Modeling of Ammonothermal Growth of Gallium Nitride Single Crystals

Ammonothermal growth of GaN crystals with a retrograde solubility has been modeled and simulated here using fluid dynamics, thermodynamics and heat transfer models. The nutrient is considered as a porous media bed and the flow in the porous charge is simulated using the Darcy-Brinkman-Forchheimer model. The resulting governing equations are solved using the finite volume method. For the case of retrograde solubility, the charge is put above the baffle. The temperature difference between the dissolving zone and growth zone is found smaller than that applied on the sidewall of autoclave. The baffle opening has a strong effect on the nutrient transport and supersaturation of GaN species in the growth zone.

Transport Phenomena in Ammonothermal Growth of Gallium Nitride

GaN can be used to fabricate blue/green/UV LEDs and high temperature, high power electronic devices. Ideal substrates are needed for high quality III-nitride epitaxy, which is an essential step for the manufacture of LEDs. GaN substrates are ideal to be lattice matched and isomorphic to nitride-based films. Bulk single crystals of GaN can be grown from supercritical fluids using the ammonothermal method, which utilizes ammonia as fluid rather than water as in the hydrothermal process. In this process, a mineralizer such as amide, imide or azide is used to attack a bulk nitride feedstock at temperatures from 200 - 500癈 and pressures from 1 - 4 kbar. Baffle design is essential for successful growth of GaN crystals. Baffle is used to separate the dissolving zone from the growth zone, and to maintain a temperature difference between the two zones. For solubility curve with a positive coefficient with respect to temperature, the growth zone is maintained at a lower temperature than that in the dissolving zone, thus the nutrient becomes supersaturated in the growth zone. The baffle opening is used to control the mixing of nutrients in the two zones, thus the transfer of nutrient from the lower part to the upper part. Ammonothermal systems have been modeled here using fluid dynamics, thermodynamics and heat transfer models. The nutrient is considered as a porous media bed and the flow is simulated using the Darcy-Brinkman-Forchheimer model. The resulting governing equations are solved using the finite volume method. We investigated the effects of baffle opening and position on the transport phenomena of nutrient from dissolving zone to the growth zone. Simulation data have been compared qualitatively with experimental data.

Codoping of magnesium with oxygen in gallium nitride nanowires

Codoping of p-type GaN nanowires with Mg and oxygen was investigated using first-principles calculations. The Mg becomes a deep acceptor in GaN nanowires with high ionization energy due to the quantum confinement. The ionization energy of Mg doped GaN nanowires containing passivated Mg-O complex decreases with increasing the diameter, and reduces to 300 meV as the diameter of the GaN nanowire is larger than 2.01 nm, which indicates that Mg-O codoping is suitable for achieving p-type GaN nanowires with larger diameters. The codoping method to reduce the ionization energy can be effectively used in other semiconductor nanostructures. (C) 2010 American Institute of Physics.

Defects in gallium nitride nanowires: First principles calculations

Atomic configurations and formation energies of native defects in an unsaturated GaN nanowire grown along the [001] direction and with (100) lateral facets are studied using large-scale ab initio calculation. Cation and anion vacancies, antisites, and interstitials in the neutral charge state are all considered. The configurations of these defects in the core region and outermost surface region of the nanowire are different. The atomic configurations of the defects in the core region are same as those in the bulk GaN, and the formation energy is large. The defects at the surface show different atomic configurations with low formation energy. Starting from a Ga vacancy at the edge of the side plane of the nanowire, a N-N split interstitial is formed after relaxation. As a N site is replaced by a Ga atom in the suboutermost layer, the Ga atom will be expelled out of the outermost layers and leaves a vacancy at the original N site. The Ga interstitial at the outmost surface will diffuse out by interstitialcy mechanism. For all the tested cases N-N split interstitials are easily formed with low formation energy in the nanowires, indicating N-2 molecular will appear in the GaN nanowire, which agrees well with experimental findings.

Structure and Electronic Properties of Saturated and Unsaturated Gallium Nitride Nanotubes

The atomic and electronic structures of saturated and unsaturated GaN nanotubes along the [001] direction with (100) lateral facets are studied using first-principles calculations. Atomic relaxation of nanotubes shows that appreciable distortion occurs in the unsaturated nanotubes. All the nanotubes considered, including saturated and unsaturated ones, exhibit semiconducting, with a direct band gap Surface states arisen from the 3-fold-coordinated N and Ga atoms at the lateral facets exist inside the bulklike band gap. When the nanotubes are saturated with hydrogen, these dangling bond bands are removed from the band gap, but the band gap decreases with increasing the wall thickness of the nanotubes.

