MOCVD growth of GaN on Si(1 1 1) substrates using an ALD-grown Al2O3 interlayer

GaN thin films have been grown on Si(1 1 1) substrates using an atomic layer deposition (ALD)-grown Al₂O₃ interlayer. This thin Al₂O₃ layer reduces strain in the subsequent GaN layer, leading to lower defect densities and improved material quality compared to GaN thin films grown by the same process on bare Si. XRD ω-scans showed a full width at half maximum (FWHM) of 549 arcsec for GaN grown on bare Si and a FWHM as low as 378 arcsec for GaN grown on Si using the ALD-grown Al₂O₃ interlayer. Raman spectroscopy was used to study the strain in these films in more detail, with the shift of the E₂(high) mode showing a clear dependence of strain on Al₂O₃ interlayer thickness. This dependence of strain on Al₂O₃ thickness was also observed via the redshift of the near bandedge emission in room temperature photoluminescence (RT-PL) spectroscopy. The reduction in strain results in a significant reduction in both crack density and screw dislocation density compared to similar films grown on bare Si. Screw dislocation density of the films grown on Al₂O₃/Si substrates approaches that of typical GaN layers on sapphire. This work shows great promise for the use of oxide interlayers for growth of GaN-based LEDs on Si.     

Microstructural characteristics and crystallographic evolutions of Ga-doped ZnO films grown on sapphire substrates at high temperatures by RF magnetron sputtering

The microstructural characteristics and crystallographic evolutions of Ga-doped ZnO (GZO) films grown at high temperatures were examined by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The GZO films with various film thicknesses were grown on (0 0 0 1) Al₂O₃ substrates at 750 °C by RF magnetron sputtering using a 2 wt% Ga-doped ZnO single target. The (0 0 0 2) ZnO peaks in the XRD patterns shifted to a higher angle with increasing film thickness and an additional (1 0 1¯ 1) ZnO peak was observed in the final stage of film growth. HRTEM showed the epitaxial growth of GZO films in the initial growth stage and the formation of surface protrusions in the intermediate stage due to elastic relaxation. The surface protrusions consisted of {1 0 1¯ 1}, {1 0 1¯ 3}, and {0 0 0 2} planes. After the surface protrusions had formed, a GZO film with many c-axis tilted grains formed due to plastic relaxation, where the tilted grain boundaries had an angle of 62° to the substrate. The formation of the protrusions and c-axis tilted grains was closely related to the strain status of the film induced by Ga incorporation, high-temperature growth and a high film thickness.     

The effect of annealing on the surface morphology of strained and unstrained InxAl1−xN thin films

In_xAl_1−xN is a particularly useful group-III nitride alloy because by adjusting its composition it can be lattice matched to GaN. Such lattice-matched layers may find application in distributed Bragg reflectors (DBRs) and high electron mobility transistors (HEMTs). However, compared with other semiconducting nitride alloys, In_xAl_1-xN has not been researched extensively. In this study, thin In_xAl_1−xN epilayers were grown by metal-organic vapour phase epitaxy (MOVPE) on GaN and Al_yGa_1−yN layers. Samples were subjected to annealing at their growth temperature of 790 °C for varying lengths of time, or alternatively to a temperature ramp to 1000 °C. Their subsequent surface morphologies were analysed by atomic force microscopy (AFM). For both unstrained In_xAl_1−xN epilayers grown on GaN and compressively strained epilayers grown on Al_yGa_1−yN, surface features and fissures were seen to develop as a consequence of thermal treatment, resulting in surface roughening. It is possible that these features are caused by the loss of In-rich material formed on spinodal decomposition. Additionally, trends seen in the strained In_xAl_1−xN layers may suggest that the presence of biaxial strain stabilises the alloy by suppressing the spinode and shifting it to higher indium compositions.     

