Fabrication of freestanding m-plane GaN wafer by using the HVPE technique on an aluminum carbide buffer layer on an m-plane sapphire substrate

A freestanding m-plane GaN wafer is fabricated by using the hydride vapor-phase epitaxy (HVPE) technique on an aluminum carbide buffer layer on an m-plane sapphire substrate. X-ray pole-figure measurements show a clear m-plane orientation of the GaN surface. The full-width at half-maximum (FWHM) of GaN (1 1¯ 0 0) X-ray rocking curve (XRC) with the scattering vector along the [1 1 2¯ 0] direction is approximately 800 arcsec; this indicates good crystallinity. On the other hand, the FWHM for the case in which the scattering vector is oriented along the [0 0 0 1] direction is broad; this suggests the influence of structural defects along this direction. In fact, basal plane stacking faults (BSF) with a density of approximately 3×10⁵ cm⁻¹ is observed by transmission electron microscopy (TEM). The preparation of a 45-mm-diameter m-plane GaN wafer due to spontaneous separation of the GaN layer from the sapphire substrate is demonstrated.     

Growth of (1 0 1¯ 3¯ ) semipolar GaN on m-plane sapphire by hydride vapor phase epitaxy

The crystalline, surface, and optical properties of the (1 0 1¯ 3¯) semipolar GaN directly grown on m-plane sapphire substrates by hydride vapor phase epitaxy (HVPE) were investigated. It was found that the increase of V/III ratio led to high quality (1 0 1¯ 3¯) oriented GaN epilayers with a morphology that may have been produced by step-flow growth and with minor evidence of anisotropic crystalline structure. After etching in the mixed acids, the inclined pyramids dominated the GaN surface with a density of 2×10⁵ cm⁻², revealing the N-polarity characteristic. In the low-temperature PL spectra, weak BSF-related emission at 3.44 eV could be observed as a shoulder of donor-bound exciton lines for the epilayer at high V/III ratio, which was indicative of obvious reduction of BSFs density. In comparison with other defect related emissions, a different quenching behavior was found for the 3.29 eV emission, characterized by the temperature-dependent PL measurement.     

Assessment of defect reduction methods for nonpolar a-plane GaN grown on r-plane sapphire

This work assesses the relative effectiveness of four techniques to reduce the defect density in heteroepitaxial nonpolar a-plane GaN films grown on r-plane sapphire by metalorganic vapour phase epitaxy (MOVPE). The defect reduction techniques studied were: 3D–2D growth, SiN_x interlayers, ScN interlayers and epitaxial lateral overgrowth (ELOG). Plan-view transmission electron microscopy (TEM) showed that the GaN layer grown in a 2D fashion had a dislocation and basal-plane stacking fault (BSF) density of (1.9±0.2)×10¹¹ cm⁻² and (1.1±0.9)×10⁶ cm⁻¹, respectively. The dislocation and BSF densities were reduced by all methods compared to this 2D-grown layer (used as a seed layer for the interlayer and ELOG methods). The greatest reduction was achieved in the (0 0 0 1) wing of the ELOG sample, where the dislocation density was <1×10⁶ cm⁻² and BSF density was (2.0±0.7)×10⁴ cm⁻¹. Of the in-situ techniques, SiN_x interlayers were most effective: the interlayer with the highest surface coverage that was studied reduced the BSF density to (4.0±0.2)×10⁵ cm⁻¹ and the dislocation density was lowered by over two orders of magnitude to (3.5±0.2)×10⁸ cm⁻².     

Polar dependence of impurity incorporation and yellow luminescence in GaN films grown by metal-organic chemical vapor deposition

We have investigated the unintentional impurities, oxygen and carbon, in GaN films grown on c-plane, r-plane as well as m-plane sapphire by metal-organic chemical vapor deposition. The GaN layer was analyzed by secondary ion mass spectroscopy. The different trend of the incorporation of oxygen and carbon has been explained in the polar (0 0 0 1), nonpolar (1 1 2¯ 0) and semipolar (1 1 2¯ 2) GaN by a combination of the atom bonding structure and the origin direction of the impurities. Furthermore, it has been found that there is a stronger yellow luminescence (YL) in GaN with higher concentration of carbon, suggesting that C-involved defects are originally responsible for the YL.     

