GaN基三维结构生长与器件应用

目前,c面氮化镓(GaN)基发光二极管的制备技术已经十分成熟并取得了商业化成功,但仍面临极化电场导致的大电流密度下效率下降(Droop效应)和黄绿光波段效率低的问题.为消除极化电场的影响,人们开始关注半极性和非极性面GaN.其中,基于传统极性面衬底通过三维结构生长来获得半极性和非极性GaN的方法,由于其低成本和生长的灵活性,受到了广泛研究.本文首先总结了三种GaN三维结构的制备方法并分析其生长机理.接着,在此基础上介绍了不同晶面InGaN量子阱的外延生长和发光特性.最后,列举了GaN基三维结构在半极性面LED、颜色可调LED和无荧光粉白光发光二极管方面的应用.     

非极性GaN薄膜及其衬底材料

本文分析了在不同衬底上生长无极性GaN薄膜的情况,这些衬底主要包括γ-LiAlO2、r面蓝宝石等.通常在蓝宝石上制备的GaN外延膜是沿c轴生长的,而c轴是GaN的极性轴,导致GaN基器件有源层量子阱中出现很强的内建电场,发光效率会因此降低,发展非极性面外延,有望克服这一物理现象,使发光效率提高.     

光学浮区法生长掺锡氧化镓单晶及性能研究

作为垂直结构的GaN基LED新型衬底材料,β-Ga2 O3单晶已经引起了人们的广泛关注.β-Ga2O3单晶的导电性是通过掺杂来实现的,Sn4掺入是其中一种很好提高-Ga2O3导电性的方法.利用光学浮区法生长了尺寸为5×20 mm2,掺杂浓度为10;的掺锡氧化镓单晶(Sn∶ β-Ga2O3),并对Sn∶ β-Ga2O3单晶的缺陷密度、导电和荧光光谱特性进行了研究.结果表明:实验制得Sn∶β-Ga2O3样品的线缺陷约为6.51×105/cm2,掺入Sn4+杂质后β-Ga2 O3的电导率增加,样品的最高电导率为2.210 S/cm,同时Sn4+的掺入会抑制β-Ga2O3的红绿光发射.     

氮化镓晶体的氨热法生长进展

GaN作为性能最为优异的第三代半导体材料,其高质量的衬底材料的研发是目前乃至近5年的研究热点,而最好的衬底材料即为GaN体单晶.在为数不多的GaN体单晶的几种生长方法中,氨热法被普遍认为是生长GaN体单晶的一种很有前途的方法.本文主要论述了在不同矿化剂生长条件下GaN晶体的氨热法生长进展,指出了存在的问题,并给出了一些解决办法.     

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。     

硼含量对含硼金刚石单晶电学性能的影响

采用碳化硼添加量不同的铁基触媒,在高温高压下合成含硼金刚石单晶.用数字电桥和自制的电阻测量夹具测量了含硼金刚石单晶的电阻;用阴极射线发光光谱测量了金刚石单晶的光子频数;用XRD检测了不同硼含量掺杂的金刚石单晶的晶体结构.结果表明:随着触媒中碳化硼添加量的增加,含硼金刚石单晶的电阻率降低,可呈现半导体电阻特性.其原因是硼元素的掺入促进了金刚石单晶的(111)晶面生长,使受主能级提高,晶体的带隙变窄,载流子浓度提高.     

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.     

HVPE生长室气流分布模拟及GaCl载气流量对GaN单晶生长的影响

采用计算流体力学软件Fluent对HVPE反应室进行了数值模拟,研究了GaCl载气流量对HVPE反应室气流分布的影响,发现GaCl载气流量是影响GaCl和NH3在衬底上均匀分布的重要因素.采用HVPE方法在不同GaCl载气流量下生长GaN单晶,研究了GaCl载气流量对GaN单晶质量的影响,得到了与模拟一致的结果.     

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.     

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.     

Defect-related emission characteristics of nonpolar m-plane GaN revealed by selective etching

A comprehensive study of the morphology and luminescence characteristics of nonpolar m-plane GaN etched in hot acids was presented. It was found that many four-sided pyramidal pits were distributed on the etched GaN surface with the long side perpendicular to the [1 1 2? 0] direction, corresponding to the threading dislocations. When compared to the as-grown GaN, DAP emission intensity and its LO-phonon coupling phenomenon in the etched GaN were greatly attenuated, whereas the intensity of BSF-related band almost kept constant due to its immunity to chemical etching. Especially, a new PSF-related emission at 3.32 eV emerged in CL spectra of etched GaN. Simultaneously, partial relaxation of compressive stress happened for the etched GaN epilayer according to the red shift of NBE emission in photoluminescence (PL) and E₂(high) phonon peak in the Raman spectra. Contrary, the DAP peak in etched GaN was blueshifted, likely due to the reduced impurity level fluctuation by etching. In addition, the different behaviors were discussed for NBE and defect-related transitions in the etched GaN, characterized by excitation power- and temperature-dependent PL.     

