AlN, GaN, and SiC thin films were grown on 100 mm diameter Si(111) and Si(100) substrates using Supersonic Jet Epitaxy (SJE). Precursor gases were seeded in lighter mass carrier gases and free jets were formed using novel slit-jet apertures. The jet design, combined with substrate rotation, allowed for a uniform flux distribution over a large area of a 100 mm wafer at growth pressures of 1–20 mTorr. Triethylaluminum, triethylgailium, and ammonia were used for nitride growth, while disilane, acetylene, and methylsilane were used for SiC growth. The films were characterized by in situ optical reflectivity, x-ray diffraction (XRD), atomic force microscopy (AFM), and spectroscopic ellipsometry (SE).

The effects of both temperature and atmosphere on the resulting morphological features of the polar faces of single crystal ZnO were investigated and characterized by atomic force microscopy (AFM). In studies where ZnO was thermally processed in flowing oxygen at atmospheric conditions within the temperature range of 500°C to 900°C for 30 minutes, the Znsurface (i.e., (000 1)) showed a tendency to reconstruct with increasing temperature until terraces became evident at 900°C. Terrace heights were as small as 0.9 nm. In contrast, the O-surface (i.e., (000 ī)) was observe to change very little during the O2-atmoshere, thermal treatment and remained comparatively rougher than the Zn-surface. ZnO samples which were thermally processed under high vacuum (i.e., 5 × 10-7 Torr) conditions exhibited a more dramatic contrast. The vacuum annealed Zn-surface was observed to develop very smooth surface features (Roughness = 0.09 nm) at annealing temperatures within the 700 – 800°C range. In contrast, and as expected, the O-surface roughness increased due to surface reduction reactions. In addition to these findings, it is noted that AFM measurements may be utilized as a convenient method to distinguish between the two polar surfaces of ZnO.

Aluminum nitride was deposited on the Zn- and O- surfaces from 700 to 850°C by pulsed laser evaporation. X-ray diffraction indicated that the AIN was c-axis oriented with no interface reaction products detected between the ZnO substrate and AIN film.

The effects of flowrate variation and geometry on the growth rate, growth uniformity and crystal quality were investigated in a horizontal Gallium Nitride vapor phase epitaxy reactor. To better understand the effects of these parameters, numerical model predictions are compared to experimentally observed values. Parasitic gas phase reactions between group III and group V sources and deposition of material on the wall are shown to lead to reduced overall growth rates and may be responsible for inferior crystal quality. A low ammonia concentration is correlated with the deposition of polycrystalline films. A low V/III ratio and an ammonia concentration lead to poor crystalline quality and increased yellow luminescence. An optimum HVPE growth process requires selection of reactor geometry and operating conditions to minimize these parasitic reactions and wall deposition while providing a uniform reactant distribution across the substrate.

Aluminum nitride thin films (∼ 100 mn) have been deposited on silicon substrate by reactive sputtering using Al target in 1:1 Ar:N2 environment. The atomic force microscopy examination revealed continuous microcrystalline film structure. The Auger electron spectroscopic analysis show the presence of oxygen in the films. The annealing at 850 C in nitrogen is found to cause recrystallization and further oxidation of the films. The films can be characterized as lossy dielectrics with relative permittivity ∼ 10, higher than the bulk value of 8.9. Annealing the films is found to reduce anion vacancies and improve the dielectric strength within a range of a few MV/cm in these thin films.

Thin III-V nitride semiconductors fidms are commonly prepared using metalorganic chemical vapor deposition (MOCVD) and molecular beam epitaxy (MBE). These methods often require high temperatures (800–1000°C) for the films to grow epitaxially. In the present work, we deposited AlxIn1-xN films on Si substrates by reactive magnetron sputttering method at low substrate temperature. The properties of the films have been studied by RBS, x-ray diffraction, and optical measurements. The AlxIn1-xN films deposited at room temperature were confirmed to be crystalline by x-ray diffraction. Band gap energies of our AlxIn1-xN alloys varies from 1.9 ev to 4.2 ev The bandgap energy vs. lattice constant curve was constructed and confirmed to bow downwards.

We report on the heteroepitaxial growth of GaN from GaCl3 and NH3 on (0001) A12O3 and (0001) 6H-SiC substrates. In order to enable homogeneous growth within the entire deposition zone one has to use low process pressures in the 10-1 mbar range, where still a growth rate of ∼ 2 μm/h can be achieved. We present a simple model to describe our process and explain our observations. A comparison of GaN deposited on different substrates and with GaN buffer layers is given by low temperature Photoluminescence (PL). Furthermore, impurities are traced by secondary ion mass spectroscopy (SIMS).

