Micropipe and dislocation density reduction in 6H-SiC and 4H-SiC structures grown by liquid phase epitaxy

We investigated silicon carbide (SiC) epitaxial layers grown by liquid phase epitaxy (LPE). The layers were grown on 6H-SiC and 4H-SiC well-oriented (0001) 35 mm diameter commercial wafers as well as on 6H-SiC Lely crystals. A few experiments were also done on off-axis 6H-SiC and 4H-SiC substrates. Layer thickness and growth rate ranged from 0.5 to 50 microns and 0.5 to 10 μm/h, respectively. Layers were investigated by x-ray diffraction, x-ray topography, and selective chemical etching in molten KOH. It was found that dislocation and micropipe density in LPE grown epitaxial layers were significantly reduced compared with the defect densities in the substrates.     

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.     

High quality AIN and GaN grown on compliant Si/SiC substrates by gas source molecular beam epitaxy

Epitaxial layers of AlN and GaN were grown by gas source molecular-beam epitaxy on a composite substrate consisting of a thin (250 nm) layer of silicon (111) bonded to a polycrystalline SiC substrate. Two dimensional growth modes of AlN and GaN were observed. We show that the plastic deformation of the thin Si layer results in initial relaxation of the AlN buffer layer and thus eliminates cracking of the epitaxial layer of GaN. Raman, x-ray diffraction, and cathodoluminescence measurements confirm the wurtzite structure of the GaN epilayer and the c-axis crystal growth orientation. The average stress in the GaN layer is estimated at 320 MPa. This is a factor of two less than the stress reported for HVPE growth on 6H-SiC (0001).     

Growth of GaN on Buffer Layers with Different Polarities by Hydride Vapor-Phase Epitaxy

This paper reports the properties of GaN grown by the hydride vapor-phase epitaxy (HVPE) technique on buffer layers with different polarities. The N-, mixed-, and Ga-polarity buffer layers were grown by molecular-beam epitaxy (MBE) on sapphire (0001) substrates; then, thicker GaN epilayers were grown on these by HVPE. The surface morphology, structural, and optical properties of these HVPE-GaN epilayers were characterized by atomic force microscopy (AFM), x-ray diffraction (XRD), scanning electron microscopy, and photoluminescence (PL) spectroscopy. The results indicate that the crystallinity of these HVPE-GaN epilayers depends on the polarity of the buffer layer.     

Application of halide vapor phase epitaxy for the growth of ultrawide band gap Ga_2O_3

Halide vapor phase epitaxy(HVPE) is widely used in the semiconductor industry for the growth of Si, GaAs, GaN, etc.HVPE is a non-organic chemical vapor deposition(CVD) technique, characterized by high quality growth of epitaxial layers with fast growth rate, which is versatile for the fabrication of both substrates and devices with wide applications. In this paper, we review the usage of HVPE for the growth and device applications of Ga_2O_3, with detailed discussions on a variety of technological aspects of HVPE. It is concluded that HVPE is a promising candidate for the epitaxy of large-area Ga_2O_3 substrates and for the fabrication of high power β-Ga_2O_3 devices.     

MBE growth and properties of GaN and AlxGa1−xN on GaN/SiC substrates

The growth of GaN and AlGaN by molecular beam epitaxy (MBE) has been studied using GaN/SiC substrates. The GaN/SiC substrates consisted of ∼3 μm thick GaN buffer layers grown on 6H-SiC wafers by metalorganic vapor phase epitaxy (MOVPE) at Crée Research, Inc. The MBE-grown GaN films exhibit excellent structural and optical properties—comparable to the best GaN grown by MOVPE. Al_xGa_1−xN films (x ∼ 0.06-0.08) and Al_xGa_1−xN/GaN multi-quantum-well structures which display good optical properties were also grown by MBE on GaN/SiC substrates.     

