Microstructure and enhanced morphology of planar nonpolar m-plane GaN grown by hydride vapor phase epitaxy

Nonpolar ( ) m-plane gallium nitride has been grown heteroepitaxially on (100) γ-LiAlO₂ by several groups. Previous attempts to grow m-plane GaN by hydride vapor phase epitaxy (HVPE) yielded films unsuitable for subsequent device regrowth because of the high densities of faceted voids intersecting the films’ free surfaces. We report here on the growth of planar m-plane GaN films on (100) γ-LiAlO₂ and elimination of bulk and surface defects. The morphology achieved is smooth enough to allow for fabrication of m-plane GaN templates and free-standing substrates for nonpolar device regrowth. The GaN films were grown in a horizontal HVPE reactor at 860–890°C. Growth rates ranged from 30 μm/h to 240 μm/h, yielding free-standing films up to 250-μm thickness. The m-plane GaN films were optically specular and mirror-like, with undulations having 50–200-nm peak-to-valley heights over millimeter length scales. Atomic force microscopy revealed a striated surface morphology, similar to that observed in m-plane GaN films grown by molecular beam epitaxy (MBE). Root-mean-square (RMS) roughness was 0.636 nm over 25-μm² areas. Transmission electron microscopy (TEM) was performed on the m-plane GaN films to quantify microstructural defect densities. Basal-plane stacking faults of 1×10⁵ cm⁻¹ were observed, while 4×10⁹ cm⁻² threading dislocations were observed in the g=0002 diffraction condition.     

Surface etching of 6H-SiC (0001) and surface morphology of the subsequently grown GaN via MOCVD

The correlation between surface morphological properties of the GaN epilayers and the surface conditions of 6H-SiC (0001) substrates etched in H₂, C₂H₄/H₂, and HCl/H₂ was studied. Etching 6H-SiC in H₂ produced a high quality surface with steps and terraces, while etching in HCl/H₂ produced either a rough surface with many pits and hillocks or a smooth surface similar to that etched in H₂, depending on the HCl concentration and temperature. The GaN epilayers were subsequently deposited on these etched substrates using either a low temperature GaN or a high temperature AlN buffer layer via MOCVD. The substrate surface defects increased the density and size of the “giant” pinholes (2–4 μm) on GaN epilayers grown on a LT-GaN buffer layer. Small pinholes (<100 nm) were frequently observed on the samples grown on a HT-AlN buffer layer, and their density decreased with the improved surface quality. The non-uniform GaN nucleation caused by substrate surface defects and the slow growth rate of planes of the islands were responsible for the formation of “giant” pinholes, while the small pinholes were believed to be caused by misfit dislocations.     

Maskless pendeo-epitaxial growth of GaN films

High-resolution x-ray diffraction (XRD) and atomic force microscopy (AFM) of pendeo-epitaxial (PE) GaN films confirmed transmission electron microscopy (TEM) results regarding the reduction in dislocations in the wings. Wing tilt ≤0.15° was due to tensile stresses in the stripes induced by thermal expansion mismatch between the GaN and the SiC substrate. A strong D°X peak at ≈3.466 eV (full-width half-maximum (FWHM) ≤300 μeV) was measured in the wing material. Films grown at 1020°C exhibited similar vertical [0001] and lateral [11 0] growth rates. Increasing the temperature increased the latter due to the higher thermal stability of the GaN(11 0). The (11 0) surface was atomically smooth under all growth conditions with a root mean square (RMS)=0.17 nm.     

Pendeo-epitaxial growth of gallium nitride on silicon substrates

Pendeo-epitaxy (PE)¹ from raised, [0001] oriented GaN stripes covered with silicon nitride masks has been employed for the growth of coalesced films of GaN(0001) with markedly reduced densities of line and planar defects on Si(111)-based substrates. Each substrate contained previously deposited 3C-SiC(111) and AlN(0001) transition layers and a GaN seed layer from which the stripes were etched. The 3C-SiC transition layer eliminated chemical reactions between the Si and the NH₃ and the Ga metal from the decomposition of triethylgallium. The 3C-SiC and the GaN seed layers, each 0.5 μm thick, were also used to minimize the cracking and warping of the GaN/SiC/silicon assembly caused primarily by the stresses generated on cooling due to the mismatches in the coefficients of thermal expansion. Tilting in the coalesced GaN epilayers of 0.2° was confined to areas of lateral overgrowth over the masks; no tilting was observed in the material suspended above the trenches. The strong, low-temperature PL band-edge peak at 3.456 eV with a FWHM of 17 meV was comparable to that observed in PE GaN films grown on AlN/6H-SiC(0001) substrates.     

