利用混合极性制备多孔缓冲层及其在GaN厚膜外延中的应用

使用分子束外延(MBE)技术在(0001)面蓝宝石衬底上生长混合极性的氮化镓(GaN)薄膜,利用不同极性面的GaN薄膜在强碱溶液中腐蚀特性的差异,混和极性样品经腐蚀处理后,得到了一层具有多孔结构的GaN层.以多孔结构的GaN作为缓冲层,用卤化物气相外延(HVPE)方法生长GaN厚膜.X射线双晶衍射和光致发光等测试结果表明,多孔结构的GaN缓冲层可以有效地释放GaN厚膜和衬底之间因热膨胀系数失配产生的应力,使GaN厚膜晶体的质量得到很大提高.     

GaN grown by hydride vapor phase epitaxy on p-type 6H-SiC layers

6H-SiC/GaN pn-heterostructures were grown by subsequent epitaxial growth of p-SiC by low temperature liquid phase epitaxy (LTLPE) and n-GaN by hydride vapor phase epitaxy (HVPE). For the first time, p-type epitaxial layers grown on 6H-SiC wafers were used as substrates for GaN HVPE growth. The GaN layers exhibit high crystal quality which was determined by x-ray diffraction. The full width at a half maximum (FWHM) for the ω-scan rocking curve for (0002) GaN reflection was ∼120 arcsec. The photoluminescence spectra for these films were dominated by band-edge emission. The FWHM of the edge PL peak at 361 nm was about 5 nm (80K).     

GaN基材料及其外延生长技术研究

介绍了GaN基材料的基本特性、三种主要外延生长技术(MOCVD、MBE、HVPE)、衬底材料的选择及缓冲层技术;分析得出目前存在的GaN体单晶技术不完善、外延成本高、衬底缺陷及接触电阻大等主要问题制约了研究的进一步发展;指出今后的研究重点是完善GaN体单晶材料的生长工艺,以利于深入研究GaN的物理特性及有效地解决衬底问题,研究缓冲层的材料、厚度、组分等以提高GaN薄膜质量。     

Giant traps on the surface of hydride vapor phase epitaxy-grown free-standing GaN

Extended defects on the top surface of a 250-μm-thick free-standing GaN sample, grown by hydride vapor phase epitaxy (HVPE), were studied by deep level transient spectroscopy (DLTS) and scanning surface potential microscopy (SSPM). For comparison, similar studies were carried out on as-grown HVPE-GaN samples. In addition to the commonly observed traps in as-grown HVPE-GaN, the DLTS measurements on free-standing GaN reveal a very high concentration of deep traps (∼1.0 eV) within about 300 nm of the surface. These traps show nonexponential capture kinetics, reminiscent of those associated with large defects, that can accumulate multiple charges. The SSPM measurements clearly reveal the presence of charged microcracks on the top surface of the sample. It appears that the “giant traps” may be associated with these microcracks, but we cannot rule out the involvement of other extended defects associated with the near-surface damage caused by the polishing/etching procedure.     

载气流量对HVPE外延生长GaN膜光学性质的影响

研究了利用水平氢化物气相外延 (HVPE)系统在蓝宝石衬底上外延氮化镓 (Ga N)的生长规律 ,重点研究了作为载气的氮气流量对 Ga N膜的结构及光学性质的影响。观察到载气流量对预反应的强弱有很大影响 ,外延膜的质量和生长速度对载气流量极为敏感。当载气流量较小时 ,样品的 X射线衍射谱 (XRD)中出现了杂峰(1 0 -1 1 )和 (1 1 -2 0 ) ,相应的光致发光谱 (PL)中出现了黄带 (YL) ,靠近带边有杂质态。而当载气流量增大时 ,样品质量改善。Ga N外延膜的结构和光学性质的相关性表明深能级的黄带与生长过程中产生的非 c轴方向晶面有关 ,据此我们推测 :Ga空位与束缚在 (1 0 -1 1 )和 (1 1 -2 0 )等原子面上的杂质构成复合结构 ,这些复合结构所产生的深能级对黄带的发射有贡献 ;由于预反应使生长过程中混入的附加产物及杂质对带边发射有重要影响     

