Selective area growth of thin films reduces the number of steps in microfabrication processing and enables novel device structures. Here, we report, for the first time, selective area epitaxy of an oxide material on a GaN surface. Chlorination of the GaN surface via wet chemical processing is found effective to disrupt Mg adsorption and selectively prevent molecular beam epitaxy growth of MgO. MgO films grown on neighboring, nonchlorinated surfaces are epitaxial with a (111) MgO||(0001) GaN crystallographic relationship. Better than 3 μm lateral resolution for the selective area growth of MgO on GaN is demonstrated.

The authors report a study of molecular beam deposition of MgO films on amorphous SiO2 and (0001) GaN surfaces over a large range of temperatures (25–400 °C) and molecular oxygen growth pressures (10−7–10−4 Torr). This study provides insight into the growth behavior of an oxide with volatile metal constituents. Unlike other materials containing volatile constituents (e.g., GaAs, PbTiO3), all components of MgO become volatile at normal epitaxial growth temperatures (≥250 °C). Consequently, defining which species is the adsorption controller becomes ambiguous. Different growth regimes are delineated by the critical substrate temperature for Mg re-evaporation and the Mg:O flux ratio. These regimes have impact on phase purity, quartz crystal microbalance calibration, and film microstructure. The universal decay in deposition rate above growth 10−5 Torr O2 is also considered. By introducing a third flux of inert argon gas, rate reduction is attributed to increased molecular scattering and not oxidation of the metal source.

Aluminum nitride (AlN) and gallium nitride (GaN) play an essential role in modern electronics, particularly in optoelectronics. Highly efficient light-emitting devices covering the ultraviolet to green spectral region are fabricated from these materials. Despite all efforts, the growth of large-size and high-quality AlN and GaN crystals for substrates, which are thermally and lattice-matched to the AlGaN-based device structures, is still in its infancy. This is due to the high equilibrium vapor pressure of nitrogen above these compounds, which requires growth techniques employing either the vapor phase or liquid solutions. The best commercially available GaN substrates show a high dislocation density of >105 per cm2 and strong bowing with a radius of curvature smaller than 10 m. This article reviews current growth techniques that look promising and may become commercially viable.

AlN bulk crystals of different crystallographic orientations were etched in aqueous KOH solution (general etchant) and molten KOH/NaOH eutectic alloy (defect selective etchant). In the general etchant, the aluminum polar surface (0001) was found to be stable while the nitrogen polar (0001) surface and non-polar m-plane (1010) surfaces showed significant etching. Etch patterns on nitrogen polar surfaces consisted of complete coverage of hexagonal pyramids while the m-plane surfaces were etched in a layer-by-layer mode. TEM studies revealed that the observed etch hillocks on nitrogen polar surfaces were not associated with extended structural defects. When etched in a defect-selective etchant, the aluminum polar surface showed well-defined hexagonal etch pits, with an etch pit density (EPD) of 2×104 cm−2. The nitrogen polar surfaces and m-plane surfaces showed etch features similar to the one obtained during general etching, however, the etch feature density was significantly lower. The etch mechanisms, etch kinetics, as well as the correlation between the observed etch features and structural defects in bulk crystals will be discussed.

Highly oriented diamond (HOD) films were grown at a high growth rate on (100) silicon substrates by microwave plasma chemical vapor deposition (MPCVD), following the standard bias-enhanced nucleation (BEN) process. The growth rate and diamond quality were investigated as a function of methane concentration in hydrogen (2-6%), and N2/CH4 ratio (0 to 0.12). A four-fold increase in the growth rate of HOD films and a three times faster expansion and coalescence of (100) facets was observed within the above process window. The films with the best quality were grown under an N2/CH4 ratio of 0.08 at methane concentration of 3.5%. The ratio of x-ray intensity between the first order twins and {111} poles was only 1%. A detailed study of the crystalline quality and phase purity as a function of methane concentration and nitrogen addition is presented.

We have demonstrated growth of large AlN single crystals using (0001)-oriented AlN seeds. Boules with a diameter of 15 mm and length up to 12 mm were obtained from 5 mm seeds. Step flow growth was observed on both Al and N-polar surfaces. N-polar face was suitable for growth within a large window of growth parameters while the Al-polar seeds yielded high-quality crystals only at low supersaturation.

The polarity control of GaN films grown on c-plane sapphire substrates by LP-MOVPE using N2 as carrier and diluent gas was investigated in detail. The polarity type depended on the substrate preparation prior to the high temperature (HT) GaN growth. Device-quality Ga-polar GaN was obtained by using a low temperature (LT) AlN buffer layer followed by a specific annealing process. Optimized buffer layer thickness was 10 nm, with an annealing time of 20 min and a temperature of 1050 °C. By using these conditions for the buffer layer growth, mirror-like Ga-polarity GaN was grown using a V/III ratio of 100. The full width at half maximum (FWHM) of Ga-polar GaN films was 360 arcsec for the symmetric (00.2) reflection and 640 arcsec for the skew-symmetric (30.2) reflection. The surface roughness was measured by AFM to be 0.2 nm RMS and the growth rate was estimated at 2.0 μm/hr. These results indicated that by exclusively using N2 carrier gas, one can achieve films of the same quality as those more commonly grown by using H2 carrier gas.

