Systematic study of epitaxy growth uniformity in a specific MOCVD reactor

Gallium nitride (GaN) is a direct bandgap semiconductor widely used in bright light‐emitting diodes (LEDs). Thin‐film GaN is grown by metal‐organic chemical vapour deposition (MOCVD) technique. Reliability, efficiency and durability of LEDs are influenced critically by the quality of GaN films. In this report, a systematic study has been performed to investigate and optimize the growth process. Fluid flow, heat transfer and chemical reactions are calculated for a specific close‐coupled showerhead (CCS) MOCVD reactor. Influences of reactor dimensions and growth parameters have been examined after introducing the new conceptions of growth uniformity and growth efficiency. It is found that GaN growth rate is mainly affected by the concentration of (CH3)3Ga:NH3 on the susceptor, while growth uniformity is mainly influenced by the recirculating flows above the susceptor caused by natural convection. Effect of gas inlet temperature and the susceptor temperature over the growth rate can be explained by two competing mechanisms. High growth efficiency can be achieved by optimizing the reactor design.     

Synthesis of GaN crystal by the reaction of Ga with Li3N in NH3 atmosphere

A novel method to synthesize GaN crystals was studied by the reaction of Ga with Li₃N under NH₃ atmosphere. We have already reported the synthesis technique of GaN by the reaction of Ga₂O₃ with Li₃N. However, the size of GaN crystals obtained by this method was limited to be smaller than several micrometers because of the solid phase reaction. In order to increase the size of GaN crystals, the method using liquid Ga as gallium source was studied for solid–liquid phase reaction. We found that the GaN crystals with the size of more than 100 μm were synthesized at 750 °C for 24 h under NH₃ atmosphere. We propose the possible reaction mechanism as follows. Lithium amide (LiNH₂) is synthesized by the reaction of Li₃N with NH₃ gas and then the crystal growth of GaN occurs by the reaction of Ga with LiNH₂. We found that LiNH₂ is a useful nitrogen source for the GaN synthesis method.     

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.     

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.     

Molecular beam epitaxy as a growth technique for achieving free-standing zinc-blende GaN and wurtzite AlxGa1-xN

Currently there is a high level of interest in the development of ultraviolet (UV) light sources for solid-state lighting, optical sensors, surface decontamination and water purification. III-V semiconductor UV LEDs are now successfully manufactured using the AlGaN material system; however, their efficiency is still low. The majority of UV LEDs require Al_xGa_1-xN layers with compositions in the mid-range between AlN and GaN. Because there is a significant difference in the lattice parameters of GaN and AlN, Al_xGa_1-xN substrates would be preferable to those of either GaN or AlN for many ultraviolet device applications. However, the growth of Al_xGa_1-xN bulk crystals by any standard bulk growth techniques has not been developed so far.There are very strong electric polarization fields inside the wurtzite (hexagonal) group III-nitride structures. The charge separation within quantum wells leads to a significant reduction in the efficiency of optoelectronic device structures. Therefore, the growth of non-polar and semi-polar group III-nitride structures has been the subject of considerable interest recently. A direct way to eliminate polarization effects is to use non-polar (001) zinc-blende (cubic) III-nitride layers. However, attempts to grow zinc-blende GaN bulk crystals by any standard bulk growth techniques were not successful.Molecular beam epitaxy (MBE) is normally regarded as an epitaxial technique for the growth of very thin layers with monolayer control of their thickness. In this study we have used plasma-assisted molecular beam epitaxy (PA-MBE) and have produced for the first time free-standing layers of zinc-blende GaN up to 100 μm in thickness and up to 3-inch in diameter. We have shown that our newly developed PA-MBE process for the growth of zinc-blende GaN layers can also be used to achieve free-standing wurtzite Al_xGa_1-xN wafers. Zinc-blende and wurtzite Al_xGa_1-xN polytypes can be grown on different orientations of GaAs substrates - (001) and (111)B respectively. We have subsequently removed the GaAs using a chemical etch in order to produce free-standing GaN and Al_xGa_1-xN wafers. At a thickness of ～30 µm, free-standing GaN and Al_xGa_1-xN wafers can easily be handled without cracking. Therefore, free-standing GaN and Al_xGa_1-xN wafers with thicknesses in the 30–100 μm range may be used as substrates for further growth of GaN and Al_xGa_1-xN-based structures and devices.We have compared different RF nitrogen plasma sources for the growth of thick nitride Al_xGa_1-xN films including a standard HD25 source from Oxford Applied Research and a novel high efficiency source from Riber. We have investigated a wide range of the growth rates from 0.2 to 3 µm/h. The use of highly efficient nitrogen RF plasma sources makes PA-MBE a potentially viable commercial process, since free-standing films can be achieved in a single day.Our results have demonstrated that MBE may be competitive with the other group III-nitrides bulk growth techniques in several important areas including production of free-standing zinc-blende (cubic) (Al)GaN and of free-standing wurtzite (hexagonal) AlGaN.     

