Na助熔剂法生长氮化镓晶体的研究进展

以高质量GaN单晶基片作为衬底实现GaN的同质外延生长,是获得GaN半导体器件优异性能的基础.高质量GaN单晶基片的缺乏已成为国际范围制约GaN器件发展的瓶颈.在GaN体单晶的几种生长方法中,由于Na助熔剂法的生长条件相对温和且成本相对较低,近年来发展较快.本文从Na助熔剂法的原理、生长工艺、助熔剂种类以及得到晶体尺寸和质量等几方面进行了综述,分析了目前Na助熔剂法生长GaN单晶中的技术问题并提出了进一步研究的一些建议.     

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.     

氮化镓单晶的液相生长

氮化镓(GaN)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衬底材料.除气相法(包括HVPE(氢化物气相外延)、MOCVD(金属有机化合物化学气相沉淀)、MBE(分子束外延))生长GaN单晶外,液相法(包括氨热法和助熔剂法)近几年在制备GaN单晶方面取得了较大的进展.本文介绍了氨热法和助熔剂法的生长原理、装备特点及生长习性;综述了两种液相生长方法的研究历程及研究进展,并对液相法生长GaN单晶的发展趋势及主要挑战进行了展望.     

7MPa氮压下Na助熔剂法生长GaN晶体的研究

采用Na助熔剂法在7 MPa氮压下并引入较大温度梯度(20～70℃/cm),获得了大量毫米级的GaN晶体,GaN晶体产率高达70%以上。光学及SEM照片显示其晶形大部分为六方锥体。晶体粉末衍射分析表明,生成的GaN单晶具有六方纤锌矿结构,与标准卡片符合得很好,而单晶衍射图谱中出现(101-1)的衍射峰,说明GaN单晶锥面为{101-1},其(101-1)面的摇摆曲线的半高宽仅为4.4 arcsec,室温下采用He-Cd 325 nm激光器激发的GaN单晶的PL谱,最高峰位于标准GaN材料的365 nm处,峰的半高宽为13.5 nm,生长的GaN单晶完整性较高。     

BaBPO5晶体的生长研究

本文采用顶部籽晶高温溶液法,以BPO4-NaF为助熔剂,生长了BaBPO5单晶.生长参数:液面以下温度梯度为1.5℃/cm,液面上温度梯度为10℃/cm,晶体旋转速度30r/min,降温速率0.5-1℃/d,可获得尺寸为30mm×20mm×15mm的BaBPO5单晶.测定了所获单晶及其挥发物的X射线粉末衍射图谱,讨论了助熔剂对BaBPO5晶体生长的影响和该晶体的物化性能.     

助熔剂法生长ZnO晶体

采用Bi4B2O9、CdB2O4和BaB2O4为助熔剂,获得了毫米级的氧化锌单晶.Muiliken的电负性理论和Viting的平均轨道电负性提供了一个选择晶体生长所采用的助熔剂的有效方法.实验结果表明ZnO晶体的生长温度比文献报道的均低,从而有效地减少了ZnO以及助熔剂的挥发.本文给出了几种有望获得大尺寸ZnO单晶的助熔剂.     

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.     

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。     

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.     

紫外倍频新晶体K2Al2B2O7的合成与生长

本文以高温固相反应合成了K2Al2B2O7(KABO);以自发成核的方法探索了KABO晶体生长的助熔剂体系,NaF为KABO晶体生长的最适宜助熔剂体系,适宜配比为KABO∶NaF=1∶2,讨论了籽晶方向对晶体生长的影响,[110]方向是KABO晶体生长的最佳籽晶方向;运用顶部籽晶生长技术以NaF为助熔剂成功生长出尺寸达50mm×20mm×17mm,重30g的高光学质量透明单晶.     

