X-ray measurement of a microdistortion tensor and its application in an analysis of the dislocation structure of thick GaN layers obtained by hydrochloride gaseous-phase epitaxy

The method of two-and three-crystal x-ray diffractometry (TCD) is used for studying the dislocation structure of thick GaN layers grown by chloride gaseous-phase epitaxy (CGE) on sapphire, as well as on a thin GaN layer, which is grown by the metalloorganic synthesis (MOS) method. Five components of the microdistortion tensor 〈?_ij〉 and the sizes of the coherent scattering regions along the sample surface and along the normal to it are obtained from the measurements of diffracted intensity in the Bragg and Laue geometries. These quantities are used to analyze the type and geometry of the dislocation arrangement and to calculate the density of the main types of dislocations. The density of the vertical screw dislocations, as well as of the edge dislocations, decreases (by a factor of 1.5 to 3) during growth on a thin GaN layer. The diffraction parameters of the thick layer on the MOS-GaN substrate suggest that it has a monocrystalline structure with inclusions of microcrystalline regions.     

Microstructural assessment of InN-on-GaN films grown by plasma-assisted MBE

The structural properties of InN thin films, grown by rf plasma-assisted molecular beam epitaxy on Ga-face GaN/Al₂O₃(0001) substrates, were investigated by means of conventional and high resolution electron microscopy. Our observations showed that a uniform InN film of total thickness up to 1 μm could be readily grown on GaN without any indication of columnar growth. A clear epitaxial orientation relationship of , was determined. The quality of the InN film was rather good, having threading dislocations as the dominant structural defect with a density in the range of 10⁹–10¹⁰ cm⁻². The crystal lattice parameters of wurtzite InN were estimated by electron diffraction analysis to be a=0.354 nm and c=0.569 nm, using Al₂O₃ as the reference crystal. Heteroepitaxial growth of InN on GaN was accomplished by the introduction of a network of three regularly spaced misfit dislocation arrays at the atomically flat interface plane. The experimentally measured distance of misfit dislocations was 2.72 nm. This is in good agreement with the theoretical value derived from the in-plane lattice mismatch of InN and GaN, which indicated that nearly full relaxation of the interfacial strain between the two crystal lattices was achieved.     

Exposure of defects in GaN by plasma etching

The effect of plasma exposure to n-type GaN surfaces has been examined. Etch pits are formed as a result of preferential sputtering at the sites of threading dislocations. Dark spots which are visible before plasma exposure can be attributed to screw dislocations, while those that emerge after plasma exposure are edge dislocations. The optimum condition for revealing defects clearly is derived, and has been adopted for the study of dislocations in a series of GaN epilayers grown under different conditions. A distinct trend in the dislocation density can be observed as the dopant concentration of the film varies. PACS 61.72.Ff; 68.37.Tj     

Molecular beam epitaxy of GaN on a substrate of MoS2 layered compound

The feasibility of MoS₂ layered compound as a substrate for GaN growth was investigated. GaN films were successfully grown on MoS₂ by plasma-enhanced molecular beam epitaxy and the crystal quality of GaN on MoS₂ was compared with that on Al₂O₃. For GaN grown on MoS₂ substrate, it was found that the surface flatness observed by atomic force microscopy, stress in the film measured by Raman spectroscopy, optical properties measured by photoluminescence spectroscopy, and threading dislocation density observed by transmission electron microscopy show superior properties compared with that grown on Al₂O₃. These results suggest the layered compound such as MoS₂, which has no dangling bonds on the surface and has lattice mismatching of 0.9% to GaN, has high potential for a substrate of GaN growth. Received: 1 March 1999 / Accepted: 8 March 1999 / Published online: 26 May 1999     

Influence of double A1N buffer layers on the qualities of GaN films prepared by metal-organic chemical vapour deposition

<正>In this paper we report that the GaN thin film is grown by metal-organic chemical vapour deposition on a sapphire (0001) substrate with double AlN buffer layers.The buffer layer consists of a low-temperature(LT) AlN layer and a high-temperature(HT) AlN layer that are grown at 600℃and 1000℃,respectively.It is observed that the thickness of the LT-AlN layer drastically influences the quality of GaN thin film,and that the optimized 4.25-min-LT-AlN layer minimizes the dislocation density of GaN thin film.The reason for the improved properties is discussed in this paper.     

