Nominally undoped cubic GaN epilayers deposited by rf-plasma assisted molecular beam epitaxy on semi-insulating GaAs substrates were investigated by electric and photoelectric spectroscopical methods. As a consequence of the existence of deep levels in the GaAs-substrate itself, special care has to be taken to separate the contributions of the substrate from that of the cubic GaN epilayer in the various spectra. Two different contact configurations (coplanar and sandwich structures) were successfully used to perform this separation. In the cubic GaN epilayer a trap with a thermal activation energy of (85±20)meV was found by thermal admittance spectroscopy and thermal stimulated currents. Optical admittance spectroscopy and photocurrent measurements furthermore revealed defects at EG-(0.04-0.13) eV, EG-(0.21-0.82) eV and two additional deeper defects at 1.91 Ev and 2.1 eV, respectively. These defect related transitions are very similar to those observed in hexagonal GaN.

The effect of hydrostatic pressure on optical transitions in InGaN/GaN multiple quantum wells (MQWs) has been studied. Photoluminescence (PL) and photomodulated transmission (PT) measurements were performed under applied pressure to examine the pressure dependence of optical transitions associated with confined states in MQWs. The PL emission from the MQWs was found to shift linearly to higher energy with applied pressure but exhibit a significantly weaker pressure dependence compared to epilayer samples with similar bandgap energies. Similar pressure coefficients obtained by PT measurements rule out the possibility of PL resulting from deep localized states. We show that the difference in the compressibility of InGaN and of GaN induces a tensile strain in the compressively strained InGaN well layers that partially compensates the applied hydrostatic pressure. This mechanical effect is the primary factor for the smaller pressure dependence of the optical transitions in the InGaN/GaN MQWs. At pressure above 100 kbar, the PL signal in MQWs samples is quenched, indicating that the carriers involved in the radiative recombination processes in the well layers originate primarily from the adjacent GaN layers.

The crystal structure and surface morphology of hydride vapour phase epitaxy grown thick (12-105 μm) GaN layers have been investigated as a function of growth rate using several structure sensitive techniques like atomic force microscopy (AFM), x-ray diffraction (XRD) in ω-2θ and ω-rocking curve measurements as well as low temperature photoluminescence (PL). PL and XRD measurements reveal rather narrow lines: full width at half maximum (FWHM) values of the strongest donor-bound exciton line are in the range from 6.0 to1.8 meV and ω-2θ FWHM values are between 80 and 23 arcsec indicating good structural quality of the films. The ω-rocking curves show a single peak for the thinnest films with a FWHM of 250 arcsec and multiple peaks with FWHM of about 250-350 arcsec in thicker films indicating the formation of several high-quality domains when increasing either thickness or growth rate. Optical microscopy and AFM images reveal a domain type of morphology and also show an appearance of spiral hillocks in layers grown at growth rates exceeding a critical value. We interpret these results as dominating 2D multilayer growth at low growth rates, and competing 2D multilayer and spiral growth mechanisms at high growth rates.

Single crystalline (0001) gallium nitride layers were implanted with beryllium and subsequently annealed within the range of 300-1100 °C for 10-60 minutes under a flux of atomic nitrogen obtained using a rf plasma source. The nitrogen flux protected the GaN surface from decomposition in vacuum at high temperatures. SIMS measurements revealed that no long range diffusion of the implanted Be occurred at 900 or 1100 °C. XRD spectra showed defect-related peaks in the as-implanted samples; these peaks disappeared upon annealing at 900 °C and higher for 10 minutes. Photoluminescence (PL) easurements showed one new line at 3.35 eV which provided strong evidence for the presence of optically active Be acceptors.

Thermal residual stresses can detrimentally affect the electronic and optical properties of epitaxial films thereby shortening device lifetime. Based on our earlier work on thermal expansion of nitrides, we provide a finite element modeling analysis of the residual stress distribution of multilayered GaN and AlN on 6H-SiC. The effects of thickness and growth temperatures are considered in the analysis.