Growth behaviour of bulk GaN single crystals grown with various flux ratios using solvent‐thermal method

Bulk GaN single crystals were grown using a solvent‐thermal method. They were grown for 200 h at 600 °C and 800 °C using 8 MPa of N₂ gas and 1–3 mm sized pyramid GaN single crystals. Pure Na, NaN₃ and Ca were used as the flux. The mole fraction of the [flux]/([flux] + [Ga]) was 0.30–0.67. The growth behavior differed according to the flux ratio. The quality of the bulk GaN single crystals was improved by increasing the flux ratio. The bulk GaN single crystals formed by spontaneous nucleation were deposited on the BN crucible wall and bottom during the first step of synthesis. The wurtzite structure of the GaN grown single crystal was confirmed by x‐ray diffration. The chemical composition was analyzed by electron probe microanalysis. The quality and optical properties of the GaN single crystal were examined by Raman spectroscopy and photoluminesence analysis. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Bulk GaN single crystals: growth conditions by flux method

Hexagonal GaN platelet crystals with a size of 1–4 mm have been grown by a Li-based flux method. The influence of growth conditions such as the molar ratio of starting materials, temperature, pressure, the position of Li₃N in the crucible on the growth of GaN single crystals was studied. The quality of GaN single crystal was checked by optical microscope and X-ray rocking curve.     

The influences of supersaturation on LPE growth of GaN single crystals using the Na flux method

The dependency of LPE growth rate and dislocation density on supersaturation in the growth of GaN single crystals in the Na flux was investigated. When the growth rate was low during the growth of GaN at a small value of supersaturation, the dislocation density was much lower compared with that of a substrate grown by the Metal Organic Chemical Vapor Deposition method (MOCVD). In contrast, when the growth rate of GaN was high at a large value of supersaturation, the crystal was hopper including a large number of dislocations. The relationship between the growth conditions and the crystal color in GaN single crystals grown in Na flux was also investigated. When at 800 °C the nitrogen concentration in Na–Ga melt was low, the grown crystals were always tinted black. When the nitrogen concentration at 850 °C was high, transparent crystals could be grown.     

Improvement of crystal quality in ammonothermal growth of bulk GaN

Several key improvements in crystal quality of bulk GaN grown by the ammonothermal method are presented. Full width at half maximum of (0 0 2) X-ray rocking curve was reduced to 53 and 62 arcsec for Ga-side and N-side, respectively. Transparent bulk GaN crystal was also demonstrated. Oxygen and sodium concentrations were reduced to mid-10¹⁸ and mid-10¹⁵ cm⁻³, respectively. We are currently searching for a growth condition that produces transparent bulk GaN with high structural quality and low impurities. Small-sized, semi-transparent GaN wafers were fabricated by slicing the grown bulk GaN crystals, which demonstrate the high feasibility of ammonothermal growth for production of GaN wafers.     

改进的升华法制备氮化铝单晶体

采用改进的升华法在氮气环境下制备氮化铝单晶体.通过优化实验条件制备出了六角形的高质量的氮化铝单晶体.实验发现,在坩埚的不同区域得到的氮化铝晶体的大小和形态有所不同.讨论了温度梯度对氮化铝晶体尺寸大小和形态的影响.     

掺杂对GaN晶体力学性能影响的研究

对GaN单晶力学性能的研究有助于解决其在生长、加工和器件应用中的开裂问题。本文围绕掺杂对GaN单晶力学性能的影响，通过纳米压痕法测试了不同掺杂类型(非掺、Si掺和Fe掺)GaN单晶的弹性模量和硬度，测试结果表明掺杂对GaN单晶的硬度有重要影响。Si掺、Fe掺GaN较非掺样品硬度有所提升，用重掺杂的氨热GaN单晶作为对照，也证明了这一结论。通过高分辨X射线衍射分析和原子力显微镜表征实验发现，晶体结晶质量、接触面积等因素对GaN单晶硬度的影响较小。对GaN表面纳米压痕滑移带长度和晶体晶格常数进行测试，结果表明，掺杂影响GaN单晶硬度的主要原因是缺陷对GaN位错增殖、滑移的阻碍作用和掺杂引起的GaN晶格常数的变化。     

