Si 基GaN 材料生长和LEDs 结构研制以及HVPE 生长厚膜GaN 的初步研究

Submitted by zhangdi (zhangdi@red.semi.ac.cn) on 2009-04-13T11:45:31Z

Characterization of Thick GaN Films Directly Grown on Wet-Etching Patterned Sapphire by HVPE

Thick GaN films of high quality are directly grown on wet-etching patterned sapphire in a vertical hydride vapour phase epitaxy reactor. The optical and structural properties of GaN films are studied using scanning electronic microscopy and cathodoluminescence. Test results show that initial growth of hydride vapour phase epitaxy GaN occurs not only on the mesas but also on the two asymmetric sidewalls of the V-shaped grooves without selectivity. After the two-step coalescence near the interface, the GaN films near the surface keep on growing along the direction perpendicular to the long sidewall. Based on Raman results, GaN of the coalescence region in the grooves has the maximum residual stress and poor crystalline quality over the whole GaN film, and the coalescence process can release the stress. Therefore, stress-free thick GaN films are prepared with smooth and crack-free surfaces by this particular growth mode on wet-etching patterned sapphire substrates.

Hillocks and hexagonal pits in a thick film grown by HVPE

A GaN film with a thickness of 250 mu m was grown on a GaN/sapphire template in a vertical hydride vapor phase epitaxy (HVPE) reactor. The full-width at half-maximum (FWHM) values of the film were 141 and 498 arcsec for the (0 0 2) and (1 0 2) reflections, respectively. A sharp band-edge emission with a FWHM of 20 meV at 50 K was observed, which corresponded to good crystalline quality of the film. Some almost circular-shaped hillocks located in the spiral growth center were found on the film surface with dimensions of 100 mu m, whose origin was related to screw dislocations and micropipes. Meanwhile, large hexagonal pits also appeared on the film surface, which had six triangular {1 0 (1) over bar 1} facets. The strong emission in the pits was dominated by an impurity-related emission at 377 nm, which could have been a high-concentration oxygen impurity. (c) 2008 Elsevier Ltd. All rights reserved.

Cathodoluminescence and Raman research of V-shape inverted pyramid in HVPE grown GaN film

Thick GaN films with high quality have been grown on (0001) sapphire substrate in a home-made vertical HVPE reactor. Micron-size hexagonal pits with inverted pyramid shape appear on the film surface, which have six triangular {10-11} facets. These I {10-11} facets show strong luminescence emission and are characteristic of doped n-type materials. Broad red emission is suppressed in {10-11} facets and is only found at the flat region out of the pit, which is related with the decreasing defects on {10-11} facets. Low CL emission intensity is observed at the apex of V-shape pits due to the enhanced nonradiative recombination. Raman spectra show that there are higher carrier concentration and low strain in the pit in comparison to the flat region out of the pit. The strain relaxation may be the main mechanism of the V-shape pits formation on the GaN film surface. (c) 2006 Elsevier B.V. All rights reserved.

Spatial variation of optical and structural properties of ELO GaN directly grown on patterned sapphire by HVPE

A 275 mu m thick GaN layer was directly grown on the SiO2-prepatterned sapphire in a home-built vertical hydride vapour phase epitaxy (HVPE) reactor. The variation of optical and structure characteristics were microscopically identified using spatially resolved cathodeluminescence and micro-Raman spectroscopy in a cross section of the thick film. The D X-0(A) line with the FWHM of 5.1 meV and etch- pit density of 9 x 10(6) cm(-2) illustrated high crystalline quality of the thick GaN epitaxial layer. Optically active regions appeared above the SiO2 masks and disappeared abruptly due to the tapered inversion domains at 210 - 230 mu m thickness. The crystalline quality was improved by increasing the thickness of the GaN/sapphire interface, but the region with a distance of 2 mu m from the top surface revealed relatively low quality due to degenerate surface reconstruction by residual gas reaction. The x-ray rocking curve for the symmetric (0 0 2) and asymmetric (1 0 2) reflections also showed good quality and a small wing tilt of the epitaxial lateral overgrowth (ELO) GaN.

