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.     

GaN layers with different polarities prepared by radio frequency molecular beam epitaxy and characterized by Raman scattering

GaN layers with different polarities have been prepared by radio-frequency molecular beam epitaxy (RF-MBE) and characterized by Raman scattering. Polarity control are realized by controlling Al/N flux ratio during high temperature AlN buffer growth. The Raman results illustrate that the N-polarity GaN films have frequency shifts at $A_{1}$(LO) mode because of their high carrier density; the forbidden $A_{1}$(TO) mode occurs for mixed-polarity GaN films due to the destroyed translation symmetry by inversion domain boundaries (IDBS); Raman spectra for Ga-polarity GaN films show that they have neither frequency shifts mode nor forbidden mode. These results indicate that Ga-polarity GaN films have a better quality, and they are in good agreement with the results obtained from the room temperature Hall mobility. The best values of Ga-polarity GaN films are 1042 cm$^{2}$/Vs with a carrier density of 1.0$\times $10$^{17}$~cm$^{ - 3}$.     

GaN缓冲层对直流反应磁控溅射AlN薄膜的影响(英文)

通过直流磁控反应溅射制备了氮化铝(AlN)薄膜,研究了沉积条件与氮化镓(GaN)缓冲层对薄膜质量的影响。利用X-射线衍射仪(XRD)和扫描电镜(SEM)表征了AlN薄膜的晶体结构和表面形貌。XRD研究结果表明,低工作压强、短靶距和适当的氮气偏压有利于(002)择优取向的AlN薄膜沉积。随着沉积时间的增加,沉积在50 nm厚的GaN缓冲层上的AlN薄膜的(002)面的衍射峰的半高宽急剧减小,而沉积在1μm厚的GaN薄膜上的AlN薄膜的(002)面的衍射峰的半高宽几乎不变。SEM测试结果表明:在沉积的初期,沉积在1μm厚的GaN薄膜上的AlN薄膜的(002)面的晶粒大小分布比沉积在50 nm厚的GaN缓冲层上的AlN薄膜的均匀,而随着沉积时间的增加,它们的晶粒大小分布几乎趋向一致。     

不同基底的GaN纳米薄膜制备及其场发射增强研究

采用脉冲激光沉积 (PLD) 方法在Si及SiC基底上制备了相同厚度的GaN纳米薄膜并对其进行了微结构表征及场发射性能测试分析. 结果表明: 基底对于GaN薄膜微结构及场发射性能具有显著的影响. 在SiC基底上所制备的GaN纳米薄膜相对于Si基底上的GaN纳米薄膜, 其场发射性能得到显著提升, 其场发射电流可以数量级增大. 场发射显著增强应源于纳米晶微结构及取向极化诱导增强效应. 本研究结果表明, 要获得优异性能场发射薄膜, 合适基底及薄膜晶体微结构需要重点考虑. 关键词： 基底 GaN 纳米薄膜 场发射     

GROWTH MODE AND SURFACE RECONSTRUCTION OF GaN(0001) THIN FILMS ON 6H-SiC(0001)

Two-dimensional growth of GaN thin films on an atomically flat C-face 6H-SiC(0001) surface prepared by ultra-high vacuum Si-etching is observed when using an AlN buffer layer in N plasma-assisted molecular beam epitaxy. Scanning tunneling microscopy and reflection high energy electron diffraction observations reveal a series of Ga-stabilized reconstructions which are consistent with those reported for an N-polar GaN(0001) film. The result, including the effect observed previously for GaN thin film on Si-terminated 6H-SiC(0001), agrees with the polarity assignment of heteroepitaxial wurtzite GaN films on polar 6H-SiC substrates, i.e., GaN film grown on SiC(0001) is <0001> oriented (N-face) while that on SiC(0001) is <0001> oriented (Ga-face).     