原位退火对HVPE生长的GaN外延层光学性质和结构的影响

研究了原位退火对用氢化物外延方法在(0001)面蓝宝石衬底上生长的氮化镓(GaN)外延薄膜的结构和光学性能的影响.测试表明,氨气气氛下在生长温度进行的原位退火,明显提高了GaN外延膜的质量.X射线衍射(XRD)分析表明,随着原位退火时间的增加,(0002)面和(1012)面摇摆曲线的半峰宽逐渐变窄.喇曼散射谱显示样品退火后E2(high)峰位向低频区移动;随着退火时间的延长,趋向于块状GaN的峰位.可见,原位退火使GaN外延膜中的双轴应力明显减少.光致发光的测试结果与XRD和喇曼散射谱的结论一致.表明原位退火能有效提高GaN外延膜的结构和光学性能.     

原位退火对HVPE生长的GaN外延层光学性质和结构的影响

研究了原位退火对用氢化物外延方法在(0001)面蓝宝石衬底上生长的氮化镓(GaN)外延薄膜的结构和光学性能的影响.测试表明,氨气气氛下在生长温度进行的原位退火,明显提高了GaN外延膜的质量.X射线衍射(XRD)分析表明,随着原位退火时间的增加,(0002)面和(1012)面摇摆曲线的半峰宽逐渐变窄.喇曼散射谱显示样品退火后E2(high)峰位向低频区移动;随着退火时间的延长,趋向于块状GaN的峰位.可见,原位退火使GaN外延膜中的双轴应力明显减少.光致发光的测试结果与XRD和喇曼散射谱的结论一致.表明原位退火能有效提高GaN外延膜的结构和光学性能.     

Gradual tilting of crystallographic orientation and configuration of dislocations in GaN selectively grown by vapour phase epitaxy methods

Cross-sectional transmission electron microscope (TEM) observation was performed for selectively grown gallium nitride (GaN) in order to examine the dependence of GaN microstructure on the growth conditions. The GaN films were grown by hydride vapour phase epitaxy (HVPE) or metalorganic vapour phase epitaxy (MOVPE) on GaN covered with a patterned mask. Thin foil specimens for TEM observation were prepared with focused ion beam (FIB) machining apparatus. It was demonstrated that the c-axis of GaN grown over the terrace of the mask tilts towards the centre of the terrace when the GaN is grown in a carrier gas of N2. The wider terrace results in a larger tilting angle if other growth conditions are identical. The tilting is attributed to 'horizontal dislocations' (HDs) generated during the overgrowth of GaN on the mask terrace. The HDs in HVPE-GaN have a semi-loop shape and are tangled with one another, while those in MOVPE-GaN are straight and lined up to form low-angle grain boundaries.     

额外HCl和氮化对HVPE GaN生长的影响

在氢化物气相外延(HVPE)生长Ga N过程中,发现了一种在成核阶段向生长区添加额外HCl来改善Ga N外延薄膜质量的方法,并且讨论了额外HCl和氮化对Ga N形貌和质量的影响.两种方法都可以大幅度地改善Ga N的晶体质量和性质,但机理不同.氮化是通过在衬底表面形成Al N小岛,促进了衬底表面的成核和薄膜的融合;而添加额外HCl则被认为是通过改变生长表面的过饱和度引起快速成核从而促进薄膜的生长而改善晶体质量和性质的     

HVPE生长的高质量GaN纳米柱的光学性能

GaN纳米材料因具有优异的晶体质量和突出的光学性能及发射性能,日益受到关注.研究了一种利用氢化物气相外廷(HVPE)系统生长高质量的GaN纳米柱的方法.使用镍作为催化剂,在蓝宝石衬底上生长出了GaN纳米柱.在不同生长时间和不同HC1体积流量下制备了多组样品,使用扫描电子显微镜(SEM)、X射线衍射(XRD)和光致发光(PL)谱对样品进行了分析表征.测试结果表明,在较低的HC1体积流量下,生长2 min的样品具有较高的晶体质量和较好的光学性质.讨论了不同生长阶段的GaN纳米结构发光特性的变化规律,认为纳米结构所产生的表面态密度大小差异会造成带边峰位的红移和展宽.     

