Defect reduction in GaN epilayers and HFET structures grown on (0 0 0 1)sapphire by ammonia MBE

The quality of GaN epilayers grown by molecular beam epitaxy on substrates such as sapphire and silicon carbide has improved considerably over the past few years and in fact now produces AlGaN/GaN HEMT devices with characteristics among the best reported for any growth technique. However, only recently has the bulk defect density of MBE grown GaN achieved levels comparable to that obtained by MOVPE and with a comparable level of electrical performance. In this paper, we report the ammonia-MBE growth of GaN epilayers and HFET structures on (0 0 0 1)sapphire. The effect of growth temperature on the defect density of single GaN layers and the effect of an insulating carbon doped layer on the defect density of an overgrown channel layer in the HFET structures is reported. The quality of the epilayers has been studied using Hall effect and the defect density using TEM, SEM and wet etching. The growth of an insulating carbon-doped buffer layer followed by an undoped GaN channel layer results in a defect density in the channel layer of 2×10⁸ cm⁻². Mobilities close to 490 cm²/Vs at a carrier density of 8×10¹⁶ cm⁻³ for a 0.4 μm thick channel layer has been observed. Growth temperature is one of the most critical parameters for achieving this low defect density both in the bulk layers and the FET structures. Photo-chemical wet etching has been used to reveal the defect structure in these layers.     

The growth of Pd thin films on a 6H-SiC(0 0 0 1) substrate

Pd thin films, grown on Si-rich 6H-SiC(0 0 0 1) substrates, were studied by atomic force microscopy, electron diffraction and high-resolution transmission electron microscopy. It is concluded that the growth is successful only when all the growth process takes place at room temperature. Under these conditions a very good epitaxial growth of Pd is achieved, despite the large misfit (about 8.6%) between Pd and the substrate and the existence of a semi-amorphous layer between the thin film and the substrate. A large number of twins appear in these films.     

Selective area growth of GaN microstructures on patterned (1 1 1) and (0 0 1) Si substrates

Selective MOVPE growth of GaN microstructure on silicon substrates has been investigated using SiO₂ mask having circular or stripe window. In case of (0 0 1)substrate, grooves with (1 1 1) facets at the sides were made by using the etching anisotropy of a KOH solution. On the (1 1 1) facets of patterned silicon substrate (or on the as opened window region of (1 1 1) substrate), growth of wurtzite GaN was performed, of which the c-axis is oriented along the 1 1 1 axis of silicon. The photoluminescence and X-ray diffraction analysis were performed to characterize the single crystal to reveal the effect of the growth conditions of the intermediated layer and the microstructure.     

GaN/GaAs(1 0 0) superlattices grown by metalorganic vapor phase epitaxy using dimethylhydrazine precursor

Superlattices of cubic gallium nitride (GaN) and gallium arsenide (GaAs) were grown on GaAs(1 0 0) substrates using metalorganic vapor phase epitaxy (MOVPE) with dimethylhydrazine (DMHy) as nitrogen source. Structures grown at low temperatures with varying layer thicknesses were characterized using high resolution X-ray diffraction and atomic force microscopy. Several growth modes of GaAs on GaN were observed: step-edge, layer-by-layer 2D, and 3D island growth. A two-temperature growth process was found to yield good crystal quality and atomically flat surfaces. The results suggest that MOVPE-grown thin GaN layers may be applicable to novel GaAs heterostructure devices.     

Transmission electron microscopy study of an AlN nucleation layer for the growth of GaN on a 7-degree off-oriented (0 0 1) Si substrate by metalorganic vapor phase epitaxy

We have investigated the morphology of the high-temperature-grown AlN nucleation layer and its role in the early stage of GaN growth, by means of transmission electron microscopy. The nitride was selectively grown on a 7-degree off-oriented (0 0 1) patterned Si substrate by metalorganic vapor phase epitaxy. AlN was deposited on the inclined unmasked (1 1 1) facet in the form of islands. The size of the islands varied along the slope, which is attributable to the diffusion of the growth species in the vapor phase. The GaN nucleation occurred at the region where rounded AlN islands formed densely. The threading dislocations were observed to generate in the GaN nucleated region.     

