A comparison study of the growth of aluminum nitride (AIN) single crystal epitaxy on 6H-SiC and 4H-SiC substrates has been performed. The material has been characterized using atomic force microscopy (AFM) and reflective high energy electron diffraction (RHEED). AIN crystals were deposited on the following 6H-SiC substrates: singular with and without an initial SiC epilayer, and 3.5° off-axis with and without an initial SIC epilayer. AIN crystals were deposited on 8.0° off-axis 4H-SiC with and without initial SIC epilayers. AFM shows that the deposition of AIN on 6H-SiC and 4H-SIC with an initial SiC epilayer displays high quality quasi-two dimensional growth as atomically flat or step flow epitaxy.

We have investigated the use of focused ion beam (FIB) etching for the fabrication of GaN-based devices. Although work has shown that conventional reactive ion etching (RME) is in most cases appropriate for the GaN device fabrication, the direct write facility of FIB etching - a well-established technique for optical mask repair and for IC failure analysis and repair - without the requirement for depositing an etch mask is invaluable. A gallium ion beam of about 20nm diameter was used to sputter GaN material. The etching rate depends linearly on the ion dose per area with a slope of 3.5 × 10-4 μm3/pC. At a current of 3nA, for example, this corresponds to an etch rate of 1.05μm3/s. Good etching qualities have been achieved with a side wall roughness significantly below 0.1μm. Changes in the roughness of the etched surface plane stay below 8nm.

Temperature-dependent photoluminescence (PL) studies have been performed on InGaN epilayers and InGaN/GaN multiple quantum wells (MQWs) grown by metalorganic chemical vapor deposition. We observed anomalous temperature dependent emission behavior (specifically an S-shaped decrease-increase-decrease) of the peak energy (EpL) of the InGaN-related PL emission with increasing temperature. In the case of the InGaN epilayer, EPL decreases in the temperature range of 10 - 50 K, increases for 50 - 110 K, and decreases again for 110 - 300 K with increasing temperature. For the InGaN/GaN MQWs, EPL decreases from 10 - 70 K, increases from 70 - 150 K, then decreases again for 150 - 300 K. The actual temperature dependence of the PL emission was estimated with respect to the bandgap energy determined by photoreflectance spectra. We observed that the PL peak emission shift has an excellent correlation with a change in carrier lifetime with temperature. We demonstrate that the temperature-induced S-shaped PL shift is caused by the change in carrier recombination dynamics with increasing temperature due to inhomogeneities in the InGaN structures.

Pendeo-epitaxy of individual GaN and AlxGa,1-xN films and single- and multi-layer heterostructures of these materials have been achieved on a columnar GaN seed layer using metallorganic vapor phase epitaxy. These structures have been characterized using scanning electron microscopy and atomic force microscopy. The RMS roughness value of the grown side wall plane (1120) of these structures was 0.099 nm.

Thin films of GaN and its alloy AlGaN are investigated with respect to their properties of the persistent photoconductivity (PPC). In this work, we show that the film-substrate interface plays an important role for the metastable electrical effect. Strongly absorbed bandgap light causes an increase of photoconductivity which is about one order of magnitude higher when the sample is illuminated from the substrate side near the interface than from the growth side. To access the interface properties at the substrate, we use temperature-dependent Hall effect measurements. The smallest PPC effect was observed for the GaN film with the best interface properties grown on SiC.

Hall effect measurements have been applied for the electrical characterization of p-type Mg-doped GaN grown by metalorganic vapor-phase epitaxy on sapphire substrates in terms of annealing temperature for dehydrogenation (N2 annealing) and hydrogenation (H2 annealing) of the acceptors. With the N2 annealing temperature from 600 to 900°C for dehydrogenation, both hole concentration and mobility increases, showing more activation of acceptors and less incorporation of unfavorable scattering centers probably originating from Mg-H bondings. The N2 annealing at higher than the growth temperature results in reduced hole concentration, but the mobility gets higher. Some defects compensating acceptors may be induced at high temperature annealing, but they seem to be no scattering centers and be inactivated by successive hydrogenation and re-dehydrogenation at the optimum dehydrogenation temperature 900°C. The electrical degradation of GaN due to thermal damage is not very destructive and can be well recovered by annealing treatments.

A new process route for lateral growth of nearly defect free GaN structures via Pendeoepitaxy is discussed. Lateral growth of GaN films suspended from {1120} 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 { 1120) 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 {1120} 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 {1120} 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.