非故意掺杂GaN薄膜方块电阻与载气中N2比例关系研究

利用金属有机气相外延方法研究了非故意掺杂GaN薄膜的方块电阻与高温GaN体材料生长时载气中N₂比例的关系.研究发现,随着载气中N₂比例的增加,GaN薄膜方块电阻急剧增加.当载气中N₂比例为50%时,GaN薄膜方块电阻达1.1×10⁸Ω/□,且GaN表面平整,均方根粗糙度为0.233nm.二次离子质谱分析发现,载气中N₂比例不同的样品中碳、氧杂质含量无明显差别.随着载气中N₂比 关键词： 半绝缘GaN薄膜 载气 金属有机气相外延 位错     

The influence of AlN interlayers on the microstructural and electrical properties of p-type AlGaN/GaN superlattices grown on GaN/sapphire templates

AlN with different thicknesses were grown as interlayers (ILs) between GaN and p-type Al_0.15Ga_0.85N/GaN superlattices (SLs) by metal organic vapor phase epitaxy (MOVPE). It was found that the edge-type threading dislocation density (TDD) increased gradually from the minimum of 2.5×10⁹?cm^?2 without AlN IL to the maximum of 1×10¹⁰?cm^?2 at an AlN thickness of 20 nm, while the screw-type TDD remained almost unchanged due to the interface-related TD suppression and regeneration mechanism. We obtained that the edge-type dislocations acted as acceptors in p-type Al _x Ga_1?x N/GaN SLs, through the comparison of the edge-type TDD and hole concentration with different thicknesses of AlN IL. The Mg activation energy was significantly decreased from 153 to 70?meV with a?10-nm AlN IL, which was attributed to the strain modulation between AlGaN barrier and GaN well. The large activation efficiency, together with the TDs, led to the enhanced hole concentration. The variation trend of Hall mobility was also observed, which originated from the scattering at TDs.     

Initial stages of misfit stress relaxation through the formation of prismatic dislocation loops in GaN–Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> composite nanostructures

The initial stages of misfit stress relaxation through the formation of rectangular prismatic dislocation loops in model composite nanostructures have been considered. The nanostructures are either spherical or cylindrical GaN shells grown on solid or hollow β-Ga²O₃ cores or planar thin GaN films on β-Ga²O₃ substrates. Three characteristic configurations of prismatic dislocation loops, namely, square loops, loops elongated along the GaN/Ga²O₃ interface, and loops elongated along the normal to the GaN/Ga²O₃ interface, have been analyzed. The generation of prismatic dislocation loops from the interface into the bulk of the GaN shell (film), from the free surface into the GaN shell (film), and from the interface into the β-Ga²O₃ core (substrate) has been investigated. It has been shown that, for the minimum known estimate of the lattice misfit (2.6%) in some of the considered nanostructures, no any prismatic dislocation loops can be generated. If the generation of prismatic dislocation loops is possible, then in all the considered nanostructures, the energetically more favorable case corresponds to prismatic dislocation loops elongated along the GaN/Ga²O₃ interfaces, and the more preferred generation of prismatic dislocation loops occurs from the GaN free surface. The GaN/Ga²O₃ nanostructures that are the most and least resistant to the formation of prismatic dislocation loops have been determined. It has been found that, among the considered nanostructures, the planar two-layer GaN/Ga²O₃ plate is the most resistant to the generation of prismatic dislocation loops, which is explained by the action of an alternative mechanism for the relaxation of misfit stresses due to the bending of the plate. The least resistant nanostructure is the planar three-layer GaN/Ga²O₃/GaN plate, in which GaN films have an identical thickness and which itself as a whole does not undergo bending. The critical thicknesses of the GaN shells (films), which must be exceeded to ensure the growth of these shells (films) so as to avoid the formation of prismatic dislocation loops, have been calculated for all the studied nanostructures and three known estimates of the lattice misfits (2.6, 4.7, and 10.1%).     

The role of strain in controlling the surface morphology of AlxGa1−xN following in situ treatment with SiH4 and NH3

Treatment of GaN with SiH₄ and NH₃ increases the size of surface pits associated with threading dislocations, allowing them to be easily imaged by atomic force microscopy. Here, we assess the effect of a similar treatment on Al_xGa_1−xN surfaces for x ≤ 0.4. For relaxed Al_xGa_1−xN epilayers, an increase in the observed size and density of threading dislocation pits is observed. However, if the Al_xGa_1−xN is under tensile strain, the treatment results in the appearance of nanometre-scale surface hillocks. These hillocks may prevent observation of the dislocation pits. The hillocks are found to consist of crystalline Al_xGa_1−xN, and hence are suggested to be formed by strain driven etching or transformation of the surface by SiH₄ and NH₃.     

