectroscopy and high resolution transmission electron microscopy studies revealed the c-axis oriented growth of single crystalline wurtzite GaN nanorods on Mo foil. Room temperature photoluminescence spectroscopy exhibited a high intense near band edge emission at ~3.4 eV with negligible deep-bands. The controlled growth of self-assembled GaN nanostructures on polycrystalline metal foil with good structural and optical properties has the potential for developing III-nitride based bendable optoelectronic devices.

Effect of surface modification and laser repetition rate on growth, structural, electronic and optical properties of GaN nanorods on flexible Ti metal foil.

The effect of flexible Ti metal foil surface modification and laser repetition rate in laser molecular beam epitaxy growth process on the evolution of GaN nanorods and their structural, electronic and optical properties has been investigated. The GaN nanostructures were grown on bare- and pre-nitridated Ti foil substrates at 700 °C for different laser repetition rates (10–30 Hz). It is found that the low repetition rate (10 Hz) promotes sparse growth of three-dimensional inverted-cone like GaN nanostructures on pre-nitridated Ti surface whereas the entire Ti foil substrate is nearly covered with film-like GaN consisting of large-sized grains for 30 Hz growth. In case of the GaN growth at 20 Hz, uniformly-aligned, dense (∼8 × 109 cm−2) GaN nanorods are successfully grown on pre-nitridated Ti foil whereas sparse vertical GaN nanorods have been obtained on bare Ti foil under similar growth conditions for both 20 and 30 Hz. X-ray photoemission spectroscopy (XPS) has been utilized to elucidate the electronic structure of GaN nanorods grown under various experimental conditions on Ti foil. It confirms Ga–N bonding in the grown structures, and the calculated chemical composition turns out to be Ga rich for the GaN nanorods grown on pre-nitridated Ti foil. For bare Ti substrates, a preferred reaction between Ti and N is noticed as compared to Ga and N leading to sparse growth of GaN nanorods. Hence, the nitridation of Ti foil is a prerequisite to achieve the growth of dense and aligned GaN nanorod arrays. The X-ray diffraction, high resolution transmission electron microscopy and Raman studies revealed the c-axis growth of wurtzite GaN nanorods on Ti metal foil with good crystallinity and structural quality. The photoluminescence spectroscopy showed that the dense GaN nanorod possesses a near band edge emission at 3.42 eV with a full width at half maximum of 98 meV at room temperature. The density-controlled growth of GaN nanorods on a flexible substrate with high structural and optical quality holds promise for potential applications in futuristic flexible GaN based optoelectronics and sensor devices.

Features of the Selective Growth of GaN Nanorods on Patterned c-Sapphire Substrates of Various Configurations

The growth features of GaN nanorods on patterned c-sapphire substrates with a regular microcone array having a different density and base diameter in the ranges of (1–5) × 107 cm–2 and 2.5–3.5 μm, respectively, are investigated. The kinetics is studied and the selective-growth regimes are determined for single GaN nanorods with a diameter of 30–100 nm at the vertices of microcones under radically lower growth rates on their slopes. The effect of the configuration of microcones, the substrate temperature, the roughness of the initial surface, and the presence of indium as a surfactant on the degree of growth selectivity is investigated.

Site-Controlled Growth of GaN Nanorods with Inserted InGaN Quantum Wells on μ-Cone Patterned Sapphire Substrates by Plasma-Assisted MBE

We report on a new approach to fabricate regular arrays of GaN nanorods (NRs) with InGaN QWs by plasma-assisted molecular-beam epitaxy (PA MBE) on micro-cone patterned sapphire substrates (μ-CPSSs). A two-stage PA MBE fabrication process of GaN NRs has been developed, starting with a high temperature nucleation layer growth at metal-rich conditions to aggregate selectively GaN nucleus on c-oriented areas of the μ-CPSSs and followed by growth of 1-μm-thick GaN NRs at strongly nitrogen-rich conditions exactly on the cone tips. These results are explained by energetically favorable GaN growth on the (000-) oriented sapphire surface. Both micro-photoluminescence and micro-cathodoluminescence confirm the formation of regular array of optically and spectrally isolated NRs without usage of any nanolithography.

