MOVPE of AlN-free hexagonal GaN/cubic SiC/Si heterostructures for vertical devices

The heterostructures of GaN/SiC/Si were prepared without using AlN or AlGaN buffer layers (AlN buffers) in the metalorganic vapor phase epitaxy of GaN on SiC. GaN (0 0 0 1) with specular surface was obtained. The AlN buffers are usually used in the conventional growth of GaN on SiC due to the poor nucleation of GaN on SiC. Instead, the nucleation of GaN was controlled by varying the partial pressure of H₂ in the carrier gas, the mixture of H₂ and N₂, during the low-temperature (600 °C) growth of GaN (LT-GaN). After the LT-GaN, the high-temperature (1000 °C) growth of GaN was performed using pure H₂ as the carrier gas. The epitaxial film of cubic SiC (1 1 1) on a Si (1 1 1) substrate was used as the SiC template. Increasing the partial pressure of H₂ in the carrier gas decreased the coverage of SiC surface by LT-GaN. It is suggested that the hydrogen atoms adsorbed on the surface of SiC is preventing the nucleation of GaN.     

Crystal growth and characterization of GaCrN nanorods on Si substrate

GaCrN nanorods were grown on GaN nanorods by RF-plasma-assisted molecular beam epitaxy. GaN nanorods were grown on Si (0 0 1) substrates with native SiO₂. Cr doping into GaCrN nanorods was conducted at substrate temperatures of 800 and 550 °C. Cross-sectional transmission electron microscopy images revealed that the diameter of GaCrN nanorod gradually increases with growth proceeding at 550 °C, while the growth at 800 °C does not change the nanorod diameter. Low-temperature growth enhances the growth perpendicular to the c-axis and decreases the growth along the c-axis. It was found that the solubility limit of Cr atoms in GaCrN is much higher for the low-temperature growth than for the high-temperature growth. It was also found that the highest saturation magnetization is obtained at some optimum Cr cell temperature.     

Investigation of void formation beneath thin AlN layers by decomposition of sapphire substrates for self-separation of thick AlN layers grown by HVPE

Void formation at the interface between thick AlN layers and (0 0 0 1) sapphire substrates was investigated to form a predefined separation point of the thick AlN layers for the preparation of freestanding AlN substrates by hydride vapor phase epitaxy (HVPE). By heating 50–200 nm thick intermediate AlN layers above 1400 °C in a gas flow containing H₂ and NH₃, voids were formed beneath the AlN layers by the decomposition reaction of sapphire with hydrogen diffusing to the interface. The volume of the sapphire decomposed at the interface increased as the temperature and time of the heat treatment was increased and as the thickness of the AlN layer decreased. Thick AlN layers subsequently grown at 1450 °C after the formation of voids beneath the intermediate AlN layer with a thickness of 100 nm or above self-separated from the sapphire substrates during post-growth cooling with the aid of voids. The 79 μm thick freestanding AlN substrate obtained using a 200 nm thick intermediate AlN layer had a flat surface with no pits, high optical transparency at wavelengths above 208.1 nm, and a dislocation density of 1.5×10⁸ cm⁻².     

Influence of growth temperature on the selective area MOVPE of InAs nanowires on GaAs (1 1 1) B using N2 carrier gas

The influence of temperature on selective area (SA) InAs nanowire growth was investigated for metal-organic vapor phase epitaxy (MOVPE) using N₂ as the carrier gas and (1 1 1) B GaAs substrates. In contrast to the growth temperature range – below 600 °C – reported for hydrogen ambient, the optimal growth temperature between 650 and 700 °C was 100 K higher than the optimal ones for H₂ carrier gas. At these temperatures, nanowires with aspect ratios of about 80 and a symmetric hexagonal shape were obtained. The results found are attributed to the physical and chemical properties of the carrier gas.     

