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Scanning spreading resistance microscopy (SSRM) measurements were performed on GaAs thick films grown by hydride vapor phase epitaxy technology under different growth conditions to evaluate their carrier concentrations. For this purpose, a calibration curve was established based on a multilayer staircase structure grown by molecular beam epitaxy. The dopant calibration range measured by secondary ion mass spectrometry is from 5 × 1016 to 1019 cm−3. An abnormal phenomenon in the calibration process was explained by taking into account the parasitic parallel resistance of the calibration samples. Finally, the calibration curve was used to quantitatively analyze the carriers inside the Zn doping p-type GaAs film from 4 × 1016 to 1018 cm−3 range. We demonstrate here the applicability of SSRM to the in-depth analysis of thick epilayers, providing new inputs for the control of thick film technologies. [ABSTRACT FROM AUTHOR]

Nanowires (NWs) are promising for the integration of III–V compound-based electrical and optical devices on Si. Selective area growth (SAG) of InxGa1–xAs NWs with compositions x varying from 0.34 to 0.90 is achieved. NWs are grown on patterned Si(111) substrates by hydride vapor phase epitaxy (HVPE) at temperatures around 690 °C. The composition is measured using EDX profiles along their lengths and found to be quite homogeneous. Theoretical analysis revealed that the NW composition is kinetically controlled and well-fit by the one-parametric Langmuir–McLean formula, with no thermodynamic factors influencing the compositional trend. This study highlights the capability of catalyst-free HVPE SAG to grow highly uniform InGaAs NW arrays with a widely tunable composition on Si substrates. [ABSTRACT FROM AUTHOR]

We demonstrate the selective area growth of InGaAs nanowires (NWs) on GaAs (111)B substrates using hydride vapor phase epitaxy (HVPE). A high growth rate of more than 50 μ m h−1 and high aspect ratio NWs were obtained. Composition along the NWs was investigated by energy dispersive x-ray spectroscopy giving an average indium composition of 84%. This is consistent with the composition of 78% estimated from the photoluminescence spectrum of the NWs. Crystal structure analysis of the NWs by transmission electron microscopy indicated random stacking faults related to zinc-blende/wurtzite polytypism. This work demonstrates the ability of HVPE for growing high aspect ratio InGaAs NW arrays. [ABSTRACT FROM AUTHOR]

High aspect ratio, rod-like and single crystal phase GaAs nanowires (NWs) were grown by gold catalyst-assisted hydride vapor phase epitaxy (HVPE). High resolution transmission electron microscopy and micro-Raman spectroscopy revealed polytypism-free zinc blende (ZB) NWs over lengths of several tens of micrometers for a mean diameter of 50 nm. Micro-photoluminescence studies of individual NWs showed linewidths smaller than those reported elsewhere which is consistent with the crystalline quality of the NWs. HVPE makes use of chloride growth precursors GaCl of which high decomposition frequency after adsorption onto the liquid droplet catalysts, favors a direct and rapid introduction of the Ga atoms from the vapor phase into the droplets. High influxes of Ga and As species then yield high axial growth rate of more than 100 μm/h. The diffusion of the Ga atoms in the liquid droplet towards the interface between the liquid and the solid nanowire was investigated by using density functional theory calculations. The diffusion coefficient of Ga atoms was estimated to be 3 × 10-9 m2/s. The fast diffusion of Ga in the droplet favors nucleation at the liquid-solid line interface at the center of the NW. This is further evidence, provided by an alternative epitaxial method with respect to metal-organic vapor phase epitaxy and molecular beam epitaxy, of the current assumption which states that this type of nucleation should always lead to the formation of the ZB cubic phase. [ABSTRACT FROM AUTHOR]

Well-ordered and vertically aligned InN nanorods with high aspect ratios are synthesized by hydride vapor phase epitaxy (HVPE) using the selective area growth (SAG) approach. The growth occurs through the apertures of a SiNx masked Ga-polar GaN/c-Al2O3 template for adjusted growth temperature and V/III ratio. The nanorods exhibit a hexagonal shape without any rotation around the growth axis. The wurtzite structure and the high crystalline quality of InN nanorods are confirmed by X-ray diffraction (XRD) as well as by high-resolution transmission electron microscopy (HR-TEM). Only few stacking faults are identified at the bottom part of the nanorods. Photoluminescence (PL) displays an emission peak centered at 0.77 eV which agrees with the band gap of InN. These promising achievements, which go far beyond the existing InN growth limitations, pave the way towards the integration of pure InN in future devices. [ABSTRACT FROM AUTHOR]