Columnar structures and stress relaxation in thick GaN films grown on sapphire by HVPE

Thick GaN films with high quality are directly grown on sapphire in a home-built vertical hydride vapour phase epitaxy (HVPE) reactor. The optical and structural properties of large scale columnar do-mains near the interface are studied using cathodoluminescence and micro-Raman scattering. These columnar do-mains Show a strong emission intensity due to extremely high free carrier concentration up to 2 x 10(19) cm(-3), which are related with impurities trapped in structural defects. The compressive stress in GaN Elm clearly decreases with increasing distance from interface. The quasi-continuous columnar domains play an important role in the stress relaxation for the upper high quality layer.

The influence of substrate nucleation on HVPE-grown GaN thick films - art. no. 684105

Thick GaN films were grown on sapphire in a home-made vertical HVPE reactor. Effect of nucleation treatments on the properties of GaN films was investigated, including the nitridation of sapphire, low temperature GaN buffer and MOCVD-template. Various material characterization techniques, including AFM, SEM, XRD, CL and PL have been used to assess these GaN epitaxial films. It was found that the surface of sapphire after high temperature nitridation was flat and showed high density nucleation centers. In addition, smooth Ga-polarity surface of epitaxial layer can be obtained on the nitridation sapphire placed in air for several days due to polarity inversion. This may be caused by the atoms re-arrangement because of oxidation. The roughness of N-polarity film was caused by the huge inverted taper domains, which can penetrate up to the surface. The low temperature GaN buffer gown at 650 degrees C is favorable for subsequent epitaxial film, which had narrow FWHM of 307 arcsec. The epitaxial growth on MOCVD-template directly came into quasi-2D growth mode due to enough nucleation centers, and high quality GaN films were acquired with the values of the FWHM of 141 arcsec for (002) reflections. After etching in boiled KOH, that the total etch-pit density was only 5 x 106 cm(-2) illustrated high quality of the thick film on template. The photoluminescence spectrum of GaN film on the MOCVD-template showed the narrowest line-width of the band edge emission in comparison with other two growth modes.

HVPE气相外延法在c面蓝宝石上选区外延生长GaN及其表征

使用气相沉积SiO2和普通光刻以及湿法腐蚀方法，在c面蓝宝石上开出不同尺寸的正方形窗口，在窗口区域中露出衬底，然后使用氢化物气相外延（HVPE）方法选区外延GaN薄膜．采用光学显微镜、原子力显微镜（AFM）、扫描电子显微镜（SEM）、高分辨率双晶X射线衍射（DCXRD）和喇曼谱测试（Raman shift）对薄膜进行分析．结果表明，在c面蓝宝石衬底上独立的正方形窗口区域中外延生长的，厚度约20μm的GaN薄膜，当窗口面积为100μm×100μm时，GaN表面无裂纹；而当窗口面积为300μm×300μm和500μm×500μm时，GaN表面有裂纹．随着窗口面积的减小，GaN双晶衍射摇摆曲线的（0002）峰的半高宽（FwHM）减小，表明晶体的质量更好，最小的半高宽为530″，从正方形窗口区的角上到边缘再到中心，GaN的面内压应力逐渐减小，分析认为这与GaN横向外延区（ELO区）与SiO2掩膜之间的相互作用，以及窗口区到ELO区的线位错的90°扭转有关．

蓝宝石衬底上HVPE-GaN厚膜生长

采用氢化物气相外延（HVPE）方法，以蓝宝石作衬底，分别在MOCVD-GaN模板和蓝宝石衬底上直接外延生长GaN。模板上的GaN生长表面平整、光亮，但开裂严重，其（0002）的双晶衍射半高宽最低为141；蓝宝石衬底上直接生长GaN外延层质量较差，其双晶衍射半高宽为168ff，但不发生开裂，HCl的载气流量对预反应有很大的影响，应力产生于外延层和衬底之间的界面处，界面孔洞的存在可以释放应力，减少开裂，光致发光（PL）谱中氧杂质引起强黄光发射。

