热丝CVD法在单晶硅衬底上低温外延生长Si和Ge薄膜的研究

采用热丝CVD法在单晶Si衬底上进行了Si和Ge 薄膜的低温外延生长,用XRD和Raman谱对其结构性能进行了分析.结果表明:在衬底温度200 ℃时,Si(111)单晶衬底上外延生长出了Raman峰位置为521.0 cm-1;X射线半峰宽(FWHM)为5.04 cm-1.结晶质量非常接近于体单晶的(111)取向的本征Si薄膜;在衬底温度为300 ℃时,在Si(100)单晶衬底上异质外延,得到了Raman峰位置为300.3 cm-1的Ge薄膜,Ge薄膜的晶体取向为Ge(220).研究表明热丝CVD是一种很好的低温外延薄膜的方法.     

氮化镓单晶衬底制备技术发展与展望

氮化镓(GaN)是第三代半导体材料中的典型代表.因其良好的物理化学性能与热稳定特性,是制作光电子器件及电力电子器件的理想材料.采用同质外延技术在GaN单晶衬底上制备GaN基器件是实现其高性能的根本途径.本文综述了GaN单晶衬底制备的氢化物气相外延技术、三卤化物气相外延技术、氨热法及助熔剂法(钠流法)的研究进展,并对未来可能的发展方向提出了展望.     

氢化物气相外延生长氮化镓单晶衬底的研究进展

氮化镓(GaN)晶体是制备蓝绿光激光器、射频微波器件以及电力电子等器件的理想衬底材料,在激光显示、5G通讯及智能电网等领域具有广阔的应用前景.目前市场上的氮化镓单晶衬底大部分都是通过氢化物气相外延(Hydride Vapor Phase Epitaxy,HVPE)方法生长制备的,在市场需求的推动下,近年来HVPE生长技术获得了快速的发展.本论文综述了近年来HVPE方法生长GaN单晶衬底的主要进展,主要内容包含HVPE生长GaN材料的基本原理、GaN单晶中的掺杂与光电性能调控、GaN单晶中的缺陷及其演变规律和GaN单晶衬底在器件中的应用.最后对HVPE生长方法的发展趋势进行了展望.     

异质衬底上HVPE法生长GaN厚膜的研究进展

氮化镓基(GaN)光电器件的快速发展,对GaN的质量提出更高的要求,同质外延可以避免由于失配引起的缺陷,厚膜生长是解决GaN体材料生长困难的有效手段.氢化物气相外延(HVPE)是目前最普遍的制备氮化镓厚膜的方法.衬底对于GaN厚膜的影响不可忽视,本文总结了在蓝宝石、碳化硅和铝酸锂衬底上制备GaN厚膜的研究进展,讨论了今后的研究方向.     

4H碳化硅单晶中的位错

4H碳化硅(4H-SiC)单晶具有禁带宽度大、载流子迁移率高、热导率高和稳定性良好等优异特性,在高功率电力电子、射频/微波电子和量子信息等领域具有广阔的应用前景。经过多年的发展,6英寸(1英寸=2.54 cm)4H-SiC单晶衬底和同质外延薄膜已得到了产业化应用。然而,4H-SiC单晶中的总位错密度仍高达10³~10⁴ cm^-2,阻碍了4H-SiC单晶潜力的充分发挥。本文介绍了4H-SiC单晶中位错的主要类型,重点讲述4H-SiC单晶生长、衬底晶圆加工以及同质外延过程中位错的产生、转变和湮灭机理,并概述4H-SiC单晶中位错的表征方法,最后讲述了位错对4H-SiC单晶衬底和外延薄膜的性质,以及4H-SiC基功率器件性质的影响。     

氮化镓单晶生长研究进展

氮化镓(GaN)作为第三代宽禁带半导体核心材料之一,具有高击穿场强、高饱和电子漂移速率、抗辐射能力强和良好的化学稳定性等优良特性,是制作宽波谱、高功率、高效率光电子、电力电子和微电子的理想材料.受制于氮化镓单晶衬底的尺寸、产能及成本的影响,当前的GaN基器件主要基于异质衬底(硅、碳化硅、蓝宝石等)制作而成,GaN单晶衬底的缺乏已成为制约GaN器件发展的瓶颈.近年来,国内外在GaN单晶衬底制备方面取得了较大的进展.本文综述了氮化镓单晶生长的最新进展,包括氢化物气相外延法、氨热法和钠助熔剂法的研究进展,分析了各生长方法面临的挑战与机遇,并对氮化镓单晶材料的发展趋势讲行了展望.     