High-resolution imaging of 1:1 [0 0 0 1] ordered a-plane Al0.3Ga0.7N

We report the observation of ordering in Al_0.3Ga_0.7N as part of an epitaxial lateral overgrowth (ELO) of GaN carried out using (1 1 2¯ 2) GaN templates grown by metal-organic chemical vapor deposition on m-plane sapphire. Transmission electron microscopy showed that the crystalline quality of the ELO GaN was greatly improved when the ELO SiO₂ mask was patterned along the [1 1 2¯ 0]_sapphire direction. The ELO GaN wings had an inclined columnar shape with smooth (0 0 0 1) and (1 1 2¯ 0) facets. Layers of 1:1 [0 0 0 1] ordered a-plane Al_0.3Ga_0.7N were observed on the a-plane GaN facets by high-resolution transmission electron microscopy and high-angle annular-dark-field scanning transmission electron microscopy. However, no ordering was observed for c-plane Al_0.3Ga_0.7N layers grown at the same time on the c-plane GaN facets.     

CrO2 (1 0 0) and TiO2 (1 0 0) film heteroepitaxy on a BaF2 (1 1 1)/Si (1 0 0) substrate

Multi-domained heteroepitaxial rutile-phase TiO₂ (1 0 0)-oriented films were grown on Si (1 0 0) substrates by using a 30-nm-thick BaF₂ (1 1 1) buffer layer at the TiO₂–Si interface. The 50 nm TiO₂ films were grown by electron cyclotron resonance oxygen plasma-assisted electron beam evaporation of a titanium source, and the growth temperature was varied from 300 to 600 °C. At an optimal temperature of 500 °C, X-ray diffraction measurements show that rutile phase TiO₂ films are produced. Pole figure analysis indicates that the TiO₂ layer follows the symmetry of the BaF₂ surface mesh, and consists of six (1 0 0)-oriented domains separated by 30° in-plane rotations about the TiO₂ [1 0 0] axis. The in-plane alignment between the TiO₂ and BaF₂ films is oriented as [0 0 1] TiO₂ || BaF₂ or [0 0 1] TiO₂ || BaF₂ . Rocking curve and STM analyses suggest that the TiO₂ films are more finely grained than the BaF₂ film. STM imaging also reveals that the TiO₂ surface has morphological features consistent with the BaF₂ surface mesh symmetry. One of the optimally grown TiO₂ (1 0 0) films was used to template a CrO₂ (1 0 0) film which was grown via chemical vapor deposition. Point contact Andreev reflection measurements indicate that the CrO₂ film was approximately 70% spin polarized.     

Hexagonal AlN films grown on nominal and off-axis Si(0 0 1) substrates

Nucleation and growth of wurtzite AlN layers on nominal and off-axis Si(0 0 1) substrates by plasma-assisted molecular beam epitaxy is reported. The nucleation and the growth dynamics have been studied in situ by reflection high-energy electron diffraction. For the films grown on the nominal Si(0 0 1) surface, cross-sectional transmission electron microscopy and X-ray diffraction investigations revealed a two-domain film structure (AlN¹ and AlN²) with an epitaxial orientation relationship of [0 0 0 1]_AlN || [0 0 1]_Si and AlN¹ || AlN² || [1 1 0]_Si. The epitaxial growth of single crystalline wurtzite AlN thin films has been achieved on off-axis Si(0 0 1) substrates with an epitaxial orientation relationship of [0 0 0 1]_AlN parallel to the surface normal and 0 1 1 0_AlN || [1 1 0]_Si.     

Enhanced two-dimensional growth of MOVPE InN films on sapphire (0 0 0 1) substrates

MOVPE growth of InN on sapphire substrates is compared using two different designs of horizontal reactor. The major difference between the two designs is a variation in the reactant-gas flow-spacing between the substrate and the ceiling of the quartz chamber: 33 mm for the Type A reactor and 14 mm for Type B. Compared with the Type A reactor, the Type B reactor brings about InN films with a larger grain size. This is especially true when InN is grown at 600°C using the Type B reactor, in which case the two-dimensional (2D) growth of InN is found to be extremely enhanced. An investigation of the NH₃/TMIn molar ratio dependence of the surface morphology of grown InN films using the two reactors suggests that the enhanced 2D growth is attributed to the decrease in the effective NH₃/TMIn ratio in the growth atmosphere. Even using the Type A reactor, a film with enhanced 2D growth can be obtained when the NH₃/TMIn ratio is considerably low (1.8×10⁴). The enhanced 2D growth results in a smaller XRC-FWHM (full-width at half maximum of the X-ray rocking curve) (1500 arcsec), than that for a 3D-grown film (5000 arcsec).     