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.     

Bulk GaN crystals grown by HVPE

We succeeded in preparing very thick c-plane bulk gallium nitride (GaN) crystals grown by hydride vapor phase epitaxy. Growth of the bulk GaN crystals was performed on templates with 3 μm GaN layer grown by metal organic chemical vapor deposition on (0 0 0 1) sapphire substrates. Colorless freestanding bulk GaN crystals were obtained through self-separation processes. The crystal's diameter and thickness were about 52 and 5.8 mm, respectively. No surface pits were observed within an area of 46 mm diameter of the bulk GaN crystal. The dislocation density decreased with growth direction (from N-face side to Ga-face side) and ranged from 5.1×10⁶ cm⁻² near the N-face surface to 1.2×10⁶ cm⁻² near the Ga-face. A major impurity was Si, and other impurities (O, C, Cl, H, Fe, Ni and Cr) were near or below the detection limits by SIMS measurements.     

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.     

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.     

Droplet epitaxy of zinc-blende GaN quantum dots

Zinc-blende GaN quantum dots were grown on 3C-AlN(0 0 1) by a vapor–liquid–solid process in a molecular beam epitaxy system. We were able to control the density of the quantum dots in a range of 5×10⁸–5×10¹² cm⁻². Photoluminescence spectroscopy confirmed the optical activity of the GaN quantum dots in a range of 10¹¹–5×10¹² cm⁻². The data obtained give an insight to the condensation mechanism of the vapor–liquid–solid process in general, because the GaN quantum dots condense in metastable zinc-blende crystal structure supplied by the substrate, and not in the wurtzite crystal structure expected from free condensation in the droplet.     

Defect reduction in nonpolar and semipolar GaN using scandium nitride interlayers

Nonpolar (1 1 2¯ 0) and semipolar (1 1 2¯ 2) GaN films were grown on sapphire by metalorganic vapour phase epitaxy using ScN interlayers of varying thicknesses. A 5 nm interlayer reduced basal plane stacking fault (BSF) densities in nonpolar films by a factor of 2 and threading dislocation (TD) densities by a factor of 100 to (1.8±0.2)×10⁹ cm⁻². An 8.5 nm interlayer reduced BSF densities in semipolar films by a factor of 5 and reduced TD densities by a factor of 200 to (1.5±0.3)×10⁸ cm⁻². Nonpolar film surface roughnesses were reduced by a factor of 20.     

Compensation effect of Mg-doped a- and c-plane GaN films grown by metalorganic vapor phase epitaxy

The electrical and optical properties of Mg-doped a- and c-plane GaN films grown by metalorganic vapor phase epitaxy were systematically investigated. The photoluminescence spectra of Mg-doped a- and c-plane GaN films exhibit strong emissions related to deep donors when Mg doping concentrations are above 1×10²⁰ cm⁻³ and 5×10¹⁹ cm⁻³, respectively. The electrical properties also indicate the existence of compensating donors because the hole concentration decreases at such high Mg doping concentrations. In addition, we estimated the N_D/N_A compensation ratio of a- and c-plane GaN by variable-temperature Hall effect measurement. The obtained results indicate that the compensation effect of the Mg-doped a-plane GaN films is lower than that of the Mg-doped c-plane GaN films.     

