The misfit between GaN and 6H-SiC is 3.5 % instead of 16 % with sapphire, the epitaxial layers have similar densities of defects on both substrates. Moreover, the lattice mismatch between AlN and 6H-SiC is only 1%. Therefore, epitaxial layer overgrowth (ELO) of GaN on AlN/6H-SiC could be a route to further improve the quality of epitaxial layers. AlN has been grown by Halide Vapour Phase Epitaxy (HVPE) on (0001) 6H-SiC, thereafter a dielectric SiO2 mask was deposited and circular openings were made by standard photolithography and reactive ion etching. We have examined GaN layers at an early stage of coalescence in order to identify which dislocations bend and try to understand why. The analysed islands have always the same hexagonal shape, limited by facets. The a type dislocations are found to fold many times from basal to the prismatic plane, whereas when a+c dislocations bend to the basal plane, they were not seen to come back to a prismatic one.

The characteristics of dry etching of the AlGaInN materials system in different reactor types and plasma chemistries are reviewed, along with the depth and thermal stability of etch-induced damage. The application to device processing for both electronics and photonics is also discussed.

We have carried out a series of lateral epitaxial overgrowths (LEO) of GaN through thin oxide windows by the hydride vapor phase epitaxy (HVPE) technique at different growth temperatures. High lateral growth rate at 1100°C allows coalescing of neighboring islands into a continuous and flat film, while the lower lateral growth rate at 1050°C produces triangular-shaped ridges over the growth windows. In either case, threading dislocations bend into laterally grown regions to relax the shear stress developed in the film during growth. In regions close to the mask edge, where the shear stress is highest, dislocations interact and multiply into arrays of edge dislocations lying parallel to the growth window. This multiplication and pileup of dislocations cause a large-angle tilting of the laterally grown regions. The tilt angle is high (∼8 degrees) when the growth is at 1050°C and becomes smaller (3-5 degrees) at 1100°C. At the coalescence of growth facets, a tilt-type grain boundary is formed. During the high-temperature lateral growth, the tensile stress in the GaN seed layer and the thermal stress from the mask layer both contribute to a high shear stress at the growth facets. Finite element stress simulations suggest that this shear stress may be sufficient to cause the observed excessive dislocation activities and tilting of LEO regions at high growth temperatures.

We report the growth of high quality GaN epitaxial layers by rf-plasma MBE. The unique feature of our growth process is that the GaN epitaxial layers are grown on top of a double layer that consists of an intermediate-temperature buffer layer (ITBL), which is grown at 690°C and a conventional low-temperature buffer layer deposited at 500°C. It is observed that the electron mobility increases steadily with the thickness of the ITBL, which peaks at 377 cm2V−1s−1 for an ITBL thickness of 800 nm. The PL also demonstrated systematic improvements with the thickness of the ITBL. Our analyses of the mobility and the photoluminescence characteristics demonstrate that the utilization of an ITBL in addition to the conventional low-temperature buffer layer leads to the relaxation of residual strain within the material resulting in improvement in the optoelectronic properties of the films. A maximum electron mobility of 430 cm2V−1s−1 can be obtained using this technique and further optimizing the growth conditions for the low-temperature buffer layer.

The behavior of threading dislocations during mass transport of GaN was investigated in detail by transmission electron microscopy. Mass transport occurred at the surface. Therefore, growing species are supplied from the in-plane direction. The behavior of threading dislocations was found to be strongly affected by the mass transport process as well as the high crystallographic anisotropy of the surface energy of the facets particular to GaN.

Diffraction-contrast TEM, focused probe electron diffraction, and high-resolution X-ray diffraction were used to characterize the dislocation arrangements in a 16µm thick coalesced GaN film grown by MOVPE LEO. As is commonly observed, the threading dislocations that are duplicated from the template above the window bend toward (0001). At the coalescence plane they bend back to lie along [0001] and thread to the surface. In addition, three other sets of dislocations were observed. The first set consists of a wall of parallel dislocations lying in the coalescence plane and nearly parallel to the substrate, with Burgers vector (b) in the (0001) plane. The second set is comprised of rectangular loops with b = 1/3 [110] (perpendicular to the coalescence boundary) which originate in the coalescence boundary and extend laterally into the film on the (100). The third set of dislocations threads laterally through the film along the [100] bar axis with 1/3<110>-type Burgers vectors These sets result in a dislocation density of ∼109 cm−2. High resolution X-ray reciprocal space maps indicate wing tilt of ∼0.5º.

The polarity of laterally epitaxially overgrown (LEO) GaN on Si(111) with an AlN buffer layer grown by MOCVD has been studied by convergent beam electron diffraction (CBED). The LEO GaN was studied by cross-section and plan-view transmission electron microscopy (TEM). The threading dislocation density is less than 108 cm−2 and no inversion domains were observed. CBED patterns were obtained at 200 kV for the <1 00> zone. Simulation was done by many-beam solution with 33 zero-order beams. The comparison of experimental CBED patterns and simulated patterns indicates that the polarity of GaN on Si(111) is Ga face.