Hydride-assisted growth of GaN nanowires on Au/Si(0 0 1) via the reaction of Ga with NH3 and H2

High quality, straight GaN nanowires (NWs) with diameters of 50 nm and lengths up to 3 μm have been grown on Si(0 0 1) using Au as a catalyst and the direct reaction of Ga with NH₃ and N₂:H₂ at 900 °C. These exhibited intense, near band edge photoluminescence at 3.42 eV in comparison to GaN NWs with non-uniform diameters obtained under a flow of Ar:NH₃, which showed much weaker band edge emission due to strong non-radiative recombination. A significantly higher yield of β-Ga₂O₃ NWs with diameters of ≤50 nm and lengths up to 10 μm were obtained, however, via the reaction of Ga with residual O₂ under a flow of Ar alone. The growth of GaN NWs depends critically on the temperature, pressure and flows in decreasing order of importance but also the availability of reactive species of Ga and N. A growth mechanism is proposed whereby H₂ dissociates on the Au nanoparticles and reacts with Ga giving Ga_xH_y thereby promoting one-dimensional (1D) growth via its reaction with dissociated NH₃ near or at the top of the GaN NWs while suppressing at the same time the formation of an underlying amorphous layer. The higher yield and longer β-Ga₂O₃ NWs grow by the vapor liquid solid mechanism that occurs much more efficiently than nitridation.     

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.     

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.     

Epitaxial lateral overgrowth on (2 1¯ 1¯ 0) a-plane GaN with [0 1¯ 1 1]-oriented stripes

Epitaxial lateral overgrowth was applied to a-plane GaN on r-plane sapphire using SiO₂ stripe masks oriented parallel to [0 1¯ 1 1]. Coalescence and defect distribution was studied using scanning electron microscopy and cathodoluminescence. Defects, i.e., threading dislocations and basal plane stacking faults from the template propagate into the overgrown layer through the mask openings. Stacking faults spread into the whole overgrown layer, whereas threading dislocations are laterally confined in the region above the mask where a part of them is terminated at the inclined coalescence boundary. Lateral overgrowth and dislocation termination at the coalescence boundary leads to an improvement in luminescence intensity and crystal quality, in comparison to the template. The measured XRD rocking curve FWHM were 453″ with incidence along the [0 0 0 1] c-direction and 280″ with incidence along the [0 1 1¯ 0] m-direction.     

Morphology transition of one-dimensional ZnO grown by metal organic vapour phase epitaxy on (0 0 0 1)-ZnO substrate

Metal organic vapour phase epitaxy (MOVPE) has been used to successfully grow one-dimensional (1D) ZnO deposits on (0 0 0 1)-ZnO substrate. Dimethylzinc–triethylamine and nitrous oxide were used as zinc and oxygen sources, respectively, with nitrogen as the carrier gas. Vertically aligned 1D ZnO structures were observed along the c-axis by using lower VI/II mole ratio R_VI/II<2025 and/or high growth temperatures (Tg>800 °C). The diameter, length, density and the mechanism of formation could be controlled with the growth time. Scanning electron microscopy (SEM) shows different structures, i.e., sharp-top, flat-top and open-top with slim bottom and large-top one-dimensional ZnO. A good structural quality was revealed by X-ray diffraction rocking curve with a full-width at half-maximum (FWHM) varying from 40 to 92 arcsec with increasing growth time.     

Low-temperature/high-temperature AlN superlattice buffer layers for high-quality AlxGa1−xN on Si (1 1 1)