Effects of N₂ Partial Pressure on Growth, Structure, and Optical Properties of GaN Nanorods Deposited by Liquid-Target Reactive Magnetron Sputter Epitaxy.

GaN nanorods, essentially free from crystal defects and exhibiting very sharp band-edge luminescence, have been grown by reactive direct-current magnetron sputter epitaxy onto Si (111) substrates at a low working pressure of 5 mTorr. Upon diluting the reactive N2 working gas with a small amount of Ar (0.5 mTorr), we observed an increase in the nanorod aspect ratio from 8 to ~35, a decrease in the average diameter from 74 to 35 nm, and a two-fold increase in nanorod density. With further dilution (Ar = 2.5 mTorr), the aspect ratio decreased to 14, while the diameter increased to 60 nm and the nanorod density increased to a maximum of 2.4 × 109 cm−2. Yet, lower N2 partial pressures eventually led to the growth of continuous GaN films. The observed morphological dependence on N2 partial pressure is explained by a change from N-rich to Ga-rich growth conditions, combined with reduced GaN-poisoning of the Ga-target as the N2 gas pressure is reduced. Nanorods grown at 2.5 mTorr N2 partial pressure exhibited a high intensity 4 K photoluminescence neutral donor bound exciton transitions (D0XA) peak at ~3.479 eV with a full-width-at-half-maximum of 1.7 meV. High-resolution transmission electron microscopy corroborated the excellent crystalline quality of the nanorods.

Site-controlled growth of GaN nanorods with inserted InGaN quantum wells on mu-cone patterned sapphire substrates by plasma-assisted MBE

AbstractWe report on a new approach to fabricate regular arrays of GaN nanorods (NRs) with InGaN QWs by plasma-assisted molecular-beam epitaxy (PA MBE) on micro-cone patterned sapphire substrates (μ-CPSSs). A two-stage PA MBE fabrication process of GaN NRs has been developed, starting with a high temperature nucleation layer growth at metal-rich conditions to aggregate selectively GaN nucleus on c-oriented areas of the μ-CPSSs and followed by growth of 1-μm-thick GaN NRs at strongly nitrogen-rich conditions exactly on the cone tips. These results are explained by energetically favorable GaN growth on the (000-) oriented sapphire surface. Both micro-photoluminescence and micro-cathodoluminescence confirm the formation of regular array of optically and spectrally isolated NRs without usage of any nanolithography.

Novel approach for III-N on Si (111) templates fabrication by low-temperature PA MBE using porous Si layer

We report on successful growth of GaN nanorods by low-temperature plasma-assisted molecular beam epitaxy on a Si(111) substrate with and without preformed thin porous Si layer (por-Si). The deposited GaN initially forms islands which act as a seed for the wires. Porous structure of the por-Si layer helps to control nucleation islands sizes and achieve homogeneous distribution of the nanorods diameters. In addition 850 nm-thick crack-free GaN layer was formed on Si(111) substrate with preformed por-Si layer.

Selective-area growth of single-crystal wurtzite GaN nanorods on SiOx/Si(001) substrates by reactive magnetron sputter epitaxy exhibiting single-mode lasing

Selective-area growth (SAG) of single-crystal wurtzite GaN nanorods (NRs) directly onto Si(001) substrates with un-etched native SiOx amorphous layer, assisted by a patterning TiNx mask fabricated by nanosphere lithography (NSL), has been realized by reactive magnetron sputter epitaxy (MSE). The GaN NRs were grown vertically to the substrate surface with the growth direction along c-axis in the well-defined nano-opening areas. A 5-step structural and morphological evolution of the SAG NRs observed at different sputtering times depicts a comprehensive growth model, listed in sequence as: formation of a polycrystalline wetting layer, predominating c-axis oriented nucleation, coarsening and coalescence of multi-islands, single NR evolution, and finally quasi-equilibrium crystal shape formation. Room-temperature cathodoluminescence spectroscopy shows a strong GaN bandedge emission with a uniform luminescence across the NRs, indicating that the SAG NRs are grown with high quality and purity. In addition, single-longitudinal-mode lasing, attributed to well-faceted NR geometry forming a Fabry–Pérot cavity, was achieved by optical pumping, paving a way for fabricating high-performance laser optoelectronics using MSE.

