不同颜色AlN单晶缺陷研究

通过物理气相传输(PVT)法在石墨系统中制备了绿色、无色和琥珀色氮化铝(AlN)单晶,在金属系统中制备了琥珀色AlN单晶.晶体中杂质含量测试结果表明石墨系统中琥珀色的AlN晶体比绿色和无色AlN晶体C、Si杂质含量低1～2个数量级,金属系统中琥珀色AlN晶体杂质含量最低,C、Si、O元素含量均在1018 cm-3级别.AlN晶体的吸收图谱和光致发光图谱的分析结果表明,AlN晶体存在着位于4.7 eV、3.5 eV、2.8 eV、1.85 eV的4个吸收峰,其中4.7 eV和3.5 eV的吸收峰导致了AlN吸收截止边的红移,该吸收峰分别源于碳占氮位(CN)的点缺陷和VAl与O杂质的复合缺陷,2.80 eV的吸收峰导致了AlN晶体的琥珀色,该吸收峰是C元素和O元素共同导致的,1.85 eV的吸收峰导致了AlN晶体的绿色,该吸收峰是Si元素和C元素导致的.     

Zn掺杂Z形GaN纳米线的制备及表征

本文以氧化镓、氧化锌和氨气为原料,通过常压化学气相沉积法(APCVD)在Au/Si(100)衬底上成功生长出了Zn掺杂的"Z"形GaN纳米线。利用场发射扫描电镜(FESEM)、X-射线衍射仪(XRD)、透射电子显微镜(TEM)、光致发光谱(PL)等测试方法对样品的形貌、晶体结构及光学性质进行了表征。结果表明:在温度为950℃,氧化镓和氧化锌的质量比为8∶1的条件下,制备出的Zn掺杂Z形GaN单晶纳米线直径为70 nm、长度为数十个微米,生长机理遵循VLS机制。Zn元素的掺杂使GaN纳米线在420 nm处出现了光致发光峰,发光性能有所改善。     

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。     

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.     

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。     

成核层温度对非掺杂GaN外延薄膜结晶质量的影响

利用金属有机化学气相沉积系统(MOCVD),在蓝宝石的(0001)面采用不同的成核层生长温度,通过两步法获得不同质量的GaN外延薄膜.利用HALL测试仪,高分辨X射线衍射仪(HRXRD),原子力显微镜(AFM)和光致发光光谱仪(PL)对GaN薄膜的表面形貌,位错密度,光学性能等进行表征,研究不同的成核温度对GaN外延薄膜晶体质量的影响.结果表明,在成核层生长温度为650℃时,所得到的GaN外延薄膜表面粗糙度和位错密度均达到最低,并且同时具有最高的带边发光峰强度,最高的载流子迁移率以及最低的载流子浓度.过低或过高的成核温度都会导致GaN外延层的晶体质量和光电性能变差.     

镶嵌在SiO2基体中SiC纳米晶的紫外光致发光

将剂量为2×1016 cm-2的C+以60 keV的能量注入到SiO2薄膜中并进行了退火处理.从样品的室温光致发光(PL)光谱中观察到六个PL峰,其峰位分别处于2.601 eV、2.857 eV、3.085 eV、3.249 eV、3.513 eV和3.751 eV.其中3.249 eV处的PL峰与4H-SiC有关.而对于尚未见报道的3.751 eV处PL峰,进行了红外吸收和荧光激发(PLE)测试:在PLE谱4.429 eV处显示出一个对应于3.751 eV处的激发峰.在红外吸收谱上证实0.205 eV(1650cm-1)处的吸收峰与3.751 eV处发光峰的起源相关,从而推断在3.751 eV处的PL峰应起源于氧空位缺陷.     

MOCVD外延生长原位光致发光谱测量方法

为了实现MOCVD外延生长过程中的PL谱原位测量.利用经过特殊改造的M680红外测温石英光学探针、分支石英光纤、半导体激光器、光谱仪、OD值为6的单波陷波滤光片,在THOMAS SWAN CCS型MOCVD反应室上实现了Si(111)衬底GaN基InGaN/GaN MQW外延生长过程原位PL谱测量.研究结果表明:该原位PL谱测量系统,能够实现激发光的导人、PL谱信号的收集、反射激光及杂散光的过滤;当温度降低至600℃以下时,MOCVD反应室内红外辐射对PL测量的影响可以忽略;该原位PL谱测量方法可推广至Al2O3衬底外延生长.该研究可为MOCVD原位PL谱测量设备开发提供参考.     

蓝宝石衬底上GaN薄膜的结构和光学特性表征

采用低压金属有机化学气相沉积(LPMOCVD)法,成功地在(0001)晶向的蓝宝石(Al2O3)衬底上制备了高质量的GaN薄膜.并利用X射线衍射(XRD)谱和椭圆偏振光谱(SE)对其结构和光学特性作了表征.XRD谱中,在34.5°和72.9°附近出现了两个尖锐的衍射峰,分析表明这两个衍射峰分别对应纤锌矿(Wurtzite) 结构GaN薄膜的(0002)和(0004)晶向.其中GaN (0002)晶向衍射峰的半高宽(FWHM)很窄,只有0.1°左右,并且GaN(0004)晶向衍射峰强度很强,二者均证实了采用LPMOCVD法制备的GaN薄膜具有高的质量.在介电函数和反射谱中,GaN高的透明性(＜3.44eV)诱导了强的干涉振荡.室温下拟合出的表征带间跃迁的光学带隙约为3.44eV.     

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.     

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.     

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.