Hexagonal boron nitride (hBN), a two dimensional (2D) material, has emerged as an important substrate and dielectric for electronic, optoelectronic, and photonic devices based on graphene and other atomically thin two dimensional materials. Here we report on the initial oxidation of (0001) hBN single crystals in ambient air as functions of temperature and time, as determined by atomic force microscopy (AFM) and scanning electron microscope with energy dispersive X-ray spectroscopy (SEM/EDS). For oxidation times of 20 minutes, the first evidence of oxidation appears at 900°C, with the formation of shallow, hexagonal-, and irregular-shaped pits that are less than 100 nm across and several nanometer deep. Oxidation at 1100°C for 20 minutes produced 1.0-2.0-micron size pits with flat and pointed bottoms that were approximately hexagonal-shaped, but with rough and irregular edges, and multiple interior steps. Oxidation was not uniform on the surface of hBN, but starts where dislocations in the crystal intersected the surfaces. Pit depth increased linearly with temperature and oxidation times. In addition to the surface pits, small particles formed on the surface. Elemental analysis of the thermally oxidized hBN crystals by SEM/EDS revealed the major elements of these particles were boron and oxygen.

Hexagonal boron nitride (hBN) crystals enriched in 10B and 11B isotopes were synthesized using a high temperature (1500° C) Ni-Cr-B reactive-precipitation growth under a N2 atmosphere. Two growth mechanisms were observed: conventional defect-facilitated bulk growth which produced crystals with a platelet-like habit with width and thickness of 20-30 μm and 5 μm, respectively, and vapor-liquid-solid interface growth of hBN whiskers with lengths and diameters as large as 70 μm and 5 μm, respectively. Similar growth mechanisms were seen for samples enriched in either isotope. Isotopic analysis via secondary-ion mass spectrometry showed boron concentrations of 84.4 at% and 93.0 at% for the majority isotopes in the 10B-rich and 11B-rich samples, respectively. Raman spectroscopy showed an increase in peak Raman shift for the 10B-rich sample, having two barely resolved peaks at 1393.5 and 1388.8 cm-1, and a decrease for the 11B-rich sample, having peak at 1359.5 cm-1 (FWHM of 9.4 cm-1), compared to that of natural hBN, with its peak at 1365.8 cm-1 (FWHM of 10.3 cm-1). Raman shift showed a linear trend with increasing 10B concentration allowing for a calibration curve to be developed to estimate 10B enrichment in hBN using non-destructive methods.

With a wide band gap of greater than 3.0 eV and the ability to self-heal from radiation damage, icosahedral boron arsenide (B12As2) is an apt candidate for use in next-generation betavoltaics. By capturing and converting high energy electrons from radioisotopes into usable electricity, “nuclear batteries” made from B12As2 could potentially power devices for decades. Compared to bulk crystals or epitaxial films, B12As2 nanowires may have lower defect densities or may even be defect-free, leading to better electrical properties and device performance. In our study, B12As2 nanowires were synthesized via vapor-liquid-solid (VLS) growth using platinum powder and nickel powder on silicon carbide and 20 nm thick nickel film on silicon substrates from 700 °C to 1200 °C. Platinum yielded the highest quality nanowires from 900 °C to 950 °C, resulting in platinum particles densely covered with wires formed by straight segments connected by sharp angular kinks. At these growth temperatures, diameters ranged from less than 30 nm to about 300 nm as determined by scanning electron microscopy and transmission electron microscopy. Growth temperatures of 850 °C or less produced curled wires 200-1000 nm in diameter. Transmission electron microscopy and selected area electron diffraction revealed excellent crystallinity in wires grown above 850 °C, while wires grown at or below 850 °C were partially amorphous. Wires grown from the 20 nm nickel film displayed similar morphologies at temperatures up to 850 °C; from 900 °C to 950 °C, straight, isolated wires were grown with diameters of 200-400 nm. Nickel powder only produced wires larger than 1 μm in diameter. The comparative quality and growth of B12As2nanowires will be discussed.