Growth of high quality a-plane GaN epi-layer on r-plane sapphire substrates with optimization of multi-buffer layer

Nonpolar (1 1–2 0) a-plane GaN films have been grown using the multi-buffer layer technique on (1–1 0 2) r-plane sapphire substrates. In order to obtain epitaxial a-plane GaN films, optimized growth condition of the multi-buffer layer was investigated using atomic force microscopy, high resolution X-ray diffraction, and transmission electron microscopy measurements. The experimental results showed that the growth conditions of nucleation layer and three-dimensional growth layer significantly affect the crystal quality of subsequently grown a-plane GaN films. At the optimized growth conditions, omega full-width at half maximum values of (11–20) X-ray rocking curve along c- and m-axes were 430 and 530 arcsec, respectively. From the results of transmission electron microscopy, it was suggested that the high crystal quality of the a-plane GaN film can be obtained from dislocation bending and annihilation by controlling of the island growth mode.     

Structural and electrical properties of Si-doped a-plane GaN grown on r-plane sapphire by MOVPE

Approximately 2-μm-thick Si-doped a-plane GaN films with different doping concentrations were grown on approximately 8-μm-thick undoped a-plane GaN/r-sapphire by metal organic vapor phase epitaxy (MOVPE). The structural and electrical properties of the Si-doped a-plane GaN films were investigated by high-resolution X-ray diffraction (HRXRD), atomic force microscopy (AFM) and temperature-dependent Hall measurement. The results showed that a small amount of Si doping can improve the surface morphology and decrease the density of pits. Upon increasing the CH₃SiH₃ flow rate, the crystalline quality of the (0 0 0 2) plane was slightly improved. The highest room-temperature mobility of 83.4 cm²/Vs was obtained at a carrier density of 6.2×10¹⁸ with a CH₃SiH₃ flow rate of 10 sccm.     

Hydrothermal growth of ZnO nanorods on a-plane GaN/sapphire template

ZnO nanorod arrays are grown on a-plane GaN template/r-plane sapphire substrates by hydrothermal technique. Aqueous solutions of zinc nitrate hexahydrate and hexamethylenetetramine were employed as growth precursors. Electron microscopy and X-ray diffraction measurements were carried out for morphology, phase and growth orientation analysis. Single crystalline nanorods were found to have off-normal growth and showed well-defined in-plane epitaxial relationship with the GaN template. The 〈0 0 0 1〉 axis of the ZnO nanorods were observed to be parallel to the 〈1 0 1¯ 0〉 of the a-plane GaN layer. Optical property of the as-grown ZnO nanorods was analyzed by room temperature photoluminescence measurements.     

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.     

Properties of Ge-doped,high-quality bulk GaN crystals fabricated by hydride vapor phase epitaxy

We investigated the properties of Ge-doped, high-quality bulk GaN crystals with Ge concentrations up to 2.4×10¹⁹ cm⁻³. The Ge-doped crystals were fabricated by hydride vapor phase epitaxy with GeCl₄ as the dopant source. Cathodoluminescence imaging revealed no increase in the dislocation density at even the highest Ge concentration, with values as low as 3.4×10⁶ cm⁻². The carrier concentration, as determined by Hall measurement, was almost identical to the combined concentration of Ge and unintentionally incorporated Si. The electron mobilities were 260 and 146 cm² V⁻¹ s⁻¹ for n=3.3×10¹⁸ and 3.35×10¹⁹ cm⁻³, respectively; these values are markedly larger than those reported in the past for Ge-doped GaN thin films. The optical absorption coefficient was quite small below the band gap energy; it slightly increased with increase in Ge concentration. Thermal conductivity, estimated by the laser-flash method, was virtually independent of Ge concentration, maintaining an excellent value around 2.0 W cm⁻¹ K⁻¹. Thermal expansion coefficients along the a- and m-axes were approximately constant at 5.0×10⁻⁶ K⁻¹ in the measured doping concentration range.     