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     

GaN薄膜的溶胶-凝胶法制备及其表征

采用溶胶凝胶法成功地制备出氮化镓薄膜.以单质镓为镓源制备镓盐溶液、柠檬酸为络合剂制备出前驱体溶胶,再甩胶于Si(111) 衬底上,在氨气氛下热处理制备出GaN薄膜.X射线衍射（XRD）分析及选区衍射分析（SAED）表明所制备的薄膜是六角纤锌矿结构GaN薄膜;XPS分析其表面,结果显示样品中的镓元素、氮元素均以化合态存在,且Ga：N约为1：1;PL谱分析结果表明所制备的薄膜具有优良的发光性能.     

Metal catalyst-assisted growth of GaN nanowires on graphene films for flexible photocatalyst applications

We report the growth of high-areal-density GaN nanowires on large-size graphene films using a nickel (Ni) catalyst-assisted vapor-liquid-solid (VLS) method. Before the nanowire growth, the graphene films were prepared on copper foils using hot-wall chemical vapor deposition and transferred onto SiO₂/Si substrates. Then, for catalyst-assisted VLS growth, Ni catalyst layers with thickness of a few nanometers were deposited on the graphene-coated substrates using a thermal evaporator. We investigated the effect of the Ni catalyst thickness on the formation of GaN nanowires. Furthermore, the structural and optical characteristics of GaN nanowires were investigated using X-ray diffraction, transmission electron microscopy, and photoluminescence spectroscopy. The GaN nanowires grown on graphene films were transferred onto polymer substrates using a simple lift-off method for applications as flexible photocatalysts. Photocatalysis activities of the GaN nanowires prepared on the flexible polymer substrates were investigated under bending conditions.     

Growth of GaN films on CoGa(001): an EELS and AES study

The formation and properties of ultra-thin GaN films were investigated by means of high-resolution electron energy-loss spectroscopy (EELS) and Auger electron spectroscopy (AES). Using the intermetallic alloy CoGa as the substrate material, GaN can be prepared on the (001) surface upon adsorption of ammonia at 80 K and subsequent thermal decomposition. Ultra-thin GaN films were grown by repeated cycles of ammonia adsorption and heating to 650 K. The GaN films show an FK mode at 695 cm⁻¹, in agreement with calculated spectra based on IR parameters. The electronic energy gap is determined to be E_g ≈ 3.5 eV.     

磁控反应溅射AlN缓冲层对GaN基LED器件性能的影响

以直流磁控反应溅射法(RMS)在图形化蓝宝石衬底上制备的AlN薄膜作为缓冲层,采用金属有机化学气相沉积法(MOCVD)外延生长了GaN基LED。与MOCVD生长的低温GaN缓冲层相比,RMS制备的AlN缓冲层具有表面更平整、颗粒更小的形核岛,有利于促进GaN外延的横向生长,减少了形核岛合并时的界面数量和高度差异,降低了缺陷和位错产生的几率。研究结果表明,溅射AlN缓冲层取代传统低温GaN缓冲层后,外延生长的GaN材料具有更高的晶体质量,LED器件在亮度、漏电和抗静电能力等光电特性上均有明显提升。     

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。     

Surface morphology of ZnO buffer layer and its effects on the growth of GaN films on Si substrates by magnetron sputtering

ZnO thin films were first prepared on Si(111) substrates using a radio frequency magnetron sputtering system. Then the as-grown ZnO films were annealed in oxygen ambient at temperatures of 700, 800, 900, and 1000°C , respectively. The morphologies of ZnO films were studied by an atom force microscope (AFM). Subsequently, GaN epilayers about 500 nm thick were deposited on the ZnO buffer layers. The GaN/ZnO films were annealed in NH₃ ambient at 900°C. The microstructure, morphology and optical properties of GaN films were studied by x-ray diffraction (XRD), AFM, scanning electron microscopy (SEM) and photoluminescence (PL). The results are shown, their properties having been investigated particularly as a function of the ZnO layers. For better growth of the GaN films, the optimal annealing temperature of the ZnO buffer layers was 900°C.     