Selective area growth of N-polar GaN nanorods by plasma-assisted MBE on micro-cone-patterned c-sapphire substrates

The site-controlled selective area growth of N-polar GaN nanorods (NR) was developed by plasma-assisted MBE (PA MBE) on micro-cone-patterned sapphire substrates (µ-CPSS) by using a two-stage growth process. A GaN nucleation layer grown by migration enhanced epitaxy provides the best selectivity for nucleation of NRs on the apexes of 3.5-µm-diameter cones, whereas the subsequent growth of 1-μm-high NRs with a constant diameter of about 100nm proceeds by standard high-temperature PA MBE at nitrogen-rich conditions. These results are explained by anisotropy of the surface energy for GaN of different polarity and crystal orientation. The InGaN single quantum wells inserted in the GaN NRs grown on the µ-CPSS demonstrate photoluminescence at 510nm with a spatially periodic variation of its intensity with a period of ∼6µm equal to that of the substrate patterning profile.

The mechanism of indium-assisted growth of (In)GaN nanorods: eliminating nanorod coalescence by indium-enhanced atomic migration.

Both well vertically aligned and uniformly separated (In)GaN nanorods (NRs) were successfully grown on Si(111) substrates by plasma-assisted molecular beam epitaxy. Effects of supplied indium (In) flux on the morphology of (In)GaN NRs were investigated systematically. The scanning electron microscopic analysis and transmission electron microscopic measurements revealed that the presence of In flux can help to inhibit NR coalescence and obtain well-separated (In)GaN NRs. By increasing the supplied In flux, the densities of (In)GaN NRs decreased and the axial growth rates increased. According to the energy dispersive X-ray spectrometry measurements and theoretical calculations, the increase of In content of the NRs enhanced Ga diffusion on the NR sidewalls, which resulted in an increased axial growth rate. A kinetic In-assisted growth model for the well-separated (In)GaN NRs is therefore proposed. The model explains that the presence of In flux not only reduces the density of (In)GaN NRs due to the increase in substrate surface migration of Ga adatoms at nucleation stage but also lead to a remarkable enhancement of axial growth rate at growth stage. Consequently, the NR coalescence was significantly suppressed. The results provide a demonstration of obtaining well-separated (In)GaN NRs and open up further possibility of developing (In)GaN NR-based optoelectronic devices.

Selective Area Growth and Characterization of GaN Nanorods Fabricated by Adjusting the Hydrogen Flow Rate and Growth Temperature with Metal Organic Chemical Vapor Deposition**Supported by the Key Program of the National Natural Science Foundation of China under Grant No 61334009, and the National High Technology Research and Development Program of China under Grant No 2014AA032604.

GaN nanorods are successfully fabricated by adjusting the flow rate ratio of hydrogen (H2)/nitrogen (N2) and growth temperature of the selective area growth (SAG) method with metal organic chemical vapor deposition (MOCVD). The SAG template is obtained by nanospherical-lens photolithography. It is found that increasing the flow rate of H2 will change the GaN crystal shape from pyramid to vertical rod, while increasing the growth temperature will reduce the diameters of GaN rods to nanometer scale. Finally the GaN nanorods with smooth lateral surface and relatively good quality are obtained under the condition that the H2:N2 ratio is 1:1 and the growth temperature is 1030°C. The good crystal quality and orientation of GaN nanorods are confirmed by high resolution transmission electron microscopy. The cathodoluminescence spectrum suggests that the crystal and optical quality is also improved with increasing the temperature.