The present work reports on the defect-selective etching (DSE) for estimating dislocation densities in icosahedral boron arsenide (B12As2) crystals using molten potassium hydroxide (KOH). DSE takes advantage of the greater reactivity of high-energy sites surrounding a dislocation, compared to the surrounding dislocation-free regions. The etch pits per area are indicative of the defect densities in the crystals, as confirmed by x-ray topography (XRT). Etch pit densities were determined for icosahedral boron arsenide crystals produced from a molten nickel flux as a function of etch time (1-5 minutes) and temperature (400-700°C). The etch pits were predominately triangle shaped, and ranged in size from 5-25μm. The average etch pit density of the triangle and oval etch-pits was on the order of 5x107cm-2 and 3x106cm-2 (respectively), for crystals that were etched for two minutes at 550°C.

The crystallographic properties of bulk icosahedral boron arsenide (B12As2) crystals grown by precipitation from molten nickel solutions were characterized. Large crystals (5-8 mm) were produced by dissolving the boron in nickel at 1150°C for 48-72 hours, reacting with arsenic vapor, and slowly cooling to room temperature. The crystals varied in color from black and opaque to clear and transparent. Raman spectroscopy, x-ray topography (XRT), and defect selective etching revealed that the B12As2 single crystals were high quality with low dislocation densities. Furthermore, XRT results suggest that the major face of the plate-like crystals was (111) type, while (100), (010) and (001) type facets were also observed optically. The predominant defect in these crystals was edge character growth dislocations with a <001> Burgers vector, and <-110> line direction. In short, XRT characterization shows that solution growth is a viable method for producing good quality B12As2 crystals.

The advantages of depositing AlN–SiC alloy transition layers on SiC substrates before the seeded growth of bulk AlN crystals were examined. The presence of AlN–SiC alloy layers helped to suppress the SiC decomposition by providing vapor sources of silicon and carbon. In addition, cracks in the final AlN crystals decreased from ∼5 × 106/mm2 for those grown directly on SiC substrates to less than 1 × 106/mm2 for those grown on AlN–SiC alloy layers because of the intermediate lattice constants and thermal expansion coefficient of AlN–SiC. X-ray diffraction confirmed the formation of pure single-crystalline AlN upon both AlN–SiC alloys and SiC substrates. X-ray topography (XRT) demonstrated that strains present in the AlN crystals decreased as the AlN grew thicker. However, the XRT for AlN crystals grown directly on SiC substrates was significantly distorted with a high overall defect density compared to those grown on AlN–SiC alloys.

AlN-SiC alloy crystals, with a thickness greater than 500 µm, were grown on 4H- and 6H-SiC substrates from a mixture of AlN and SiC powders by the sublimation-recondensation method at 1860-1990 °C. On-axis SiC substrates produced a rough surface covered with hexagonal grains, while 6H- and 4H- off-axis SiC substrates with different miscut angles (8° or 3.68°) formed a relatively smooth surface with terraces and steps. The substrate misorientation ensured that the AlN-SiC alloy crystals grew two dimensionally as identified by scanning electron microscopy (SEM). X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed that the AlN-SiC alloys had the wurtzite structure. Electron probe microanalysis (EPMA) and x-ray photoelectron spectroscopy (XPS) demonstrated that the resultant alloy crystals had non-stoichiometric ratios of Al:N and Si:C and a uniform composition throughout the alloy crystal from the interface to the surface. The composition ratio of Al:Si of the alloy crystals changed with the growth temperature, and differed from the original source composition, which was consistent with the results predicted by thermodynamic calculation of the solid-vapor distribution of each element. XPS detected the bonding between Si-C, Si-N, Si-O for the Si 2p spectra. The dislocation density decreased with the growth, which was lower than 106 cm−2 at the alloy surface, more than two orders of magnitude lower compared to regions close to the crystal/substrate interface, as determined by TEM.