AlGaN epitaxial lateral overgrowth on Ti-evaporated GaN/sapphire substrate

AlGaN growth using epitaxial lateral overgrowth (ELO) by metalorganic chemical vapor deposition on striped Ti, evaporated GaN on sapphire, has been investigated. AlGaN/AlN films growth on GaN/AlGaN superlattices (SLs) structure on the Ti masks, with various SLs growth temperature (1030, 1060 and 1090 °C) were grown. With increasing the growth temperature, AlGaN surface became flat. The AlGaN film had a cathodoluminescence peak around 345 nm. However, in secondary ion mass spectrometry (SIMS) measurement, Ti signal was detected on the top of AlGaN surface when GaN/AlGaN SLs was grown on Ti striped masks. By inserting the AlN blocking layer on SLs, Ti diffusion was stopped at the AlN layer, and the AlGaN crystalline quality was improved.     

MOVPE growth of single-crystal hexagonal AlN on cubic diamond

We have obtained single-crystal aluminum nitride (AlN) layers on diamond (1 1 1) substrates by metalorganic vapor-phase epitaxy (MOVPE). When the thermal cleaning temperature of the substrate and growth temperature of the AlN layer were below 1100 °C, the AlN layer had multi-domain structures mainly consisting of rotated domains. An interface layer, consisting of amorphous carbon and poly-crystal AlN, was formed between the AlN layer and the diamond substrate. On the other hand, when the thermal cleaning temperature and growth temperature were above 1200 °C, a single-crystal AlN layer was grown and no interface layer was formed. Therefore, we attribute the multi-domain structures to the interface layer. Even at the growth temperature of 1100 °C, by performing the thermal cleaning at 1200 °C, the single-crystal AlN layer was obtained, indicating that the thermal cleaning temperature of the substrate is a critical factor for the formation of the interface layer. The epitaxial relationship between the single-crystal AlN layer and the diamond (1 1 1) substrate was determined to be [0 0 0 1]_AlN∥[1 1 1]_diamond and [1 0 1¯ 0]_AlN∥[1 1¯ 0]_diamond. The AlN surface had Al polarity and no inversion domains were observed in the AlN layer.     

Growth of GaN films on PLD-deposited TaC substrates

GaN films were grown by metal organic chemical vapor deposition on TaC substrates that were created by pulsed laser deposition of TaC onto (0 0 0 1) SiC substrates at ∼1000 °C. This was done to determine if good quality TaC films could be grown, and if good quality GaN films could be grown on this closely lattice matched to GaN, conductive material. This was done by depositing the TaC on on-axis and 3° or 8° off-axis (0 0 0 1) SiC at temperatures ranging from 950 to 1200 °C, and examining them using X-ray diffraction, scanning electron microscopy, atomic force microscopy, and transmission electron microscopy. The GaN films were grown on as-deposited TaC films, and films annealed at 1200, 1400, or 1600 °C, and examined using the same techniques. The TaC films were polycrystalline with a slight (1 1 1) texture, and the grains were ∼200 nm in diameter. Films grown on-axis were found to be of higher quality than those grown on off-axis substrates, but the latter could be improved to a comparable quality by annealing them at 1200–1600 °C for 30 min. TaC films deposited at temperatures above 1000 °C were found to react with the SiC. GaN films could be deposited onto the TaC when the surface was nitrided with NH₃ for 3 min at 1100 °C and the low temperature buffer layer was AlN. However, the GaN did not nucleate easily on the TaC film, and the crystallites did not have the desired (0 0 0 1) preferred orientation. They were ∼10 times larger than those typically seen in films grown on SiC or sapphire. Also the etch pit concentration in the GaN films grown on the TaC was more than 2 orders of magnitude less than it was for growth on the SiC.     