Analysis of reactor geometry and diluent gas flow effects on the metalorganic vapor phase epitaxy of AIN and GaN thin films on α(6H)-SiC substrates

The influence of diluent gas on the metalorganic vapor phase epitaxy of AlN and GaN thin films has been investigated. A computational fluid dynamics model using the finite element method was employed to improve film uniformity and to analyze transport phenomena. The properties of AlN and GaN thin films grown on α(6H)-SiC(0001) substrates in H₂ and N₂ diluent gas environments were evaluated. Thin films of AlN grown in H₂ and N₂ had root mean square (rms) roughness values of 1.5 and 1.8 nm, respectively. The surface and defect microstructures of the GaN thin films, observed by scanning and transmission electron microscopy, respectively, were very similar for both diluents. Low temperature (12K) photoluminescence measurements of GaN films grown in N₂ had peak intensities and full widths at half maximum equal to or better than those films grown in H₂. A room temperature Hall mobility of 275 cm²/V·s was measured on 1 μm thick, Si-doped, n-type (1×10¹⁷ cm⁻³) GaN films grown in N₂. Acceptor-type behavior of Mg-doped GaN films deposited in N₂ was repeatably obtained without post-growth annealing, in contrast to similar films grown in H₂. The GaN growth rates were ∼30% higher when H₂ was used as the diluent. The measured differences in the growth rates of AlN and GaN films in H₂ and N₂ was attributed to the different transport properties of these mixtures, and agreed well with the computer model predictions. Nitrogen is shown to be a feasible alternative diluent to hydrogen for the growth of AlN and GaN thin films.     

Electronic transport through GaN/AlN single barriers: Effect of polarisation and dislocations

In this work, we study electronic and conduction properties of a single AlN barrier (thickness from 0.5 to 5 nm) embedded in GaN. The electronic structure was simulated using a self-consistent Schrödinger-Poisson solver, and verified by photoluminescence (PL) measurements. For 0.5- and 1-nm-thick barriers, we can identify the PL line related to recombination from the first electron confined level at the bottom interface of the barrier to the first hole confined level at the top interface. The PL evolution with bias reveals that most of the applied voltage drops in the depleted cap layer. Carrier transport was studied using conductive atomic force microscopy (C-AFM). Reference GaN layers display a rectifying behaviour between the C-AFM tip and the GaN surface. In samples with a barrier thickness from 1 to 3 nm, blockage by the barrier results in negligible current under direct bias, except for hot spots at dislocations (density ∼1×10⁷ cm⁻²). Finally, in samples with 5-nm-thick AlN barriers, a high-current density appears at reverse bias, which assigned to defects induced by AlN relaxation, as verified by transmission electron microscopy.     

Thermal oxidation of polycrystalline and single crystalline aluminum nitride wafers

Two types of aluminum nitride (AlN) samples were oxidized in flowing oxygen between 900°C and 1150°C for up to 6 h—highly (0001) textured polycrystalline AlN wafers and low defect density AlN single crystals. The N-face consistently oxidized at a faster rate than the Al-face. At 900°C and 1000°C after 6 h, the oxide was 15% thicker on the N-face than on the Al-face of polycrystalline AlN. At 1100°C and 1150°C, the oxide was only 5% thicker on the N-face, as the rate-limiting step changed from kinetically-controlled to diffusion-controlled with the oxide thickness. A linear parabolic model was established for the thermal oxidation of polycrystalline AlN on both the Al- and N-face. Transmission electron microscopy (TEM) confirmed the formation of a thicker crystalline oxide film on the N-face than on the Al-face, and established the crystallographic relationship between the oxide film and substrate. The oxidation of high-quality AlN single crystals resulted in a more uniform colored oxide layer compared to polycrystalline AlN. The aluminum oxide layer was crystalline with a rough AlN/oxide interface. The orientation relationship between AlN and Al₂O₃ was (0001) AlN//( ) Al₂O₃ and ( ) AlN//( ) Al₂O₃.     