Structural properties of 10 μm thick InN grown on sapphire (0001)

The structural properties of a 10 μm thick In-face InN film, grown on Al₂O₃ (0001) by radio-frequency plasma-assisted molecular beam epitaxy, were investigated by transmission electron microscopy and high resolution x-ray diffraction. Electron microscopy revealed the presence of threading dislocations of edge, screw and mixed type, and the absence of planar defects. The dislocation density near the InN/sapphire interface was 1.55×10¹⁰ cm⁻², 4.82×10⁸ cm⁻² and 1.69×10⁹ cm⁻² for the edge, screw and mixed dislocation types, respectively. Towards the free surface of InN, the density of edge and mixed type dislocations decreased to 4.35×10⁹ cm⁻² and 1.20×10⁹ cm⁻², respectively, while the density of screw dislocations remained constant. Using x-ray diffraction, dislocations with screw component were found to be 1.2×10⁹ cm⁻², in good agreement with the electron microscopy results. Comparing electron microscopy results with x-ray diffraction ones, it is suggested that pure edge dislocations are neither completely randomly distributed nor completely piled up in grain boundaries within the InN film.     

Computational study of adsorption, diffusion, and dissociation of precursor species on the GaN (0 0 0 1) surface during GaN MOCVD

The adsorption, diffusion, and dissociation of precursor species, MMGa (monomethylgallium) and NH₃, on the GaN (0 0 0 1) surface have been investigated using the DFT (density functional theory) calculation combined with a GaN (0 0 0 1) surface cluster model. The energetics of NH₃(ad) dissociation on the surface proposed of NH₃(ad) via NH₂(ad) to NH(ad) was facile with small activation barriers. A combined analysis with surface diffusion of adatoms demonstrated Ga(ad) and NH(ad) become primary reactant species for 2D film growth, and N(ad) develops into a nucleation center. Our studies suggest the control of NH₃(ad) dissociation are essential to improve epitaxial film quality as well as Ga-rich condition. In addition, the adsorbability of H(ad)s resulted from NH₃(ad) dissociation were found to influence on the surface chemistry during film growth.     

界面形核时间对GaN薄膜晶体质量的影响

利用金属有机化学气相沉积技术系统研究了界面形核时间对c面蓝宝石衬底上外延生长GaN薄膜晶体质量的影响机理. 用原子力显微镜、扫描电子显微镜、高分辨X射线衍射仪以及光致发光光谱仪表征材料的晶体质量以及光学性质. 随着形核时间的延长, 退火后形成的形核岛密度减小、尺寸增大、均匀性变差, 使得形核岛合并过程中产生的界面数量先减小后增大, 导致GaN外延层的螺位错和刃位错密度先减小后增大, 这与室温光致发光光谱中得到的带边发光峰与黄带发光峰的比值先增大后降低一致. 研究结果表明, 外延生长过程中, 界面形核时间会对GaN薄膜中的位错演变施加巨大影响, 从而导致GaN外延层的晶体质量以及光学性质的差异.     

斜切蓝宝石衬底MOCVD生长GaN薄膜的透射电镜研究

利用MOCVD技术在斜切角度为0.3°的c面蓝宝石衬底上生长了非故意掺杂 GaN 薄膜, 并采用透射电子显微镜对材料的质量和材料内部缺陷进行了分析. 研究发现斜切蓝宝石衬底上外延的GaN材料中,位错在距离衬底0.8 μm附近大量湮灭, 同时位错扎堆出现.基于上述现象, 提出了斜切衬底上GaN材料中位错的湮灭机制, 解释了斜切衬底能够提高GaN晶体质量的原因.     

Quantum dots-templated growth of strain-relaxed GaN on a c-plane sapphire by radio-frequency molecular beam epitaxy

We investigated the quantum dots-templated growth of a(0001) GaN film on a c-plane sapphire substrate.The growth was carried out in a radio-frequency molecular beam epitaxy system.The enlargement and coalescence of grains on the GaN quantum dots template was observed in the atom force microscopy images,as well as the more ideal surface morphology of the GaN epitaxial film on the quantum dots template compared with the one on the AlN buffer.The Ga polarity was confirmed by the reflected high energy electron diffraction patterns and the Raman spectra.The significant strain relaxation in the quantum dots-templated GaN film was calculated based on the Raman spectra and the X-ray rocking curves.Meanwhile,the threading dislocation density in the quantum dots-templated film was estimated to be 7.1×107cm-2,which was significantly suppressed compared with that of the AlN-buffered GaN film.The roomtemperature Hall measurement showed an electron mobility of up to 1860cm2 /V·s in the two-dimensional electron gas at the interface of the Al 0.25Ga0.75 N/GaN heterojunction.     