Structural properties of epitaxially laterally overgrown (ELO) GaN on patterned GaN ‘substrates’ by hydride vapor phase epitaxy (HVPE) have been investigated. The epitaxially lateral overgrowth of GaN on SiO2 areas is realized and a planar ELO GaN film is obtained. Scanning electron microscope, transmission electron microscope (TEM) and atomic force microscope (AFM) are used to study the structure and surface morphology of the ELO GaN materials. AFM images indicate that no observable step termination is detected over a 4 μm2 area in the ELO region. TEM observations indicate that the dislocation density is very low in the ELO region. No void at the coalescence interface is observed. Lattice bending as high as 3.3° is observed and attributed to pileup of threading dislocations coming from the underlying GaN “seeding layer” and tilting horizontally and quenching at the coalescence interface.

Recent advances in the processing of complex-oxide materials has allowed us to monolithically grow ferroelectrics of lead lanthanum zirconate titanate (PLZT) and barium strontium titanate (BST) systems on a GaN/sapphire structure. High quality films of PLZT and BST were grown on GaN/c-Al2O3 in a thickness range of 0.3-5 µm by a solgel technique. Field-induced birefringence, as large as 0.02, was measured from a PLZT layer grown on a buffered GaN/sapphire structure. UV illumination was found to result in more symmetrical electrooptic hysteresis loop. BST films on GaN demonstrated a low frequency dielectric constant of up to 800 with leakage current density as low as 5.5⋅10−8A/cm2.

We present preliminary results on gallium nitride growth by HVPE on C-plane sapphire with 2, 4 and 6 degrees misorientation towards M and A directions. A nucleation GaN buffer layer is deposited prior the growth by MOVPE. Surface morphology and growth rates are compared with those obtained on exact C-plane oriented sapphire, for various growth conditions. As expected, the steps already present on the substrate surface help to initiate a directed step-flow growth mode. The large hillocks, which are typical for HVPE GaN layers on (0001) sapphire planes, are replaced by more or less parallel macro-steps. The width and height of these steps, due to step bunching effect, depend directly on the angle of misorientation and on the growth conditions, and are clearly visible by optical or scanning electron microscopy. Atomic force microscopy and X-ray diffraction measurements have been carried out to quantify the surface roughness and crystal quality.

We report on an improved quality of thick HVPE-GaN grown on MOCVD-GaN ‘template’ layers compared to the material grown directly on sapphire. The film-substrate interface revealed by cathodoluminescence measurements shows an absence of highly doped columnar structures which are typically present in thick HVPE-GaN films grown directly on sapphire. This improved structure results in a reduction of two orders of magnitude of the free carrier concentration from Hall measurements. It was found that the structure, morphology, electrical and optical properties of homoepitaxial thick GaN layers grown by HVPE were strongly influenced by the properties of the MOCVD-GaN ‘template’. Additionally the effect of Si doping of the GaN buffer layers on the HVPEGaN properties was analysed.

The nature and impact of ZnO buffer layers on the initial stages of the hydride vapor phase epitaxy (HVPE) of GaN have been studied by x-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), x-ray diffraction (XRD) and photoluminescence (PL). During pre-growth heating, the surface ZnO layer was found to both desorb from ZnO-coated sapphire and react with the underlying sapphire surface forming a thin ZnAl2O4 alloy layer between ZnO and sapphire surface. This ZnO-derived surface promotes the initial nucleation of the GaN and markedly improves material surface morphology, quality and growth reproducibility.

Erbium-doped films were grown on sapphire and silicon substrates by reactive sputtering, with different Er concentrations in the film. GaN films deposited at 800 K were determined to be polycrystalline by x-ray diffraction analysis, and retained their polycrystalline structure after annealing in nitrogen at 1250 K. The Er-doped films showed optical transmission beginning at about 360 nm, and the Er dose and film purity were determined with Rutherford backscattering spectroscopy. Photoluminescence and cathodoluminescence spectroscopy showed sharp emission lines corresponding to Er 3+ intra 4fn shell transitions over the range from 9 - 300 K. At above-bandgap optical and electron excitation, the 4S3/2 and 4F9/2 transition dominate, and are superposed on the "yellow band" emission. The infrared emission line at 1543 nm, corresponding to the Er 4I13/2 to 4I5/2 transition is also observed.

We report the growth kinetics of GaN thin films using the single source precursor bisazido dimethylaminopropyl gallium (BAZIGA) in a cold wall reactor. Transparent, smooth, epitaxial (FWHM of the α-GaN 0002 rocking curve = 129.6 arcsec) and stoichiometric GaN films were grown on c-plane Al2O3 substrates in the temperature range of 870 – 1320K and high growth rates were obtained (up to 4000 nm/hr). Film growth was studied as a function of substrate temperature as well as reactor pressure. Although high quality films were obtained without using any additional source of nitrogen such as ammonia, we have investigated the effect of ammonia on the growth and properties of the resulting films. The films obtained were characterized by XRD, RBS, XPS, AES, AFM, SEM and the room temperature PL spectroscopy of GaN films grown exhibited the correct near band edge luminescence at 3.45 eV.