Maskless Lateral Epitaxial Growth of Gallium Nitride Using Dimethylhydrazine as a Nitrogen Precursor

Lateral epitaxial growth (LEG) is a key technology to improve the lifetime of III-V nitride-based laser diodes (LDs) by reducing the dislocation density in the materials. To increase the area of low dislocation density, the lateral growth rate needs to be increased. In addition, suppression of the vertical growth is strongly desired to avoid unnecessarily thick growth, which would result in cracks in the epitaxial film. This paper reports the maskless LEG of GaN with extremely high lateral-to-vertical growth rate ratio using dimethylhydrazine as a nitrogen precursor. The lateral growth only occurs from the sidewalls of the etched mesa stripes without any dielectric masks. The lateral growth rate toward the direction is extremely high, as high as 10 μm/h, while no vertical growth is observed on the top of unmasked mesa. The cross-sectional transmission electron microscopic image shows that the threading dislocations in the wing region extend only toward the lateral direction. Note that almost smooth coalescence between the wing regions is confirmed by atomic force microscopy. X-ray diffraction measurements reveal that this maskless LEG drastically improves the crystallographic twist down to 97 arc-s, which is as comparably low as that of a free-standing GaN substrate. The presented maskless LEG is advantageous for optical device applications.     

PAMBE growth of (1 1 2¯ 2)-oriented GaN/AlN nanostructures on m-sapphire

We report on the plasma-assisted molecular-beam epitaxial growth of (1 1 2¯ 2)-oriented GaN/AlN nanostructures on (1 1¯ 0 0) m-plane sapphire. Moderate N-rich conditions enable to synthesize AlN(1 1  2) directly on m-sapphire, with in-plane epitaxial relationships [1 1 2¯ 3¯]_AlN∥[0 0 0 1]_sapphire and [1  0 0]_AlN∥[1 1 2¯ 0]_sapphire. In the case of GaN, a Ga-excess of one monolayer is necessary to achieve two-dimensional growth of GaN(1 1 2¯ 2). Applying these growth conditions, we demonstrate the synthesis of (1 1 2¯ 2)-oriented GaN/AlN quantum well structures, showing a strong reduction of the internal electric field. By interrupting the growth under vacuum after the deposition of few monolayers of GaN under slightly Ga-rich conditions, we also demonstrate the feasibility of quantum dot structures with this orientation.     

Comparative Study on MOCVD Growth of a-Plane GaN Films on r-Plane Sapphire Substrates Using GaN, AlGaN, and AlN Buffer Layers

In this work, we have comparatively investigated the effects of the GaN, AlGaN, and AlN low-temperature buffer layers (BL) on the crystal quality of a-plane GaN thin films grown on r-plane sapphire substrates. Scanning electron microscopy images of the a-plane GaN epilayers show that using an AlGaN BL can significantly reduce the density of surface pits. The full-width at half-maximum values of the x-ray rocking curve (XRC) are 0.19°, 0.36°, and 0.48° for the films grown using Al_0.15Ga_0.85N, GaN, and AlN BLs, respectively, indicating that an AlGaN BL can effectively reduce the mosaicity of the films. Room-temperature photoluminescence shows that the AlGaN BL results in lower impurity incorporation in the subsequent a-plane GaN films, as compared with the case of GaN and AlN BLs. The higher crystal quality of a-plane GaN films produced by the Al_0.15Ga_0.85N BL could be due to improvement of BL quality by reducing the lattice mismatch between the BL and r-sapphire substrates, while still keeping the lattice mismatch between the BL and epitaxial a-plane GaN films relatively small.     