The anti-surfactant effect of silane on the facets-controlled growth of GaN nanorods by MOCVD

N-polar GaN nanorods were selective area grown by continuous mode metalorganic chemical vapor deposition (MOCVD) under a Ga-rich and high silane flow condition. The interruption comparing with continuous supply of silane flow was performed to study the role of silane flux. High resolution scanning electron microscopy (SEM), x-ray diffraction (XRD), cathodoluminescence (CL) and x-ray photoelectron spectroscopy (XPS) measurements were performed. The enhanced vertical growth rate was achieved as 42 μm/h and sharp smooth m-plane, r-plane and c-plane facets were obtained for the nanorods with high silane flux. SiN bonds were clarified to be formed on the surface of the nanorod by XPS spectra. The silane acting as anti-surfactant was suggested to explain the diffusion and incorporation of the species on the facets of GaN nanorods.

Self-Catalyzed Growth of Vertically Aligned InN Nanorods by Metal-Organic Vapor Phase Epitaxy.

Vertically aligned hexagonal InN nanorods were grown mask-free by conventional metal-organic vapor phase epitaxy without any foreign catalyst. The In droplets on top of the nanorods indicate a self-catalytic vapor-liquid-solid growth mode. A systematic study on important growth parameters has been carried out for the optimization of nanorod morphology. The nanorod N-polarity, induced by high temperature nitridation of the sapphire substrate, is necessary to achieve vertical growth. Hydrogen, usually inapplicable during InN growth due to formation of metallic indium, and silane are needed to enhance the aspect ratio and to reduce parasitic deposition beside the nanorods on the sapphire surface. The results reveal many similarities between InN and GaN nanorod growth showing that the process despite the large difference in growth temperature is similar. Transmission electron microscopy, spatially resolved energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and Raman spectroscopy have been performed to analyze the structural properties. Spatially resolved cathodoluminescence investigations are carried out to verify the optical activity of the InN nanorods. The InN nanorods are expected to be the material of choice for high-efficiency hot carrier solar cells.

Vertically Oriented Growth of GaN Nanorods on Si Using Graphene as an Atomically Thin Buffer Layer.

The monolithic integration of wurtzite GaN on Si via metal-organic vapor phase epitaxy is strongly hampered by lattice and thermal mismatch as well as meltback etching. This study presents single-layer graphene as an atomically thin buffer layer for c-axis-oriented growth of vertically aligned GaN nanorods mediated by nanometer-sized AlGaN nucleation islands. Nanostructures of similar morphology are demonstrated on graphene-covered Si(111) as well as Si(100). High crystal and optical quality of the nanorods are evidenced through scanning transmission electron microscopy, micro-Raman, and cathodoluminescence measurements supported by finite-difference time-domain simulations. Current-voltage characteristics revealed high vertical conduction of the as-grown GaN nanorods through the Si substrates. These findings are substantial to advance the integration of GaN-based devices on any substrates of choice that sustains the GaN growth temperatures, thereby permitting novel designs of GaN-based heterojunction device concepts.

Inclined angle-controlled growth of GaN nanorods on m-sapphire by metal organic chemical vapor deposition without a catalyst

In this study, we have intentionally grown novel types of (11-22)- and (1-10-3)-oriented and self-assembled inclined GaN nanorods (NRs) on (10-10) m-sapphire substrates using metal organic chemical vapor deposition without catalysts and ex situ patterning. Nitridation of the m-sapphire surface was observed to be crucial to the inclined angle as well as the growth direction of the GaN NRs. Polarity-selective KOH etching confirmed that both (11-22) and (1-10-3) GaN NRs are nitrogen-polar. Using pole figure measurements and selective area electron diffraction patterns, the epitaxial relationship between the inclined (11-22) and (1-10-3) GaN NRs and m-sapphire substrates was systematically demonstrated. Furthermore, it was verified that the GaN NRs were single-crystalline wurtzite structures. We observed that stacking fault-related defects were generated during the initial growth stage using high-resolution transmission electron microscopy. The blue-shift of the near band edge (NBE) peak in the inclined angle-controlled GaN NRs can be explained by a band filling effect through carrier saturation of the conduction band, resulting from a high Si-doping concentration; in addition, the decay time of NBE emission in (11-22)- and (1-10-3)-oriented NRs was much shorter than that of stacking fault-related emission. These results suggest that defect-free inclined GaN NRs can be grown on m-sapphire without ex situ treatment.