This paper presents a concept of growing near single crystal quality GaN films over large areas through self-oriented growth of GaN platelets on molten gallium. The experiments were performed by nitridation of Ga films on amorphous quartz substrates using nitrogen plasma at low pressures of few mTorr. XRD texture analysis of the free standing GaN flakes with areas over 25 mm2 exhibited an overall c-axis tilt of 2.2°, while showing primary reflections from (0002) and (0004) planes. Further more, the cross-sectional TEM micrographs showed that the resulting GaN films are free from dislocation crops inside the grains but showed diffraction contrast due to small misorientation between the grains. The twist and tilt angles between adjacent columnar grains were determined using convergent beam electron diffraction technique to be less than 8° and 1°, respectively. HRTEM micrographs of the grain boundaries showed sharp interfaces with both twisted and perfect attachments.

Ongoing efforts of growing large AlN single crystals at NCSU using an induction-heated, high-temperature reactor are based on (1) engineered expansion of single crystalline grains with increasing boule length, as well as (2) the development of a growth process that enables seeded growth on AlN surfaces previously exposed to air. The growth process is based on physical vapor transport (PVT), where AlN powder is sublimed in a high purity nitrogen atmosphere. The growth temperature was typically in the range of 2250 to 2300 °C. In this study, tungsten crucibles were used in combination with graphite insulation and were found to be durable for AlN growth. Boule growth was interrupted several times in order to refill the AlN powder source and the growth surface was subjected to surface preparation to facilitate epitaxial re-growth. Grain expansion was studied as a function of process parameters. Crystalline quality of large single crystalline grains was correlated with their surface morphology.

For nitride based devices such as LEDs, high power FETs and laser diodes, single crystal substrates of AlN are highly desirable. While the sublimation technique is suitable for growing bulk AlN crystals, appropriate seeds are also necessary for growing large diameter oriented boules. 4H- and 6H-SiC substrates which are readily available commercially can potentially be implemented as seeds for bulk AlN growth. However, issues regarding SiC decomposition at high temperatures, thermal expansion mismatch, single crystal growth, etc. need to be addressed. Towards this end, a series of growth experiments have been carried out in a resistively heated reactor using on and off-axis 4H- and 6H-SiC substrates as seeds for AlN growth from the vapor phase. Several hundred microns thick AlN layers have been grown under different growth conditions. Synchrotron white beam x-ray topography (SWBXT) has been used to map the defect distribution in the grown layers and high resolution triple axis x-ray diffraction (HRTXD) experiments were carried out to record reciprocal space maps from which tilt, mismatch and strain data can be obtained. These results are analyzed with respect to the growth conditions in order to gain a better understanding of this growth process.

The polarity control of GaN films grown on c-plane sapphire substrates by low pressure metal organic chemical vapor deposition (MOCVD) was achieved by using N2 as a diluent and transport gas. The type of polarity was governed by the substrate treatment prior to the GaN growth. N-face (-c) GaN films were only obtained by pre-nitridation of the sapphire substrate after a H2 anneal, while Ga-face (+c) GaN films were grown directly on the substrates or on properly annealed AlN buffer layers. In addition, GaN films on improperly annealed AlN buffer layers, that is, under- or over-annealed buffer layers, yielded films with mixed polarity. Smooth N-face GaN films with 2.5 nm RMS roughness, as determined by atomic force microscopy (AFM), were obtained with shorter nitridation times (less than 2 min). Wet chemical etching in an aqueous solution of potassium hydroxide (KOH) was used to determine the polarity type.

Growth of AlN bulk single crystals by sublimation of AlN powder was carried out in a resistively heated reactor at temperatures up to 2300°C. A variety of crucible materials, such as BN, W, Ta, Re, ZrO2, TaN, and TaC, were evaluated. Our studies have shown that the morphology of crystals grown by spontaneous nucleation strongly depends on the growth temperature and contamination in the reactor. Crucible selection had a profound effect on contamination in the crystal growth environment, thus influencing nucleation, coalescence, and crystal morphology. Spontaneously grown single crystals up to 15 mm in size were characterized by x-ray diffraction (XRD), x-ray topography (XRT), glow discharge mass spectrometry (GDMS), and secondary ion mass spectrometry (SIMS). Average dislocation densities were on the order of 103 cm−3, with extended areas virtually dislocation-free, while high-resolution XRD showed rocking curves as narrow as 7 arcsec.

Polycrystalline diamond films previously grown on silicon were polished to an RMS roughness of 15 nm and bonded to the silicon in a dedicated ultrahigh vacuum bonding chamber. Successful bonding under a uniaxial mechanical stress of 32 MPa was observed at temperatures as low as 950°C. Scanning acoustic microscopy indicated complete bonding at fusion temperatures above 1150°C. Cross-sectional transmission electron microscopy later revealed a 30 nm thick intermediate amorphous layer consisting of silicon, carbon and oxygen.

AlN single crystals were grown by two different vapor phase processes: by vaporization of metallic Al in a nitrogen atmosphere, or by sublimation of an AlN source. Growth experiments were carried out under quasi-stagnant flow conditions, with typical flow rates of 100 sccm at reactor pressures ranging from 300 to 700 Torr. Growth temperatures ranged from 1800 to 2300°C. In Al vaporization experiments, the crystal shape and fastest growth direction was found to strongly depend on the growth temperature: at relatively low temperatures (1800-1900°C) long needles were grown, temperatures around 1900-2000°C yielded twinned platelets, while c-platelets were formed at temperatures above 2100°C. These c-plates grew at a rate of 5 mm/hr in the c-plane. When using AlN as a source material, growth rates were considerably slower, however, long-term stability of the Al flux was greatly improved. Seeded growth was demonstrated under these conditions. All grown single crystals were transparent and virtually colorless. Analytical results indicated very high crystalline quality and dislocation densities lower than 104cm-3.