Ca3N2 as a flux for crystallization of GaN

In this work Ca₃N₂ was investigated as a potential flux for crystallization of GaN. Melting temperature of the potential flux at high N₂ pressure evaluated by thermal analysis as 1380 °C is in good agreement with the theoretical prediction. It is shown that Ca₃N₂ present in the liquid gallium in small amount (1 at%) dramatically accelerates synthesis of GaN from its constituents. On the other hand, it does not influence significantly the rate of GaN crystallization from solution in gallium in temperature gradient for both unseeded and seeded configurations. However the habit and color of the spontaneously grown GaN crystals change drastically. For 10 mol% Ca₃N₂ content in the liquid Ga it was found that the GaN thick layer and GaN crystals (identified by micro-Raman scattering measurements) were grown on the substrate. For growth from molten Ca₃N₂ (100%) with GaN source, the most important observations were (i) GaN source material was completely dissolved in the molten Ca₃N₂ flux and (ii) after experiment, GaN crystals were found on the sapphire substrate.     

Growth of Epitaxial Layers of GaN from GaBr3 · 4 NH3 Complex

A method of obtaining GaN from GaBr₃ · 4 NH₃ by radiation heating of the substrate is described. The results of investigations are given concerning the growth rate of polycrystalline GaN layers on [111] oriented silicon substrates in dependence on the changes of the temperature of reaction, evaporation temperature of GaBr₃ · 4 NH₃, and the rate of gas flow. The results of X-ray investigations and light absorption coefficient are described. Some facts were observed, namely a considerable influence of the nozzle form on the kinetics of the transporting gas stream on the growth rate of GaN, as well as the fact that not the whole complex undergoes pyrolysis on the substrate at temperatures below 500°C.     

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.     

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.     

Interface of GaN grown on Ge(1 1 1) by plasma assisted molecular beam epitaxy

Early efforts to grow GaN layers on germanium substrates by plasma assisted molecular beam epitaxy led to GaN domains, rotated by 8° relative to each other. Increased insight in the growth of GaN on germanium resulted in the suppression of these domain and consequently high quality layers. In this study the interface of these improved layers is investigated with transmission electron microscopy. The GaN layers show high crystal quality and an atomically abrupt interface with the Ge substrate. A thin, single crystalline Ge₃N₄ layer is observed in between the GaN layer and Ge substrate. This Ge₃N₄ layer remains present even at growth temperatures (850 °C) far above the decomposition temperature of Ge₃N₄ in vacuum (600 °C). Triangular voids in the Ge substrate are observed after growth. Reducing the Ga flux at the onset of GaN growth helps to reduce the triangular defect size. This indicates that the formation of voids in the Ge substrate strongly depends on the presence of Ga atoms at the onset of growth. However complete elimination was not achieved. The formation of voids in the germanium substrate leads to diffusion of Ge into the GaN layer. Therefore we examined the diffusion of Ge atoms into the GaN layer and Ga atoms into the Ge substrate. It was found that the diffusion of Ge into the GaN layer and Ga into the Ge substrate can be influenced by the growth temperature but cannot be completely suppressed. Our results suggest that Ga atoms diffuse through small imperfections in the Ge₃N₄ interlayer and locally etch the Ge substrate, leading to the diffusion of Ga and Ge atoms.     

