Control of polarity of heteroepitaxial ZnO films by interface engineering

Control of polarity of heteroepitaxial ZnO films has been examined by interface engineering. ZnO films were grown by plasma-assisted molecular beam epitaxy on Ga-polar GaN template and c-plane sapphire substrates. Polarity of all the samples is determined by coaxial impact collision ion scattering spectroscopy. Zn- and O-polar ZnO films have successfully grown by Zn- and O-plasma pre-exposures on Ga-polar GaN templates prior to ZnO growth. High-resolution transmission electron microscopy revealed formation of a single-crystalline monoclinic Ga₂O₃ interface layer by O-plasma pre-exposure on Ga-polar GaN templates, while no interface layer was observed for Zn pre-exposed ZnO films. The polarity of ZnO films grown under oxygen ambient on c-plane sapphire with MgO buffer is revealed as O-polar. Fabrication of polarity inverted ZnO heterostructure has been studied: polarity of ZnO films on Ga-polar GaN templates was changed from Zn-polar to O-polar by inserting a MgO layer. High-resolution transmission electron microscopy revealed atomically flat interfaces at both lower and upper ZnO/MgO interfaces and no inversion domain boundaries were detected in the upper ZnO layer.     

蓝宝石表面处理对氮化镓薄膜的影响

采用化学方法腐蚀c-面蓝宝石衬底,以形成一定的图案;利用LP-MOCVD在经过不同腐蚀时间的蓝宝石衬底上外延生长GaN薄膜。采用高分辨率双晶X射线衍射（DCXRD）、三维视频光学显微镜（OM）、扫描电子显微镜（SEM）和原子力显微镜（AFM）进行分析。结果表明,对蓝宝石衬底腐蚀50min情况下,外延生长的GaN薄膜晶体质量最优,其（0002）面上的XRD 半峰全宽为202.68arcsec,（10-12）面上的XRD 半峰全宽为300.24arcsec;其均方根粗糙度（RMS）为0.184nm。     

一种外延生长高质量GaN薄膜的新方法

采用化学方法腐蚀c-面蓝宝石衬底，以形成一定的图案；利用LP-MOCVD在经过表面处理的蓝宝石衬底上以及常规c-面蓝宝石衬底上外延生长GaN薄膜.采用高分辨率双晶X射线衍射(DCXRD)、三维视频光学显微镜(OM)、扫描电子显微镜(SEM)和原子力显微镜(AFM)进行分析，结果表明，在经过表面处理形成一定图案的蓝宝石衬底上外延生长的GaN薄膜明显优于在常规蓝宝石衬底上外延生长的GaN薄膜，其(0002)面上的XRD FWHM为208.80弧秒，(1012)面上的为320.76弧秒.同时，此方法也克服了传统 关键词： 表面处理 MOCVD 横向外延生长 GaN薄膜     

Elimination of Crystallographic Wing Tilt of Canti-Bridged Epitaxial Laterally Overgrown GaN Films by Optimizing Growth Procedure

Canti-bridged epitaxial lateral overgrowth （CBELO） of GaN is performed by metalorganic chemical vapour deposition （MOCVD） on maskless V-grooved sapphire substrates prepared by wet chemical etching with different mesa widths. The wing tilt usually observed in ELO is not found in the CBELO GaN with wide mesa widths, while it can be detected obviously in the GaN with narrow mesa widths. The wing tilt of CBELO GaN grown on a grooved sapphire substrate with narrow mesa can be controlled by adjusting the thickness of the nucleation layer. The dependence of the wing tilt on the nucleation layer thickness is studied. Cross-sectional scanning electron microscopy is used to characterize the geometry of the wing regions, and double crystal x-ray diffraction is used to analyse the structural characteristics and to measure the magnitude of the crystalline wing tilt. It is found that the crystalline wing tilt can be eliminated completely by first growth of a thin nucleation GaN layer then the CBELO GaN. Possible reason and the origin of the wing tilt in CBELO GaN films are also discussed.     