Optical properties of thick-film GaN grown by hydride vapor phase epitaxy on MgAl2O4 substrate

A hydride vapor phase epitaxy was employed to grow the 10∼240 μm thick GaN films on a (111) MgAl₂O₄ substrate. The GaN films on a MgAl₂O₄ substrate revealed characteristics of photoluminescence (PL) in impurity doped GaN, which may be due to the out-diffusion and auto-doping of Mg from the MgAl₂O₄ substrate during GaN growth. The PL peak energy of neutral donor bound exciton emission and the frequency of Raman E₂ mode were decreased by increasing the GaN thickness, due to the residual strain relaxation in the epilayers. The dependence of Raman E₂ mode of GaN films on residual strain can be estimated as Δ ω/Δ σ=3.93 (cm⁻¹/GPa).     

X-ray diffraction and high resolution transmission electron microscopy of 3C-SiC/AlN/6H-SiC(0001)

The structure and crystal quality of epitaxial films of SiC/AlN/6H-SiC(0001) prepared by chemical vapor deposition were evaluated by high resolution transmission electron microscopy (HRTEM) and x-ray diffraction techniques. Cross-sectional HRTEM revealed an abrupt AlN layer-6H-SiC substrate junction, but the transition between the AlN and SiC layers was much rougher, leading to the formation of a highly disordered SiC region adjacent to the interface. The AlN layer was relatively defect free, while the SiC layer contained many microtwins and stacking faults originating at the top SiC/AlN interface. The SiC layer was the 3C-polytype, as determined by double crystal x-ray rocking curves. The SiC layers were under in-plane compressive stress, with calculated defect density between 2–4×10⁷ defects/cm⁻².     

Pulsed laser deposition and processing of wide band gap semiconductors and related materials

The present work describes the novel, relatively simple, and efficient technique of pulsed laser deposition for rapid prototyping of thin films and multi-layer heterostructures of wide band gap semiconductors and related materials. In this method, a KrF pulsed excimer laser is used for ablation of polycrystalline, stoichiometric targets of wide band gap materials. Upon laser absorption by the target surface, a strong plasm a plume is produced which then condenses onto the substrate, kept at a suitable distance from the target surface. We have optimized the processing parameters such as laser fluence, substrate temperature, background gas pressure, target to substrate distance, and pulse repetition rate for the growth of high quality crstalline thin films and heterostructures. The films have been characterized by x-ray diffraction, Rutherford backscattering and ion channeling spectrometry, high resolution transmission electron microscopy, atomic force microscopy, ultraviolet (UV)-visible spectroscopy, cathodoluminescence, and electrical transport measurements. We show that high quality AlN and GaN thin films can be grown by pulsed laser deposition at relatively lower substrate temperatures (750–800°C) than those employed in metal organic chemical vapor deposition (MOCVD), (1000–1100°C), an alternative growth method. The pulsed laser deposited GaN films (∼0.5 μm thick), grown on AlN buffered sapphire (0001), shows an x-ray diffraction rocking curve full width at half maximum (FWHM) of 5–7 arc-min. The ion channeling minimum yield in the surface region for AlN and GaN is ∼3%, indicating a high degree of crystallinity. The optical band gap for AlN and GaN is found to be 6.2 and 3.4 eV, respectively. These epitaxial films are shiny, and the surface root mean square roughness is ∼5–15 nm. The electrical resistivity of the GaN films is in the range of 10⁻²–10² Θ-cm with a mobility in excess of 80 cm²V⁻¹s⁻¹ and a carrier concentration of 10¹⁷–10¹⁹ cm⁻³, depending upon the buffer layers and growth conditions. We have also demonstrated the application of the pulsed laser deposition technique for integration of technologically important materials with the III–V nitrides. The examples include pulsed laser deposition of ZnO/GaN heterostructures for UV-blue lasers and epitaxial growth of TiN on GaN and SiC for low resistance ohmic contact metallization. Employing the pulsed laser, we also demonstrate a dry etching process for GaN and AlN films.     