Properties of ZnO films grown on (0 0 0 1) sapphire substrate using H2O and N2O as O precursors by atmospheric pressure MOCVD

In this paper, we compare the properties of ZnO thin films (0 0 0 1) sapphire substrate using diethylzinc (DEZn) as the Zn precursor and deionized water (H₂O) and nitrous oxide (N₂O) as the O precursors, respectively in the main ZnO layer growth by atmospheric pressure metal–organic chemical vapor deposition (AP-MOCVD) technique. Surface morphology studied by atomic force microscopy (AFM) showed that the N₂O-grown ZnO film had a hexagonal columnar structure with about 8 μm grain diameter and the relatively rougher surface compared to that of H₂O-grown ZnO film. The full-widths at half-maximum (FWHMs) of the (0 0 0 2) and () ω-rocking curves of the N₂O-grown ZnO film by double-crystal X-ray diffractometry (DCXRD) measurement were 260 and 350 arcsec, respectively, indicating the smaller mosaicity and lower dislocation density of the film compared to H₂O-grown ZnO film. Compared to H₂O-grown ZnO film, the free exciton A (FX_A) and its three phonon replicas could be clearly observed, the donor-bound exciton A⁰X (I₁₀):3.353 eV dominated the 10 K photoluminescence (PL) spectrum of N₂O-grown ZnO film and the hydrogen-related donor-bound exciton D⁰X (I₄):3.363 eV was disappeared. The electron mobility (80 cm²/V s) of N₂O-grown ZnO film has been significantly improved by room temperature Hall measurement compared to that of H₂O-grown ZnO film.     

Fabrication of 2D ordered arrays of cobalt silicide nanodots on (0 0 1)Si substrates

Two-dimensional (2D) periodic arrays of Co metal and Co silicide nanodots were successfully fabricated on (0 0 1)Si substrate by using the polystyrene (PS) nanosphere lithography (NSL) technique and thermal annealing. The epitaxial CoSi₂ was found to start growing in samples after annealing at 500 °C. The sizes of the Co silicide nanodots were observed to shrink with annealing temperature. From the analysis of the selected-area electron diffraction (SAED) patterns, the crystallographic relationship between the epitaxial CoSi₂ nanodots and (0 0 1)Si substrates was identified to be [0 0 1]CoSi₂//[0 0 1]Si and (2 0 0)CoSi₂//(4 0 0)Si. By combining the planview and cross-sectional TEM examination, the epitaxial CoSi₂ nanodots formed on (0 0 1)Si were found to be heavily faceted and the shape of the faceted epitaxial CoSi₂ nanodot was identified to be inverse pyramidal. The observed results present the exciting prospect that with appropriate controls, the PS NSL technique promises to offer an effective and economical patterning method for the growth of a variety of large-area periodic arrays of uniform metal and silicide nanostructures on different types of silicon substrates.     

Surface and interfacial structure of epitaxial SrTiO3 thin films on (0 0 1) Si grown by molecular beam epitaxy

Effects of relaxation of interfacial misfit strain and non-stoichiometry on surface morphology and surface and interfacial structures of epitaxial SrTiO₃ (STO) thin films on (0 0 1) Si during initial growth by molecular beam epitaxy (MBE) were investigated. In situ reflection high-energy electron diffraction (RHEED) in combination with X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray photoelectron spectrometry (XPS) and transmission electron microscopy (TEM) techniques were employed. Relaxation of the interfacial misfit strain between STO and Si as measured by in situ RHEED indicates initial growth is not pseudomorphic, and the interfacial misfit strain is relaxed during and immediately after the first monolayer (ML) deposition. The interfacial strain up to 15 ML results from thermal mismatch strain rather than lattice mismatch strain. Stoichiometry of STO affects not only surface morphology but interfacial structure. We have identified a nanoscale Sr₄Ti₃O₁₀ second phase at the STO/Si interface in a Sr-rich film.     

Investigations on the effect of InSb and InAsSb step-graded buffer layers in InAs0.5Sb0.5 epilayers grown on GaAs (0 0 1)

We report the structural and electrical properties of InAsSb epilayers grown on GaAs (0 0 1) substrates with mid-alloy composition of 0.5. InSb buffer layer and InAs_xSb_1−x step-graded (SG) buffer layer have been used to relax lattice mismatch between the epilayer and substrate. A decrease in the full-width at half-maximum (FWHM) of the epilayer is observed with increasing the thickness of the InSb buffer layer. The surface morphology of the epilayer is found to change from 3D island growth to 2D growth and the electron mobility of the sample is increased from 5.2×10³ to 1.1×10⁴ cm²/V s by increasing the thickness of the SG layers. These results suggest that high crystalline quality and electron mobility of the InAs_0.5Sb_0.5 alloy can be achieved by the growth of thick SG InAsSb buffer layer accompanied with a thick InSb buffer layer. We have confirmed the improvement in the structural and electrical properties of the InAs_0.5Sb_0.5 epilayer by quantitative analysis of the epilayer having a 2.09 μm thick InSb buffer layer and 0.6 μm thickness of each SG layers.     