We report the morphological and compositional characteristics of Er-doped GaN grown by MBE on Si(111) substrates and their effect on optical properties. The GaN was grown by molecular beam epitaxy using solid sources (for Ga and Er) and a plasma gas source for N2. The films emit by photoexcitation in the visible and near infrared wavelengths from the Er atomic levels. The morphology of the GaN:Er films was examined by AFM. Composition was determined by SIMS depth profiling that revealed a large Er concentration at 4.5 × 1021 atoms/cm3 accompanied by a high oxygen impurity concentration.

Transmission electron microscope (TEM) and transmission electron diffraction (TED) examination has been performed to investigate microstructural properties of gas source molecular beam epitaxial GaN(As,P) layers grown on (0001) GaN/sapphire at temperatures in the range 500–760 °C. As for the GaNAs, we report the observation of ordering with a space group P3ml in the layer grown at 730 °C. The layers grown at temperatures below 600 °C are polycrystalline, whist the 730°C GaNAs layer has epitaxial relation to the GaN substrate. It is also shown that the GaNAs layers experience a structural change from a zinc-blende phase to a wurtzite phase, as the growth temperature increases. As for the GaNP, it is shown that the layers grown at temperatures ≤ 600 °C experience phase separation resulting in a mixture of GaN-rich and GaP-rich GaNP with zinc-blende structure. However, the layers grown at temperatures ≥ 730 °C are found to be binary zinc-blende GaN(P) single crystalline materials. The layers grown at temperatures ≥ 730 °C consist of two types of micro-domains, i.e., GaN(P)1 and GaN(P)11; the former having twin relation to the latter.

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”.

Thin films of GaN grown by MOCVD on (0001) sapphire were studied by transmission electron microscopy in order to correlate the observed extended defects with crystal polarity of the films. We propose relatively simple and unambiguous method of polarity determination for wurtzite group III nitrides based on the dependence of the intensity of diffracted beams upon thickness of the specimen. Due to the dynamic scattering by polar structure, the convergent beam electron diffraction patterns lose inversion symmetry and become in fact fingerprints of the structure carrying information about crystal polarity. In this study, we have used the thinnest regions of the specimens (< 15 nm) and multiple diffraction spots in high-symmetry orientation for polarity determination. The films were found to have Ga-polar surfaces, either being unipolar, or containing thin (10-30 nm in diameter) columnar inversion domains (IDs) of N-polarity. The occurrence of IDs was correlated with specific types of dislocation distribution in the films.

We report on the first artificial fabrication of self-assembling AlGaN quantum dots (QDs) on AIGaN surfaces using metal organic chemical vapor deposition (MOCVD). The AlGaN QDs are fabricated using a growth mode change from 2-dimensional step-flow growth to 3-dimensional island formation by modifying the AlGaN surface energy with Si anti-surfactant. The average lateral size and the thickness of fabricated AlGaN QDs, as determined by AFM, are approximately 20 nm and 6nm, respectively. The dot density was found to be controlled from 5×1010cm-2 down to 2×109 cm-2 by increasing the dose of Si anti-surfactant. We obtained the photoluminescence (PL) from AlGaN QDs embedded with Al0.38Ga0.62N capping layers. The Al incorporation in AlGaN QDs was controllable within the range of 1-5 %.

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 III-V nitride semiconductors appear to be excellent host materials for optical device applications involving thin films doped with rare earth atoms. In particular, GaN epilayers doped with Er ions have shown a highly reduced thermal quenching of the Er luminescence intensity from cryogenic to elevated temperatures. The remarkable thermal stability of the light emission may be due to the large energy bandgap of the material, as well as to the optical inactivity of material defects in the GaN film. In this paper we present recent developments concerning the luminescence characteristics of Er-doped GaN thins films. We have used two methods for doping GaN films with Er ions, ion implantation and in-situ incorporation during gas source metal-organic molecular beam epitaxy (MOMBE). Bandedge (at ∼ 0.34 μm) and infrared (at ∼ 1.54 μm) photoluminescence (PL) spectra have been measured for both types of Er-doped GaN films. Considerably different emission spectra have been observed depending upon the incorporation method and the heat treatment procedure. In situ Er-doped GaN layers have been processed into hybrid light emitting devices and emission spectra at 1.54 Pm have been measured.