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.     

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。     

Effects of the sputtering time of ZnO buffer layer on the quality of GaN thin films

ZnO thin films with different thickness (the sputtering time of ZnO buffer layers was 10 min, 15 min, 20 min, and 25 min, respectively) were first prepared on Si substrates using radio frequency magnetron sputtering system and then the samples were annealed at 900 °C in oxygen ambient. Subsequently, a GaN epilayer about 500 nm thick was deposited on ZnO buffer layer. The GaN/ZnO films were annealed in NH₃ ambient at 950 °C. X-ray diffraction (XRD), atom force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) were used to analyze the structure, morphology, composition and optical properties of GaN films. The results show that their properties are investigated particularly as a function of the sputtering time of ZnO layers. For the better growth of GaN films, the optimal sputtering time is 15 min.     

Atomic Design of Polarity of GaN Films Grown on SiC(0001)

Ab initio total energy calculations are used to determine the interface structure of GaN films grown on 6H-SiC(0001) with different substrate reconstructions. The results indicate that GaN films grown on bare SiC(0001) are of the Ga-polarity, while GaN films grown on SiC(0001) with Si adlayer are of the N-polarity if there is no N-Si interchange at the interface. With the interchange, the GaN films are of the Ga-polarity.     

梯度铝镓氮缓冲层对氮化镓外延层性质的影响

采用金属有机物化学气相沉积系统在硅面碳化硅衬底的(0001)面上生长氮化铝缓冲层,并通过改变3层梯度铝镓氮(Al_xGa_(1-x)N:x=0.8,0.5,0.2)缓冲层的生长温度和氨气流量,制备出了高质量的氮化镓外延层。分别采用X射线衍射、原子力显微镜、光致发光谱和拉曼光谱对氮化镓外延层进行表征。实验结果表明,随着氮化镓外延层中张应力的降低,样品的晶体质量、表面形貌和光学质量都有显著提高。在最优的梯度铝镓氮缓冲层的生长条件下,氮化镓外延层中的应力值最小,氮化镓(0002)和(1012)面的摇摆曲线半峰宽分别为191 arcsec和243 arcsec,薄膜螺位错密度和刃位错密度分别为7×10~7cm~(-2)和3.1×108cm~(-2),样品表面粗糙度为0.381 nm。这说明梯度铝镓氮缓冲层可以改变氮化镓外延层的应力状态,显著提高氮化镓外延层的晶体质量。     

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.     

Effect of nanoporous GaN templates with different pore diameters on the subsequent thick GaN layers by HVPE

A set of GaN films were overgrown by hydride vapor phase epitaxy (HVPE) on nanoporous GaN templates with different pore diameters. These samples have various properties as seen from the measurements of X-ray diffraction (XRD) and photoluminescence (PL). Cross-sectional observations under a scanning electron microscopy (SEM) reveal that the overgrowth mechanism and process are strongly related to the dimension of nanopores, indicating that an optimum diameter exists for the properties of subsequent HVPE–GaN layers. When the diameters of nanopores are less than the optimum value, the pores on top of GaN templates can be left, and the properties of HVPE–GaN films show significant improvement. In contrast, the pores are almost stuffed with HVPE–GaN films, which obviously limit the improvement degree of HVPE–GaN films.     

室温下Ga1-xHoxN (x=0.0 and 0.05)稀磁半导体薄膜磁性

采用热蒸镀技术和后续氨退火制备了Ho掺杂GaN稀磁半导体薄膜. X射线衍射分析表明,所有的峰属于六角纤锌矿结构. 利用扫描电子显微镜和能量色散谱分别进行了表面形貌和成分分析. 用振动样品磁强计在室温测定了Ga_1-xHo_xN(x=0.0,0.05)的室温铁磁性. 磁性测量结果表明,未掺杂薄膜GaN具有抗磁性行为,而Ho掺杂Ga_0.95Ho_0.05N的薄膜表现出铁磁行为.