高温溶液法生长SiC单晶的研究进展

碳化硅(SiC)作为第三代半导体材料,不仅禁带宽度较大,还兼具热导率高、饱和电子漂移速率高、抗辐射性能强、热稳定性和化学稳定性好等优良特性,在高温、高频、高功率电力电子器件和射频器件中有很好的应用潜力。高质量、大尺寸、低成本SiC单晶衬底的制备是实现SiC器件大规模应用的前提。受技术与工艺水平限制,目前SiC单晶衬底供应仍面临缺陷密度高、成品率低和成本高等问题。高温溶液生长(high temperature solution growth, HTSG)法生长SiC单晶具有晶体结晶质量高、易扩径、易实现p型掺杂等独特的优势,有望成为大规模量产SiC单晶的主要方法之一,目前该方法的主流技术模式是顶部籽晶溶液生长(top seeded solution growth, TSSG)法。本文首先回顾总结了TSSG法生长SiC单晶的发展历程,接着介绍和分析了该方法的基本原理和生长过程,然后从晶体生长热力学和动力学两方面总结了该方法的研究进展,并归纳了该方法的优势,最后分析了TSSG法生长SiC单晶技术在未来的研究重点和发展方向。     

大尺寸Nd,Ce∶YAG激光晶体的生长及缺陷研究

双掺Nd,Ce∶YAG晶体相比传统的Nd∶YAG具有输出能量高、激光振荡阈值低的优点。近几年高能效固体激光器的发展对大尺寸、高质量Nd,Ce∶YAG晶体的需求越来越大。采用提拉法生长大尺寸Nd,Ce∶YAG时,极易出现包裹物和开裂缺陷。本文通过理论与实践相结合的方式分析了晶体在生长过程中产生缺陷的原因,并提出了解决办法,成功生长出直径ø50 mm等径长150 mm的高质量Nd,Ce∶YAG单晶。本研究可为批量化生长大尺寸Nd,Ce∶YAG晶体的质量改进提供方向和指导。     

Growth of YCOB single crystals by flux technique and their characterization

Nonlinear optical single crystals of YCOB with good optical quality were grown by the flux technique for the first time. Polycrystalline YCOB samples were synthesized by solid state reaction method. The thermal analysis of the sample was performed with lithium carbonate flux in different weight proportions and the growth temperature was optimised. Single crystals of YCOB with dimensions 3 × 3 × 5 mm³ were obtained by the method of ‘slow‐cooling’. The grown crystals were characterized by XRD, UV‐VIS‐NIR, EDAX, FTIR and etching studies. The powder XRD pattern revealed the formation of YCOB compound. The lattice parameters were identified through single crystal XRD studies. The UV‐VIS‐NIR results showed that the crystal has a sharp cutoff at 220 nm and is nearly 55% transparent over a wide wavelength range enabling applications in the UV region. The EDAX measurement revealed the ‘flux‐free’ crystal formation. The presence of the functional groups belonging to the YCOB crystals was identified by the FTIR results. ‘Hillock‐like’ patterns are observed in the etching studies. The primary emphasis in this study is laid to describe ‘flux technique’ as an alternative method to grow YCOB crystals. The results are presented and discussed. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Surface morphology studies on sublimation grown GaN by atomic force microscopy

Bulk single crystals and selectively grown gallium nitride (GaN) have been obtained using the sublimation technique. Crystals of size about 2–3 mm in length and 0.8–1.0 mm in width have been grown successfully. Atomic force microscopy has been employed to analyze the surface morphology of the as-grown samples to understand the growth mechanism. In free standing bulk GaN single crystals, two-dimensional growth is dominated by step growth mechanism. However, in the selective growth of GaN by sublimation, spiral growth originating from screw dislocation dominates.