AIN films grown on sapphire by MOCVD with different V/IAR ratios were investigated by XRD, TEM and AFM. The AIN films show single crystalline character as well as columnar structure. The growth of AIN has three zones: (1) high-density nucleation layer (2) fine columnar growth and (3) grain merging and lateral growth. The films grown at intermediate V/III ratio have the maximum value of [0002] FWHM. When the V/HI ratio increases, the thickness of the nucleation zone and the film misorientation increase, but when the ratio is increased further, the nucleation zone decreases and the AIN film has a more highly oriented growth. These results suggest that the AIN films with optimum crystalline quality can be obtained by varying the V/III ratio during growth.

In-situ optical reflectance is used to monitor the morphological evolution of the two-step GaN growth on sapphire. The amount of H2 carrier gas used in the growth is observed to strongly influence the morphological evolution of the low temperature buffer layer and the subsequent high temperature nucleation behavior, which in turn affects the structural and electrical properties of the GaN epitaxial films. The optical reflectance transients correlate with the sizes and distributions of nuclei as observed by AFM.

Thin films of AIN and GaN were deposited on α(6H)-SiC(0001) wafers using metalorganic vapor phase epitaxy (MOVPE) and H2 and N2 diluents. A computational fluid dynamic model of the deposition process was used to analyze the film growth conditions for both diluents. Low temperature (12 K) photoluminescence of the GaN films grown in N2 had peak intensities and full widths at half maximum of ∼7 meV which were equal to or better than those films grown in H2. Cross-sectional and plan-view transmission electron microscopy of films grown in both diluents showed similar microstructures with a typical dislocation density of 109/cm2. Hall measurements of n-type (Si doped) GaN grown in N2 revealed Hall mobilities equivalent to those films grown in H2. Acceptor-type behavior of Mg-doped GaN grown in N2 was repeatably obtained without post-growth annealing. Secondary ion mass spectrometry revealed equivalent levels of H in Mg-doped GaN films grown in both diluents.

Process for mass production of GaN and its related alloys, InGaN and AlGaN, have been optimized to achieve high device yield and low cost of ownership. Here we present some of the latest results obtained from AIX 2000 HT Planetary Reactor® in a configuration of 7×2” which provides unique uniformity capabilities due to the two fold rotation of the substrates. GaiN single layers with background electron concentrations below 5·1016 cm-3 and intended doping levels up to 1018 cm-3 p-type and 1020 cm-3 n-type with state of the art homogeneities have been achieved. Thickness homogeneities have been shown to be better than 1% standard deviation on full 2” wafers, while composition uniformity of ternary material is determined by room temperature photoluminescence mappings. Low temperature photoluminescence and reflectance spectra of single layer GaN revealed free exciton transitions.

GaN epitaxial thin films were grown on a nitridated sapphire at low temperature (550°C) using remote plasma enhanced ultrahigh vacuum chemical vapor deposition system and these films were investigated by Rutherford backscattering spectroscopy (RBS), X-ray diffraction(XRD) θ-rocking technique and the Ultraviolet-Visible-Nearinfrared (UV-VIS-NIR) absorption spectrum. The FWHM of the X-ray θ-rocking curve was about 0.4 degree using the (0002) reflection from the GaN layer with 5000Å thickness grown on the nitridated sapphire. An analysis of XRD and the UV-VIS-NIR absorption spectrum showed that the crystalline and optical qualities of GaN are dependent on the nitridation time of the sapphire even at low temperature when a plasma source is used for nitridation. This means that the density of protrusion, which is formed by a relaxation of the elastic energy caused by the lattice difference between the sapphire and AlxO1-xN, with the sapphire nitridation time plays a key role in the crystalline and optical properties of grown GaN films. The RBS channeling data and the FWHM value of the θ-rocking curve for GaNr(0002) also indicated that the truncated hexagonals are tilted towards each other. These results showed that the GaN epitaxial film can be successfully grown on nitridated sapphire by RPE-UHVCVD even at low temperature.