Microstructure and enhanced morphology of planar nonpolar m-plane GaN grown by hydride vapor phase epitaxy

Nonpolar ( ) m-plane gallium nitride has been grown heteroepitaxially on (100) γ-LiAlO₂ by several groups. Previous attempts to grow m-plane GaN by hydride vapor phase epitaxy (HVPE) yielded films unsuitable for subsequent device regrowth because of the high densities of faceted voids intersecting the films’ free surfaces. We report here on the growth of planar m-plane GaN films on (100) γ-LiAlO₂ and elimination of bulk and surface defects. The morphology achieved is smooth enough to allow for fabrication of m-plane GaN templates and free-standing substrates for nonpolar device regrowth. The GaN films were grown in a horizontal HVPE reactor at 860–890°C. Growth rates ranged from 30 μm/h to 240 μm/h, yielding free-standing films up to 250-μm thickness. The m-plane GaN films were optically specular and mirror-like, with undulations having 50–200-nm peak-to-valley heights over millimeter length scales. Atomic force microscopy revealed a striated surface morphology, similar to that observed in m-plane GaN films grown by molecular beam epitaxy (MBE). Root-mean-square (RMS) roughness was 0.636 nm over 25-μm² areas. Transmission electron microscopy (TEM) was performed on the m-plane GaN films to quantify microstructural defect densities. Basal-plane stacking faults of 1×10⁵ cm⁻¹ were observed, while 4×10⁹ cm⁻² threading dislocations were observed in the g=0002 diffraction condition.     

AlGaN缓冲层结构对Si基GaN材料性能的影响

Si衬底与GaN之间较大的晶格失配和热失配引起的张应力使GaN外延层极易产生裂纹,如何补偿GaN所受到的张应力是进行Si基GaN外延生长面临的首要问题.采用金属有机化合物化学气相沉积(MOCVD)技术在4英寸(1英寸=2.54 cm)Si (111)衬底上制备了GaN外延材料并研究了不同AlGaN缓冲层结构对Si基GaN外延材料性能的影响,并采用高分辨X射线衍射仪(HRXRD)、原子力显微镜(AFM)、喇曼光谱以及光学显微镜对制备的GaN材料的性能进行了表征.采用3层A1GaN缓冲层结构制备了表面光亮、无裂纹的GaN外延材料,其(002)晶面半高宽为428 arcsec,表面粗糙度为0.194 nm.结果表明,采用3层A1GaN缓冲层结构可以有效地降低GaN材料的张应力和位错密度,进而遏制表面裂纹的出现,提高晶体质量.     

Silicon effect on GaN surface morphology

Si-doped GaN epitaxial layers have been grown at 1050 °C on optimized-AlN buffered (0001) sapphire substrates by atmospheric pressure metalorganic vapor phase epitaxy. In order to investigate the Si effect on the surface morphology of GaN epilayers, several samples were grown by varying the silane partial pressure. When the silane partial pressure increases above 1.7×10⁻⁸ atm, the surface quality becomes rough. This shows the Si surfactant effect. A correlation between an in situ laser reflectometry and ex situ optical and atomic force microscopy characterizations on the one hand and between electrical properties and surface quality on the other hand were made. As the electron concentration increases, the surface becomes more and more rough and the mobility drops dramatically.     

Hydride vapor phase epitaxy for gallium nitride substrate

Due to the remarkable growth rate compared to another growth methods for gallium nitride(GaN)growth,hydride vapor phase epitaxy(HVPE)is now the only method for mass product GaN substrates.In this review,commercial HVPE systems and the GaN crystals grown by them are demonstrated.This article also illustrates some innovative attempts to develop homebuilt HVPE systems.Finally,the prospects for the further development of HVPE for GaN crystal growth in the future are also discussed.     

Growth and characterization of ZnO thin films on GaN epilayers

Dense ZnO(0001) films formed at 500°C via coalescence of islands grown via metalorganic vapor phase epitaxy (MOVPE) either on GaN/AlN/SiC(0001) substrates or on initial, coherent ZnO layers. Conical crystallites formed due to thermal expansion-induced stresses between the ZnO and the substrate. Interfaces between the ZnO films on GaN epilayers exposed either simultaneously to diethylzinc and oxygen or only to diethylzinc at the initiation of growth were sharp and epitaxial. Interfaces formed after the exposure of the GaN to O₂ were less coherent, though an interfacial oxide was not observed by cross-sectional transmission electron microscopy (TEM). Threading dislocations and stacking faults were observed in all films.     

