氮化铝纳米结构的生长与物性研究

氮化铝(AlN)纳米结构除了具备AlN本身宽带隙、高热导率、高击穿场强和高热稳定性等优异物理性能外,还具备表面效应和小尺寸效应所引起的独特物理和化学性质,因而受到人们的广泛关注.在国内外研究学者多年的不懈努力和研究下,目前已经能够生长结晶质量较高的AlN纳米结构,并在光学、电学和磁学等领域发挥着重要的作用.在本文中,首先探讨了包括化学气相沉积法、物理气相传输法、直流电弧放电法、氢化物气相外延法、分子束外延法等不同AlN纳米结构制备方法的研究进展.随后系统地总结了在不同方法制备过程中,温度、源、气氛、生长时间和催化剂等因素对AlN纳米结构的形貌和结晶质量的影响,并分析了它们的生长机理.最后还详细介绍和讨论了AlN纳米结构的物理性质.     

PVT法AlN单晶生长技术研究进展及其面临挑战

氮化铝(AlN)具有超宽禁带宽度(6.2 eV)、高热导率(340 W/(m·℃))、高击穿场强(11.7 MV/cm)、良好的紫外透过率、高化学和热稳定性等优异性能,是氮化镓基(GaN)高温、高频、高功率电子器件以及高Al组分深紫外光电器件的理想衬底材料.物理气相传输(PVT)法是制备大尺寸高质量AlN单晶最有前途的方法.本文介绍了AlN单晶的晶体结构、基本性质及PVT法生长AlN晶体的原理与生长习性.基于AlN单晶PVT生长策略,综述了自发形核工艺、同质外延工艺及异质外延工艺的研究历程,各生长策略的优缺点及其最新进展.最后对PVT法生长AlN单晶的发展趋势及其面临的挑战进行了简要展望.     

PVT法钨坩埚系统中自发生长自支撑AlN单晶及其表征分析

采用物理气相传输(PVT)法在AlN原料表面自发生长出大量毫米级尺寸的AlN单晶.本文对该工艺下AlN单晶的自然形貌、极性、杂质含量等进行了分析.实验及分析结果表明,在实验工艺条件下,原料表面生长的AlN晶粒具有规则的六方外形,晶粒沿C向择优生长且具有高的生长速率(约200～ 250 μm/h),但径向生长受限于{10-10}(m面).不同颜色的AlN晶粒经机械切割及化学机械抛光(CMP)后,形成高表面质量的C轴取向抛光片.通过化学湿法腐蚀和SEM表征发现,淡黄色晶粒为Al极性晶体,暗棕色晶粒为N极性晶体,淡黄-暗棕混合色晶粒为Al/N混合极性晶体,其内部可以观察到清晰的两种极性分界.通过GDMS与EGA对不同颜色晶粒内部的主要杂质元素含量进行了分析,结果表明,淡黄色晶粒内氧元素的含量相比暗棕色晶粒的含量低,而碳含量则相反.     

氮化物宽禁带半导体的MOCVD大失配异质外延

以氮化镓(GaN)、AlN(氮化铝)为代表的Ⅲ族氮化物宽禁带半导体是研制短波长光电子器件和高频、高功率电子器件的核心材料体系.由于缺少高质量、低成本的同质GaN和AlN衬底,氮化物半导体主要通过异质外延,特别是大失配异质外延来制备.由此导致的高缺陷密度、残余应力成为当前深紫外发光器件、功率电子器件等氮化物半导体器件发展的主要瓶颈,严重影响了材料和器件性能的提升.本文简要介绍了氮化物半导体金属有机化学气相沉积(MOCVD)大失配异质外延的发展历史,重点介绍了北京大学在蓝宝石衬底上AlN、高Al组分AlGaN的MOCVD外延生长和p型掺杂、Si衬底上GaN薄膜及其异质结构的外延生长和缺陷控制等方面的主要研究进展.最后对Ⅲ族氮化物宽禁带半导体MOCVD大失配异质外延的未来发展做了简要展望.     