We describe the development of a new deposition method for thin oriented films of GaN on basal plane sapphire using an exclusively inorganic single-source precursor free of carbon and hydrogen, Cl2GaN3. The films have been characterized by Rutherford backscattering spectroscopy (RBS) and cross sectional transmission electron microscopy (TEM) for composition morphology and structure. RBS analysis confirmed stoichiometric GaN and TEM observations of the highly conformal films revealed heteroepitaxial columnar growth of crystalline wurrtzite material on sapphire. Auger and RBS oxygen and carbon resonance profiles indicated that the films were pure and highly homogeneous. We also report the reactions of Cl2GaN3 with organometallic nitriles to yield a crystalline, novel gallium carbon nitride of composition GaC3N3. Quantitative X-ray powder diffraction has been used to refine the cubic structure of this material which consists of Ga atoms octahedrally surrounded by on the average three C and three N atoms. The structurally analogous LiGaC4N4 phase has also been prepared and characterized.

GaN thin films were grown on various substrates by GSMBE using ECR nitrogen and ammonia. The growth of GaN was monitored by real time analysis, time of flight low energy ion scattering (TOF-LEIS) and RHEED.

Growth of GaN on GaAs, ZnO, Ge and Al2O3 was investigated. The substrates’ surfaces were analyzed during pre-growth annealing and during GaN growth. The removal of surface contaminants and the modification of the surface stoichiometry from these surfaces are presented.

GaN films on sapphire (0001) grown under different conditions were examined real time by low energy ion scattering mass spectroscopy of recoiled ion (MSRI) and the relationship between the in-situ surface composition with ex-situ photoluminescence measurement results are discussed.

Gallium Nitride epitaxial films were grown by migration enhanced epitaxy directly on sapphire (0001) without using any pre-growth substrate nitridation or low temperature buffer layers. In comparison with our material grown directly on sapphire by conventional molecular beam epitaxy, a significant improvement in the surface morphology and layer properties, measured by reflection high energy electron diffraction, X-ray diffraction, scanning electron microscopy, room temperature photoluminescence and the Hall effect, was observed for material grown by migration enhanced epitaxy.

We have grown gallium nitride (GaN), aluminum nitride (AIN) and boron nitride (BN) thin films by mass separated ion beam deposition. All deposited films were found to be almost stoichiometric. AIN and GaN films are crystalline even after room temperature deposition whereas for the formation of crystalline boron nitride temperatures above 150°C are necessary. The influence on the phase formation and the film structure of ion energy and substrate temperature on the one hand, and bond ionicity on the other hand, was investigated for these three systems.

Using reactive rf sputtering, we have grown (0001) oriented ZnO films in situ on heated c-axis sapphire substrates, that are promising, particularly in terms of surface roughness, as buffer layers for the subsequent epitaxial growth of III-V nitride films. We compare the effects of on-axis and off-axis sputter geometries on the film epitaxy and smoothness. We also examined the effect of substrate temperature on the growth and smoothness and quality of the film. X-ray diffraction was used to verify the hexagonal ZnO phase, its c-axis orientation and, qualitatively, the degree of its epitaxy. Atomic Force Microscopy (AFM) was used to determine the ZnO growth morphology and roughness. Our best films, obtained by off-axis sputter deposition, have a surface roughness of less than 1 nm.

We investigated the possibilities of vapour phase epitaxy in an open tube chloride system for thick GaN film deposition on sapphire substrates. The methodes of the buffer layer deposition were proposed and developed. The methods of fast ( up to 100 microns / hour ) was developed. Parameters of good quality gallium nitride epitaxy were obtained.

To determine the quality of fast grown epitaxial layers we used X-ray diffraction and photoluminescence measurements. The halfwidth of the rocking curve for the best samples was equal to 4-6 minutes. Luminescense spectrum ( T=77K ) had a maximum near 3.46 eV. A signal in the visible wavelength range was hardly observed. Polished layers were transparent.

A special initial treatment of the substrates allowed us to separate thick ( up to 300 micron ) epitaxial gallium nitride layers from sapphire. It was shown that it is possible to use separated films for homoepitaxy of GaN.

An empirical relationship linking surface energy to bulk modulus is presented which suggests that the thermodynamic growth mode for heteroepitaxy on compliant substrates should be 3-D. As an example of this behavior, GaN growth on Sc is shown for various growth conditions. 2-D growth is obtained when the GaN is grown on top of a low temperature GaN nucleation layer. Our results indicate that surface and interface energies, in addition to, lattice matching and thermal matching play an important role in determining the heteroexpitaxial growth morphology of GaN. There appears to be no net reduction in the dislocation density for GaN films grown on the Sc layers, because the GaN film has to be grown on a low temperature nucleation layer.

A new apparatus for III-V nitride growth by selected energy epitaxy (SEE) is described. The multi-chamber system comprises a doubly differentially pumped molecular beam source, UHV-compatible growth chamber, x-ray photoelectron spectroscopy (XPS) chamber, UHV transfer line, and loadlock. The growth chamber is equipped for in situ quadrupole mass spectrometry and reflection high-energy electron diffraction (RHEED). Preliminary results of GaN SEE using hyperthermal beams of trimethylgallium (TMG) and ammonia (NH3) are presented.