Fe掺杂GaN晶体非极性面的光学各向异性研究

本文利用低温光致发光谱(PL)研究了Fe掺杂GaN晶体非极性a面{1120}、m面{1100} 的带边峰和Fe³⁺相关峰(⁴T₁(G)- ⁶A₁(S))的偏振发光特性。结果表明:a面与m面光学各向异性差别较小,线偏振光的电矢量E平行于c轴[0001]时(E∥c),GaN带边峰强度最小,而Fe³⁺零声子峰(1.299 eV)强度最强。带边峰线偏振度小,而Fe³⁺零声子峰线偏振度大,a面带边峰的线偏振度为26％,Fe³⁺零声子峰的偏振度在a面和m面分别达到55%和58%。在5 K低温下,进一步测量了Fe³⁺精细峰和声子伴线的偏振特性,结果表明,除了一个微弱的峰外,其他精细峰和声子伴线与Fe³⁺零声子峰偏振特性一致。本研究有助于拓展Fe掺杂GaN晶体材料在新型偏振光电器件领域的应用。     

Characterization of polycrystalline GaN grown on silica glass substrates

The structural, optical, and electrical properties of GaN films grown on silica glass substrate by metalorganic chemical vapor deposition were studied. X-ray diffraction showed that the films were grown in hexagonal structure with a predominant (0 0 0 2) peak. A broad and strong band-edge emission and very weak yellow luminescence in photoluminescence (PL) spectra were observed. And the temperature dependence of the PL spectra was extensively studied. The thermal quenching activation energy was found to be very close to the donor activation energy determined from the temperature dependence of the carrier concentration. Longitudinal optical phonons were found to be responsible for the PL broadening above 100 K.     

Growth of Eu-doped GaN by gas source molecular beam epitaxy and its optical properties

Eu-doped GaN with various Eu concentrations were grown by gas source molecular beam epitaxy, and their structural and optical properties were investigated. With increasing Eu concentration from 0.1 to 2.2 at%, deterioration of the structural quality was observed by reflection high-energy electron diffraction, atomic force microscopy and X-ray diffraction. Such a deterioration may be caused by an enhancement of island growth and formation of dislocations. On the other hand, room temperature photoluminescence spectra showed red emission at 622 nm due to an intra-atomic f–f transition of Eu³⁺ ion and Fourier transform infrared spectra indicated an absorption peak at about 0.37 eV, which may be due to a deep defect level. The intensity of the red luminescence and the defect-related absorption peak increased with increasing Eu concentration, and a close correlation in the increasing behavior was observed between them. These results suggest that the deep defect level plays an important role in the radiative transition of Eu³⁺ ion in GaN and the optical process for the luminescence at 622 nm was discussed with relation to the defect.     

Studies on the effect of ammonia flow rate induced defects in gallium nitride grown by MOCVD

Gallium nitride (GaN) epitaxial layers were grown with different V/III ratios by varying the ammonia (NH₃) flow rate, keeping the flow rate of the other precursor, trimethylgallium (TMG), constant, in an MOCVD system. X-ray rocking curve widths of a (1 0 2) reflection increase with an increase in V/III ratio while the (0 0 2) rocking curve widths decrease. The dislocation density was found to increase with an increase in ammonia flow rate, as determined by hot-wet chemical etching and atomic force microscopy. 77 K photoluminescence studies show near band emission at 3.49 eV and yellow luminescence peaking at 2.2 eV. The yellow luminescence (YL) intensity decreases with an increase in V/III ratio. Positron annihilation spectroscopy studies show that the concentration of Ga-like vacancies increases with an increase in ammonia flow rate. This study confirms that the yellow luminescence in the GaN arises due to deep levels formed by gallium vacancies decorated with oxygen atoms.     

Luminescence studies of defects and piezoelectric fields in InGaN/GaN single quantum wells

Transmission electron microscopy (TEM), cathodoluminescence in the scanning electron microscope (SEM-CL) and photoluminescence (PL) studies were performed on a 30 nm GaN/2 nm In_0.28Ga _0.72N/2 μm GaN/(0 0 0 1) sapphire single quantum well (SQW) sample. SEM-CL was performed at low temperatures ≈8 K, and at an optimum accelerating voltage, around 4–6 kV to maximise the quantum well (QW) luminescence. The CL in the vicinity of characteristic “V-shaped” pits was investigated. The near band edge (BE) luminescence maps from the GaN showed bright rings inside the boundaries of the pits while the QW luminescence maps showed pits to be regions of low intensity. These observations are consistent with TEM observations showing the absence of QW material in the pits. Variations in both the BE and QW maps in the regions between the pits are ascribed to threading edge dislocations. The CL and PL QW luminescence was observed to blue-shift and broaden with increasing excitation intensity. This was accompanied by decreasing spatial resolution in the CL QW maps implying an increasing carrier diffusion length in the InGaN layer. The reasons for this behaviour are discussed. It is argued that screening of the piezoelectric field in the material may account for these observations.     