A kinetic model is presented to explain GaN growth. The model is based on established values for the N and Ga desorption kinetics and well founded assumptions on the adsorption and decomposition of the N and Ga containing precursors. When grown on similar nucleation layers, it is shown that high quality GaN films are achieved when the V/III ratio is chosen to be slightly larger than the Ga and N desorption rates. The model is verified by comparing the structural, optical, and electrical properties of the GaN to the growth temperature and V/III ratio. The model explains several features of GaN growth including, growth conditions for smooth surface morphology, growth conditions for highly resistive GaN, and a possible explanation for the origin of Ga and N vacancies in GaN. Based on the growth model, ordering of the GaN during growth is achieved via an adsorption/desorption cycle where Ga and N containing species are exchanged between the gas phase boundary layer and the solid surface. Consequences of the model on establishing growth conditions and run-to-run reproducability are also discussed.

GaP1-x-yAsyNx. (x ∼,2.3%, 0< y <19%) quaternary alloy semiconductor films on GaP substrates have been successfully grown by metalorganic vapor phase epitaxy (MOVPE). With the fixed supplies of trimethylgallium(TMG), AsH3 and dimethylhydrazine(DMHy) during the growth, the As concentration in the solid increased with increasing AsH3 supply, while the N concentration was almost unaffected. It has been demonstrated that the crystalline quality of the alloy films is much improved with the close lattice-matching to the GaP substrate, giving a superior surface morphology without any cross-hatches, a much narrower x-ray diffraction linewidth, and a significantly higher photoluminescence(PL) intensity.

Films of AlN were grown on MgO(100), Al2O3, and Si under vacuum pressure (10-3 to 10-4 Torr) at different substrate temperatures. They were examined ex situ with infrared reflectance spectroscopy, scanning electron microscopy, x-ray diffraction and rutherford backscattering spectroscopy. Highly oriented smooth films were grown at film thicknesses below 1 μm. Thicker films showed significantly more roughness but remained oriented with respect to the substrate. AIN growth was faster on Si than MgO(100) or Al2O3 and Si was the only substrate that growth was observed at 500°C.

The epitaxy, defect structure, and heterointerface microstructure of MOVPE-grown AlN on <111> oriented Si were studied by transmission electron microscopy (TEM) in an investigation of the affects of the growth temperature (925°C–1 175°C) on the microstructure of low thickness (∼0.2 μm) films. A film grown at 1175°C was single crystalline with the following orientation relationship: (0001)AlN||(111)Si, <1120> and <1010>AlN||<211> Si. All AlN films grown at temperatures below 1100°C were wire-textured polycrystals with (0001)AlN largely parallel to (111)si and some in-plane preferred orientation similar to that of 1175°C AlN epifilms. Columnar grains/domains with faceted top surfaces were observed for the entire growth temperature range. The mean column diameters decreased from 50 nm to 35 nm as the growth temperature decreased. The columnar grain/domain structure and the faceted tops resulted in peakto-valley surface roughness on the order of 20 nm. Sharp interfaces of AlN/Si were generally observed in all AIN films studied by HREM except for the 1075°C film where a transitional layer of approximately 15Å thick was observed at some interface regions. Defects typically encountered in large lattice mismatched heteroepitaxial systems were observed.

This paper reviews experimental results of phase separation and atomic long-range ordering in A1GaInN alloys, grown by plasma-assisted MBE. Phase separation has been observed in InxGal-x alloys and atomic ordering has been observed in AlxGa1-xN alloys, using XRD studies. Specifically, we find that alloys with In content in excess of 30% show an extra diffraction peak corresponding to an alloy with high In concentration (close to pure InN). The effect of phase separation on the optical properties of the films was also investigated by transmission and photoluminescence measurements. From these studies, we find that the degree of phase separation depends on the thickness of the alloy layer. Atomic long-range ordering has been observed in AlxGal-xN alloys over the entire alloy composition. The phenomenon was investigated by studying the superlattice peaks (0001), (0003) and (0005). The relative intensity of these peaks was found to be largest for the Al content in the 40–50 % range in qualitative agreement with expectations for an ordered structure of ideal Al0.5Ga0.5N stoichiometry. We found that the ratio of III/V fluxes has a significant effect on the degree of ordering.