Application of halide vapor phase epitaxy for the growth of ultrawide band gap Ga_2O_3

Halide vapor phase epitaxy(HVPE) is widely used in the semiconductor industry for the growth of Si, GaAs, GaN, etc.HVPE is a non-organic chemical vapor deposition(CVD) technique, characterized by high quality growth of epitaxial layers with fast growth rate, which is versatile for the fabrication of both substrates and devices with wide applications. In this paper, we review the usage of HVPE for the growth and device applications of Ga_2O_3, with detailed discussions on a variety of technological aspects of HVPE. It is concluded that HVPE is a promising candidate for the epitaxy of large-area Ga_2O_3 substrates and for the fabrication of high power β-Ga_2O_3 devices.     

以金属为缓冲层在Si(111)上分子束外延GaN及其表征

用电子束蒸发方法在Si(111)衬底上蒸发了Au/Cr和Au/Ti/Al/Ti 两种金属缓冲层,然后在金属缓冲层上用气源分子束外延(GSMBE)生长GaN. 两种缓冲层的表面都比较平整和均匀,都是具有Au(111)面择优取向的立方相Au层. 在Au/Cr/Si(111)上MBE生长的GaN,生长结束后出现剥离. 在Au/Ti/Al/Ti/Si(111)上无AlN缓冲层直接生长GaN,得到的是多晶GaN;先在800℃生长一层AlN缓冲层,然后在710℃生长GaN,得到的是沿GaN(0001)面择优取向的六方相GaN. 将Au/Ti/Al/Ti/Si(111)在800℃下退火20min,金属层收缩为网状结构,并且成为多晶,不再具有Au(111)方向择优取向.     

用液相外延法生长3～7μm波段InAs/InAs1-ySby及其光学和电学性质

用液相外延(LPE)法在InAs衬底上生长了3～7μm波段的InAs1-ySby外延层,研究了外延多层的组份与禁带宽度和晶格常数的关系。用光学显微镜、傅立叶变换红外(FTIR)透射、光荧光(PL)谱测试以及偏振光椭圆仪研究了外延材料的光学特性。电学性质是将计算值与实测有效霍尔(Hall)参数的厚度关系拟合得到的。结果表明,本文生长的材料在中红外光伏型探测器上具有良好的应用前景。     

The effect of GaN and ain buffer layers on GaN film properties grown on both C-plane and A-plane sapphire

This paper presents a comparative study of the properties of GaN grown by organometallic vapor phase epitaxy, using both a GaN and A1N buffer layer, as a function of sapphire orientation (c-plane vs a-plane). Results are presented for varying the thickness of the buffer layer, varying the growth temperature of the GaN film, and also varying the ammonia/trimethylgallium mass flow ratio. The electron Hall mobilities of GaN films grown on an A1N buffer layer were, in general, higher compared to films grown using a GaN buffer layer. In addition, growth on a-plane sapphire resulted in higher quality films (over a wider range of buffer thicknesses) than growth on c-plane sapphire. The room temperature electron mobilities were also found to be dependent on, not only the growth temperature, but also the ammonia/trimethylgallium mass flow ratio.     

Extended defects and polarity of hydride vapor phase epitaxy GaN

Hydride vapor phase epitaxy (HVPE) GaN layers on sapphire substrates and so-called free-standing platelets (layers removed from the sapphire) were studied by different transmission electron microscopy (TEM) techniques. Polarity, determined by convergent beam electron diffraction (CBED), and distribution of structural defects, determined by conventional TEM, are discussed. The HVPE layers were found to grow primarily with Ga-polarity. A few inversion domains (areas with N-polarity) were observed on the substrate side of one of the free-standing layers. The dominant structural defects in HVPE GaN layers are threading dislocations. A systematic reduction of their density with an increase in layer thickness was observed for all of the samples. The experimental results indicate that the density of dislocations is inversely proportional to the distance from the substrate, which agrees with the theoretical model.