Low-temperature growth of GaN by atomic nitrogen based on a dielectric barrier discharge

GaN films were deposited on sapphire(0 0 0 1) and Si(1 0 0) substrates by MOCVD using an atomic nitrogen source based on a dielectric barrier discharge (DBD) method. Molecule nitrogen and trimethylgallium (TMG) were separately delivered to the substrates. Wurtzite GaN films, with no trace of cubic GaN, were successfully grown on -Al₂O₃ substrates even at relatively low temperatures (<800°C). Sapphire substrate RMS roughness was 5.01 and 4.93 Å before and after the exposure to DBD N-source, respectively. This shows negligible irradiation damage of accelerated N₂⁺ ion as well as the effect of smoothening the substrate surfaces with DBD N-source. The PL results exhibited small luminescence at the spectral region of blue and UV but a luminescence around the yellow region (2.5 eV) was detected. This is caused by oxygen impurity from AES analysis.     

MOVPE homoepitaxy of high-quality GaN: Crystal growth and devices

Epitaxial growth on GaN bulk single crystal substrates sets new standards in GaN material quality. The outstanding properties provide insights into fundamental material parameters (e.g. lattice constants, exciton binding energies, etc.) with a precision not obtainable from heteroepitaxial growth on sapphire or SiC. With metalorganic vapor phase epitaxy (MOVPE) we realized unstrained GaN layers with dislocation densities about six orders of magnitude lower than in heteroepitaxy. By the use of dry etching techniques for surface preparation, an important improvement of crystal quality is achieved. Those layers reveal an exceptional optical quality as determined by a reduction of the low-temperature photoluminescence (PL) linewidth from 5 meV to 0.1 meV and a reduced X-ray diffraction (XRD) rocking curve width from 400 to 20 arcsec. As a consequence of the narrow PL linewidths, new features as, e. g. a fivefold fine structure of the donor-bound exciton line at 3.471 eV was detected. Additionally, all three free excitons as well as their excited states are visible in PL at 2 K.

Dry etching techniques for surface preparation allow morphologies of the layers suitable for device applications. We report on InGaN/GaN multi-quantum-well (MQW)_ structures as well as GaN pn- and InGaN/GaN double heterostructure light emitting diodes (LEDs) on GaN bulk single crystal substrates. Those LEDs are twice as bright as their counterparts grown on sapphire. In addition they reveal an improved high power characteristics, which is attributed to an enhanced crystal quality and an increased p-doping.     

Room-temperature luminescence study on the effect of Mg activation annealing on p-GaN layers grown by MOCVD

An Mg-doped p-GaN layer was grown by the metalorganic chemical vapor deposition method. The dissociation extent of hydrogen-passivated Mg acceptors in the p-GaN layer through Mg activation annealing was estimated by using room-temperature cathodoluminescence (CL) spectroscopy. The CL measurement revealed that the CL spectra intensities tend to increase with increasing the activation annealing temperature. The sample annealed at 925 °C showed the most intense emission and the narrowest width among the emission peaks. Consequently, it was the most excellent dissociation extent of Mg–H complexes caused by the Mg activation annealing. The hole concentration under this optimum condition was 1.3×10¹⁷ cm⁻³ at room temperature. The photoluminescence (PL) measurement showed a 2.8 eV band having characteristically a broad peak in heavily Mg-doped GaN at room temperature. By analyzing the PL results, we learned that this band was associated with the deep donor–acceptor pair (DAP) emission rather than with the emission caused by the transition from the conduction band to deep acceptor level. The four emission peaks in the resolved 2.8 eV band were emitted by transiting from deep donor levels of 0.14, 0.26, 0.40, and 0.62 eV below the conduction band to the shallow Mg acceptor level of 0.22 eV above the valence band.     

Homoepitaxy on bulk ammonothermal GaN

In this work results of extensive characterization of homoepitaxial layers grown on truly bulk ammonothermal gallium nitride (GaN) substrates are presented. The 2-μm-thick layers were deposited using metalorganic chemical vapor deposition. The photoluminescence (PL) and reflectance results show very intensive, perfectly resolved excitonic structure in range of band-edge emission of gallium nitride. This structure consists of both lines related to free excitons emission and very narrow lines (full-width at half-maximum (FWHM) value of the order of 0.3 meV) related with excitons bound to neutral acceptor and different neutral donors. In high excitation condition the biexciton emission was observed. The luminescence is uniform in the whole sample surface range. High PL homogeneity corresponds with structural and microscopic measurements performed on these layers. It proves that ammonothermal GaN substrates with perfect crystalline properties enable to grow excellent quality, strain-free homoepitaxial layers.