MPCVD单晶金刚石初始及断续生长界面的表征与分析

采用微波等离子体化学气相沉积(MPCVD)技术制备的大尺寸、高质量单晶金刚石材料具备卓越的物理化学性能,在珠宝、电子、核与射线探测等消费品、工业和国防科技领域极具应用前景.研究发现在化学气相沉积单晶金刚石生长过程中,在衬底与外延层之间,以及生长中途停止-继续生长的生长层之间出现明显的界面区.本文采用偏光显微镜、拉曼光谱、荧光光谱(PL)等手段对界面区域进行了测试分析,界面区在偏光显微镜下表现出因应力导致的亮区,且荧光光谱(PL)及其线扫描显示该区域的NV色心含量远高于衬底及其前后外延层,表明该界面区具有较高的缺陷和杂质含量.结果表明在生长高品质单晶金刚石初期就应当采取一定手段进行品质调控,并尽量在一个生长周期内完成制备.     

物理气相传输法合成AlN单晶性能表征

采用物理气相传输(PVT)法通过同质外延生长获得14 mm×12 mm的AlN单晶样品。对样品进行切割、研磨、化学机械抛光处理后，采用拉曼光谱仪、高分辨X射线衍射仪、X射线光电子能谱仪、光致发光光谱仪对样品进行测试表征。拉曼测试结果表明，晶体中心区域的拉曼光谱E₂(high)声子模的半峰全宽为3.3 cm^-1,边缘区域E₂(high)声子模的半峰全宽为4.3 cm^-1,晶体呈现较高的结晶质量。XRD摇摆曲线表征结果显示，外延生长后的晶体中心和边缘区域的摇摆曲线半峰全宽增大至100″和205″,表明晶体内存在缺陷。XPS测试结果表明，晶体内存在C、O、Si杂质元素，杂质的原子数分数分别为0.74%、1.43%、2.14%,晶体内发现以氧杂质为主的Al—O、N—Al—O等特征峰。光致发光光谱测试结果显示，晶体内存在V_Al-O_N复合缺陷和V_Al点缺陷。     

硅基片上异质外延SiC的机理研究

本文利用低压高温MOCVD系统,成功地在Si(111)基片上外延出了具有高质量的SiC薄膜,并对其反应机理做了一些初步的研究.大部分观点认为,SiC/Si的异质外延,其最初的状态应该为Si衬底中Si的扩散.但是,本文通过在不同流量比的条件下,SiC薄膜在Si基片以及Al2O3基片上外延的比较,发现在SiC/Si的异质外延过程中起重大作用的并非Si衬底中Si的扩散,而是很大程度上作用于C向Si衬底的扩散.同时,还发现反应速率的快慢受SiH4流量所限制.当SiH4流量增加时,反应速率会明显加快,但是结晶质量会相对变差.     

大尺寸光通讯磁光薄膜衬底钆镓石榴石（Gd3Ga5O12）单晶的生长研究

随着光纤通讯产业的迅猛发展,市场对3英寸光通讯磁光薄膜衬底钆镓石榴石（分子式为Gd3Ga5O12,简称GGG）的需求量急剧增加。本文从磁光薄膜（YIG以及类YIG）对其外延基底单晶GGG物化性能的要求出发,综述了在利用传统的提拉法生长大尺寸、符合磁光薄膜衬底要求的Gd3Ga5O12单晶的过程中,出现的诸如Ga2O3组分挥发,界面翻转,螺旋生长和晶体的开裂等问题,针对各个问题讨论了它们的形成机制并提出了它们的解决方法。最后,还根据目前磁光膜的发展情况,预见了纯GGG和掺质GGG单晶的研究和发展趋势。     

HVPE growth of semi-polar (1 1 2¯ 2)GaN on GaN template (1 1 3)Si substrate

The hydride-vapour-phase-epitaxial (HVPE) growth of semi-polar (1 1 2¯ 2)GaN is attempted on a GaN template layer grown on a patterned (1 1 3) Si substrate. It is found that the chemical reaction between the GaN grown layer and the Si substrate during the growth is suppressed substantially by lowering the growth temperatures no higher than 900 °C. And the surface morphology is improved by decreasing the V/III ratio. It is shown that a 230-μm-thick (1 1 2¯ 2)GaN with smooth surface is obtained at a growth temperature of 870 °C with V/III of 14.     