在Si(100)上以AlN作过渡层低温外延生长ZnO薄膜

采用脉冲激光沉积(PLD)方法在Si(100)上成功生长了高度c轴取向的AlN薄膜,并以此为衬底,实现了ZnO薄膜的低温准外延生长.通过X射线衍射(XRD)、原子力显微镜(AFM)以及荧光分光光度计表征ZnO薄膜的结构、表面形貌和发光性能.结果表明,ZnO薄膜能在AlN过渡层上沿c轴准外延生长,采用AlN过渡层后,其荧光强度也有大幅提高.     

AlN单晶生长行为研究

本文采用物理气相传输法对不同衬底温度和温差下制备的氮化铝(AlN)晶体形貌进行研究,研究结果表明AlN晶体生长受到AlN晶面表面能、Al基元平均动能和AlN晶体表面极性的共同影响.当温差为60℃时,AlN晶体(0001)面生长速率小于(10-10)面,AlN以带状形式生长.将该工艺应用于AlN同质生长中,研究结果表明:温差为60℃时AlN晶体(0001)面呈现畴生长模式,该晶体质量最差;温差为35℃时AlN晶体(0001)面呈现台阶流生长模式,该晶体质量最优;温差为20℃时AlN晶体(0001)面呈现台阶簇生长模式,该晶体容易开裂.通过工艺优化最终获得了直径为40 mm AlN单晶衬底,完全满足器件制备需求.     

升华法制备m面非极性-AlN单晶体的研究

AlN晶体在c轴方向具有很强的自发和压电极化效应,影响了其器件的性能.生长高质量的非极性面AlN晶体材料是解决该问题的有效途径.本研究结合AlN晶体沿c轴择优生长的特点,使用自行设计的双区电阻加热生长装置,升华制备出尺寸为厘米级m面非极性AlN单晶体,并利用X射线衍射和能谱对样品进行测试分析.实验结果表明AlN单晶体的方向为(100),铝和氮原子比例为50.3;和49.7;,接近理想比例1∶1.最后,对m面非极性AlN单晶体的形成机理进行探讨.     

以尿素为氮源合成AlN粉体过程中非晶碳的石墨化

针对有机合成过程中碳及碳化物的残余,传统方法中普遍使用除碳的工艺,而很少有文章针对非晶碳的结构和形貌进行表征。为此,本文采用高尿素含量的前驱盐体系,通过在氮气保护气氛中煅烧获得AlN粉体。采用X射线衍射分析、红外和拉曼光谱分析、扫描电子显微镜和透射电子显微镜对850~1 500 ℃温度范围内煅烧获得产物的结构和形貌进行表征,对AlN合成过程中含碳产物结构形貌的变化,以及AlN和含碳产物之间相互的依存生长关系进行分析。结果表明,AlN生长的过程中伴随着无定形碳的石墨化转变,AlN颗粒的形貌也受含碳残余产物形貌的影响而出现有规律的变化。     

AlN晶体PVT生长装置的智能控制系统研究

AlN晶体的物理气相传输(PVT)法生长条件要求苛刻,如0.3~5 atm的高纯氮气生长气氛和2100~2400 ℃的生长温度.结合AlN晶体PVT生长工艺的特点,通过可编程逻辑控制器(PLC)进行适用于氮化铝(AlN)晶体PVT生长装置的智能控制系统的研究.首先,提出了倒置温场的生长工艺以降低AlN晶体PVT生长的成核数量,并通过自动控制程序设计满足不同生长阶段的温场要求;其次,针对设备可能存在超温、超压及冷却水断流等实验安全问题,设计并实现系统的自动化报警及自处理操作;最后,在实验操作上,实现AlN晶体生长的"一键式"全自动化工作.     

