Preparation of a crack-free AlN template layer on sapphire substrate by hydride vapor-phase epitaxy at 1450 °C

A crack-free aluminum nitride (AlN) template layer was grown on a (0 0 0 1) sapphire substrate at 1450 °C using a thin (100 nm) protective AlN layer grown at 1065 °C by hydride vapor-phase epitaxy (HVPE). Full-width at half-maximum (FWHM) values of X-ray rocking curves (XRCs) for (0 0 0 2) and (1 0 1¯ 0) planes of the AlN layer were 378 and 580 arcsec, respectively. The formation of voids was observed at the interface between the thin protective AlN layer and the sapphire substrate due to decomposition reaction of sapphire during heating up to 1450 °C. The voids relaxed the tensile stress in the AlN layer, which resulted in the suppression of cracks.     

Investigation of void formation beneath thin AlN layers by decomposition of sapphire substrates for self-separation of thick AlN layers grown by HVPE

Void formation at the interface between thick AlN layers and (0 0 0 1) sapphire substrates was investigated to form a predefined separation point of the thick AlN layers for the preparation of freestanding AlN substrates by hydride vapor phase epitaxy (HVPE). By heating 50–200 nm thick intermediate AlN layers above 1400 °C in a gas flow containing H₂ and NH₃, voids were formed beneath the AlN layers by the decomposition reaction of sapphire with hydrogen diffusing to the interface. The volume of the sapphire decomposed at the interface increased as the temperature and time of the heat treatment was increased and as the thickness of the AlN layer decreased. Thick AlN layers subsequently grown at 1450 °C after the formation of voids beneath the intermediate AlN layer with a thickness of 100 nm or above self-separated from the sapphire substrates during post-growth cooling with the aid of voids. The 79 μm thick freestanding AlN substrate obtained using a 200 nm thick intermediate AlN layer had a flat surface with no pits, high optical transparency at wavelengths above 208.1 nm, and a dislocation density of 1.5×10⁸ cm⁻².     

Growth and characterization of c-plane AlGaN on γ-LiAlO2

This study demonstrates a pure c-plane AlGaN epilayer grown on a γ-LiAlO₂ (1 0 0) (LAO) substrate with an AlN nucleation layer grown at a relatively low temperature (LT-AlN) by metal-organic chemical vapor deposition (MOCVD). The AlGaN film forms polycrystalline film with m- and c-plane when the nucleation layer grows at a temperature ranging from 660 to 680 °C. However, a pure c-plane AlGaN film with an Al content of approximately 20% can be obtained by increasing the LT-AlN nucleation layer growth temperature to 700 °C. This is because the nuclei density of AlN increases as the growth temperature increases, and a higher nuclei density of AlN deposited on LAO substrate helps prevent the deposition of m-plane AlGaN. Therefore, high-quality and crack-free AlGaN films can be obtained with a (0 0 0 2) ω-rocking curve FWHM of 547 arcsec and surface roughness of 0.79 nm (root-mean-square) using a 700-°C-grown LT-AlN nucleation layer.     

HVPE growth of semi-polar (1 1 2¯ 2)GaN on GaN template (1 1 3)Si substrate

The hydride-vapour-phase-epitaxial (HVPE) growth of semi-polar (1 1 2¯ 2)GaN is attempted on a GaN template layer grown on a patterned (1 1 3) Si substrate. It is found that the chemical reaction between the GaN grown layer and the Si substrate during the growth is suppressed substantially by lowering the growth temperatures no higher than 900 °C. And the surface morphology is improved by decreasing the V/III ratio. It is shown that a 230-μm-thick (1 1 2¯ 2)GaN with smooth surface is obtained at a growth temperature of 870 °C with V/III of 14.     