Comparison of various buffer schemes to grow GaN on large-area Si(111) substrates using metal-organic chemical-vapor deposition

A comparison of gallium-nitride (GaN) films grown on large-area Si(111) using a single aluminum-nitride (AlN) buffer, an AlN/graded-Al_xGa_1−xN buffer, and the introduction of additional low-temperature (LT)-grown AlN interlayers is reported. A graded-AlGaN buffer followed by additional LT-AlN interlayers is shown to completely eliminate cracking in nitride films of thickness >2 μm and also reduce the threading-dislocation density significantly. A partial compensation of GaN-tensile strain by the compressive-lattice strain induced by the AlGaN and AlN layers is responsible for this effect. The surface roughness is increased by the introduction of the LT-AlN buffers.     

Flat GaN epitaxial layers grown on Si(111) by metalorganic vapor phase epitaxy using step-graded AlGaN intermediate layers

In this work, we report on the growth by metalorganic vapor phase epitaxy (MOVPE) of GaN layers on AlN/Si(111) templates with step-graded AlGaN intermediate layers. First, we will discuss the optimization of the AlN/Si(111) templates and then we will discuss the incorporation of step-graded AlGaN intermediate layers. It is found that the growth stress in GaN on high-temperature (HT) AlN/Si(111) templates is compressive, although, due to relaxation, the stress we have measured is much lower than the theoretical value. In order to prevent the stress relaxation, step-graded AlGaN layers are introduced and a crack-free GaN epitaxial layer of thickness >1 μm is demonstrated. Under optimized growth conditions, the total layer stack, exceeding 2 μm in total, is kept under compressive stress, and the radius of the convex wafer bowing is as large as 119 m. The crystalline quality of the GaN layers is examined by high-resolution x-ray diffraction (HR-XRD), and the full-width-at-half maximums (FWHMs) of the x-ray rocking curve (0002) ω-scan and (−1015) ω-scan are 790 arc sec and 730 arc sec, respectively. It is found by cross-sectional transmission electron microscopy (TEM) that the step-graded AlGaN layers terminate or bend the dislocations at the interfaces.     

Growth and fabrication of AlGaN/GaN HEMT based on Si(1 1 1) substrates by MOCVD

AlGaN/GaN high electron mobility transistor (HEMT) hetero-structures were grown on the 2-in Si (1 1 1) substrate using metal-organic chemical vapor deposition (MOCVD). Low-temperature (LT) AlN layers were inserted to relieve the tension stress during the growth of GaN epilayers. The grown AlGaN/GaN HEMT samples exhibited a maximum crack-free area of 8 mm×5 mm, XRD GaN (0 0 0 2) full-width at half-maximum (FWHM) of 661 arcsec and surface roughness of 0.377 nm. The device with a gate length of 1.4 μm and a gate width of 60 μm demonstrated maximum drain current density of 304 mA/mm, transconductance of 124 mS/mm and reverse gate leakage current of 0.76 μA/mm at the gate voltage of −10 V.     

<Emphasis Type="Italic">In Situ</Emphasis> Stress Measurements During GaN Growth on Ion-Implanted AlN/Si Substrates

In situ wafer curvature measurements were used in combination with postgrowth structural characterization to study the evolution of film stress and microstructure in GaN layers grown by metalorganic chemical vapor deposition on N⁺ ion-implanted AlN/Si (111) substrates. The results were compared with growth on identical unimplanted substrates. In situ stress measurements revealed that, for the unimplanted sample, the GaN initiated growth under compressive stress of −1.41 GPa which arose due to lattice mismatch with the AlN buffer layer. In contrast, GaN growth on the ion-implanted sample began at lower compressive stress of −0.84 GPa, suggesting a reduction in epitaxial stress. In both cases, the compressive growth stress was fully relaxed after ~0.7 μm and minimal tensile stress was generated during growth. During post-growth cooling, tensile stress was introduced in the GaN layer of both samples due to thermal expansion mismatch. Post-growth optical microscopy characterization, however, demonstrated that the ion-implanted sample had lower density of channeling cracks compared with the unimplanted sample. Cross-sectional transmission electron microscopy images of the sample grown on ion-implanted Si with no post-implantation nitrogen annealing revealed the formation of horizontal cracks in the implanted region beneath the AlN buffer layer. The weakened layer acts to decouple the GaN film from the Si substrate and thereby reduces the density of channeling cracks in the film after growth.     