Structural properties of ZnSy Se1−yZnSe/GaAs (001) heterostructures grown by photoassisted metalorganic vapor phase epitaxy

ZnS_ySe_1−yZnSe/GaAs (001) heterostructures have been grown by photoassisted metalorganic vapor phase epitaxy, using the sources dimethylzinc, dimethylselenium, diethylsulfur, and irradiation by a Hg arc lamp. The solid phase composition vs gas phase composition characteristics have been determined for ZnSy_ySe_1−y grown with different mole fractions of dimethylselenium and different temperatures. Although the growth is not mass-transport controlled with respect to the column VI precursors, the solid phase composition vs gas phase composition characteristics are sufficiently gradual so that good compositional control and lattice matching to GaAs substrates can be readily achieved by photoassisted growth in the temperature range 360°C ≤ T ≤ 400°C. ZnSe/GaAs (001) single heterostructures were grown by a two-step process with ZnSe thicknesses in the range from 54 nm to 776 nm. Based on 004 x-ray rocking curve full width at half maximums (FWHMs), we have determined that the critical layer thickness is h_c ≤200 nm. Using the classical method involving strain, lattice relaxation is undetectable in layers thinner than 270 nm for the growth conditions used here. Therefore, the rocking curve FWHM is a more sensitive indicator of lattice relaxation than the residual strain. For ZnS_ySe_1−y layers grown on ZnSe buffers at 400°C, the measured dislocation density-thickness product Dh increases monotonically with the room temperature mismatch. Lower values of the Dh product are obtained for epitaxy on 135 nm buffers compared to the case of 270 nm buffers. This difference is due to the fact that the 135 nm ZnSe buffers are pseudomorphic as deposited. For ZnS_ySe_1−y layers grown on 135 nm ZnSe buffers at 360°C, the minimum dislocation density corresponds approximately to room-temperature lattice matching (y ∼ 5.9%), rather than growth temperature lattice matching (y ∼ 7.6%). Epitaxial layers with lower dislocation densities demonstrated superior optical quality, as judged by the near-band edge/deep level emission peak intensity ratio and the near band edge absolute peak intensity from 300K photoluminescence measurements.     

Optical properties and recombination mechanisms in GaN and GaN:Mg grown by metalorganic vapor phase epitaxy

Photoluminescence (PL) and reflection spectra of undoped and Mg-doped GaN single layers grown on sapphire substrates by metalorganic vapor phase epitaxy (MOVPE) were investigated in a wide range of temperatures, excitation intensities, and doping levels. The undoped layers show n-type conductivity (μ=400 cm²/Vs, n=3×10¹⁷ cm⁻³). After annealing at T=600–700°C, the Mg-doped layers showed p-type conductivity determined by the potential-profiling technique. A small value of the full width at half maximum (FWHM=2.8 meV) of the excitonic emission and a high ratio between excitonic and deep level emission (≈5300) are evidences of the high layer quality. Two donor centers with activation energies of 35 and 22 meV were observed in undoped layers. A fine structure of the PL band with two narrow lines in the spectral range of the donor-acceptor pair (DAP) recombination was found in undoped layers. An anomaly was established in the temperature behavior of two groups of PL lines in the acceptor-bound exciton and in donor-acceptor pair regions in Mg doped layers. The lower energy line quenched with increasing temperature appreciably faster than the high energy ones. Our data does not agree with the DAP recombination model. It suggests that new approaches are required to explain the recombination mechanisms in undoped and Mg-doped GaN epitaxial layers.     

Lateral epitaxial overgrowth of GaN films on SiO2 areas via metalorganic vapor phase epitaxy

Lateral epitaxial growth and coalescence of GaN regions over SiO₂ masks previously deposited on GaN/AlN/6H-SiC(0001) substrates and containing 3 μm wide rectangular windows spaced 7 μm apart have been achieved. The extent and microstructural characteristics of these regions of lateral overgrowth were a complex function of stripe orientation, growth temperature, and triethylgallium (TEG) flow rate. The most successful growths were obtained from stripes oriented along 〈1 00〉 at 1100°C and a TEG flow rate of 26 μmol/min. A density of ∼10⁹ cm⁻² threading dislocations, originating from the underlying GaN/AlN interface, were contained in the GaN grown in the window regions. The overgrowth regions, by contrast, contained a very low density of dislocations. The surfaces of the coalesced layers had a terrace structure and an average root mean square roughness of 0.26 nm.     