Statistical investigation on morphology development of gallium nitride in initial growth stage

Morphology of Gallium Nitride (GaN) in initial growth stage was observed with atomic force microscopy (AFM) and scanning electron microscopy (SEM), It was found that the epilayer developed from islands to coalesced film. Statistics based on AFM observation was carried out to investigate the morphology characteristics. It was found that the evolution of height distribution could be used to describe morphology development. Statistics also clearly revealed variation of top-face growth rate among islands. Indium-doping effect on morphology development was also statistically studied. The roughening and smoothing behavior in morphology development was explained. (C) 2002 Elsevier Science B.V. All rights reserved.

Improvement of the photoluminescence from gallium nitride layers grown by MBE with an additional incident indium flux

The effect of using an indium flux during the MBE growth of GaN layers was investigated. The properties of these layers were studied using electron probe microanalysis, secondary ion mass spectroscopy, photoluminescence and cathodoluminescence. The optical properties of the GaN layers are shown to improve as compared with undoped GaN layers grown under nominally the same conditions but without an additional indium flux.

Influence of rapid thermal annealing on the optical properties of gallium nitride grown by gas-source molecular-beam epitaxy

Raman scattering, photoluminescence (PL), and nuclear reaction analysis (MA) have been employed to investigate the effects of rapid thermal annealing (RTA) on GaN films grown on sapphire (0001) substrates by gas-source molecular-beam epitaxy, The Raman spectra showed the presence of the E-2 (high) mode of GaN and shift of this mode from 572 to 568 cm(-1) caused by annealing. The results showed that RTA has a significant effect on the strain relaxation caused by the lattice and thermal expansion misfit between the GaN epilayer and the substrate. The PL peak exhibited a blueshift in its energy position and a decrease in the full width at half maximum after annealing, indicating an improvement in the optical quality of the film. Furthermore, a green luminescence appeared after annealing and increased in intensity with increasing annealing time. This effect was attributed to H concentration variation in the GaN film, which was measured by NRA. A high H concentration exists in as-grown GaN, which can neutralize the deep level, and the H-bonded complex dissociates during RTA, This leads to the appearance of a luminescent peak in the PL spectrum. (C) 1998 American Institute of Physics.

Some properties of gallium nitride films grown on (0001) oriented sapphire substrates by gas source molecular beam epitaxy

The Raman and photoreflectivity spectra of gallium nitride (GaN) films grown on (0001) oriented sapphire substrates by gas source molecular beam epitaxy (GSMBE) have been investigated. The Raman spectra showed the presence of the E-2(high) mode and a shift in the wavenumber of this mode with respect to the GaN epilayer thickness. The Raman scattering results suggest the presence of stress due to lattice and thermal expansion misfit in the films, and also indicate that the buffer layer play an important role in the deposition of high quality GaN layers. The residual stress changes from tensile to compressive as the epilayer thickness increases. Samples subjected to anneal cycles showed an increase in the mobility due probably to stress relaxation as suggested by an observed shift in the E-2(high) mode in the Raman spectra after annealing.

Surface transformation and inversion domain boundaries in gallium nitride nanorods

Phase transformation and subdomain structure in [0001]-oriented gallium nitride (GaN) nanorods of different sizes are studied using molecular dynamics simulations. The analysis concerns the structure of GaN nanorods at 300 K without external loading. Calculations show that a transformation from wurtzite to a tetragonal structure occurs along {0110} lateral surfaces, leading to the formation of a six-sided columnar inversion domain boundary (IDB) in the [0001] direction of the nanorods. This structural configuration is similar to the IDB structure observed experimentally in GaN epitaxial layers. The transformation is significantly dependent on the size of the nanorods.