High quality MOCVD GaN film grown on sapphire substrates using HT-AlN buffer layer

In this work we report on the growth and characterization of high quality MOCVD GaN film grown on Al₂O₃ substrates by using a HT (>1150 °C)-AlN buffer layer. We have investigated the most favorable growth conditions in terms of temperature, thickness and growth rate of AlN buffer layer in order to optimize the high temperature GaN layer. The improved morphological and structural properties of GaN layer were verified by AFM and XRD measurements. The optimized GaN layer presents a smooth surface with a rms value of 1.4 Å. The full width at half maximum (FWHM) for 800 nm thick GaN films is 144″. Furthermore PL measurements and C–V analysis confirm that in GaN layer grown on HT-AlN buffer layer defect density is drastically reduced.     

MOCVD growth of GaN on Si(1 1 1) substrates using an ALD-grown Al2O3 interlayer

GaN thin films have been grown on Si(1 1 1) substrates using an atomic layer deposition (ALD)-grown Al₂O₃ interlayer. This thin Al₂O₃ layer reduces strain in the subsequent GaN layer, leading to lower defect densities and improved material quality compared to GaN thin films grown by the same process on bare Si. XRD ω-scans showed a full width at half maximum (FWHM) of 549 arcsec for GaN grown on bare Si and a FWHM as low as 378 arcsec for GaN grown on Si using the ALD-grown Al₂O₃ interlayer. Raman spectroscopy was used to study the strain in these films in more detail, with the shift of the E₂(high) mode showing a clear dependence of strain on Al₂O₃ interlayer thickness. This dependence of strain on Al₂O₃ thickness was also observed via the redshift of the near bandedge emission in room temperature photoluminescence (RT-PL) spectroscopy. The reduction in strain results in a significant reduction in both crack density and screw dislocation density compared to similar films grown on bare Si. Screw dislocation density of the films grown on Al₂O₃/Si substrates approaches that of typical GaN layers on sapphire. This work shows great promise for the use of oxide interlayers for growth of GaN-based LEDs on Si.     

Strain-reduced GaN thick-film grown by hydride vapor phase epitaxy utilizing dot air-bridged structure

A 300 μm GaN thick-film, in diameter 1.5 in, was demonstrated without any crack by hydride vapor phase epitaxy (HVPE) growth. The technique used in relaxing the residual stress caused by differences of thermal expansion coefficients (TEC) and lattice constants between GaN and sapphire substrate to prevent GaN film from crack is called a dot air-bridged structure. After the laser lift-off process, 300-μm-thick freestanding GaN wafer, in diameter 1.5 in, could be fabricated. The compressive stress in the dot air-bridged structure was measured by micro-Raman spectroscopy with the E₂(high) phonon mode. The compressive stress could be reduced to as small as 0.04 GPa, which could prevent the crack during the epitaxial process for GaN growth by HVPE. It is important to obtain a large-area crack-free GaN thick-film, which can be used for fabricating freestanding GaN wafer.     

Synthesis of gallium nitride by ammonia injection into gallium melt

Gallium nitride (GaN) was synthesized by injecting ammonia gas into molten gallium at 900–980°C under atmospheric pressure. A large amount of GaN powder was reproducibly obtained using a simple apparatus. The synthesized powder was characterized by scanning electron microscopy, X-ray diffraction, photoluminescence and energy dispersive X-ray spectroscopy, and was found to consist of fine crystals of hexagonal GaN of good quality. The total of GaN obtained was far more than the amount calculated from expected saturation solubility in the Ga melt at that temperature. We speculate that the GaN crystals were largely formed by direct reaction between Ga and the gaseous N source at the surface of the NH₃ bubbles in the melt. GaN synthesized by this method may be useful as a starting material for bulk growth.     

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.     