Producing high purity aluminum nitride crystals by the sublimation-recondensation technique is difficult due to the inherently reactive crystal growth environment, normally at temperature in excess of 2100 °C. The durability of the furnace fixture materials (crucibles, retorts, etc.) at such a high temperature remains a critical problem. In the present study, the suitability of several refractory materials for AlN crystal growth is investigated, including tantalum carbide, niobium carbide, tungsten, graphite, and hot-pressed boron nitride. The thermal and chemical properties and performance of these materials in inert gas, as well as under AlN crystal growth conditions are discussed. TaC and NbC are the most stable crucible materials with very low elemental vapor pressures in the crystal growth system. Compared with refractory material coated graphite crucibles, HPBN crucible is better for AlN self-seeded growth, as crystals tend to nucleate in thin colorless platelets with low dislocation density.

Thick (up to 1 mm) AlN-SiC alloy crystals were grown on off-axis Si-face 6H-SiC (0001) substrates by the sublimation-recondensation method from a mixture of AlN and SiC powders at 1860–1990 °C in a N2 atmosphere. The color of the crystals changed from clear to dark green with increasing growth temperature. Raman spectroscopy and x-ray diffraction (XRD) confirmed an AlN-SiC alloy was formed with the wurtzite structure and good homogeneity. Three broad peaks were detected in the Raman spectra, with one of those related to an AlN-like and another one to a SiC-like mode, both shifted relative to their usual positions in the binary compounds, and the third broad peak with possible contributions from both AlN and SiC. Scanning Auger microanalysis (SAM) and electron probe microanalysis (EPMA) demonstrated the alloy crystals had an approximate composition of (AlN)0.75(SiC)0.25 with a stoi chiometric ratio of Al:N and Si:C. The substrate mi sorientati on ensured a two-dimensional growth mode confirmed by scanning electron microscopy (SEM).

The chemical vapor deposition of icosahedral boron arsenide, B12As2, on 6H-SiC (0001) (on and off-axis) substrates was studied using hydrides as the reactants. The effects of temperature and reactant flow rates on the phases deposited and the crystal quality were determined. The growth rate increased with temperature from 1.5μm/h at 1100°C to 5 μm/h at 1400°C and decreased thereafter. X-ray diffraction revealed that the deposits were amorphous when the deposition temperature is below 1150° C. Above 1150°C, smooth B12As2 films were formed on 6H-SiC substrates with an orientation of (0001) B12As2 parallel to 6H-SiC (0001). Raman spectroscopy confirmed the strongly c-axis oriented nature of B12As2 film on 6H-SiC.

Anisotropic chemical etching is an important means for characterizing the polarity and defect density of single crystals. In this letter, we present the results of our studies on the etching of bulk AlN crystals in aqueous potassium hydroxide solution. The nitrogen polarity (0001) basal plane initially etched rapidly, while the aluminum polarity basal plane, and prismatic (100) planes were not etched. The etch rate of the nitrogen polarity basal plane eventually decreased to zero, as the surface became completely covered with hexagonal hillocks which were bounded by {101} planes. The hillock density for the self-seeded AlN crystals studied was typically in the range of 5×107cm −2 to 109cm −2. From our analysis of etched AlN crystals, we infer that freely nucleated crystals predominately have the nitrogen to aluminum direction pointing out from the nucleation surface, that is the ends of the AlN crystals facing the source are aluminum polarity.

A study of the initial stage of AIN growth on SiC substrate by the sublimation re-condensation technique was undertaken to understand the origin of crystal defects in bulk AIN crystals. When SiC was used as a seed crystal the AIN crystals did not completely coalesce, and individual grains were observed. Such crystal growth features were determined by the initial nucleation of the crystals. in this study, the nucleation of AIN on 6H-SiC(0001) was investigated by Scanning Electronic Microscopy (SEM), S-4700 Hitachi, and Electron Backscattered Diffraction (EBSD), Thermo Noran Phase ID.