Damage accumulation in gallium nitride irradiated with various energetic heavy ions

In this work a study of damage production in gallium nitride via elastic collision process (nuclear energy deposition) and inelastic collision process (electronic energy deposition) using various heavy ions is presented. Ordinary low-energy heavy ions (Fe+ and Mo+ ions of 110 keV), swift heavy ions (Pb-208(27+) ions of 1.1 MeV/u) and slow highly-charged heavy ions (Xen+ ions of 180 keV) were employed in the irradiation. Damage accumulation in the GaN crystal films as a function of ion fluence and temperature was studied with RBS-channeling technique, Raman scattering technique, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). For ordinary low-energy heavy ion irradiation, the temperature dependence of damage production is moderate up to about 413 K resulting in amorphization of the damaged layer. Enhanced dynamic annealing of defects dominates at higher temperatures. Correlation of amorphization with material decomposition and nitrogen bubble formation was found. In the irradiation of swift heavy ions, rapid damage accumulation and efficient erosion of the irradiated layer occur at a rather low value of electronic energy deposition (about 1.3 keV/nm(3)),. which also varies with irradiation temperature. In the irradiation of slow highly-charged heavy ions (SHCI), enhanced amorphization and surface erosion due to potential energy deposition of SHCI was found. It is indicated that damage production in GaN is remarkably more sensitive to electronic energy loss via excitation and ionization than to nuclear energy loss via elastic collisions.

Studies of high DC current induced degradation in III-V nitride based heterojunctions

We report experiments on high de current stressing in commercial III-V nitride based heterojunction light-emitting diodes. Stressing currents ranging from 100 mA to 200 mA were used. Degradations in the device properties were investigated through detailed studies of the current-voltage (I-V) characteristics, electroluminescence, deep-level transient Fourier spectroscopy and flicker noise. Our experimental data demonstrated significant distortions in the I-V characteristics subsequent to electrical stressing. The room temperature electro-luminescence of the devices exhibited a 25% decrement in the peak emission intensity. Concentration of the deep-levels was examined by deep-level transient Fourier spectroscopy, which indicated an increase in the density of deep-traps from 2.7 x 10(13) cm(-3) to 4.2 x 10(13) cm(-3) at E-1 = E-C - 1.1 eV. The result is consistent with our study of 1/f noise, which exhibited up to three orders of magnitude increase in the voltage noise power spectra. These traps are typically located at energy levels beyond the range that can be characterized by conventional techniques including DLTS. The two experiments, therefore, provide a more complete picture of trap generation due to high dc current stressing.

Modeling Ammonothermal Growth of GaN Single Crystals: The Role of Transport

Single crystal gallium nitride (GaN) is an important technological material used primarily for the manufacture of blue light lasers. An important area of contemporary research is developing a viable growth technique. The ammonothermal technique is an important candidate among many others with promise of commercially viable growth rates and material quality. The GaN growth rates are a complicated function of dissolution kinetics, transport by thermal convection and crystallization kinetics. A complete modeling effort for the growth would involve modeling each of these phenomena and also the coupling between these. As a first step, the crystallization and dissolution kinetics were idealized and the growth rates as determined purely by transport were investigated. The growth rates thus obtained were termed ‘transport determined growth rates’ and in principle are the maximum growth rates that can be obtained for a given configuration of the system. Using this concept, a parametric study was conducted primarily on the geometric and the thermal boundary conditions of the system to optimize the ‘transport determined growth rate’ and determine conditions when transport might be a bottleneck.

Cathodoluminescence study on in composition inhomogeneity of thick InGaN layer

We have investigated the optical properties of thick InGaN film grown on GaN by cathodeluminescence (CL) spectroscopy. It is found that there is obvious In composition variation in both growth and lateral direction of InGaN film. The depth distribution of In composition is closely related to the strain relaxation process of InGaN film. Accompanied with the relaxation of compressive strain, the In composition of InGaN layer increases and the CL peak energy shifts towards red. Moreover, a rather apparent In composition fluctuation is found in the relaxed upper part of InGaN layer as confirmed by CL imaging.

Microstructure and strain analysis of GaN epitaxial films using in-plane grazing incidence x-ray diffraction

This paper investigates the major structural parameters, such as crystal quality and strain state of (001)-oriented GaN thin films grown on sapphire substrates by metalorganic chemical vapour deposition, using an in-plane grazing incidence x-ray diffraction technique. The results are analysed and compared with a complementary out-of-plane x-ray diffraction technique. The twist of the GaN mosaic structure is determined through the direct grazing incidence measurement of (100) reflection which agrees well with the result obtained by extrapolation method. The method for directly determining the in-plane lattice parameters of the GaN layers is also presented. Combined with the biaxial strain model, it derives the lattice parameters corresponding to fully relaxed GaN films. The GaN epilayers show an increasing residual compressive stress with increasing layer thickness when the two dimensional growth stage is established, reaching to a maximum level of -0.89 GPa.