低温AlN插入层降低硅基GaN膜微裂

为了降低MOCVD外延硅基GaN膜层中的应力、减少硅基厚GaN层的微裂;在高温GaN层中插入低温AlN.低温AlN插入层可平衡HT-GaN生长和降温过程引起的张应力,降低厚膜外延层的微裂,已研制出厚度超过1.8微米无微裂GaN外延层.本文重点研究了低温AlN生长温度对HT-GaN材料的影响,给出了较佳的LT-AlN生长温度.采用扫描电子显微镜(SEM),原子力显微镜(AFM)和高分辨率双晶X射线衍射(DCXRD),对样品进行了测试分析.试验和测试结果表明低温AlN的生长温度至关重要,生长温度过低影响GaN晶体质量,甚至不能形成晶体;生长温度过高同样会影响GaN结晶质量,同时降低插入层的应力平衡作用;实验结果表明最佳的LT-AlN插入层的生长温度为680℃左右.     

PVT法同质外延制备大尺寸Al极性氮化铝晶体生长工艺及其表征分析研究

本文基于自主设计的氮化铝生长炉,开展了四组不同工艺条件下Al极性面氮化铝籽晶同质外延生长氮化铝单晶的生长特征及其结晶质量表征研究。研究发现:不同工艺条件下生长的晶体的拉曼图谱E₂(high)特征峰峰位表明,晶体内部均存在较小的拉应力;在坩埚顶部在相对较高温度2 210 ℃、坩埚底部与顶部温差42 ℃的低过饱和度生长条件下,晶体表面光滑,呈现阶梯流生长形貌,并具有典型的氮化铝单晶生长习性面,晶体初始扩张角大于40°,高分辨率X射线衍射(HRXRD)测得0002、1012反射摇摆曲线及拉曼光谱检测结果表明,该条件下生长的氮化铝晶体结晶质量优异,并可实现快速扩径。基于该生长条件,通过外延生长后成功获得尺寸ϕ45~47 mm的氮化铝单晶锭,相关表征结果表明生长的氮化铝晶体具有优越的结晶性能。     

用于晶体生长的氮化铝保温材料的研究

在不添加任何添加剂的情况下,采用氮化铝粉体作高温气相法生长氮化铝晶体的保温材料.实验结果表明:氮化铝保温材料具有耐高温、对钨坩埚材料没有损伤、使用寿命长、不易在晶体中引入杂质等优点,是一种优良的高温保温材料.与目前常用的石墨保温材料相比较,氮化铝存在热导率相对较高、在高温过程中会少量升华污染炉腔等缺点,在使用中要采取一定的对策,以消除其不利影响.     

气相生长氮化铝单晶的新方法

通过在钨坩埚盖开小孔的方法改变氮化铝结晶衬底上的温度场分布,在开孔处形成局部低温区;由于孔的几何尺寸的限制和氮化铝晶体生长的各向异性,开孔处的氮化铝晶体单晶化;随后,开孔处的单晶起籽晶的作用,逐渐长成较大尺寸、较高质量的氮化铝单晶.目前用该方法已经制备出直径大于2mm的氮化铝单晶体.     

Effects of real-time monitored growth interrupt on crystalline quality of AlN epilayer grown on sapphire by molecular beam epitaxy

Crack-free aluminum nitride (AlN) epilayers were grown on sapphire using growth-interrupt technique by radio-frequency assisted molecular beam epitaxy. In-situ reflectance spectroscopy was introduced for real-time monitoring of the growth of AlN epilayers. X-ray diffraction and atomic force microscopy measurements reveal that the threading dislocation density decreases considerably by using the growth-interrupt technique. Raman spectroscopy is used to characterize the residual stress of AlN epilayers. The optical transmittance and absorption spectra of AlN epilayers show a high transmittance and a sharp absorption edge.     

AlInN MOVPE: growth chemistry and analysis of trends

Comprehensive model of AlInN Metal-Organic Vapor Phase Epitaxy (MOVPE) accounting for the gas-phase and surface chemistry including parasitic reactions/particle formation is developed. Experimental data and modeling results suggest that as V/III ratio increases from several tens (growth of pure AlN) to several thousands (growth of AlInN), the partial AlN growth rate decreases even in the absence of strong particle formation. This effect is associated with the formation of heavy molecular weight/low diffusivity gas-phase dimer species at high ammonia concentration. At elevated pressures growth rate decreases with pressure at a weakly changing composition, which is related to the gas-phase losses of In- and Al-containing species due to reaction with AlN particles. Model allows the prediction of both the AlInN growth rate and composition versus group-III flow rates, temperature, and pressure.     