Reduction of dislocations in a (1 1 2¯ 2)GaN grown by selective MOVPE on (1 1 3)Si

Two-step selective epitaxy (SAG/ELO) of (1 1 2¯ 2)GaN on (1 1 3)Si substrate is studied to reduce the defect density in the epitaxial lateral overgrowth. The first SAG/ELO is to prepare a (1 1 2¯ 2)GaN template on a (1 1 3)Si and the second SAG/ELO is to get a uniform (1 1 2¯ 2)GaN. It is found that the reduction of the defect density is improved by optimizing the mask configuration in the second SAG/ELO. The minimum dark spot density obtained is 3×10⁷/cm², which is two orders of magnitude lower than that found in a (0 0 0 1)GaN grown on (1 1 1)Si.     

Investigation of nonpolar (1 1 2¯ 0) a-plane ZnO films grown under various Zn/O ratios by plasma-assisted molecular beam epitaxy

Structural and optical properties of nonpolar a-plane ZnO films grown with different II/VI ratios on r-plane sapphire substrates by plasma-assisted molecular beam epitaxy were investigated. Even by increasing the II/VI ratio across the stoichiometric flux condition a consistent surface morphology of striated stripes along the ZnO 〈0 0 0 1〉 direction without any pit formation was observed, which is contrary to polar c-plane ZnO films. Root mean square surface roughness, full width at half maximum values of X-ray rocking curves, defect densities, and photoluminescence were changed with the II/VI ratio. The sample grown with stoichiometric flux condition showed the lowest value of rms roughness, the smallest threading dislocation and stacking fault densities of ∼4.7×10⁸ cm⁻² and ∼9.5×10⁴ cm⁻¹, respectively, and the highest intensity of D^oX peak. These results imply that the stoichiometric flux growth condition is suitable to obtain superior structural and optical properties compared to other flux conditions.     

Electrical properties and deep traps spectra in undoped M-plane GaN films prepared by standard MOCVD and by selective lateral overgrowth

Electrical properties, deep traps spectra and structural performance were studied for m-GaN films grown on m-SiC substrates by standard metalorganic chemical vapor deposition (MOCVD) and by MOCVD with lateral overgrowth (ELO) or sidewall lateral overgrowth (SELO). Standard MOCVD m-GaN films with a very high dislocation density over 10⁹ cm⁻² are semi-insulating n-type with the Fermi level pinned near E_c−0.7 eV when grown at high V/III ratio. For lower V/III they become more highly conducting, with the electrical properties still dominated by a high density (∼10¹⁶ cm⁻³) of E_c−0.6 eV electron traps. Lateral overgrowth that reduces the dislocation density by several orders of magnitude results in a marked increase in the uncompensated shallow donor density (∼10¹⁵ cm⁻³) and a substantial decrease of the density of major electron traps at E_c−0.25 and E_c−0.6 eV (down to about 10¹⁴ cm⁻³). Possible explanations are briefly discussed.     

Mg doping behavior of MOVPE InxGa1−xN (x∼0.4)

The Mg doping behavior of MOVPE indium gallium nitride (InGaN), such as secondary ion mass spectrometry (SIMS) Mg profile, crystalline quality and n–p conversion of the films are described and discussed in this paper. The SIMS analysis reveals that the memory effect of Cp₂Mg as a doping source deteriorates the controllability of Mg doping level and profile, especially for thin (−0.4 μm) InGaN. The high residual donors (10¹⁹–10²⁰ cm⁻³) in InGaN with In content from 0.05 to 0.37 can be compensated by Mg doping and p-type conduction is obtained for those with In content up to 0.2. It is found that a higher Cp₂Mg flow rate is needed to get p-type conduction in InGaN with a higher In content x; for example, Cp₂Mg/(TEG+TMI)≈0.5% for x=0 (GaN), ≈2% for x=0.05 and ≈4% for x=0.2. Such a high Cp₂Mg flow rate is needed due to the high residual donor concentration (10¹⁹–10²⁰ cm⁻³) of InGaN films and the low activation efficiency of Mg. The crystalline quality of InGaN is deteriorated with increasing In content as well as Mg doping level. To achieve a p-type InGaN with a lower Mg doping, it is essential to improve the crystalline quality of non-doped InGaN. For this purpose, the use of a thicker GaN interlayer is effective.