Structural and Optical Performance of GaN Thick Film Grown by HVPE

Thick GaN films were grown on GaN/sapphire template in a vertical HVPE reactor. Various material characterization techniques,including AFM, SEM, XRD, RBS/Channeling, CL, PL, and XPS, were used to characterize these GaN epitaxial films. It was found that stepped/terraced structures appeared on the film surface,which were indicative of a nearly step-flow mode of growth for the HVPE GaN despite the high growth rate. A few hexagonal pits appeared on the surface, which have strong light emission. After being etched in molten KOH, the wavy steps disappeared and hexagonal pits with {1010} facets appeared on the surface. An EPD of only 8 ×10~6cm~(-2) shows that the GaN film has few dislocations. Both XRD and RBS channeling indicate the high quality of the GaN thick films. Sharp band-edge emission with a full width at half maximum（FWHM）of 67meV was observed, while the yellow and infrared emissions were also found. These emissions are likely caused by native defects and C and O impurities.

Measurement for Thermal Effusivity of AlxGa1-xN Alloys Using Thermoreflectance with Periodic Heating

AlxGa1-xN alloys with x=0.375, 0.398, 0.401, 0.592 and 0.696 were deposited on sapphire substrate by the hydride-vapor-phase epitaxy (HVPE) method. Thermal effusivity measurements were carried out on AlxGa1-xN alloys using a thermal microscope at room temperature. The lag between sinusoidal heating laser wave and thermoreflectance wave was used to measure the thermal diffusivity. Thermal conductivity values of the AlxGa1-xN alloys were also obtained as a function of AIN mole fraction in the alloy. The thermal conductivity was found to decrease with increasing AIN fraction and the experimental data agree with values estimated using the virtual crystal model.

Microstructure and Optical Properties of Nonpolar m-Plane GaN Films Grown on m-Plane Sapphire by Hydride Vapor Phase Epitaxy

Thick nonpolar (10 (1) over bar0) GaN layers were grown on m-plane sapphire substrates by hydride vapor phase epitaxy (HVPE) using magnetron sputtered ZnO buffers, while semipolar (10 (1) over bar(3) over bar) GaN layers were obtained by the conventional two-step growth method using the same substrate. The in-plane anisotropic structural characteristics and stress distribution of the epilayers were revealed by high. resolution X-ray diffraction and polarized Raman scattering measurements. Atomic force microscopy (AFM) images revealed that the striated surface morphologies correlated with the basal plane stacking faults for both (10 (1) over bar0) and (10 (1) over bar(3) over bar) GaN films. The m-plane GaN surface showed many triangular-shaped pits aligning uniformly with the tips pointing to the c-axis after etching in boiled KOH, whereas the oblique hillocks appeared on the semipolar epilayers. In addition, the dominant emission at 3.42eV in m-plane GaN films displayed a red shift with respect to that in semipolar epilayers, maybe owing to the different strain states present in the two epitaxial layers. [DOI: 10.1143/JJAP.47.3346]

Growth of (10(1)over-bar(3)over-bar) semipolar GaN on m-plane sapphire by hydride vapor phase epitaxy

The crystalline, surface, and optical properties of the (10 (1) over bar(3) over bar) 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 (10 (1) over bar(3) over bar) 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 X 10(5) cm(-2), revealing the N-polarity characteristic. In the low-temperature PL spectra, weak BSF-related emission at 3.44eV 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. (C) 2009 Elsevier B.V. All rights reserved.

Mechanical Deformation Behavior of Nonpolar GaN Thick Films by Berkovich Nanoindentation

In this study, the deformation mechanisms of nonpolar GaN thick films grown on m-sapphire by hydride vapor phase epitaxy (HVPE) are investigated using nanoindentation with a Berkovich indenter, cathodoluminescence (CL), and Raman microscopy. Results show that nonpolar GaN is more susceptible to plastic deformation and has lower hardness than c-plane GaN. After indentation, lateral cracks emerge on the nonpolar GaN surface and preferentially propagate parallel to the < 11 (2) over bar0 > orientation due to anisotropic defect-related stresses. Moreover, the quenching of CL luminescence can be observed to extend exclusively out from the center of the indentations along the < 11 (2) over bar0 > orientation, a trend which is consistent with the evolution of cracks. The recrystallization process happens in the indented regions for the load of 500 mN. Raman area mapping indicates that the distribution of strain field coincides well with the profile of defect-expanded dark regions, while the enhanced compressive stress mainly concentrates in the facets of the indentation.