Possibility of AlN growth using Li–Al–N solvent

The possibility of AlN growth using Li–Al–N solvent was investigated. Based on theoretical prediction, we selected Li₃N as a suitable nitrogen source for AlN growth. First, vapor phase epitaxy using Li₃N and Al as source materials was performed to confirm the following reaction on the growth surface: Li₃N+Al=AlN+3Li. The results suggest that the reaction proceeds to form AlN on the substrate under appropriate conditions. Next, AlN growth using Li–Al–N solvent was carried out. The Li–Al–N solvent was prepared by annealing of mixtures composed of Li₃N and Al. The results imply that AlN was formed under an Al-rich condition. Moreover, it was found that Li was swept out from AlN grains during growth. The results suggest that AlN growth using Li–Al–N solvent might be a key technology to obtain an AlN crystal boule.     

双靶磁控溅射聚焦共沉积AlN薄膜生长速率研究

采用直流双靶磁控溅射聚焦共沉积技术在Fe衬底上高速率生长A lN薄膜,结果表明,双靶共沉积技术有效地提高了A lN薄膜生长速率,相同工作气压或低N2浓度时双靶磁控溅射沉积速率约为单靶沉积速率的2倍;随着溅射系统内工作气压或N2浓度的升高,薄膜生长速率不断减小;薄膜择优取向与薄膜生长速率相互影响,随着工作气压的升高,(100)晶面的择优生长减缓了薄膜生长速率的降低,随着N2浓度的升高,(002)晶面的择优生长加剧了薄膜生长速率的降低,而相对较低的溅射沉积速率有利于(002)晶面择优取向生长。     

Effects of initial stages on the crystal quality of nonpolar a-plane AlN on r-plane sapphire by low-pressure HVPE

A 4–6 μm thick a-plane (1 1 2¯ 0) AlN was grown on r-plane sapphire substrate by low-pressure hydride vapor phase epitaxy (LP-HVPE), using a direct growth without any nitridation and buffer layer, a single-step nitridation growth, a two-step nitridation growth and a two-step buffer growth method. For the two-step buffer growth procedure, smoother surface is observed with the lower full widths at half maximum (FWHM) of X-ray rocking curves (XRC) compared with the other two kinds of nitridation procedures. A smaller FWHM of in-plane XRC peak anisotropy features are reversed, which is consistent with the smaller in-plane stress anisotropic distribution in a-plane AlN, when the two-step nitridation or buffer growth method is used. In four kinds of initial growth procedures, the two-step buffer method is the suitable method for the growth of a-plane AlN by HVPE with the high crystal quality and more isotropic distribution.     

Growth of AlN single crystals on 6H‐SiC (0001) substrates with AlN MOCVD buffer layer

6H‐SiC (0001) deposited 300 nm thick AlN film by MOCVD was used as the substrate to grow AlN crystals by the physical vapour transport (PVT) method. It was confirmed that c‐axis oriented AlN films were grown and this material had a 3D growth mode. The root mean square (RMS) value for the film was measured to be 2.17 nm. Nucleation and further growth of AlN on so prepared substrate was investigated. Colorless and transparent AlN crystal with 1 mm thick and 40 mm in diameter was obtained after 4 h growth on this substrate. The transparent AlN showed strong (0001) texture XRD patterns, only the (0002) reflection was observed in symmetric θ‐2θ scans. The full width at half maximum for a (0002) X‐ray rocking curve was less than 0.1° indicating good crystalline quality. Anisotropic etchings in molten KOH shows that the growth (0001) plane exposed to the AlN source predominately has an aluminum polarity, no N‐polar inversion domains were observed. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)