Hydride-assisted growth of GaN nanowires on Au/Si(0 0 1) via the reaction of Ga with NH3 and H2

High quality, straight GaN nanowires (NWs) with diameters of 50 nm and lengths up to 3 μm have been grown on Si(0 0 1) using Au as a catalyst and the direct reaction of Ga with NH₃ and N₂:H₂ at 900 °C. These exhibited intense, near band edge photoluminescence at 3.42 eV in comparison to GaN NWs with non-uniform diameters obtained under a flow of Ar:NH₃, which showed much weaker band edge emission due to strong non-radiative recombination. A significantly higher yield of β-Ga₂O₃ NWs with diameters of ≤50 nm and lengths up to 10 μm were obtained, however, via the reaction of Ga with residual O₂ under a flow of Ar alone. The growth of GaN NWs depends critically on the temperature, pressure and flows in decreasing order of importance but also the availability of reactive species of Ga and N. A growth mechanism is proposed whereby H₂ dissociates on the Au nanoparticles and reacts with Ga giving Ga_xH_y thereby promoting one-dimensional (1D) growth via its reaction with dissociated NH₃ near or at the top of the GaN NWs while suppressing at the same time the formation of an underlying amorphous layer. The higher yield and longer β-Ga₂O₃ NWs grow by the vapor liquid solid mechanism that occurs much more efficiently than nitridation.     

Effect of NH3 flow rate on m-plane GaN growth on m-plane SiC by metalorganic chemical vapor deposition

This paper reports a study of the effect of NH₃ flow rate on m-plane GaN growth on m-plane SiC with an AlN buffer layer. It is found that a reduced NH₃ flow rate during m-plane GaN growth can greatly improve the recovery of in situ optical reflectance and the surface morphology, and narrow down the on-axis (1 0 1¯ 0) X-ray rocking curve (XRC) measured along the in-plane a-axis. The surface striation along the in-plane a-axis, a result of GaN island coalescence along the in-plane c-axis, strongly depends on the NH₃ flow rate, an observation consistent with our recent study of kinetic Wulff plots. The pronounced broadening of the (1 0 1¯ 0) XRC measured along the c-axis is attributed to the limited lateral coherence length of GaN domains along the c-axis, due to the presence of a high density of basal-plane stacking faults, most of which are formed at the GaN/AlN interface, according to transmission electron microscopy.     

Low temperature Si homo-epitaxy by reduced pressure chemical vapor deposition using dichlorosilane,silane and trisilane

Dichlorosilane (DCS), silane and trisilane have been investigated as Si precursors for low temperature (<700 °C) Si reduced pressure chemical vapor deposition. DCS and silane are limited to growth temperatures higher than 600–650 and 500 °C, respectively. At lower temperatures, absence of either Cl or H desorption from the surface impedes Si growth with acceptable growth rate (>5 Å/min). Trisilane permits the growth of Si at lower temperatures below 350 °C due to a specific growth mechanism enhancing H desorption. Layers grown at temperatures lower than 500 °C are defective, irrespective of the carrier gas, pressure and precursor flow used.     

Impact of the gas flow ratio on the physical properties of GaN grown by vertical flow metalorganic chemical vapour deposition

We studied the effect of gas flow ratio of the H₂ carrier gas to the NH₃ precursor on the physical and crystal properties of GaN. GaN was grown by vertical reactor metalorganic chemical vapour deposition (MOCVD) on a low-temperature-deposited GaN buffer layer. A (0 0 0 1) sapphire substrate was used. The impact of the gas flow ratio as it was varied from 0.25 to 1 was investigated and discussed. With increase in flow ratio, the concentrations of magnesium and carbon impurities in GaN increased. The flow ratio of 0.5 is the optimum value to minimise the background electron concentration and to maintain crystal quality. The decrease in the background electron concentration is due to the compensation mechanism of acceptor-like magnesium and carbon impurities.     

HRTEM investigation of high-reflectance AlN/GaN distributed Bragg-reflectors by inserting AlN/GaN superlattice

A high-quality AlN/GaN distributed Bragg-reflectors (DBR) was successfully grown on sapphire substrate by low-pressure metal-organic chemical vapor deposition using ultra-thin AlN/GaN superlattice insertion layers (SLILs). The reflectivity of AlN/GaN DBR with ultra-thin AlN/GaN SLIL was measured and achieved blue peak reflectivity of 99.4% at 462 nm. The effect of ultra-thin AlN/GaN superlattice insertion layer was examined in detail by transmission electron microscopy, and indicated that the crack of AlN/GaN DBR can be suppress by inserting AlN/GaN SLIL. For electronic properties, the turn on voltage is about 4.1 V and CW laser action of vertical-cavity surface-emitting laser (VCSEL) was achieved at a threshold injection current of 1.4 mA at 77 K, with an emission wavelength of 462 nm.     