Influence of substrate temperature on nitridation of (0 0 1) GaAs using RF-radical source

The mechanism of nitridation of (0 0 1) GaAs surface using RF-radical source was systematically studied with changing substrate temperature, nitridation time and supplying As molecular beam. It was found from atomic forth microscopy (AFM) measurements that supplying As is very important to suppress the re-evaporation of As atoms and to keep the surface smooth. Reflection high-energy electron diffraction (RHEED) measurements shows that surface lattice constant (SLC) of GaAs of 0.565 nm decreases with increasing the substrate temperature and that it finally relaxes to the value of c-GaN of 0.452 nm, at 570 °C in both [1 1 0] and [1¯ 1 0] directions without concerning with the supply of As molecular beam. But, in the medium temperature range (between 350 and 520 °C), SLC of [1 1 0] direction was smaller than that of [1¯ 1 0] direction. This suggests a relation between the surface structure and the relaxing mechanism of the lattice. The valence band discontinuity between the nitridated layer and the GaAs layer was estimated by using X-ray photoemission spectroscopy (XPS). It was between 1.7 and 2.0 eV, which coincides well with the reported value of c-GaN of 1.84 eV. This suggests that the fabricated GaN layer was in cubic structure.     

MOVPE growth of InN films using 1,1-dimethylhydrazine as a nitrogen precursor

InN films have been successfully grown on sapphire substrates by MOVPE using trimethylindium (TMIn) and 1,1-dimethylhydrazine (DMHy) with N₂ carrier. DMHy is an advantageous precursor of N as it decomposes efficiently at relatively low temperature (T₅₀=420 °C) compatible with the InN growth. The reactor is specially designed so as to avoid parasitic reaction between TMIn and DMHy occurring at room temperature. The growth feature was studied by varying growth temperature, V/III ratio, TMIn flow and reactor pressure. The InN films were obtained at 500–570 °C and 60–200 Torr with a V/III ratio optimized to 100–200. The In droplets are seen on the grown surfaces, indicating an excess supply of TMIn. It is demonstrated that the InN films grows on the sapphire substrate in a single domain with an epitaxial relationship, [1 01¯ 0]_InN//[1 1 2¯ 0]_sapphire.     

Molecular beam epitaxial growth of hexagonal boron nitride on Ni(1 1 1) substrate

We demonstrate hexagonal boron nitride (h-BN) epitaxial growth on Ni(1 1 1) substrate by molecular beam epitaxy (MBE) at 890 °C. Elemental boron evaporated by an electron-beam gun and active nitrogen generated by a radio-frequency (RF) plasma source were used as the group-III and -V sources, respectively. Reflection high-energy electron diffraction revealed a streaky (1×1) pattern, indicative of an atomically flat surface in the ongoing growth. Correspondingly, atomic force microscopy images exhibit atomically smooth surface of the resulting h-BN film. X-ray diffraction characterization confirmed the crystallinity of the epitaxial film to be h-BN, and its X-ray rocking curve has a full-width at half-maximum of 0.61°, which is the narrowest ever reported for h-BN thin film. The epitaxial alignments between the h-BN film and the Ni substrate were determined to be [0 0 0 1]_h−BN∥[1 1 1]_Ni, [1 1 2¯ 0]_h−BN∥[1¯ 1 0]_Ni, and [1 1¯ 0 0]_h−BN∥[1¯ 1¯ 2]_Ni.     

Growth characteristics of AlN on sapphire substrates by modified migration-enhanced epitaxy

We investigated the effect of growth parameters for obtaining high-quality AlN grown directly on sapphire substrates by a hybridized method, derived from simultaneous source supply and conventional migration-enhanced epitaxy. At an optimal growth temperature of 1200 °C, AlN was atomically smooth and pit-free, while below and above 1200 °C, AlN was rough and with pits, respectively. Surface morphologies also depended on the V/III ratio. Rough surfaces became atomically smooth but then pits appeared, as the V/III ratio increased. The crystallinity revealed by X-ray diffraction changed accordingly. The 600-nm-thick AlN grown under the optimal conditions showed X-ray line widths of as narrow as ∼43 and ∼250 arcsec for (0 0 0 2) and (1 0 1¯ 2) diffractions, respectively.     