Optical properties of GaN/AlGaN single quantum well (SQW) and multi quantum well (MQW) structures grown by nitrogen plasma assisted MBE on MOCVD-grown GaN/sapphire have been characterised by low temperature photoluminescence. Photoluminescence (PL) peaks corresponding to emission from very narrow (10 Å wide) SQWs are blue shifted with respect to the bulk GaN emissions but reveal strong red shift for wider SQWs (40 and 60 Å wide). Structural properties of SQW and MQW structures have been characterised by X-ray reciprocal lattice mapping in order to determine the strain conditions and composition of ternary AlGaN alloys. The results clearly demonstrate that in all structures under investigation the ternary (barrier) alloys are fully strained to underlying MOCVD-grown GaN/sapphire substrates. Despite of the fact that GaN quantum wells (QW) are unstrained, photoluminescence experiments clearly reveal the presence of extremely strong electric fields in the QW regions, which can be attributed to the interplay of the piezoelectric-type polarisation in the well and barrier layers due to Fermi level alignment.

InxGa1−xN films with x=0.06 to x=0.49 were characterized by optical transmittance, Raman, and photoluminescence excitation spectroscopies. Previous microstructural characterizations detected phase separation only in films with x>0.2. The transmittance data suggest that compositional inhomogeneity is also present in the lower-x films (x<0.2). Both Raman and photoluminescence excitation spectra show features that correlate with compositional inhomogeneity and phase separation in the films with x>0.2. The composition dependence of the Raman spectra, from x=0.28 to x=0.49, is consistent with an increase in the size of the phase-separated regions with increasing x.

While significant strides have been made in the optimization of GaN-based devices on foreign substrates, a more attractive alternative would be homoepitaxy on GaN substrates. The primary motivation of this work is to explore the growth of thick films of GaN from the melt for the ultimate use as substrate material. We have previously demonstrated the synthesis of polycrystalline, wurtzitic gallium nitride and indium nitride by saturating gallium metal and indium metal with atomic nitrogen from a microwave plasma source. Plasma synthesis avoids the high equilibrium pressures required when molecular nitrogen is used as the nitrogen source. Here we report the growth of thick oriented GaN layers using the same technique by the introduction of (0001) sapphire into the melt to serve as a substrate. The mechanism of this growth is not established, but may involve transport of the metal as a liquid film onto the sapphire and subsequent reaction with atomic nitrogen. The films were characterized by x-ray diffraction, scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. X-ray diffraction showed that the GaN films were oriented with their c-axes parallel to the sapphire c-axis. The TEM analysis confirmed the orientation and revealed a dislocation density of approximately 1010 cm−2. The E2 Raman active phonon modes were observed in the GaN films.

P-type doping with Mg and n-type doping with Si of cubic GaN (c-GaN) epilayers is reported. Cubic GaN films are grown by rf-plasma assisted MBE on semi-insulating GaAs (001) substrates at a substrate temperature of 720°C. Elemental Mg and Si are evaporated from thermal effusions cells. Secondary ion mass spectroscopy (SIMS), low temperature photoluminescence (PL) and temperature dependent Hall-effect measurements are used to study the incorporation, optical and electrical properties. A Mg related shallow donor-acceptor transiton at 3.04 eV with an acceptor activation energy of EA= 0.230 eV is observed by low temperature PL. At Mg concentrations above 1018 cm−3 the dominance of a broad blue band indicates that also in c-GaN Mg is incorporated at different lattice sites or forms complexes. Si-doped c-GaN epilayers are ntype with electron concentrations up to 5*1019 cm−3. The incorporation of Si follows exactly the vapor pressure curve of Si, indicating a sticking coefficient of 1 for Si in cGaN. With increasing Si-concentration the intensity of the near-band luminescence continuously increases and broadens.

We report on the growth of high-quality cubic phase InGaN on GaAs by MOCVD. The cubic InGaN layers are grown on cubic GaN buffer layers on GaAs (001) substrates. The surface morphology of the films are mirror-like. The cubic nature of the InGaN films is obtained by X-ray diffraction (XRD) measurements. The InGaN layers show strong photoluminescence (PL) at room temperature. Neither emission peak from wurtzite GaN nor yellow luminescence is observed in our films. The highest In content as determined by XRD is about 17% with an PL emission wavelength of 450 nm. The FWHM of the cubic InGaN PL peak are 153 meV and 216 meV for 427 nm and 450 nm emissions, respectively. It is found that the In compositions determined from XRD are not in agreement with those estimated from PL measurements. The reasons for this disagreement are discussed.