At high temperatures (>1800°C) in the presence of AIN, the surface of the SiC substrate first decomposed along remnant polishing scratches[l], ultimately leaving hexagonal hillocks; simultaneously, the AIN nucleated on these SiC hillocks. Surprisingly, the AIN nuclei appeared out of alignment with the underlying SiC hillocks. By measuring several points from the SEM image (figure 1), this misorientation is in the range of 15° to 30°.

The effect of substrate preparation on the sublimation growth of AlN at about 1800 °C and 400 torr on (0001) 6H-SiC was investigated. The AlN grew in the step flow growth mode on an off-axis 6H-SiC substrate with a 6H-SiC epilayer, an island growth mode on as-received substrates, and a 2-D growth mode on substrates first coated with an AlN epitaxial layer by MOCVD. Cracks in the deposited AlN crystal due to the lattice and thermal expansion coefficient mismatches were always observed by SEM and optical microscopy.

Single crystalline platelets of aluminum nitride (AlN) were successfully grown by a new technique. It consists of (1) depositing an AlN buffer layer on a SiC substrate by metal organic chemical vapor deposition (MOCVD) below 1100°C, (2) forming an (AlN)x(SiC)1−x alloy film on the AlN film by condensing vapors sublimated at a temperature of 1800°C from a source mixture of AlN-SiC powders, followed by (3) condensing vapors sublimated from a pure AlN source (at 1800°C). The necessity of the first two steps for the successful AlN sublimation growth on SiC substrate was illustrated by the initial nucleation studies of alloys on SiC substrates with and without MOCVD AlN buffer layers: an AlN MOCVD buffer layer leads to continuous, single grain growth mode; The (AlN)x(SiC)1−x alloy film reduces the crack density because its thermal expansion coefficient is intermediate between SiC and AlN. X-ray diffraction (XRD) and Raman spectroscopy studies indicated the high quality of the AlN single crystal.

We report on the Raman analysis of the phonon lifetimes and phonon decay channels of the A1(LO), E1(LO) and E2(high) phonons of single crystalline bulk AlN grown by the sublimationrecondensation method. The temperature dependence of the phonon lifetimes was investigated from 10K to 1275K. Our experimental results show that amongst the various possible decay channels, the A1(LO) phonons of AlN decay primarily into two phonons of equal energy (Klemens model), most likely longitudinal-acoustic (LA) phonons. AlN is therefore in great contrast to GaN, where a symmetric decay of the A1(LO) phonons is not possible due to a large energy gap between the acoustic and optical phonon branches. For the E2(high) phonon, we find an asymmetric phonon decay into a high-energy and a low-energy phonon. Possible decay channels of the E2(high) phonon include combinations of E2(low) and acoustic phonons. For the E1(LO) phonons, the temperature dependence of the phonon lifetime is consistent with a symmetric phonon decay. Phonon lifetimes of the A1(LO), the E1(LO) and the E2(high) phonon of 0.75ps, 1.2ps and 2.9ps, respectively, were measured at 10K.

The morphology and composition of AlN crystals on 6H-SiC (0001) at the initial stage of crystal growth by sublimation re-condensation technique were investigated by SEM and SAM. Discontinuous AlN coverage occurred after 15 minutes growth. The AlN nuclei size, and growth rate increased as temperature increased or pressure decreased. The SiC substrate decomposed leaving hexagonal hillocks; simultaneously, the AlN nucleated on these SiC hillocks apparently rotated by 15° to 30°. The chemical composition of the substrate and different AlN crystal facets were characterized by SAM. The bare substrate area was stoichiometric SiC with insignificant conversion to silicon nitride, while Si and C preferentially incorporated in the AlN at the initial stages of growth on specific crystal planes.

Analysis of the phase behavior, structure, and composition of aluminum nitride thin films with up to 22% boron prepared by ion-beam assisted deposition is presented. the c-lattice constant of the film decreased with increasing boron content as expected from the formation of an aIN - wurtzite BN alloy. there was no evidence for separate boron nitride precipitation from either X-ray diffraction or FTIR. IN contrast, auger electron spectroscopy of the boron present in the films suggested that two types of boron bonding was present.