Thermogravimetric analysis and microstructural observations on the formation of GaN from the reaction between Ga2O3 and NH3

Thermogravimetric analysis (TGA) and microstructural observations were carried to investigate the nitridation mechanism of β-Ga₂O₃ powder to GaN under an NH₃/Ar atmosphere. Non-isothermal TGA showed that nitridation of β-Ga₂O₃ starts at ∼650 °C, followed by decomposition of GaN at ∼1100 °C. Isothermal TGA showed that nitridation follows linear kinetics in the temperature range 800–1000 °C. At an early stage of nitridation, small GaN particles (∼5 nm) are deposited on the β-Ga₂O₃ crystal surface and they increase with time. We proposed a mechanism for the nitridation of Ga₂O₃ by NH₃ whereby nitridation of β-Ga₂O₃ proceeds via the intermediate vapor species Ga₂O(g).     

Growth and characterization of c-plane AlGaN on γ-LiAlO2

This study demonstrates a pure c-plane AlGaN epilayer grown on a γ-LiAlO₂ (1 0 0) (LAO) substrate with an AlN nucleation layer grown at a relatively low temperature (LT-AlN) by metal-organic chemical vapor deposition (MOCVD). The AlGaN film forms polycrystalline film with m- and c-plane when the nucleation layer grows at a temperature ranging from 660 to 680 °C. However, a pure c-plane AlGaN film with an Al content of approximately 20% can be obtained by increasing the LT-AlN nucleation layer growth temperature to 700 °C. This is because the nuclei density of AlN increases as the growth temperature increases, and a higher nuclei density of AlN deposited on LAO substrate helps prevent the deposition of m-plane AlGaN. Therefore, high-quality and crack-free AlGaN films can be obtained with a (0 0 0 2) ω-rocking curve FWHM of 547 arcsec and surface roughness of 0.79 nm (root-mean-square) using a 700-°C-grown LT-AlN nucleation layer.     

Effects of morphologies on the field emission characteristics of GaN nanorods grown on Si (0 0 1) by MBE

GaN nanorods were grown on Si (0 0 1) substrates with a native oxide layer by molecular beam epitaxy. The changes in the morphologies and their effects on the field emission characteristics of GaN nanorods were investigated by varying growth conditions, namely, growth time of low-temperature GaN buffer layer, growth time of GaN nanorods, Ga flux during growth of GaN nanorods, and growth temperature of GaN nanorods. GaN nanorods with a low aspect ratio measured by diode configuration showed better field emission characteristics than those with a high aspect ratio, which may be due to the effects of screening and the surface depletion layer. In addition, the distance between the GaN nanorods and the anode played an important role in the field emission characteristics such as turn-on field, field enhancement factor, and field distribution on the emitter surface.     

The influence of indium on the growth of GaN from solution under high pressure

The influence of significant fraction (10–50 mole%) indium in liquid gallium on GaN crystallization from a ternary Ga–In–N solution was analyzed. Crystallization experiments of GaN on GaN-sapphire templates from Ga–In solutions, at 1350–1450 °C, with prior to the growth seed wetting at 1500 °C, and 1.0 GPa N₂ pressure, without solid GaN source showed faster growth of GaN on the seed (by a factor of 1.5–2) than using pure gallium solvent. Nevertheless the new grown crystals were morphologically unstable. The instability was reduced by decrease of the wetting temperature down to 1100 °C or by omitting the wetting procedure entirely, which indicated that GaN dissolves much faster in Ga–In melt than in pure Ga and that the unstable growth was caused most likely by complete dissolution of GaN template before the growth. It was observed that the crystals grown on bulk GaN substrates did not show morphological instability observed for GaN-sapphire templates. The influence of indium on thermodynamic and thermal properties of the investigated system is discussed.     