We have investigated AlxGa1−xN /GaN heterostructures (0<x<0.22) grown by metal organic vapor phase epitaxy on sapphire with photoluminescence (PL), reflexion and cathodo-luminescence experiments. The energetic positions of the free A-exciton in GaN and AlGaN as a function of the alloy compositions are deduced from temperature dependent PL and from reflexion measurements. We obtain a small bowing parameter and no evidence for a Stokes shift between absorption and emission. The AlxGa1−xN films induce additional compressive strain on the underlying GaN film. Compositional inhomogeneities are present, but the fluctuations are too small to be important for carrier localisation. The broadening of the luminescence line width in the alloy can be described by statistical disorder of a random alloy.

We present density–functional theory studies for a variety of surfaces and extended defects in GaN. According to previous theoretical studies1{100} type surfaces are electrically inactive. They play an important role in GaN since similar configurations occur at open–core screw dislocations and nanopipes as well as at the core of threading edge dislocations. Domain boundaries are found to consist of four–fold coordinated atoms and are also found to be electrically inactive. Thus, except for full–core screw dislocations which possess heavily strained bonds all investigated extended defects do not induce deep states into the band–gap. However, electrically active impurities in particular gallium vacancies and oxygen related defect complexes are found to be trapped at the stress field of the extended defects.

Electron beam induced electromigration of ON+ and H+ impurities in unintentionally n-doped GaN was investigated using cathodoluminescence (CL) kinetics profiling, CL imaging of regions pre-irradiated with a stationary electron beam, and wavelength dispersive x-ray spectrometry (WDS). The presented results (i) illustrate induced impurity diffusion in wide bandgap semiconductors, (ii) provide experimental evidence for the (VGa−ON)2− model of yellow luminescence in GaN with low Si content1, (iii) confirm the roles of O in frequently reported bound exciton and donor-acceptor pair emissions and (iv) suggest the involvement of ON+ and hydrogenated gallium vacancies in a blue emission in autodoped GaN.

InGaN layers grown by molecular beam epitaxy are investigated in terms of their compositional homogeneity using transmission electron microscopy and cathodoluminescence spectroscopy performed with high spatial resolution. Strong fluctuations of the indium content were found in bulklike layers, which could be partially reduced by modulating the indium flux during growth, i. e. by nominally growing a short period GaN/InGaN superlattice. For indium compositions above x ≅ 0.1 this approach fails. Strained InGaN in quantum wells exhibits lateral fluctuations on an atomic scale and on a scale of several hundred nanometers. The results are discussed in view of the origin of inhomogeneous indium incorporation.

Pendeo-epitaxy is a type of selective growth of thin films from the sidewalls of etched forms. The resulting films are suspended from the sidewalls and do not interface with the substrate. This process route has advantages over conventional lateral epitaxial overgrowth (LEO) techniques. In this research, pendeo-epitaxial growth of GaN films has been achieved on elongated GaN seed columns. The seed columns were etched from GaN grown on 6H-SiC (0001) substrates via metalorganic vapor phase epitaxy (MOVPE). Silicon nitride mask layers atop the GaN seed columns forced growth from the sidewalls. Pendeo-epitaxial growth of GaN was investigated using several growth temperatures. Higher growth temperatures resulted in improved coalescence due to greater lateral to vertical growth ratios.

A new process route for lateral growth of nearly defect free GaN structures via Pendeo-epitaxy is discussed. Lateral growth of GaN films suspended from {110} side walls of [0001] oriented GaN columns into and over adjacent etched wells has been achieved via MOVPE technique without the use of, or contact with, a supporting mask or substrate. Pendeo-epitaxy is proposed as the descriptive term for this growth technique. Selective growth was achieved using process parameters that promote lateral growth of the {110} planes of GaN and disallow nucleation of this phase on the exposed SiC substrate. Thus, the selectivity is provided by tailoring the shape of the underlying GaN layer itself consisting of a sequence of alternating trenches and columns, instead of selective growth through openings in SiO2 or SiNx mask, as in the conventional lateral epitaxial overgrowth (LEO).