Crystallography and cathodoluminescence of ultra‐long GaN nanowires

Ultra‐long GaN nanowires have been synthesized via a simple thermal evaporation process by heating mixed GaN and Ga₂O₃ powders in a conventional resistance furnace under ammonia gas at 1150 °C. The average length of GaN nanowires is estimated to be more than 100 μm after 30‐min growth, corresponding to a fast growth rate of more than 200 μm/h. Scanning electron microscope (SEM) observation indicated that the diameter of GaN nanowires was rather uniform along the growth direction and in the range of 100–200 nm. X‐ray diffraction (XRD) and transmission electron microscope (TEM) measurements confirmed that the GaN nanowires are crystalline wurtzite‐type hexagonal structure. Room‐temperature cathodoluminescence (CL) measurement indicated that an obvious red‐shift of the near band‐edge emission peak centered at 414 nm of the ultra‐long GaN nanowires and a wide shoulder in the range of 600–700 nm were observed. Possible reasons responsible for the red‐shift of the near band‐edge emission of the ultra‐long GaN nanowires was discussed. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Inversion domains and parallel growth in ammonothermally grown GaN crystals

Macro-defects such as twins, inversion domains, crevices, and columnar growth occasionally appear in ammonothermally grown GaN crystals. Twinning mechanisms and parallel growth are proposed to explain the formation of these defects. As a polar crystal with wurtzite structure, GaN can have several different kinds of twins depending on the polarity arrangement of each individual twin. Inversion domains are formed in one of the twinning mechanisms. Parallel growth is used to explain the formation of pits on the nitrogen face and the columnar growth on the gallium face. Etching in hot H₃PO₄ is used to reveal the polarities and defects of GaN crystals when they are indistinguishable. Optical microscopy, scanning electron microscope, and cathodoluminescence are also employed to study these defects. In addition, seed quality, avoidance of macro-defect formation, and impurity effects are also discussed.     

The growth of high-quality and self-separation GaN thick-films by hydride vapor phase epitaxy

About 1.2 mm thick GaN bulk crystals were obtained by combining a pulsed NH₃-flow modulation (PFM) method and a self-separation method of short-shutting NH₃ flow when using hydride vapor phase epitaxy (HVPE). High crystal quality of bulk GaN was evaluated by X-ray rocking curves (XRC) and the full width at half maximum (FWHM) values were 110, 72 and 83 arcsec for (002), (102) and (100) reflection planes, respectively. The PFM method is proved to be effective in reducing cracks and keeping the surface smooth. And the method of short-shutting NH₃ flow can lead to GaN thick layer separate from sapphire substrate when cooling from the high growth temperature. Growth and separation mechanisms were investigated. Two states were found in PFM method. With PFM method modulating between high quality state and low stress state, 300 μm thick GaN layers without cracks were obtained. Study of spontaneous separation mechanism revealed that the separation attributed to formation of voids inside the GaN layer.     

Growth behaviour of bulk GaN single crystals grown with various flux ratios using solvent‐thermal method

Bulk GaN single crystals were grown using a solvent‐thermal method. They were grown for 200 h at 600 °C and 800 °C using 8 MPa of N₂ gas and 1–3 mm sized pyramid GaN single crystals. Pure Na, NaN₃ and Ca were used as the flux. The mole fraction of the [flux]/([flux] + [Ga]) was 0.30–0.67. The growth behavior differed according to the flux ratio. The quality of the bulk GaN single crystals was improved by increasing the flux ratio. The bulk GaN single crystals formed by spontaneous nucleation were deposited on the BN crucible wall and bottom during the first step of synthesis. The wurtzite structure of the GaN grown single crystal was confirmed by x‐ray diffration. The chemical composition was analyzed by electron probe microanalysis. The quality and optical properties of the GaN single crystal were examined by Raman spectroscopy and photoluminesence analysis. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Selective area growth of GaN nanorods on patterned W/SiO2/Si substrates by RF-MBE

We report on the selective area growth (SAG) of GaN nanorods on Si substrates masked with W or SiO₂ and also on bare Si substrates by RF plasma-assisted molecular beam epitaxy (RF-MBE). The growth of GaN (i.e. irradiation of Ga and RF plasma-activated N₂) on the W mask layer results in the appearance of a ring reflection high-energy electron diffraction (RHEED) pattern coming from α-W. In contrast, broken ring RHEED patterns from GaN nanorods are clearly observed on SiO₂ and Si surfaces. Ex-situ scanning Auger microscopy analysis confirms that no growth of GaN takes place on W. Utilizing this phenomenon, we have demonstrated the SAG of GaN nanorods on Si substrates partly masked with W. We will discuss this phenomenon in terms of the difference in the desorption energy of Ga on W, SiO₂, and Si.