We present MOVPE-grown, high-quality Al_xGa_1−x N layers with Al content up to x=0.65 on Si (1 1 1) substrates. Crack-free layers with smooth surface and low defect density are obtained with optimized AlN-based seeding and buffer layers. High-temperature AlN seeding layers and (low temperature (LT)/high temperature (HT)) AlN-based superlattices (SLs) as buffer layers are efficient in reducing the dislocation density and in-plane residual strain. The crystalline quality of Al_xGa_1−xN was characterized by high-resolution X-ray diffraction (XRD). With optimized AlN-based seeding and SL buffer layers, best ω-FWHMs of the (0 0 0 2) reflection of 540 and 1400 arcsec for the (1 0 1¯ 0) reflection were achieved for a ∼1-μm-thick Al_0.1Ga_0.9N layer and 1010 and 1560 arcsec for the (0 0 0 2) and (1 0 1¯ 0) reflection of a ∼500-nm-thick Al_0.65Ga_0.35N layer. AFM and FE-SEM measurements were used to study the surface morphology and TEM cross-section measurements to determine the dislocation behaviour. With a high crystalline quality and good optical properties, Al_xGa_1−x N layers can be applied to grow electronic and optoelectronic device structures on silicon substrates in further investigations.     

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.     

N-type doping of GaN/Si(1 1 1) using Al0.2Ga0.8N/ALN composite buffer layer and Al0.2Ga0.8N/GaN superlattice

The characteristics of Si-doped and undoped GaN/Si(1 1 1) heteroepitaxy with composite buffer layer (CBL) and superlattice are compared and discussed. While as-grown Si-doped GaN/Si(1 1 1) heteroepitaxy shows lower quality compared to undoped GaN, crack-free n-type and undoped GaN with the thickness of 1200 nm were obtained by metalorganic chemical vapor deposition (MOCVD). In order to achieve the crack-free GaN on Si(1 1 1), we have introduced the scheme of multiple buffer layers; composite buffer layer of Al_0.2Ga_0.8N/AlN and superlattice of Al_0.2Ga_0.8N/GaN on 2-in. Si(1 1 1) substrate, simultaneously. The FWHM values of the double-crystal X-ray diffractometry (DCXRD) rocking curves were 823 arcsec and 745 arcsec for n-GaN and undoped GaN/Si(1 1 1) heteroepitaxy, respectively. The average dislocation density on GaN surface was measured as 3.85×10⁹ and 1.32×10⁹ cm⁻² for n-GaN and undoped GaN epitaxy by 2-D images of atomic force microscopy (AFM). Point analysis of photoluminescence (PL) spectra was performed for evaluating the optical properties of the GaN epitaxy. We also implemented PL mapping, which showed the distribution of edge emission peaks onto the 2 inch whole Si(1 1 1) wafers. The average FWHMs of the band edge emission peak was 367.1 and 367.0 nm related with 3.377 and 3.378 eV, respectively, using 325 nm He-Cd laser as an excitation source under room temperature.     

Optical properties of MOVPE-grown a-plane GaN and AlGaN

a-Plane GaN and AlGaN were grown on r-plane sapphire by low-pressure metal-organic vapor epitaxy (LP-MOVPE), and the effects of reactor pressure (from 40 to 500 Torr) and growth temperature (from 1020 to 1100 °C) on the crystalline quality and surface morphology of a-plane GaN were studied. The a-plane GaN grown under 40 Torr had a smooth-surface morphology but a poor crystalline quality; however, the a-plane GaN grown under 500 Torr had higher crystalline quality and optical properties, whose full-width at half-maximum of the X-ray rocking curve (XRC-FWHM) and intensity of yellow luminescence (YL) were smaller. Furthermore, the optical properties of a-plane GaN were investigated by photoluminescence (PL) in detail. We also studied the emission properties of a-plane Al_0.35Ga_0.65N grown at room temperature.     

Ternary system Li2O–K2O–Nb2O5: Re-examination of the 30 mol% K2O isopleth and growth of fully stoichiometric potassium lithium niobate single crystals by the micro-pulling down technique