Growth of nonpolar a-plane GaN on nano-patterned r-plane sapphire substrates

Sapphire substrates were nano-patterned by inductive coupled plasma etching process. Nonpolar a-plane GaN films were grown on planar and nano-patterned r-plane sapphire substrates by metal organic chemical vapor deposition. The anisotropic characteristic and the crystalline quality of the a-plane GaN films were studied through XRD rocking curves. The cross section and surface morphologies of the a-plane GaN films were studied using SEM and AFM measurements, respectively. The crystal quality and surface flatness of the nonpolar a-plane GaN were greatly improved through the usage of the nano-patterned r-plane sapphire substrates.     

石英衬底上GaN薄膜沉积及其光学性能的研究

GaN薄膜材料广泛应用于发光二极管(LED),激光二极管(LD)等光电器件。但是GaN基器件的制备与应用以及器件推广很大一部分取决于其器件的价格,常用的方式是在单晶蓝宝石衬底上沉积制备GaN薄膜样品,单晶蓝宝石衬底晶向择优,可以制备出高质量的GaN薄膜样品,但是单晶蓝宝石衬底价格昂贵,一定程度上限制了其GaN基器件推广使用。如何在廉价衬底上直接沉积高质量的GaN薄膜,满足器件的要求成为研究热点。石英玻璃价格廉价,但是属于非晶体,没有择优晶向取向,很难制备出高质量薄膜样品。本研究采用等离子体增强金属有机物化学气相沉积系统在非晶普通石英衬底上改变氮气反应源流量低温制备GaN薄膜材料。制备之后采用反射高能电子衍射谱、X射线衍射光谱、室温透射光谱和光致光谱对制备的薄膜进行系统的测试分析。其结果表明：在氮气流量适当的沉积参数条件下,所制备的薄膜具有高C轴的择优取向,良好的结晶质量以及优异的光学性能。     

Ga2O3/GaN/蓝宝石模板上β-Ga2O3薄膜的生长

为获得高质量的β-Ga2O3薄膜,将c面蓝宝石上生长的GaN薄膜进行高温氧化制成了Ga2O3/GaN/蓝宝石模板,进而在模板上利用金属有机化学气相沉积(MOCVD)工艺进行了β-Ga2O3薄膜的同质外延。通过X射线衍射仪、原子力显微镜、场发射扫描电子显微镜等方法对样品的晶体结构、表面形貌等性质进行测试与分析。结果表明,该方法获得的β-Ga2O3薄膜晶体质量受GaN薄膜氧化效果与MOCVD工艺条件等因素影响较大。通过优化实验条件,得到了质量较高的β-Ga2O3薄膜。与蓝宝石上或GaN薄膜上异质外延得到的β-Ga2O3薄膜相比,薄膜的晶体质量明显提高。通过对比不同样品的晶体质量、表面形貌和制备过程,发现该方法成功地将β-Ga2O3薄膜在蓝宝石衬底或GaN/蓝宝石模板上异质外延转化为了Ga2O3/GaN/蓝宝石模板上的同质外延,有效地减小了β-Ga2O3薄膜和蓝宝石、GaN之间较大的晶格失配和热失配,有利于提高β-Ga2O3薄膜的晶体质量。     

Dislocation Reduction Mechanisms in Gallium Nitride Films Grown by Canti-Bridge Epitaxy Method

By using the special maskless V-grooved c-plane sapphire as the substrate, we previously developed a novel GaN LEO method, or the so-called canti-bridge epitaxy （CBE）, and consequently wing-tilt-free GaN films were obtained with low dislocation densities, with which all the conventional difficulties can be overcome [J. Vacuum Sci. Technol. B 23 （2005） 2476]. Here the evolution manner of dlslocations in the CBE GaN films is investigated using transmission electron microscopy. The mechanisms of dislocation reduction are discussed. Dislocation behaviour is found to be similar to that in the conventional LEO GaN films except the enhanced dislocation-combination at the coalescence boundary that is a major dislocation-reduction mechanism for the bent horizontal-propagating dislocations in the CBE GaN films. The enhancement of this dislocation-combination probability is believed to result from the inclined shape and the undulate morphology of the sidewalls, which can be readily obtained in a wide range of applicable film-growth conditions during the GaN CBE process. Further development of the GaN CBE method and better crystal-quality of the GaN film both are expected.     