The growth of GaN 3-D microstructures is investigated by SAG-HVPE. Capitalizing on the properties of this kinetically-controlled process, the main experimental parameters and physical mechanisms that control the shaping of 3D GaN prisms and pyramids in SAG-HVPE are highlighted. Growth experiments performed on N-polar AlN/Si(100) and Ga-polar GaN/Si(111) substrates also provide insight into how to switch from a pyramid to a prismatic shape for a given substrate polarity. The aspect ratio of GaN rods could be tuned by playing with the HCl partial pressure additionally introduced during growth. The influence of both mass transport and surface kinetics is discussed, as the crystal growth rate varies with increasing surface area as time goes by. Ammonia treatment prior to the growth, aimed at blocking the r planes thanks to H2 passivation, is proposed to tune the morphology of the GaN rods. Raman spectroscopy performed on individual GaN rods shows no relevant strain field and no structural differences between the rods and state-of-the-art bulk GaN. [ABSTRACT FROM AUTHOR]

The growth of GaN by HVPE has been analysed by means of a thermodynamical and kinetic study. Two mechanisms involved in the growth of (00.1) GaN HVPE have been deduced from the numerous experiments performed on (0 0 1) GaAs by the chloride method. The parameters of these two growth mechanisms have been resolved from the experimental variations of HVPE GaN growth rate. Experiments performed in conditions of expected fast etching by HCl, in a mixed H2/N2 carrier gas, led to a new growth mechanism by considering a combined Cl desorption by GaCl as GaCl2 and an etching by HCl. The apparent activation energy of the new Cl desorption reaction is the only new parameter introduced in the third growth mechanism. In this paper, we present the results obtained for the determination of a more accurate value of this new parameter. The growth rate was measured versus the growth temperature for different H2 concentrations in the carrier gas. A quite good agreement was obtained between experimental and theoretical values. [Copyright &y& Elsevier]

Selective area growth by hydride vapor phase epitaxy of GaN nanostructures with different shapes was investigated versus the deposition conditions including temperature and ammonia flux. Growth experiments were carried out on templates of GaN on sapphire masked with SiN x . We discuss two occurrences related to axial and radial growth of GaN nanowires. A growth suppression phenomenon was observed under certain conditions, which was circumvented by applying the cyclic growth mode. A theoretical model involving inhibiting species was developed to understand the growth suppression phenomenon on the masked substrates. Various morphologies of GaN nanocrystals were obtained by controlling the competition between the growth and blocking mechanisms as a function of the temperature and vapor phase composition. The optimal growth conditions were revealed for obtaining regular arrays of ∼5 μ m long GaN nanowires., (© 2024 IOP Publishing Ltd.)

Controlled growth of In-rich InGaN nanowires/nanorods (NRs) has long been considered as a very challenging task. Here, we present the first attempt to fabricate InGaN NRs by selective area growth using hydride vapor phase epitaxy. It is shown that InGaN NRs with different indium contents up to 90% can be grown by varying the In/Ga flow ratio. Furthermore, nanowires are observed on the surface of the grown NRs with a density that is proportional to the Ga content. The impact of varying the NH 3 partial pressure is investigated to suppress the growth of these nanowires. It is shown that the nanowire density is considerably reduced by increasing the NH 3 content in the vapor phase. We attribute the emergence of the nanowires to the final step of growth occurring after stopping the NH 3 flow and cooling down the substrate. This is supported by a theoretical model based on the calculation of the supersaturation of the ternary InGaN alloy in interaction with the vapor phase as a function of different parameters assessed at the end of growth. It is shown that the decomposition of the InGaN solid alloy indeed becomes favorable below a critical value of the NH 3 partial pressure. The time needed to reach this value increases with increasing the input flow of NH 3 , and therefore the alloy decomposition leading to the formation of nanowires becomes less effective. These results should be useful for fundamental understanding of the growth of InGaN nanostructures and may help to control their morphology and chemical composition required for device applications.

Homogenous InGaN nanowires with a controlled indium composition up to 90% are grown on GaN/c-Al 2 O 3 templates by catalyst-free hydride vapor phase epitaxy using InCl 3 and GaCl as group III element precursors. The influence of the partial pressures on the growth rate and composition of InGaN nanowires is investigated. It is shown how the InN mole fraction in nanowires can be finely tuned by changing the vapor phase composition. Thermodynamic calculations are presented that take into account different interconnected reactions in the vapor phase and show a good agreement with the compositional data. Energy dispersive x-ray spectroscopy profiles performed on single nanowires show a homogenous indium composition along the entire nanowire length. X-ray diffraction measurements performed on nanowires arrays confirm these data. High-resolution transmission electron microscopy analysis shows the wurtzite crystal structure with a reduced defect density for InGaN nanowires with the highest indium content.