Bulk GaN crystals grown by HVPE

We succeeded in preparing very thick c-plane bulk gallium nitride (GaN) crystals grown by hydride vapor phase epitaxy. Growth of the bulk GaN crystals was performed on templates with 3 μm GaN layer grown by metal organic chemical vapor deposition on (0 0 0 1) sapphire substrates. Colorless freestanding bulk GaN crystals were obtained through self-separation processes. The crystal's diameter and thickness were about 52 and 5.8 mm, respectively. No surface pits were observed within an area of 46 mm diameter of the bulk GaN crystal. The dislocation density decreased with growth direction (from N-face side to Ga-face side) and ranged from 5.1×10⁶ cm⁻² near the N-face surface to 1.2×10⁶ cm⁻² near the Ga-face. A major impurity was Si, and other impurities (O, C, Cl, H, Fe, Ni and Cr) were near or below the detection limits by SIMS measurements.     

The origin of the residual conductivity of GaN films on ferroelectric materials

In this paper, the origin of the conductivity of GaN films grown on ferroelectric materials was investigated using XPS, AES, and XRD analysis tools. Depth profiles confirmed the existence of impurities in the GaN film originating from the substrates. Bonding energy analysis from XPS and AES verified that oxygen impurities from the substrates were the dominant origin of the conductivity of the GaN film. Furthermore, Ga-rich GaN films have a greater chance of enhancing diffusion of lithium oxide from the substrates, resulting in more substrate phase separation and a wider inter-mixed region confirmed by XRD. Therefore, the direct GaN film growth on ferroelectric materials causes impurity diffusion from the substrates, resulting in highly conductive GaN films. Future work needs to develop non-conductive buffer layers for impurity suppression in order to obtain highly resistive GaN films.     

LPE生长GaN的不同极性面的光学性质

极化效应会导致GaN基发光器件的效率降低,因此关于非极性和半极性GaN单晶的研究受到了广泛关注。为了进一步探究不同极性GaN的发光特性和杂质掺入的内在机理,本文利用钠助熔剂法侧向生长出的不同极性面的GaN单晶作为研究对象,对比了不同极性面的光学性质及杂质掺入特点,讨论了黄光带(YL)峰的起源及其影响因素。首先利用阴极荧光(CL)、光致发光(PL)对液相外延(LPE)法生长的不同极性方向的GaN的光学性质进行了研究。结果表明,不同的生长极性面会显露出不同的光学特性。朝着侧向生长的 [1122] 和 [1120] GaN的CL和PL特性相似,但与 [0001] GaN的光谱有较大差异。PL杂质峰包含两个肩峰peak 1(2.2 eV)和peak 2 (2.6 eV),在不同极性面中强度占比各不相同,推测分别与C_NO_N和C_N缺陷的0/+能级的跃迁有关。通过SIMS元素分析,C元素分布较为均匀,O元素分布存在较大差异,在[1122]区域沿着生长方向O含量逐渐增加,结合PL中2.2 eV处峰的强度增加,进一步证明了2.2 eV处的峰强与O含量存在正相关性。     

Interface of GaN grown on Ge(1 1 1) by plasma assisted molecular beam epitaxy

Early efforts to grow GaN layers on germanium substrates by plasma assisted molecular beam epitaxy led to GaN domains, rotated by 8° relative to each other. Increased insight in the growth of GaN on germanium resulted in the suppression of these domain and consequently high quality layers. In this study the interface of these improved layers is investigated with transmission electron microscopy. The GaN layers show high crystal quality and an atomically abrupt interface with the Ge substrate. A thin, single crystalline Ge₃N₄ layer is observed in between the GaN layer and Ge substrate. This Ge₃N₄ layer remains present even at growth temperatures (850 °C) far above the decomposition temperature of Ge₃N₄ in vacuum (600 °C). Triangular voids in the Ge substrate are observed after growth. Reducing the Ga flux at the onset of GaN growth helps to reduce the triangular defect size. This indicates that the formation of voids in the Ge substrate strongly depends on the presence of Ga atoms at the onset of growth. However complete elimination was not achieved. The formation of voids in the germanium substrate leads to diffusion of Ge into the GaN layer. Therefore we examined the diffusion of Ge atoms into the GaN layer and Ga atoms into the Ge substrate. It was found that the diffusion of Ge into the GaN layer and Ga into the Ge substrate can be influenced by the growth temperature but cannot be completely suppressed. Our results suggest that Ga atoms diffuse through small imperfections in the Ge₃N₄ interlayer and locally etch the Ge substrate, leading to the diffusion of Ga and Ge atoms.     

Lateral confined epitaxy of GaN layers on Si substrates

We developed a novel, simple procedure for achieving lateral confined epitaxy (LCE). This procedure enables the growth of uncracked GaN layers on a Si substrate, using a single, continuous metalorganic chemical vapor deposition (MOCVD) run. The epitaxial growth of GaN is confined to mesas, defined by etching into the Si substrate prior to the growth. The LCE-GaN layers exhibit improved morphological and optical properties compared to the plain GaN-on-Si layers grown in the same MOCVD system. By performing a set of LCE growth runs on mesas of varying lateral dimensions, we specified the crack-free range of GaN on Si as 14.0±0.3 μm.     