Two modes of initiation of the pendeo-epitaxial GaN growth via MOVPE were observed: Mode A - promoting the lateral growth of the {110} side facets into the wells faster than the vertical growth of the (0001) top facets; and Mode B - enabling the top (0001) faces to grow initially faster followed by the pendeo-epitaxial growth over the wells from the newly formed {110} side facets. Four-to-five order decrease in the dislocation density was observed via transmission electron microscopy (TEM) in the pendeo-epitaxial GaN relative to that in the GaN columns. TEM observations revealed that in pendeo-epitaxial GaN films the dislocations do not propagate laterally from the GaN columns when the structure grows laterally from the sidewalls into and over the trenches. Scanning electron microscopy (SEM) studies revealed that the coalesced regions are either defect-free or sometimes exhibit voids. Above these voids the PEGaN layer is usually defect free.

A comparison was made of 6H-SiC surfaces etched with H2, C2H4/H2, and HCl/H2, and the resulting crystal quality of epitaxial GaN films deposited on these substrates. To remove the many fine scratches and to smooth the rough surfaces typical of commercial SiC substrates, the Si-face 6H-SiC substrates were etched in H2, C2H4/H2, and HCl/H2 at 145 °C. GaN was subsequently deposited on these etched surfaces after first depositing a low temperature GaN buffer layer via metalorganic chemical vapor deposition (MOCVD). The surface morphologies after etching and after GaN deposition were characterized by atomic force microscopy and Normaski differential interference contrast microscopy, while the crystal quality of the GaN films was assessed by double crystal x-ray rocking curves and x-ray topography. 6H-SiC substrate surfaces were improved in terms of the removal of scratches and the reduction of surface roughness, and both surface morphology and crystal quality of the subsequently deposited GaN films were enhanced. However, the dislocation density was not decreased by the surface etching. The best GaN film was produced by etching the substrate in pure H2 for 40 minutes before growth. Recommendations for the optimum substrate treatment are made.

Zinc Oxide crystals have historically been grown in hydrothermal autoclaves with a basic mineralizer; however, doubts have been raised about the quality of such crystals because they have often exhibited large x-ray rocking curve widths and low photoluminescence (PL) yield with large linewidths. Several ZnO crystals were grown hydrothermally and sliced parallel to the c-plane. This resulted in opposite surfaces (the C+ and C−) exhibiting pronounced chemical and mechanical differences. Different surface treatments were investigated and compared by PL both at room temperature and liquid helium temperatures, and by double axis X-ray rocking curve measurements. The high quality of hydrothermally-grown ZnO is substantiated by the narrow rocking curve widths and sharp PL peaks obtained. A critical factor in obtaining these results was found to be surface preparation.

Interdiffusion of In and Ga is observed in InGaN multiple-quantum-well superlattices for annealing temperatures of 1250 to 1400°C. Hydrostatic pressures of up to 15 kbar were applied during the annealing treatments to prevent decomposition of the InGaN and GaN. In as-grown material, x-ray diffraction spectra show InGaN superlattice peaks up to the fourth order. After annealing at 1400°C for 15 min, only the zero-order InGaN peak is observed, a result of compositional disordering of the superlattice. Composition profiles from secondary ion mass spectrometry indicate significant diffusion of Mg from the p-type GaN layer into the quantum well region. This Mg diffusion may lead to an enhancement of superlattice disordering. For annealing temperatures between 1250 and 1300°C, a blue shift of the InGaN spontaneous emission peak is observed, consistent with interdiffusion of In and Ga in the quantum-well region.

Arsenic-doped GaN films and GaNAs films have been synthesized by MOCVD. Samples were grown on sapphire, GaN-coated sapphire, and GaAs substrates. Composition, structure, and phase distribution were characterized by EPMA, SIMS, XRD, and TEM. The arsenic content increases demonstrably as the growth temperature descreases from 1030 to 700 °C. In the high temperature limit, high quality arsenic-doped GaN forms on GaN-coated sapphire. In the low temperature regime, nitrogen-rich GaNAs forms under some growth conditions, with a maximum arsenic mole fraction of 3%, and phase segregation in the form of GaAs precipitates occurs with an increase in arsine pressure. Preferential formation of the nitrogen-rich phase on GaN-coated sapphire suggests the presence of substrate-induced “composition pulling”.