Growth of epitaxial ZnO films on Si (1 1 1) substrates with Cr compound buffer layer by plasma-assisted molecular beam epitaxy

Single crystalline ZnO film was grown on (1 1 1) Si substrate through employing an oxidized CrN buffer layer by plasma-assisted molecular beam epitaxy. Single crystalline characteristics were confirmed from in-situ reflection high energy electron diffraction, X-ray pole figure measurement, and transmission electron diffraction pattern, consistently. Epitaxial relationship between ZnO film and Si substrate is determined to be (0 0 0 1)_ZnO‖(1 1 1)_Si and [1 1 2¯ 0]_ZnO‖[0 1 1]_Si. Full-width at half-maximums (FWHMs) of (0 0 0 2) and (1 0 1¯ 1) X-ray rocking curves (XRCs) were 1.379° and 3.634°, respectively, which were significantly smaller than the FWHMs (4.532° and 32.8°, respectively) of the ZnO film grown directly on Si (1 1 1) substrate without any buffer. Total dislocation density in the top region of film was estimated to be ∼5×10⁹ cm⁻². Most of dislocations have a screw type component, which is different from the general cases of ZnO films with the major threading dislocations with an edge component.     

Low-pressure HVPE growth of crack-free thick AlN on a trench-patterned AlN template

A thick AlN layer was grown on a trench-patterned AlN/sapphire template by low-presssure hydride vapor phase epitaxy (LP-HVPE). Compared with the AlN layer grown on a flat AlN/sapphire template, the AlN layer grown on the trench-patterned AlN/sapphire template had a crack-free and smooth surface. The typical full-widths at half-maximum (FWHMs) of X-ray rocking curves (XRC) for the (0 0 0 2), (1 0 1¯ 2), and (1 0 1¯ 0) diffractions of the AlN layer on the trench-patterned AlN/sapphire template were 132, 489, and 594 arcsec, respectively. In addition, atomic steps were observed on the AlN layer on the trench-patterned AlN/sapphire template, and the root-mean-square (RMS) roughness of the AlN layer was determined to be 0.602 nm by atomic force microscopy (AFM).     

Epitaxial growth of InN films on lattice-matched EuN buffer layers

Indium nitride (InN) films have been grown on lattice matched europium nitride (EuN) buffer layers by pulsed laser deposition (PLD) and their structural properties have been investigated. It has been revealed that the growth of EuN films on Al₂O₃ (0 0 0 1) substrates leads to the formation of polycrystalline EuN films, whereas epitaxial EuN (1 1 1) films grow on MgO (1 1 1) substrates at 860 °C. By using the EuN (1 1 1) films as buffer layers for InN growth, we have succeeded in the epitaxial growth of InN (0 0 0 1) films at 490 °C with an in-plane epitaxial relationship of [1 1 2¯ 0]_InN∥[1 1¯ 0]_EuN∥[1 1¯ 0]_MgO, which minimized the lattice mismatch between InN and EuN.     

Effects of temperature and carrier gas flow amount on the formation of GaN nanorods by the HVPE method

We fabricated one-dimensional GaN nanorods on AlN/Si (1 1 1) substrates at various temperatures, and carrier gas flow amount, using the hydride vapor phase epitaxy (HVPE) method. An AlN buffer layer of 50 nm thickness was deposited by RF sputtering for 25 min. Stalagmite-like GaN nanorods formed at a growth temperature of 650 °C. The diameters and lengths of GaN nanorods increase with growth time, whereas the density of nanorods decreases. And we performed the experiments by changing the carrier gas flow amount at a growth temperature of 650 °C and HCl:NH₃ flow ratio of 1:40. GaN nanorods, with an average diameter of 50 nm, were obtained at a carrier gas flow amount of 1340 sccm. The shape, structures, and optical characteristics of the nanorods were investigated by field-emission scanning electron microscopy, X-ray diffraction, and photoluminescence.     