AlN buffer layer growth for GaN epitaxy on (1 1 1) Si: Al or N first?

AlN is generally used as buffer layer for the epitaxial growth of GaN on Si(1 1 1) substrate. In this work, we specifically address the relationship between the way the AlN growth is initiated on the Si(1 1 1) surface and the overall properties of the final GaN epitaxial layer. The growth is performed by molecular beam epitaxy with ammonia (NH₃) as nitrogen source. Two procedures have been compared: exposing the Si surface first to NH₃ or Al. The AlN nucleation is followed in real-time by reflection high-energy electron diffraction and critical stages are also investigated in real space using scanning tunnelling microscopy and transmission electron microscopy. Atomic force microscopy, X-ray diffraction and photoluminescence are also used to assess the properties of the final GaN epitaxial layer. It is shown that best results in terms of GaN overall properties are obtained when the growth is initiated by exposing the Si(1 1 1) surface to NH₃ first. This is mainly due to the fact that almost an order of magnitude decrease of the dislocation density is obtained.     

In-situ cyclic pulse annealing of InN on AlN/Si during IR-lamp-heated MBE growth

To improve crystal quality of InN, an in-situ cyclic rapid pulse annealing during growth was carried out using infrared-lamp-heated molecular beam epitaxy. A cycle of 4 min growth of InN at 400 °C and 3 s pulse annealing at a higher temperature was repeated 15 times on AlN on Si substrate. Annealing temperatures were 550, 590, 620, and 660 °C. The back of Si was directly heated by lamp irradiation through a quartz rod. A total InN film thickness was about 200 nm. With increasing annealing temperature up to 620 °C, crystal grain size by scanning electron microscope showed a tendency to increase, while widths of X-ray diffraction rocking curve of (0 0 0 2) reflection and E₂ (high) mode peak of Raman scattering spectra decreased. A peak of In (1 0 1) appeared in X-ray diffraction by annealing higher than 590 °C, and In droplets were found on the surface by annealing at 660 °C.     

Optimization of hydrothermal growth ZnO Nanorods for enhancement of light extraction from GaN blue LEDs

In this study, we report on the enhancement in the light extraction efficiency of GaN blue LEDs topped with ZnO nanorods. The ZnO nanorods were grown by a two-step hydrothermal synthesis with pre-coated ZnO nanoparticles under optimized condition to give the appropriate size and quality, giving an increase in the light output efficiency of 66%. This improvement is attributed to the optimal rod size and spacing with improved thermal dissipation as compared to light extraction from plain GaN surface. During the ZnO growth on the LEDs, 0.55 M of NH₃ was added and the ZnO sample was later annealed at 475 °C in N₂ ambient, to drive out interstitial oxygen atoms from the tetrahedral unstable site. As a result, a high ratio of UV to orange defect band emission was achieved. The two-step growth of ZnO nanorods on GaN LEDs was effective in generating array of ZnO nanorods which serve as reflector to enhance light extraction from LEDs.     

Characterizations of GaN film growth by ECR plasma chemical vapor deposition

The electron cyclotron resonance plasma-enhanced metalorganic chemical vapor deposition technology (ECR–MOPECVD) is adopted to grow GaN films on (0 0 0 1) α-Al₂O₃ substrate. The gas sources are pure N₂ and trimethylgallium (TMG). Optical emission spectroscopy (OES) and thermodynamic analysis of GaN growth are applied to understand the GaN growth process. The OES of ECR plasma shows that TMG is significantly dissociated in ECR plasma. Reactants N and Ga in the plasma, obtained easily under the self-heating condition, are essential for the GaN growth. They contribute to the realization of GaN film growth at a relatively low temperature. The thermodynamic study shows that the driving force for the GaN growth is high when N₂:TMG>1. Furthermore, higher N₂:TMG flow ratio makes the GaN growth easier. Finally, X-ray diffraction, photoluminescence, and atomic force microscope are applied to investigate crystal quality, morphology, and roughness of the GaN films. The results demonstrate that the ECR–MOPECVD technology is favorable for depositing GaN films at low temperatures.