A theoretical study on various models for the domain boundaries in epitaxial GaN films

Various domain boundaries that are found in epitaxial Wurtzite GaN films were studied by molecular dynamics simulation. The Ewald summation algorithm and Keating potential model are adopted to calculate the long-range Coulomb interaction and the short-range bonding force in the semiconductor system, respectively. The research results show that the domain formation energies of (100) and (110) boundaries are significantly different. The latter ones have general quite higher formation energies than the formers. The like-atom (i.e. atoms of the same kind) bonding domain boundaries (LABDB) have higher formation energies than their counterparts of unlike-atom (i.e. atoms of different kinds) bonding domain boundaries (UABDB) in all GaN (100) and (110) interfaces. The UABDB structures are all stable while most of the LABDB are unstable. The advantage and the limitation of Keating potential model in Molecular Dynamics simulation for covalent crystal are discussed. Received: 7 April 1999 / Accepted: 1 November 1999 / Published online: 8 March 2000     

Effect of thickness on the microstructure of GaN films on Al2O3 (0001) by laser molecular beam epitaxy

Heteroepitaxial GaN films are grown on sapphire (0001) substrates using laser molecular beam epitaxy. The growth processes are in-situ monitored by reflection high energy electron diffraction. It is revealed that the growth mode of GaN transformed from three-dimensional (3D) island mode to two-dimensional (2D) layer-by-layer mode with the increase of thickness. This paper investigates the interfacial strain relaxation of GaN films by analysing their diffraction patterns. Calculation shows that the strain is completely relaxed when the thickness reaches 15 nm. The surface morphology evolution indicates that island merging and reduction of the island-edge barrier provide an effective way to make GaN films follow a 2D layer-by-layer growth mode. The 110-nm GaN films with a 2D growth mode have smooth regular hexagonal shapes. The X-ray diffraction indicates that thickness has a significant effect on the crystallized quality of GaN thin films.     

Investigation of GaN layer grown on different low misoriented sapphire by MOCVD

GaN layer on c-plane misoriented sapphire, grown by metal organic chemical vapor deposition, has been studied. It was observed that the random and non-uniform distribution of the step was caused by the step reconstruction for GaN grown on 0° sapphire by atomic force microscopy. The image quality parameter analysis of electron back-scatter diffraction indicated that the strains were reduced for GaN grown on 0.2° and 0.3° sapphire, and optical and electrical properties were improved. The electroluminescence intensity of LED grown on 0.2° and 0.3° sapphire was 2 times as that of 0° sapphire.     

Synthesis of single crystalline GaN nanoribbons on sapphire (0001) substrates

Single crystalline GaN nanoribbons were synthesized through nitriding Ga₂O₃ thin films deposited on sapphire (0001) substrates by radio frequency magnetron sputtering. The component and structure of nanoribbons were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The flat and smooth ribbon-like nanostructures are high quality single crystalline hexagonal wurtzite GaN. The thickness and width-to-thickness ratio of the grown GaN nanoribbons are in the range of 8-15 nm and ∼5-10, respectively.     