Effect of NH3 flow rate on m-plane GaN growth on m-plane SiC by metalorganic chemical vapor deposition

This paper reports a study of the effect of NH₃ flow rate on m-plane GaN growth on m-plane SiC with an AlN buffer layer. It is found that a reduced NH₃ flow rate during m-plane GaN growth can greatly improve the recovery of in situ optical reflectance and the surface morphology, and narrow down the on-axis (1 0 1¯ 0) X-ray rocking curve (XRC) measured along the in-plane a-axis. The surface striation along the in-plane a-axis, a result of GaN island coalescence along the in-plane c-axis, strongly depends on the NH₃ flow rate, an observation consistent with our recent study of kinetic Wulff plots. The pronounced broadening of the (1 0 1¯ 0) XRC measured along the c-axis is attributed to the limited lateral coherence length of GaN domains along the c-axis, due to the presence of a high density of basal-plane stacking faults, most of which are formed at the GaN/AlN interface, according to transmission electron microscopy.     

In-situ cyclic pulse annealing of InN on AlN/Si during IR-lamp-heated MBE growth

To improve crystal quality of InN, an in-situ cyclic rapid pulse annealing during growth was carried out using infrared-lamp-heated molecular beam epitaxy. A cycle of 4 min growth of InN at 400 °C and 3 s pulse annealing at a higher temperature was repeated 15 times on AlN on Si substrate. Annealing temperatures were 550, 590, 620, and 660 °C. The back of Si was directly heated by lamp irradiation through a quartz rod. A total InN film thickness was about 200 nm. With increasing annealing temperature up to 620 °C, crystal grain size by scanning electron microscope showed a tendency to increase, while widths of X-ray diffraction rocking curve of (0 0 0 2) reflection and E₂ (high) mode peak of Raman scattering spectra decreased. A peak of In (1 0 1) appeared in X-ray diffraction by annealing higher than 590 °C, and In droplets were found on the surface by annealing at 660 °C.     

The effects of annealing on non-polar (1 1 2¯ 0) a-plane GaN films

Non-polar a-plane (1 1 2¯ 0) GaN films were grown on r-plane sapphire by metal–organic vapor phase epitaxy and were subsequently annealed for 90 min at 1070 °C. Most dislocations were partial dislocations, which terminated basal plane stacking faults. Prior to annealing, these dislocations were randomly distributed. After annealing, these dislocations moved into arrays oriented along the [0 0 0 1] direction and aligned perpendicular to the film–substrate interface throughout their length, although the total dislocation density remained unchanged. These changes were accompanied by broadening of the symmetric X-ray diffraction 1 1 2¯ 0 ω-scan widths. The mechanism of movement was identified as dislocation glide, occurring due to highly anisotropic stresses (confirmed by X-ray diffraction lattice parameter measurements) and evidenced by macroscopic slip bands observed on the sample surface. There was also an increase in the density of unintentionally n-type doped electrically conductive inclined features present at the film–substrate interface (as observed in cross-section using scanning capacitance microscopy), suggesting out-diffusion of impurities from the substrate along with prismatic stacking faults. These data suggest that annealing processes performed close to film growth temperatures can affect both the microstructure and the electrical properties of non-polar GaN films.     

MOVPE of AlN-free hexagonal GaN/cubic SiC/Si heterostructures for vertical devices

The heterostructures of GaN/SiC/Si were prepared without using AlN or AlGaN buffer layers (AlN buffers) in the metalorganic vapor phase epitaxy of GaN on SiC. GaN (0 0 0 1) with specular surface was obtained. The AlN buffers are usually used in the conventional growth of GaN on SiC due to the poor nucleation of GaN on SiC. Instead, the nucleation of GaN was controlled by varying the partial pressure of H₂ in the carrier gas, the mixture of H₂ and N₂, during the low-temperature (600 °C) growth of GaN (LT-GaN). After the LT-GaN, the high-temperature (1000 °C) growth of GaN was performed using pure H₂ as the carrier gas. The epitaxial film of cubic SiC (1 1 1) on a Si (1 1 1) substrate was used as the SiC template. Increasing the partial pressure of H₂ in the carrier gas decreased the coverage of SiC surface by LT-GaN. It is suggested that the hydrogen atoms adsorbed on the surface of SiC is preventing the nucleation of GaN.     