By controlling the Stranski-Krastanov growth mode of strained GaN deposited by molecular beam epitaxy on AlN, it is shown that islands with nanometric dimensions can be elaborated. The luminescence energy of the wetting layer is 4.6 eV, determined by cathodoluminescence experiments. The luminescence of dots with a mean size of 14 nm in diameter and 2nm in height is 3.8 eV and remains constant in intensity with increasing temperature, as an evidence of 0-dimension confinement effect. Theoretical analysis of the wetting layer luminescence energy is carried out, taking into account the non parabolicity in the conduction band.

The growth of GaN layers was carried out on c-plane sapphire substrates by molecular beam epitaxy (MBE) using NH3. Undoped GaN layers were grown at 830°C with growth rates larger than 1 μm/h. Optical properties are characteristics of high quality GaN material and the linewidth of x-ray diffraction (0002) rocking curve is less than 350 arcsec. N- and p-type doping were achieved by using solid sources of Si and Mg. No post-growth annealing was needed to activate the Mg acceptors. As-grown GaN:Mg layers exhibit hole concentrations of 3×1017 cm−3and mobilities of 8 cm2/Vs at 300 K. Light emitting diodes (LEDs) based on GaN p-n homojunction have been processed. The turn on voltage is 3 V and the forward voltage is 3.7 V at 20 mA. The 300 K electroluminescence (EL) peaks at 390 nm.

The stress in GaN thin films grown on sapphire is shown to be determined by lattice mismatch, by differences in thermal-expansion-coefficients and by the incorporation of point defects. It can be controlled by the buffer layer thickness, the buffer layer growth temperature, the V/III flux ratio, and by doping. It is argued that a Fermi-level dependence of defect formation energies affects the material stoichiometry and thereby lattice constants and stresses. We observed that stress relaxation occurred if the stresses exceeded a critical compressive or tensile stress value. The stress changes materials properties. As an example, it is demonstrated that the electron Hall mobility in GaN:Si can be increased with constant electron carrier concentration if large compressive stress is present.

GaN growth was performed on 6H-SiC (0001) substrates by gas-source molecular beam epitaxy (GSMBE), using ammonia (NH3) as a nitrogen source. Two kinds of reflection high-energy electron diffraction (RHEED) patterns, named (1×1) and (2×2), were observed during the GaN growth depending on the growth conditions. By careful RHEED study, it was verified that the (1×1) pattern was corresponded to a H2-related nitrogen-rich surface, while (2×2) pattern was resulted from a Ga-rich surface. By x-ray diffraction (XRD), photoluminescence (PL) and atomic force microscopy (AFM) characterizations, it was found that the GaN quality changed drastically grown under different RHEED patterns. GaN film grown under the (1×1) RHEED pattern showed much better qualities than that grown under the (2×2) one.

Growth of high quality c-GaN on atomic-H treated (001) GaAs was examined by rf plasma-assisted MBE. First the initial growth stages (atomic-H treatment of GaAs, nitridation/deposition of a thin GaN buffer layer, the post deposition annealing of the buffer layer, and epitaxy of c-GaN) were studied by RHEED and AFM observations. It was found that atomically flat GaAs surface with one monolayer-height steps and ragged step edges could be obtained by the atomic-H treatment at high temperatures. It was found that the atomic-H treated GaAs surface was preferable to grow high quality c-GaN; the FWHM of the X-ray rocking curve for the (002) c-GaN was as small as 70 – 90 arcsec.