The influence of the Al pre-deposition on the properties of AlN buffer layer and GaN layer grown on Si (1 1 1) substrate

The influence of Al pre-deposition on the properties of AlN buffer layer and GaN layer grown on Si (1 1 1) substrate by metalorganic chemical vapor deposition (MOCVD) has been systematically studied. Compared with the sample without Al pre-deposition, optimum Al pre-deposition time could improve the AlN buffer layer crystal quality and reduce the root mean square (RMS) roughness. Whereas, overlong Al-deposition time deteriorated the AlN crystal quality and Al-deposition patterns could be found. Cracks and melt-back etching patterns appeared in the GaN layer grown without Al pre-deposition. With suitable Al-deposition time, crack-free 2.0 μm GaN was obtained and the full-width at half-maximum (FWHM) of (0 0 2) plane measured by double crystal X-ray diffraction (DCXRD) was as low as 482 arcsec. However, overlong Al-deposition time would result in a great deal of cracks, and the crystal quality of GaN layer deteriorated. The surface of GaN layer became rough in the region where the Al-deposition patterns were formed due to overlong Al-deposition time.     

Growth of GaN based structures on Si(1 1 0) by molecular beam epitaxy

The growth of GaN based structures on Si(1 1 0) substrates by molecular beam epitaxy using ammonia as the nitrogen precursor is reported. The structural, optical and electrical properties of such structures are assessed and are quite similar to the ones obtained on Si(1 1 1) in-spite of the very different substrate surface symmetry. A threading dislocation density of 3.7×10⁹ cm⁻² is evaluated by transmission electron microscopy, which is in the low range of typical densities obtained on up to 2 μm thick GaN structures grown on Si(1 1 1). To assess the potential of such structure for device realization, AlGaN/GaN high electron mobility transistor and InGaN/GaN light emitting diode heterostructures were grown and their properties are compared with the ones obtained on Si(1 1 1).     

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.     

In situ optical monitoring of AlGaN thickness and composition during MOVPE growth of AlGaN/GaN microwave HFETs

Real-time spectral reflectometry has been implemented to monitor the MOVPE growth of AlGaN/GaN microwave HFET structures. The aim is to monitor and control the thickness and composition of the thin AlGaN layer during growth. In order to extract useful information from the in situ spectra the optical constants of AlGaN as a function of alloy composition are required at the growth temperature (1050°C). As the first step to obtaining the high temperature optical constants, a room temperature spectroscopic ellipsometry study (energy range 1.65–4.95 eV) has been carried out on thin AlGaN films of various thickness (30 and 100 nm) and aluminium content (0.15 and 0.25). The multilayer model of each sample from the ellipsometry study is used to generate a reflectance spectrum which is compared with the in situ spectral reflectometry spectrum of the same sample acquired at room temperature to verify the technique. Further work is in progress to model the bandgap and optical constants of GaN and AlGaN at growth temperature.     

Molecular beam epitaxy (MBE) growth and structural properties of GaN and AlN on 3C-SiC(0 0 1) substrates

AlN and GaN was deposited by molecular beam epitaxy (MBE) on 3C-SiC(0 0 1) substrates on low-temperature (LT) GaN and AlN buffer layers. It is shown that not only GaN but also epitaxial AlN can be stabilized in the metastable zincblende phase. The zincblende AlN is only obtained on a zincblende LT-GaN buffer layer; on the other hand, AlN crystallizes in the wurtzite phase if it is grown directly on a 3C-SiC(0 0 1) substrate or on a LT-AlN buffer layer. The structural properties of the layers and in particular the orientation relationship of the wurtzite AlN on the 3C-SiC(0 0 1) were analyzed by conventional and high-resolution transmission electron microscopy.     

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.     

Subtle interplay between polytypism and preferred growth direction alignment in GaN nanorods non-catalytically grown on Si(1 1 1) substrates by using hydride vapor phase epitaxy

GaN nanorods were grown on Si(1 1 1) substrates by using hydride vapor phase epitaxy, and the crystallographic characteristics associated with their preferred growth directions were investigated by utilizing synchrotron X-ray reciprocal space mapping in a grazing incidence geometry and scanning electron microscopy. Crystallographic analysis reveals that the nanorods containing both wurtzite and zinc blende phase tend to have narrower distribution of the preferred growth directions than those containing only wurtzite phase. This tendency is partly attributed to the subtle interplay between polytypism and the preferred growth directions of GaN nanorods.