蓝宝石R面上ZnO薄膜的NH3掺杂研究

以NH₃为掺杂源,利用金属有机化学气相沉积(MOCVD)系统在蓝宝石R面上生长出掺氮ZnO薄膜。通过XRD,SEM测量优化了其生长参数,在610℃和在80sccm的NH₃流量下生长出了〈1120〉单一取向的ZnO薄膜。经Hall电阻率测量,得知该薄膜呈现弱p型或高电阻率,并对其光电子能谱进行了研究。     

位错形态与GaN外延薄膜电阻率之间的关系

利用金属有机化学气相沉积（MOCVD）,通过改变生长过程中成核层退火阶段的反应室压力,在蓝宝石衬底上制得了不同阻值的GaN外延薄膜。利用原子力显微镜（AFM）、X射线衍射（XRD）和透射电子显微镜（TEM）对所生长的GaN薄膜的表面形貌、位错密度和位错形态进行了研究。结果表明,GaN的电阻率与位错形态之间存在密切联系,由此建立了模型来解释两者之间的关系。由于刃型位错附近存在负电荷,因此可为电子提供传导通道。在低阻GaN中,绝大多数位错发生弯曲和相互作用,在平行于基底方向上形成负电荷的导通通道,GaN薄膜的电导率较高。在高阻GaN中,位错生长方向垂直于基底,负电荷很难在平行于基片方向上传导,GaN薄膜的电导率很低,由此得到高阻GaN。     

Temperature programmed desorption investigations of hydrogen and ammonia reactions on GaN

We report data for chemisorption and reaction of deuterium and isotopically labeled ammonia on single-crystalline GaN films grown on sapphire substrates. Temperature programmed desorption (TPD) and Auger electron spectroscopy (AES) studies, following exposure of the clean GaN film at room temperature to the probe reactant species, were conducted under UHV conditions. Deuterium desorption took place over a wide temperature range, 525–;800 K, with molecular deuterium as the only product. At low exposures, two distinct deuterium desorption peaks at ∼ 660 and 770 K were observed. The deuterium desorption peak at 660 K shifted to lower temperatures with increasing D adatom coverages. TPD experiments after ammonia adsorption on GaN revealed small amounts of hydrogen desorbed at ∼ 600 K and over a range 660–;770 K, suggesting partial decomposition of ammonia. Molecular ammonia desorption was observed at ∼ 560 and 600 K, with the low temperature desorption state growing with increasing ammonia exposures. Further studies on deuterium-precovered GaN films indicated that ammonia production resulted from recombination of NH_x species and hydrogen adatoms on the surface.     

Morphological and luminescent characteristics of GaN dots deposited on AlN by alternate supply of TMG and NH3

GaN dots were deposited on AlN underlayers by alternate supply of trimethylgallium (TMG) and ammonia (NH₃) in an inductively heated quartz reactor operated at atmospheric pressure. Various growth parameters including deposition temperature, TMG admittance and pulse time between TMG and NH₃ exposures were proposed to investigate the influence of growth parameters on the size distribution of GaN dots. It appears that GaN dots with uniform size distribution can be achieved under certain growth conditions. Based on the study of atomic force microscopy (AFM), high deposition temperature was found to be in favor of forming large GaN dots with small dot density. Decrement of TMG flow rate or reduction in the number of growth cycle tends to enable the formation of GaN dots with small dot sizes. The results of room temperature (RT) cathodoluminescence (CL) measurements of the GaN dots exhibit an emission peak at 3.735 eV. A remarkable blue shift of GaN dot emission was observed by reduced temperature photoluminescence (PL) measurements.     

Growth and characterisation of GaN with reduced dislocation density

Two GaN MOVPE growth methods to reduce the threading dislocation (TD) density have been explored. The combined effects of (1) in situ SiN_x masking of the sapphire substrate and (2) starting the epitaxial growth at low V-to-III ratio on the GaN film quality were studied by atomic force microscopy, transmission electron microscopy and high-resolution X-ray diffraction. It was found that the annealing condition of the low-temperature nucleation layer after in situ SiN_x masking is critical in order to decrease the density of nucleation sites and hence increase the average grain size to about 5 μm. However, the coalescence of large grains with vertical side facets results in the formation of dense bundles of TDs at the grain boundaries combined with large numbers of basal-plane dislocation loops throughout the film. The formation of these dislocations can be prevented by starting the epilayer growth at low V-to-III ratio, resulting in the formation of grains with inclined side facets. The interaction of the TDs with the inclined side facets causes the dislocations to bend 90 as the grains grow in size and coalesce. GaN films with dislocation densities as low as 1×10⁸ cm⁻², giving full-width at half-maximum values of 180 and 220 arcsec for respectively (002) and (302) omega scans, were achieved by the combination of in situ masking and low V–III ratio epilayer growth. Hall carrier mobility values in excess of 900 cm² V ⁻¹ s⁻¹ were deduced for Si-doped layers.