Fast epitaxial growth of high-purity 4H-SiC( $$000\bar 1$$ ) in a vertical hot-wall chemical vapor deposition) in a vertical hot-wall chemical vapor deposition

4H-SiC( ) epitaxial layers with a 14–28-μm thickness have been grown at high growth rates of 14–19 μm/h by chimney-type, vertical hot-wall, chemical vapor deposition (CVD) at 1,750°C. The 3C hillocks are formed on the epilayers grown under relatively low C/Si ratios. When grown at a relatively higher C/Si ratio of 0.6, the hillock density has been decreased to 1 cm⁻². Under the C-rich condition, the concentrations of residual impurity (nitrogen) and intrinsic defects (Z_1/2 and EH_6/7) have been reduced. When growth has been performed at low C/Si ratios of 0.4 and 0.5, all the micropipes in the substrates (more than 100 micropipes for each condition) have been closed during CVD growth.     

Laser-beam-induced current mapping of spatial nonuniformities in molecular beam epitaxy As-grown HgCdTe

The formation of dislocations and corresponding built-in electric fields in molecular beam epitaxy (MBE)-grown HgCdTe can have a major impact on the performance and yield of photodetectors fabricated from this material. This paper investigates the presence of such built-in electric fields arising from dislocation segregation in MBE as-grown HgCdTe, and their subsequent removal via a low-temperature Hg-saturated anneal. The electrical properties and surface morphology of an HgCdTe layer grown on a thin CdTe buffer layer are compared with those of an HgCdTe layer grown directly on the CdZnTe substrate. Laser-beam-induced current (LBIC) imaging is a nondestructive technique capable of mapping built-in electric fields present in a semiconductor material, which, in the present case, has been used to reveal dislocation distributions present in as-grown, unintentionally doped, MBE-grown Hg_0.71Cd_0.29Te. Two-dimensional scanning LBIC measurements at 160 K allow spatial mapping of electric fields across the HgCdTe wafer. Subsequent isothermal annealing of the wafer in an Hg atmosphere has been found to decrease the magnitude of the built-in electric fields to below the LBIC detection limit. However, of particular note, is that before and after annealing, crosshatch patterns can be seen using Nomarski microscopy, with the crosshatching being predominantly in the [01 ] direction and, to a lesser extent, in the [ 31] and [ 13] directions. Defect-decoration etching of the annealed wafer reveals dislocation banding parallel to the [01 ] direction, which closely resembles the contrast observed in the LBIC image of the wafer before annealing. These Nomarski and LBIC images are compared with those of a second wafer, which incorporates a 40-nm CdTe buffer layer. The second wafer does not show significant Nomarski or LBIC contrast, indicating a flat, electrically uniform as-grown layer. Variable magnetic-field Hall measurements at 77 K and quantitative mobility-spectrum analysis (QMSA) indicate predominately p-type conduction with a doping density of 2×10¹⁵ cm⁻³ in the as-grown layer. After Hg annealing at 240°C, no LBIC signals are observed at 160 K, and Hall measurements at 77 K indicate the presence of two n-type carriers, with a combined doping density of 2×10¹⁵ cm⁻³. Double-crystal x-ray diffraction measurements show no evidence of twinned crystal volumes in the layers before or after annealing, or any change in the full-width at half-maximum (FWHM) (41 arcsec) of the (422) reflection. The similarity between the dislocation density distribution, as revealed by defect decoration, and the LBIC image suggests that Hg out-diffusion during growth is expedited in regions of high dislocation concentration, thus creating a nonuniform Hg vacancy-acceptor concentration. The as-grown acceptor concentration, in turn, modulates the hole concentration, creating p⁺/p⁻ junctions and built-in electric fields in the material. Low-temperature annealing in a saturated-Hg atmosphere does not remove the crosshatch patterns or dislocation banding, but it fills the Hg vacancies, revealing the uniformly distributed n-type background, thus reducing the magnitude of any built-in electric fields. The LBIC mapping of MBE as-grown HgCdTe samples is, thus, capable of revealing defect distributions that would otherwise require a destructive technique, such as defect-decoration etching, to determine.