Improvements in a-plane GaN crystal quality by AlN/AlGaN superlattices layers

Non-polar (1 1 2¯ 0) a-plane GaN films have been grown by low-pressure metal-organic vapor deposition on r-plane (1 1¯ 0 2) sapphire substrate. We report on an approach of using AlN/AlGaN superlattices (SLs) for crystal quality improvement of a-plane GaN on r-plane sapphire. Using X-ray diffraction and atomic force microscopy measurements, we show that the insertion of AlN/AlGaN SLs improves crystal quality, reduces surface roughness effectively and eliminates triangular pits on the surface completely.     

Growth and properties of semi-polar GaN on a patterned silicon substrate

Adopting anisotropy etching method, a (1 1 1) facet of Si is obtained on a Si substrate and selective area growth (SAG) of GaN is performed with metal-organic vapor phase epitaxy on the facet. The epitaxial lateral overgrowth of (1 1¯ 0 1), (1 1 2¯ 2) GaN is investigated on (0 0 1) and (1 1 3) Si substrate, respectively, and the incorporation properties of Si, C, and Mg elements are discussed in relation to the atomic configuration on the surface. Analyzing the optical and electrical properties of C-doped (1 1¯ 0 1) GaN layer, it is shown that carbon creates a shallow acceptor level. On the thus prepared (1 1¯ 0 1) GaN layer, a light emitting diode (LED) with a C-doped p-type layer is fabricated.     

Growth of GaN films on PLD-deposited TaC substrates

GaN films were grown by metal organic chemical vapor deposition on TaC substrates that were created by pulsed laser deposition of TaC onto (0 0 0 1) SiC substrates at ∼1000 °C. This was done to determine if good quality TaC films could be grown, and if good quality GaN films could be grown on this closely lattice matched to GaN, conductive material. This was done by depositing the TaC on on-axis and 3° or 8° off-axis (0 0 0 1) SiC at temperatures ranging from 950 to 1200 °C, and examining them using X-ray diffraction, scanning electron microscopy, atomic force microscopy, and transmission electron microscopy. The GaN films were grown on as-deposited TaC films, and films annealed at 1200, 1400, or 1600 °C, and examined using the same techniques. The TaC films were polycrystalline with a slight (1 1 1) texture, and the grains were ∼200 nm in diameter. Films grown on-axis were found to be of higher quality than those grown on off-axis substrates, but the latter could be improved to a comparable quality by annealing them at 1200–1600 °C for 30 min. TaC films deposited at temperatures above 1000 °C were found to react with the SiC. GaN films could be deposited onto the TaC when the surface was nitrided with NH₃ for 3 min at 1100 °C and the low temperature buffer layer was AlN. However, the GaN did not nucleate easily on the TaC film, and the crystallites did not have the desired (0 0 0 1) preferred orientation. They were ∼10 times larger than those typically seen in films grown on SiC or sapphire. Also the etch pit concentration in the GaN films grown on the TaC was more than 2 orders of magnitude less than it was for growth on the SiC.     

Preparation of single-crystalline ZnO films on ZnO-buffered a-plane sapphire by chemical bath deposition

High-quality zinc oxide (ZnO) films were successfully grown on ZnO-buffered a-plane sapphire (Al₂O₃ (1 1 2¯ 0)) substrates by controlling temperature for lateral growth using chemical bath deposition (CBD) at a low temperature of 60 °C. X-ray diffraction analysis and transmission electron microscopy micrographs showed that the ZnO films had a single-crystalline wurtzite structure with c-axis orientation. Rocking curves (ω-scans) of the (0 0 0 2) reflections showed a narrow peak with full width at half maximum value of 0.50° for the ZnO film. A reciprocal space map indicated that the lattice parameters of the ZnO film (a=0.3250 nm and c=0.5207 nm) were very close to those of the wurtzite-type ZnO. The ZnO film on the ZnO-buffered Al₂O₃ (1 1 2¯ 0) substrate exhibited n-type conduction, with a carrier concentration of 1.9×10¹⁹ cm⁻³ and high carrier mobility of 22.6 cm² V⁻¹ s⁻¹.