A new rf plasma nitrogen source has been characterized for growth of GaN on basal-plane sapphire by molecular beam epitaxy. For rf power of 500 W and N2 flow rate of 2 sccm, a maximum GaN growth rate of 0.80 μm/hr is obtained, implying a source efficiency greater than 5%. It is found that the GaN surface roughness is extremely sensitive to V:Il ratio near unity and independent of growth rate in the range 0.3-0.8 μm/hr. Roughness as small as 1.0 nm (rms) is measured by atomic-force microscopy. Microstructure of the high-growth-rate films is similar to other GaN films, as observed in cross-section transmission electron microscope images. The electroluminescence spectra from homojunction light-emitting diodes exhibit a band of nearultraviolet emissions corresponding to the energy separation of the intentional donor and acceptor levels on the two sides of the junction. The intensity of these emissions relative to the visible spectrum increases with drive current density, implying saturation of deep trap levels responsible for the visible light output.

The growth of gallium nitride films on sapphire substrates has not been straightforward because of the large lattice mismatch between gallium nitride and sapphire. Zinc oxide is structurally the closest material to gallium nitride and therefore is finding use as the substrate for gallium nitride. Single crystal wafers of zinc oxide are hard to obtain and very expensive. However, a thin layer of zinc oxide on a suitable substrate might solve this problem. In this work, highly c-axis oriented zinc oxide buffer layers were grown on Si(lll) substrates at temperatures 410–540 °C by chemical vapor deposition of bis(2,2,6,6-tetramethyl–3,5-heptanedionato)zinc, Zn(tmhd)2, and the hexagonal GaN films were subsequently deposited on them at 500 °C using the single precursor tris(diethyl -μ-amido-gallium), [(C2H5)2 GaNH2]3. The compound Zn(tmhd)2 was found to require oxygen for the deposition of zinc oxide. In the case of gallium nitride, low pressure chemical vapor deposition of tris(diethyl-μ-amido-gallium) worked reasonably well with or without a carrier gas. The buffer layers and the GaN films were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM), and reflection high energy elctron diffraction (RHEED).

ZnO layers have been deposited by electron beam (EB) evaporation and laser ablation molecular beam epitaxy (MBE) as buffer layers to grow GaN by metal organic vapor phase epitaxy (MOVPE). The photoluminescence spectrum of the ZnO layer deposited by an EB evaporator shows an emission peaks of 367 nm. GaN was grown on ZnO/Si, Si and sapphire substrates under the same growth condition employing low-temperature-grown AIN buffers to prevent the dissociation of ZnO during the high GaN growth. The GaN on ZnO/Si shows sharp photoluminescence spectra at room temperature and 10 K. These results indicate a potential use of ZnO/Si substrates for GaN based blue-UV optical devices such as vertical-cavity surface-emitting lasers (VCSELs).

Close proximity of the lattice constant for tungsten disulfide and aluminum nitride has lead to an investigation to use WS2 as a potential substrate for the growth of AIN. Metal organic chemical vapor deposition(MOCVD) has been develop to fabricated WS2 thin films on Si(001) with their basal planes parallel to the substrate. AIN thin film was subsequently grown by atomic layer growth (ALG) process using dimethylamine-alane (DMEAA) and ammonia (NH3). Deposition conditions for WS2 thin films by MOCVD, and AIN growth on WS2 by ALG are described.

Heterostructures involving ZnS/GaN show promise for the injection of holes from p-GaN into n-ZnS. This combination could result in multi-color electroluminescent displays. We have grown single crystal ZnS on GaN and sapphire (0001) by MBE using elemental sources. The ZnS was grown at temperatures from 150°C–400°C, with beam flux equivalent pressures of (0.3 – 2.0) × 10−7 torr. Growth rates of up to 0.4 μm per hour were observed for the lower growth temperatures, with rapidly diminishing rates for temperatures above 350μC. The GaN substrate consisted of a 3 μm epilayer grown on sapphire by MOCVD. XPS analysis revealed the presence of carbon surface contamination on the GaN, which was removed by in situ exposure to an RF nitrogen plasma. RHEED observations indicate that the zincblende ZnS layers commonly contain (111) twins, although twin free films may be grown at a high substrate temperature. The samples were characterized using photoluminescence and X-ray diffraction. X-ray peaks typically had FWHM of 400 arcsec for ω/2θ scans, and somewhat worse for ω scans. Photoluminescence spectra of the ZnS films doped with Ag and Al demonstrated the well known blue donor acceptor transition at 440 nm.

The review of structural and optical properties of homoepitaxial layers grown by MOVCD on single crystals GaN substrates is presented. The TEM technique is used to characterise the structural properties of epi-layers. It is found that the structural properties of GaN homoepitaxial layers are determined by the polarity of the substrate surface on which the growth takes place. It is shown that threading dislocations are present only in the layers grown on the [0001] “smooth” surface. On the other hand the layers grown on the [0001] “rough” surface are free from vertical defects. The characteristic feature of the growth on the “rough” surface are pinholes. The optical properties of homoepitaxial layers are predominantly determined by the growth polarity as well. It is shown also that the reflectivity measurement is the most precise way to determine the exciton energies and that emissions due to free excitons are strongly affected by polariton effects.