New design of nozzle structures and its effect on the surface and crystal qualities of thick GaN using a horizontal HVPE reactor

High-quality thick GaN films without cracks were achieved by using a new nozzle structure in the reactor grown by the hydride vapor phase epitaxy on sapphire substrates. Optical contrast microscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray double diffraction (XRD) and cathodoluminescence (CL) were carried out to reveal the surface, crystal and optical properties of the GaN epilayer. It was found that the nozzle structure in the reactor has a large effect on the growth rate, surface flat, crystal quality, and the uniformity of the growth. Compared with the old one, the new nozzle structure (denoted as multi-layers nozzle) can improve dramatically the properties of thick GaN. Mirror, colorless and flat GaN thick film was obtained and its (0 0 0 2) FWHM results were reduced from 1000 to 300 arcsec when the new nozzle was used. AFM result revealed a step flow growth mode for GaN layer with the new nozzle. Room-temperature CL spectra on the GaN films showed a strong near-band-edge peak for the new nozzle, but there is only weak emitting peak for the old nozzle. New nozzle structure can improve the uniform of flow field near the surface of substrates compared with the old one, which leads to the improvement of properties of GaN thick film by hydride vapor phase epitaxy (HVPE).     

淀积在不同小倾角蓝宝石衬底的n型GaN的研究

采用金属有机物化学淀积技术在不同倾角（0°—03°）的蓝宝石衬底上外延n型GaN.通过原子力显微镜观察到n型GaN均呈台阶流生长模式,02°和03°倾角衬底的n型GaN表面台阶朝向相同、分布均匀,明显地看到在0°倾角衬底的n型GaN表面由台阶重构直接导致的台阶朝向随机分布、疏密不匀的形貌.电子背散射分析表明,在0°倾角衬底的n型GaN外延层的应力随外延厚度增加而增加,而02°和03°倾角衬底的n型GaN外延层的应力没有明显的变化.电学和光学特性研究表明,02°和03°倾角衬底的n型GaN有较高的电子浓度和较低的黄光带与近带边强度之比. 关键词： 金属有机物化学淀积 氮化物 原子力显微镜 光致发光     

蓝宝石邻晶面衬底MBE生长GaN薄膜的瞬态光电导弛豫特性研究

在实验优化MBE工艺条件的基础上，采用蓝宝石(0001)邻晶面衬底制备出了具有较高质量的GaN薄膜.XRD分析表明邻晶面衬底生长的GaN薄膜晶体结构质量明显提高，AFM表征结果显示邻晶面生长的样品表面形貌显著改善.蓝宝石衬底GaN薄膜的瞬态光电导弛豫特性对比实验研究发现，常规衬底生长的GaN薄膜光电导弛豫特性出现双分子复合、单分子复合和弛豫振荡三个过程，持续时间分别为0.91，7.7和35.5ms；蓝宝石邻晶面衬底生长的GaN薄膜光电导弛豫过程主要是双分子复合和单分子复合过程，持续时间分别为0.78和14ms.理论分析表明MBE生长GaN薄膜的持续光电导效应主要起源于本生位错缺陷引发的深能级. 关键词： 邻晶面蓝宝石衬底 GaN薄膜 瞬态光电导 弛豫特性     

斜切蓝宝石衬底MOCVD生长GaN薄膜的透射电镜研究

利用MOCVD技术在斜切角度为0.3°的c面蓝宝石衬底上生长了非故意掺杂 GaN 薄膜, 并采用透射电子显微镜对材料的质量和材料内部缺陷进行了分析. 研究发现斜切蓝宝石衬底上外延的GaN材料中,位错在距离衬底0.8 μm附近大量湮灭, 同时位错扎堆出现.基于上述现象, 提出了斜切衬底上GaN材料中位错的湮灭机制, 解释了斜切衬底能够提高GaN晶体质量的原因.     