Hydride vapor phase epitaxy for gallium nitride substrate

Due to the remarkable growth rate compared to another growth methods for gallium nitride(GaN)growth,hydride vapor phase epitaxy(HVPE)is now the only method for mass product GaN substrates.In this review,commercial HVPE systems and the GaN crystals grown by them are demonstrated.This article also illustrates some innovative attempts to develop homebuilt HVPE systems.Finally,the prospects for the further development of HVPE for GaN crystal growth in the future are also discussed.     

HVPE生长厚层GaN基片V/Ⅲ对结晶质量的影响

采用HVPE法,通过改变V/Ⅲ生长厚层GaN基片。分别采用X射线双晶衍射摇摆曲线、拉曼光谱及扫描探针显微镜进行生长晶体结晶质量和显微形貌分析。生长出表面光亮、无坑、无裂痕的60μm以上厚层GaN基片,并简要介绍厚层GaN基片生长过程中V/Ⅲ影响成核岛演变的规律。     

Investigation of high quality GaAs:In layers grown by liquid phase epitaxy

Indium-doped GaAs layers are investigated by low-field Hall effect, photoluminescence, and double crystal x-ray diffraction in order to study the influence of the In concentration on the electrical, optical, and crystallographic properties. The layers were grown by liquid phase epitaxy from solution with In concentrations in the range 0–10 at.%. It was found that epitaxial growth from the melt with 7 at.% In content produces the highest quality epitaxial layers.     

额外HCl和氮化对HVPE GaN生长的影响

在氢化物气相外延(HVPE)生长Ga N过程中,发现了一种在成核阶段向生长区添加额外HCl来改善Ga N外延薄膜质量的方法,并且讨论了额外HCl和氮化对Ga N形貌和质量的影响.两种方法都可以大幅度地改善Ga N的晶体质量和性质,但机理不同.氮化是通过在衬底表面形成Al N小岛,促进了衬底表面的成核和薄膜的融合;而添加额外HCl则被认为是通过改变生长表面的过饱和度引起快速成核从而促进薄膜的生长而改善晶体质量和性质的     

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.     

Direct growth of CdZnTe/Si substrates for large-area HgCdTe infrared focal plane arrays

Direct epitaxial growth of high-quality 100lCdZnTe on 3 inch diameter vicinal {100}Si substrates has been achieved using molecular beam epitaxy (MBE); a ZnTe initial layer was used to maintain the {100} Si substrate orientation. The properties of these substrates and associated HgCdTe layers grown by liquid phase epitaxy (LPE) and subsequently processed long wavelength infrared (LWIR) detectors were compared directly with our related efforts using CdZnTe/ GaAs/Si substrates grown by metalorganic chemical vapor deposition (MOCVD). The MBE-grown CdZnTe layers are highly specular and have both excellent thickness and compositional uniformity. The x-ray full-width at half-maximum (FWHM) of the MBE-grown CdZnTe/Si increases with composition, which is a characteristic of CdZnTe grown by vapor phase epitaxy, and is essentially equivalent to our results obtained on CdZnTe/GaAs/Si. As we have previously observed, the x-ray FWHM of LPE-grown HgCdTe decreases, particularly for CdZnTe compositions near the lattice matching condition to HgCdTe; so far the best value we have achieved is 54 arc-s. Using these MBE-grown substrates, we have fabricated the first high-performance LWIR HgCdTe detectors and 256 x 256 arrays using substrates consisting of CdZnTe grown directly on Si without the use of an intermediate GaAs buffer layer. We find first that there is no significant difference between arrays fabricated on either CdZnTe/Si or CdZnTe/GaAs/Si and second that the results on these Si-based substrates are comparable with results on bulk CdZnTe substrates at 78K. Further improvements in detector performance on Si-based substrates require a decrease in the dislocation density.     