We have studied crystal structure and associated defects in GaN films grown on sapphire under nitrogen-deficient conditions by metalorganic chemical vapor deposition (MOCVD) and pulsed laser deposition (PLD). The structural quality of the PLD films grown at 750 °C was comparable with those grown by MOCVD at 1050 °C having threading dislocations density of about 1010 cm-2 at a film thickness 150-200 nm. Microstructure of the PLD films grown at temperatures above 780°C was found to be similar to that of nitrogen-deficient MOCVD films indicating the loss of nitrogen due to thermal decomposition of the nitride layers. Nitrogen-deficient MOCVD and PLD films exhibit polycrystalline structure with a mixture of cubic zinc-blende and wurtzite hexagonal GaN grains retaining tetragonal bonding across the boundaries and hence the epitaxial orientations and polarity. Renucleation of the wurtzite phase at different {111} planes of cubic GaN results in a rough and faceted surface of the film. Most of the stoichiometric films displayed (0001) Ga-face polarity, but the renucleated inclined wurtzite grains grew in the opposite N-face polarity. The major defects related to the cubic structural metastability are stacking faults and microtwins which being nuclei of the metastable cubic phase have an extremely low energy. We elucidate that the cubic phase is more stable under the nitrogen deficiency and, therefore, can exist without decomposition at higher nitrogen vacancy concentrations in the material.

The current status of GaN crystallization under high nitrogen pressure will be presented. Both conductive and semi-insulating GaN crystals will be characterized.

In particular the influence of Mg on the growth mechanisms will be discussed. The influence of Mg doping on morphology of Mg-doped crystals grown under pressure and Mg-doped homoepitaxial layers will be shown. It will be also shown that the addition of about I at.% of Mg into the solution improves significantly the structural quality of crystals reducing dislocation density at least by 3 orders of magnitude comparing to the crystals grown without an intentional doping. As it was estimated by selective wet etching and transmission electron microscopy the dislocation densities in the Mg-doped GaN is as low as 10 cm-1. The introduction of Mg also lowers the optical absorption coefficients for energies below fundamental edge by 2 to 3 orders of magnitude what is explained by disappearance of defect related states in the gap.

The procedures for preparation of atomically flat epi-ready (000 1 ) surfaces without subsurface damage will be described. It will be shown that high quality homoepitaxial layers growing by monoatomic steps are possible on these substrates.

InGal-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.

Patterning the group-III nitrides has been challenging due to their strong bond energies and relatively inert chemical nature as compared to other compound semiconductors. Plasma etch processes have been used almost exclusively to pattern these films. The use of high-density plasma etch systems, including inductively coupled plasmas (ICP), has resulted in relatively high etch rates (often greater than 1.0 μm/min) with anisotropic profiles and smooth etch morphologies. However, the etch mechanism is often dominated by high ion bombardment energies which can minimize etch selectivity. The use of an ICP-generated BCl3/Cl2 plasma has yielded a highly versatile GaN etch process with rates ranging from 100 to 8000 Å/min making this plasma chemistry a prime candidate for optimization of etch selectivity. In this study, we will report ICP etch rates and selectivities for GaN, AIN, and InN as a function of BCl3/C12 flow ratios, cathode rf-power, and ICP-source power. GaN:InN and GaN:AIN etch selectivities were typically less than 7:1 and showed the strongest dependence on flow ratio. This trend may be attributed to faster GaN etch rates observed at higher concentrations of atomic Cl which was monitored using optical emission spectroscopy (OES).

We have investigated the thermal stability of GaN using Raman scattering. Noninvasive optical monitoring of the degradation of GaN during high-temperature processing has been demonstrated. GaN samples grown by molecular-beam epitaxy (MBE) and metalorganic vapor phase epitaxy (MOCVD) were studied. Characteristic features in the Raman spectrum identify three thermal stability regimes: (1) annealing below 900°C does not affect the GaN Raman spectrum; (2) annealing between 900°C and 1000°C results in the appearance of disorder-induced Raman scattering between the E2 and A1(LO) phonon; (3) annealing at temperatures higher than 1000°C gives rise to distinct Raman modes at 630 cm-1, 656 cm-1 and 770 cm-1. The evolution of the Raman spectrum of GaN with increasing annealing temperature is discussed in terms of disorder-induced Raman scattering. We find clear indications for an interfacial reaction between GaN and sapphire for annealing temperatures higher than 1000°C.

Ensemble Monte Carlo calculations of electron transport at high applied electric field strengths in bulk, wurtzite phase InN are presented. The calculations are performed using a full band Monte Carlo simulation that includes a pseudopotential band structure, all of the relevant phonon scattering agents, and numerically derived impact ionization transition rates. The full details of the first five conduction bands, which extend in energy to about 8 eV above the conduction band minimum, are included in the simulation. The electron initiated impact ionization coefficients and quantum yield are calculated using the full band Monte Carlo model. Comparison is made to previous calculations for bulk GaN and ZnS. It is found that owing to the narrower band gap in InN, a lower breakdown field exists than in either GaN or ZnS.