A new approach to grow thick GaN layers by hydride vapor phase epitaxy (HVPE) is described. Selective growth is carried out at the beginning of growth. The coalescence of selectively grown facet structures makes it possible to achieve a flat surface over the entire substrate. As a result, crack-free GaN films with mirror-like surfaces are successfully grown even to a thickness of about 100 μm on a 2-inch-diameter sapphire substrate. The extended defect density is as low as 6×107 cm−2. The reduction mechanism for dislocation is discussed based on TEM observation. The high optical properties of FIELO GaN are confirmed by 5 K photoluminescence and reflectance measurements.

GaN, AIN and AIGaN layers were grown by hydride vapor phase epitaxy. 6H-SiC wafers were used as substrates. Properties of AIN/GaN and AIGaN/GaN structures were investigated. AIGaN growth rate was about 1 μm/min. The thickness of the AIGaN layers ranged from 0.5 to 5 μm. The AIN concentration in AIGaN layers was varied from 9 to 67 mol. %. Samples were characterised by electron beam micro analysis, Auger electron spectroscopy, X-ray diffraction and cathodoluminescence.

Electrical measurements performed on AIGaN/GaN/SiC samples indicated that undoped AIGaN layers are conducting at least up to 50 mol. % of AIN.

For the first time, GaN pn-junctions were fabricated by hydride vapor phase epitaxy. GaN pn-structures were grown directly on 6H-SiC substrates without any buffer layer. Undoped GaN layers were n-type with Nd-Na concentration ranged from 1×1017 to 5×1018 cm−3. Magnesium was used as an acceptor to grow p-type GaN layers. Mg atomic concentration determined by secondary ion mass spectroscopy ranged from 5×1019 to 5×1020 cm−3. As-grown GaN layers doped with Mg were p-type, and p-type conductivity was improved by post-growth anneal. Mesa diodes with a vertical current flow geometry were formed by reactive ion etching. The position of the GaN pn-junction was determined by the electron beam induced current method. The electrical characteristics of the pn diodes were studied. Electroluminescence from the pn diodes was measured.

Recent successful results on the selective area growth (SAG) of GaN that has been done by MOVPE and HVPE are shown. The SAG were carried out on MOVPE-grown GaN (0001) / sapphire substrates with lined or dotted SiO2 masks. Sub-micron GaN dot and line structures are fabricated by the SAG in MOVPE, so that smoothly overgrown GaN layers are successfully realized using the epitaxially lateral overgrowth (ELO) technique. The ELO structures are confirmed to be good quality GaN single crystal with a smooth surface, no grain boundaries, and low-dislocation densities. In addition, thick GaN bulk single crystals without any cracks are grown by the SAG in HVPE. Crystalline and optical properties of the GaN bulk are much improved. The reduction in the thermal strain due to the growth on the limited area as well as the ELO are found to be effective to reduce crystalline defects of the GaN bulk single crystals.

GaN wafers 200 μm thick and 30 mm diameter were fabricated. GaN was grown by hydride vapor phase epitaxy on SiC substrates and removed from the substrate by reactive ion etching. Lateral size of the GaN wafers was equal to the size of the initial SiC substrates. GaN wafers were cleaved in pieces and these pieces were characterised. It was found that after the fabrication, GaN crystals were slightly deformed and strained. An anneal at 830°C in nitrogen ambient eliminated the residual strains. The FWHM of ω-scan (0002) x-ray rocking curve for annealed crystals was less than 140 arcsec for both sides of the best GaN crystals. The lattice constants measured from both sides of the crystals were c =5.1853±0.0003 Å and a = 3.1889±0.0001 Å. The Nd – Na concentration determined by a mercury probe was about 2×1017cm−3 for as-grown GaN surface and about 2×1019cm−3 for former interface surface. Photoluminescence spectrum taken at 17 K revealed an edge peak at 3.472 eV with the FWHM value of 2.3 meV. A ratio of the edge peak intensity to the intensity of yellow band was higher than 1000. Initial TEM experiments were performed.