GaN基材料及其外延生长技术研究

介绍了GaN基材料的基本特性、三种主要外延生长技术(MOCVD、MBE、HVPE)、衬底材料的选择及缓冲层技术;分析得出目前存在的GaN体单晶技术不完善、外延成本高、衬底缺陷及接触电阻大等主要问题制约了研究的进一步发展;指出今后的研究重点是完善GaN体单晶材料的生长工艺,以利于深入研究GaN的物理特性及有效地解决衬底问题,研究缓冲层的材料、厚度、组分等以提高GaN薄膜质量。     

Metalorganic vapor phase epitaxial growth and structural characterization of GaAs/InP heterostructures

Highly mismatched GaAs epitaxial layers with thickness ranging from 15 nm to 7 μm have been grown on InP substrates by atomospheric pressure metalorganic vapor phase epitaxy. Layers thinner than 30 nm exhibited 3-D growth mechanism; in the thicker layers, the islands coalesced and then the growth followed the layer by layer mechanism. The elastic strain and the extended defects have been studied by high resolution x-ray diffraction and transmission electron microscopy, respectively. The common observation of planar defects, misfit, and threading dislocations in the layers has been confirmed. The results on the elastic strain release have been discussed on the basis of the equilibrium theory.     

Structural study of GaN grown on (001) GaAs by organometallic vapor phase epitaxy

Detailed transmission electron microscope (TEM) and transmission electron diffraction (TED) examination has been performed on organometallic vapor phase epitaxial GaN layers grown on (001) GaAs substrate to investigate microstructures and phase stability. TED and TEM results exhibit the occurrence of a mixed phase of GaN. The wurtzite (α) phase grains are embedded in the zinc-blende (β) phase matrix. It is shown that there are two types of the wurtzite GaN phase, namely, the epitaxial wurtzite and the tilted wurtzite. The tilted wurtzite grains are rotated some degrees ranging from ∼5° to ∼35° regarding the GaAs substrate. A simple model is presented to describe the occurrence of the mixed phases and the two types of the wurtzite phase.     

HVPE生长的高质量GaN纳米柱的光学性能

GaN纳米材料因具有优异的晶体质量和突出的光学性能及发射性能,日益受到关注.研究了一种利用氢化物气相外廷(HVPE)系统生长高质量的GaN纳米柱的方法.使用镍作为催化剂,在蓝宝石衬底上生长出了GaN纳米柱.在不同生长时间和不同HC1体积流量下制备了多组样品,使用扫描电子显微镜(SEM)、X射线衍射(XRD)和光致发光(PL)谱对样品进行了分析表征.测试结果表明,在较低的HC1体积流量下,生长2 min的样品具有较高的晶体质量和较好的光学性质.讨论了不同生长阶段的GaN纳米结构发光特性的变化规律,认为纳米结构所产生的表面态密度大小差异会造成带边峰位的红移和展宽.     

初始层生长条件和Mg活性剂对MOVPE方法生长GaN薄膜质量的影响

The initial growth conditions of a 100 nm thick GaN layer and Mg-surfactant on the quality of the GaN epilayer grown on a 6H-SiC substrate by metal-organic vapor phase epitaxy have been investigated in this research. Experimental results have shown that a high Ⅴ/Ⅲ ratio and the initially low growth rate of the GaN layer are favorable for two-dimension growth and surface morphology of GaN and the formation of a smoother growth surface. Mg-surfactant occurring during GaN growth can reduce the dislocations density of the GaN epilayer but increase the surface RMS, which are attributed to the change of growth mode.