Potassium lithium niobate (KLN) single crystals have attractive properties for non-linear optical applications based on frequency conversion of laser diodes in the blue range. Especially, fully stoichiometric K₃Li₂Nb₅O₁₅ crystals would be capable of doubling a laser light in the near UV range. Using powder X-ray diffraction and DSC experiments, we have re-investigated the 30 mol% K₂O isopleth of the ternary system Li₂O–K₂O–Nb₂O₅ in order to explore the possibility of a limited existence field for this phase. From our results, it was shown that the stoichiometric KLN phase exists between 970 and 1040 °C, temperature at which it undergoes a non-congruent melting. From this conclusion, compositionally homogeneous a-axis oriented single crystals fibers of stoichiometric K₃Li₂Nb₅O₁₅ were successfully grown by the micro-pulling down technique with pulling rates in the range 0.3–0.7 mm min⁻¹. The crystal length was between 10 and 120 mm for an apparent diameter near 500 μm. The fibers, characterized by optical microscopy, X-ray diffraction and Raman spectroscopy, appeared free of macro-defects and of good quality and their stoichiometric composition was also confirmed.     

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.     

Growth of thick GaInN on grooved (1 0 1¯ 1¯) GaN/(1 0 1¯ 2¯) 4H-SiC

We succeeded in growing high-crystalline-quality thick (1 0 1¯ 1¯) Ga_0.92In_0.08N films on a grooved (1 0 1¯ 1¯) GaN/(1 0 1¯ 2¯) 4H-SiC underlying layer. We also fabricated GaInN/GaN multiple quantum wells (MQWs) with a peak wavelength of 580 nm on a high-crystalline-quality thick GaInN film. The photoluminescence intensity of the MQWs is about six times higher than that of MQWs grown on planar GaN and twice as high as that of MQWs grown on a GaN underlying layer having the same grooved structure.     

Epitaxial growth of tin oxide film on TiO2(1 1 0) using molecular beam epitaxy

Growth of tin oxide thin films using molecular beam epitaxy in a pyrolyzed nitrogen dioxide atmosphere on a titanium dioxide (1 1 0) substrate was investigated using X-ray photoelectron spectroscopy (XPS), electron diffraction, and atomic force microscopy (AFM). Properties of deposited films were studied for their dependence on substrate temperature and oxidation gas pressure. Analyses using XPS data revealed that tin atoms were fully oxidized to Sn⁴⁺ and SnO₂ films were grown epitaxially in deposition conditions of substrate temperatures of 627 K or higher and NO₂ pressure greater than 3×10⁻³ Pa. At a substrate temperature of 773 K, a smooth surface with atomic steps was visible in the SnO₂ films, but above or below this temperature, fine grains with crystal facets or porous structures appeared. At pressures of 8×10⁻⁴ to 3×10⁻⁴ Pa, the randomly oriented SnO phase was dominantly grown. Further decreasing the pressure, the Sn metal phase, which was epitaxially crystallized at less than 500 K, was also grown.     

Relaxation and recovery processes of AlxGa1−xN grown on AlN underlying layer

The processes as in title of relaxation of the lattice mismatch and the recovery of crystalline quality in thick Al_xGa_1−xN on high-temperature-grown AlN were investigated. When x=0.3, rapid lattice relaxation occurred over a few microns, then the crystalline quality gradually recovered over 10 μm. In contrast, when x=0.7, relaxation of the lattice mismatch gradually occurred over 5 μm.     

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.     

Defects and stresses in MBE-grown GaN and Al0.3Ga0.7N layers doped by silicon using silane

The electric and structural characteristics of silicon-doped GaN and Al_0.3Ga_0.7N layers grown by molecular beam epitaxy (MBE) using silane have been analyzed by the Hall effect, Raman spectroscopy, and high-resolution X-ray diffractometry. It is established that the electron concentration linearly increases up to n = 4 × 10²⁰ cm^?3 with an increase in the silane flow rate for GaN:Si, whereas the corresponding dependence for Al_0.3Ga_0.7N:Si is sublinear and the maximum electron concentration is found to be n = 4 × 10¹⁹ cm^?3. X-ray measurements of sample macrobending indicate a decrease in biaxial compressive stress with an increase in the electron concentration in both GaN:Si and Al_0.3Ga_0.7N:Si layers. The parameters of the dislocation structure, estimated from the measured broadenings of X-ray reflections, are analyzed.