MOVPE of AlN-free hexagonal GaN/cubic SiC/Si heterostructures for vertical devices

The heterostructures of GaN/SiC/Si were prepared without using AlN or AlGaN buffer layers (AlN buffers) in the metalorganic vapor phase epitaxy of GaN on SiC. GaN (0 0 0 1) with specular surface was obtained. The AlN buffers are usually used in the conventional growth of GaN on SiC due to the poor nucleation of GaN on SiC. Instead, the nucleation of GaN was controlled by varying the partial pressure of H₂ in the carrier gas, the mixture of H₂ and N₂, during the low-temperature (600 °C) growth of GaN (LT-GaN). After the LT-GaN, the high-temperature (1000 °C) growth of GaN was performed using pure H₂ as the carrier gas. The epitaxial film of cubic SiC (1 1 1) on a Si (1 1 1) substrate was used as the SiC template. Increasing the partial pressure of H₂ in the carrier gas decreased the coverage of SiC surface by LT-GaN. It is suggested that the hydrogen atoms adsorbed on the surface of SiC is preventing the nucleation of GaN.     

Investigation of preparation and properties of epitaxial growth GaN film on Si(1 1 1) substrate

In this paper, a single crystalline GaN grown on Si(1 1 1) is reported using a GaN buffer layer by a simple vacuum reactive evaporation method. Scanning electron microscopy (SEM), X-ray diffraction (XRD), photoluminescence measurement (PL), and Hall measurement results indicate that the single crystalline wurtzite GaN was successfully grown on the Si(1 1 1) substrate. The surface of the GaN films is flat and crack-free. A pronounced GaN(0 0 0 2) peak appears in the XRD pattern. The full-width at half-maximum (FWHM) of the double-crystal X-ray rocking curve (DCXRC) for (0 0 0 2) diffraction from the GaN epilayer is 30 arcmin. The PL spectrum shows that the GaN epilayer emits light at the wavelength of 365 nm with an FWHM of 8 nm (74.6 meV). Unintentionally doped films were n-type with a carrier concentration of 1.76×10¹⁸/cm³ and an electron mobility of 142 cm³/V s. The growth technique described was simple but very powerful for growing single crystalline GaN films on Si substrate.     

TEM investigations of GaN layers grown on silicon and sintered GaN nano‐ceramic substrates

GaN nano‐ceramics were analyzed using transmission electron microscopy (TEM), showing that these ceramics are characterized by highly disoriented grains of the linear size of 100–150 nm. These GaN ceramics were used as substrates for GaN epitaxy in standard MOVPE conditions. For the comparison, MOVPE GaN layers on silicon substrates were grown using similar conditions. It is shown that MOVPE growth of GaN layers is highly anisotropic for both cases. However, the disorientation of the highly mismatched GaN layer on silicon is different from that characterizing GaN layer deposited on the ceramic substrate. In the latter case the disorientation is much higher, and three dimensional in nature, causing creation of polycrystalline structure having large number of the dislocations. In the case of the GaN layer grown on the silicon substrate the principal disorientation is due to rotation around c‐axis, causing creation of mosaic structure of edge dislocations. Additionally, it is shown that the typical grain size in AlN nucleation layer on Si is smaller, of order of 20 nm. These two factors contribute to pronounced differences in later stage of the growth of GaN layer on the ceramic. Due to high growth anisotropy an appropriately thick GaN layer can, eventually, develop flat surfaces suitable for construction of optoelectronic and electronic structures. As shown by the TEM data, this can be achieved only at the cost of creation of the relatively large density of dislocations and stacking faults. The latter defects were not observed for the GaN growth on Si substrates. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and properties of semi-polar GaN on a patterned silicon substrate

Adopting anisotropy etching method, a (1 1 1) facet of Si is obtained on a Si substrate and selective area growth (SAG) of GaN is performed with metal-organic vapor phase epitaxy on the facet. The epitaxial lateral overgrowth of (1 1¯ 0 1), (1 1 2¯ 2) GaN is investigated on (0 0 1) and (1 1 3) Si substrate, respectively, and the incorporation properties of Si, C, and Mg elements are discussed in relation to the atomic configuration on the surface. Analyzing the optical and electrical properties of C-doped (1 1¯ 0 1) GaN layer, it is shown that carbon creates a shallow acceptor level. On the thus prepared (1 1¯ 0 1) GaN layer, a light emitting diode (LED) with a C-doped p-type layer is fabricated.