Effect of ZnO sacrificial layer thickness on the structure and optical properties of GaN nanoparticles prepared by RF magnetron sputtering

GaN nanoparticles were prepared on sapphire (0001) substrates with ZnO sacrificial layers by self assembly of Ga₂O₃ films in their reaction with NH₃. ZnO sacrificial layers with different thicknesses and Ga₂O₃ films were deposited on sapphire substrates in turn by a radio frequency (RF) magnetron sputtering system. Nitridation of the Ga₂O₃ films was then carried out in a quartz tube furnace. The effect of ZnO sacrificial layer thickness on the structure and optical properties of nanoparticles prepared by RF magnetron sputtering were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and photoluminescence (PL). GaN nanoparticles with ZnO sacrificial layers of different thicknesses possess hexagonal wurtzite crystal structure and have a preferred orientation with c axis perpendicular to the sapphire substrates. XRD, SEM, and AFM results reveal that the better-crystallinity, uniform, and well-dispersed GaN nanoparticles (～30 nm) without agglomeration were obtained with a ZnO sacrificial layer 300-nm thick. The PL result reveals that the optical properties of the GaN nanoparticles are improved with a ZnO sacrificial layer 300-nm thick. Therefore, we suggest that a ZnO sacrificial layer 300-nm thick is the most suitable condition for obtaining better-quality GaN nanoparticles with good luminescence performance. Moreover, the mechanism of the formation of GaN nanoparticles with ZnO sacrificial layers is also discussed.     

Influence of Different Interlayers on Growth Mode and Properties of InN by MOVPE

We grow InN epilayers on different interlayers by metal organic vapour phase epitaxy （MOVPE） method, and investigate the effect of interlayer on the properties and growth mode of InN films. Three InN samples were deposited on nitrided sapphire, low-temperature InN （LT-InN） and high-temperature GaN （HT-GaN）, respectively. The InN layer grown directly on nitrided sapphire owns the narrowest x-ray diffraction rocking curve （XRC） width of 300 aresee among the three samples, and demonstrates a two-dimensional （2D） step-flow-like lateral growth mode, which is much different from the three-dimensional （3D） pillar-like growth mode of LT-InN and HT-GaN buffered samples. It seems that mismatch tensile strain is helpful for the lateral epitaxy of InN film, whereas compressive strain promotes the vertical growth of InN films.     

Effects of Ⅴ/Ⅲ ratio on species diffusion anisotropy inthe MOCVD growth of non-polar a-plane GaN films

Non-polar a-plane (110) GaN films have been grown on r-plane (102) sapphire substrates by metal organic chemical vapour deposition. The influences of Ⅴ/Ⅲ ratio on the species diffusion anisotropy of a-plane GaN films were investigated by scanning electron microscopy, cathodoluminescence and high-resolution x-ray diffraction measurements. The anisotropy of a-plane GaN films may result from the different migration length of adatoms along two in-plane directions. Ⅴ/Ⅲ ratio has an effect on the growth rates of different facets and crystal quality. The stripe feature morphology was obviously observed in the film with a high V/III ratio because of the slow growth rate along the [100] direction. When the Ⅴ/Ⅲ ratio increased from 1000 to 6000, the in-plane crystal quality anisotropy was decreased due to the weakened predominance in migration length of gallium adatoms.     

位错形态与GaN外延薄膜电阻率之间的关系

利用金属有机化学气相沉积（MOCVD）,通过改变生长过程中成核层退火阶段的反应室压力,在蓝宝石衬底上制得了不同阻值的GaN外延薄膜。利用原子力显微镜（AFM）、X射线衍射（XRD）和透射电子显微镜（TEM）对所生长的GaN薄膜的表面形貌、位错密度和位错形态进行了研究。结果表明,GaN的电阻率与位错形态之间存在密切联系,由此建立了模型来解释两者之间的关系。由于刃型位错附近存在负电荷,因此可为电子提供传导通道。在低阻GaN中,绝大多数位错发生弯曲和相互作用,在平行于基底方向上形成负电荷的导通通道,GaN薄膜的电导率较高。在高阻GaN中,位错生长方向垂直于基底,负电荷很难在平行于基片方向上传导,GaN薄膜的电导率很低,由此得到高阻GaN。