Widegap III-nitride alloys have enabled new classes of optoelectronic devices including light emitting diodes, lasers and solar cells, but it is admittedly challenging to extend their operating wavelength to the yellow-red band. This requires an increased In content x in In x Ga 1-x N, prevented by the indium segregation within the miscibility gap. Beyond the known advantage of dislocation-free growth on dissimilar substrates, nanowires may help to extend the compositional range of InGaN. However, the necessary control over the material homogeneity is still lacking. Here, we present In x Ga 1-x N nanowires grown by hydride vapor phase epitaxy on silicon substrates, showing rather homogeneous compositions and emitting from blue to red. The InN fraction in nanowires is tuned from x = 0.17 up to x = 0.7 by changing the growth temperature between 630 °C and 680 °C and adjusting some additional parameters. A dedicated model is presented, which attributes the wide compositional range of nanowires to the purely kinetic growth regime of self-catalyzed InGaN nanowires without macroscopic nucleation. These results may pave a new way for the controlled synthesis of indium-rich InGaN structures for optoelectronic applications in the extended spectral range.

Gold-free GaAs nanowires on silicon substrates can pave the way for monolithic integration of photonic nanodevices with silicon electronic platforms. It is extensively documented that the self-catalyzed approach works well in molecular beam epitaxy but is much more difficult to implement in vapor phase epitaxies. Here, we report the first gallium-catalyzed hydride vapor phase epitaxy growth of long (more than 10 μm) GaAs nanowires on Si(111) substrates with a high integrated growth rate up to 60 μm h -1 and pure zincblende crystal structure. The growth is achieved by combining a low temperature of 600 °C with high gaseous GaCl/As flow ratios to enable dechlorination and formation of gallium droplets. GaAs nanowires exhibit an interesting bottle-like shape with strongly tapered bases, followed by straight tops with radii as small as 5 nm. We present a model that explains the peculiar growth mechanism in which the gallium droplets nucleate and rapidly swell on the silicon surface but then are gradually consumed to reach a stationary size. Our results unravel the necessary conditions for obtaining gallium-catalyzed GaAs nanowires by vapor phase epitaxy techniques.

We report the Au catalyst-assisted synthesis of 20 μm long GaAs nanowires by the vapor-liquid-solid hydride vapor phase epitaxy (HVPE) exhibiting a polytypism-free zincblende phase for record radii lower than 15 nm down to 5 nm. HVPE makes use of GaCl gaseous growth precursors at high mass input of which fast dechlorination at the usual process temperature of 715 °C results in high planar growth rate (standard 30-40 μm/h). When it comes to the vapor-liquid-solid growth of nanowires, fast solidification at a rate higher than 100 μm/h is observed. Nanowire growth by HVPE only proceeds by introduction of precursors in the catalyst droplets from the vapor phase. This promotes almost pure axial growth leading to nanowires with a constant cylinder shape over unusual length. The question of the cubic zincblende structure observed in HVPE-grown GaAs nanowires regardless of their radius is at the heart of the paper. We demonstrate that the vapor-liquid-solid growth in our conditions takes place at high liquid chemical potential that originates from very high influxes of both As and Ga. This yields a Ga concentration systematically higher than 0.62 in the Au-Ga-As droplets. The high Ga concentration decreases the surface energy of the droplets, which disables nucleation at the triple phase line thus preventing the formation of wurtzite structure whatever the nanowire radius is.

GaN nanowires with exceptional lengths are synthesized by vapor-liquid-solid coupled with near-equilibrium hydride vapor phase epitaxy technique on c-plane sapphire substrates. Because of the high decomposition frequency of GaCl precursors and a direct supply of Ga through the catalyst particle, the growth of GaN nanowires with constant diameters takes place at an exceptional growth rate of 130 μm/h. The chemical composition of the catalyst droplet is analyzed by energy dispersive X-ray spectroscopy. High-resolution transmission electron microscopy and selective area diffraction show that the GaN nanowires crystallize in the hexagonal wurzite structure and are defect-free. GaN nanowires exhibit bare top facets without any droplet. Microphotoluminescence displays a narrow and intense emission line (1 meV line width) associated to the neutral-donor bound exciton revealing excellent optical properties of GaN nanowires.