An aluminum nitride (AlN) film deposited on silicon (100) was used as the substrate for growing manganese (Mn) doped AlN film by metal organic chemical vapor deposition (MOVCD). The (15.78 µm) under layer of AlN was grown at 615°C at a pressure of 10−4 Torr. The (2.1 µm) top layer of Mn-AlN was grown at the same temperature and pressure but doped with pulse valve introduction of the manganese decacarbonyl (100 ms on, 100 ms off). The film was then characterized ex situ with IR reflectance microscopy, X-ray diffraction, scanning electron microscopy imaging, cathodoluminescence, and X-ray fluorescence. The IR reflectance measurements showed a strong (A1) LO mode for AlN at 920 cm−1 and 900 cm−1 with a shoulder at 849 cm−1. X-ray Diffraction yielded three diffraction peaks at a 2θ position of 33, 36 and 38 degrees corresponding to 100, 002, and 101 lattice planes respectively. Cathodoluminescence results show strong visible emitted light from incorporated manganese. The relative percentage of manganese to aluminum was below the detection limit (0.01 %) of the X-ray fluorescence spectrometer. Amorphous Mn doped AlN films have also been grown using a low temperature atomically abrupt sputter epitaxial system. The amorphous Mn doped AlN showed no cathodoluminescence.

Laterally resolved high resolution X-ray diffraction (HRXRD) and photoluminescence spectroscopy (PL) have been used to assess In incorporation efficiency in InxGa1−xN/GaN heterostructures grown through rf-plasma-assisted molecular beam epitaxy. Average alloy composition over a set of InxGa1−xN/GaN superlattices has been found to depend systematically upon both substrate temperature (Tsub) and V/III flux ratio during growth. A pronounced thermally activated In loss (with more than an order-of-magnitude decrease in average alloy composition) is observed over a narrow temperature range (590–670°C), with V/III flux ratio fixed. Additionally, the V/III flux ratio is observed to further strongly affect In incorporation efficiency for samples grown at high Tsub, with up to an order-of-magnitude enhancement in In content despite only a minor increase in V/III flux ratio. PL spectra reveal redshifts as In content is increased and luminescence efficiency which degrades rapidly with decreasing Tsub. Results are consistent with In loss arising from thermally activated surface segregation + surface desorption processes during growth.

The surface morphology of GaN films grown by molecular beam epitaxy (MBE) is investigated by scanning tunneling microscopy (STM). A comparison is made between flat and vicinal surfaces. The wurtzite structure of GaN leads to special morphological features such as step pairing and triangularly shaped islands. Spiral mounds due to growth at screw threading dislocations are dominant on flat surfaces, whereas for vicinal GaN, the surfaces show no spiral mound but evenly spaced steps. This observation suggests an effective suppression of screw threading dislocations in the vicinal films. This finding is confirmed by transmission electron microscopy (TEM) studies. Continued growth of the vicinal surface leads to step bunching that is attributed to the effect of electromigration.

A series of experiments were performed to explore the growth of InN by Molecular Beam Epitaxy (MBE). The growth conditions were optimized based on the study of RHEED during growth and InN dissociation experiments. Characterization of the InN thin films were performed by various techniques such as TEM and XRD.

The presence of oxygen throughout the nominally AlN nucleation layer of a RF assisted MBE grown III-N HEMT was revealed upon examination by Electron Energy Loss Spectroscopy (EELS) in a Scanning Transmission Electron Microscope (STEM). The nucleation layer generates the correct polarity (gallium face) required for producing a piezoelectric induced high mobility two dimensional electron gas at the AlGaN/GaN heterojunction. Only AlN or AlGaN nucleation layers have provided gallium face polarity in RF assisted MBE grown III-N’s on sapphire. The sample was grown at Cornell University in a Varian GenII MBE using an EPI Uni-Bulb nitrogen plasma source. The nucleation layer was examined in the Cornell University STEM using Annular Dark Field (ADF) imaging and Parallel Electron Energy Loss Spectroscopy (PEELS). Bright Field TEM reveals a relatively crystallographically sharp interface, while the PEELS reveal a chemically diffuse interface. PEELS of the nitrogen and oxygen K-edges at approximately 5-Angstrom steps across the GaN/AlN/sapphire interfaces reveals the presence of oxygen in the AlN nucleation layer. The gradient suggests that the oxygen has diffused into the nucleation region from the sapphire substrate forming this oxygen containing AlN layer. Based on energy loss near edge structure (ELNES), oxygen is in octahedral interstitial sites in the AlN and Al is both tetrahedrally and octahedrally coordinated in the oxygen rich region of the AlN.

Evidence is presented that nitrogen plasma sources utilizing a pyrolytic boron nitride liner may be a significant source of B contamination during growth and processing. Auger electron spectroscopy analysis performed during nitridation of sapphire indicate the resulting layers contain a significant amount of BN. The formation of Al1-xBxN would explain the observation of a lattice constant several percent smaller than AlN as measured by reflection high-energy electron diffraction. The presence of cubic inclusions in layers grown on such a surface may be related to the segregation of BN during the nitridation into its cubic phase.