Optimization of High-Quality AlN Epitaxially Grown on (0001) Sapphire by Metal-Organic Vapor-Phase Epitaxy

A systematic study is performed to optimize aluminum nitride (AlN) epilayers grown on (0001) sapphire by metal-organic vapor-phase epitaxy. Specifically, the impact of the AlN nucleation conditions on the crystalline quality and surface morphology of AlN epilayers is studied. Atomic force microscopy (AFM) and x-ray diffraction (XRD) results reveal that the nucleation layer plays a critical role in the growth of subsequent layers. The magnitude of the TMAl flow of AlN nucleation layer is found to have a strong effect on the crystalline quality and surface morphology of the high-temperature (HT) AlN epilayer. A simple Al adatom-diffusion-enhancement model is presented to explain the strong dependence of the crystalline quality and surface morphology on TMAl flow. Furthermore, ammonia flow, nucleation temperature, and growth time of the AlN nucleation layer are found to affect the surface morphology and the crystalline quality as well. A trade-off is found between surface morphology and crystalline quality; that is, we do not obtain the best surface morphology and the highest crystalline quality for the same growth parameters. For optimized AlN nucleation layers and HT AlN epilayers, a clear and continuously linear step-flow pattern with saw-tooth shaped terrace edges is found by AFM on AlN epilayers. Triple-axis x-ray rocking curves show a full-width at half-maximum (FWHM) of 11.5 arcsec and 14.5 arcsec for the (002) and (004) reflection, respectively. KOH etching reveals an etch-pit density (EPD) of 2 × 10⁷ cm⁻², as deduced from AFM measurements.     

Crystal growth of AlN: Effect of SiC substrate

The morphology of AlN crystal grown under the same growth conditions by the PVT method on four kinds of 4H-SiC substrates (SiC (0001), SiC (000−1), 8° off-axis SiC (0001), and 8° off-axis SiC (000−1), off-oriented from the basal plane toward the 〈11–20〉 direction) was investigated. It is found that the nucleation more easily occurs on the Si face substrate than on the C face substrate at 1800–1900 °C. Hexagonal flakes nucleated on the SiC (0001) substrate, while tetrahedral grains nucleated on the 8° off-axis SiC (0001) substrate. AlN grown on the 8° off-axis SiC (000−1) substrate was strikingly different, and flower pattern structure AlN deposited on the substrate. A stepped structure with smooth terraces was obtained on the 8° off-axis SiC (0001) substrate at 1900 °C for 4 h. We conclude that the AlN grown on the 8° off-axis SiC (0001) substrate was first by island nucleation then by the step-flow growth mode.     

使用溅射AlN成核层实现大规模生产深紫外LED

高质量AlN薄膜对制造高性能深紫外器件非常重要,但是目前还很难使用大型工业MOCVD生长出高质量的AlN薄膜.采用磁控溅射制备了不同厚度的用作成核层的AlN薄膜,使用大型工业MOCVD直接在成核层上高温生长AlN外延层,研究了不同成核层对AlN外延层质量的影响.通过扫描电子显微镜和原子力显微镜对成核层AlN薄膜的表面形貌进行表征;使用高分辨X射线衍射仪对AlN外延层晶体质量进行表征,结果表明:在溅射成核层上生长的AlN外延层的晶体质量有显著提高.使用大型工业MOCVD在蓝宝石衬底上成功制备出中心波长为282 nm的可商用深紫外LED,在注入电流为20 mA时,单颗深紫外LED芯片的光输出功率达到了1.65 mW,对应的外量子效率为1.87%,饱和光输出功率达到4.31 mW.     

Optical and microstructural characterization of the effects of rapid thermal annealing of CdTe thin films grown on Si (100) substrates

The effects of rapid thermal annealing (RTA) on CdTe/Si (100) heterostructures have been studied in order to improve the structural quality of CdTe epilayers. Samples of CdTe (111) polycrystalline thin films grown by vapor phase epitaxy (VPE) on Si (100) substrates have been investigated. The strained structures were rapidly thermally annealed at 400°C, 450°C, 500°C, 550°C, and 600°C for 10 sec. The microstructural properties of the CdTe films were characterized by carrying out scanning electron microscopy (SEM), x-ray diffraction (XRD), and atomic force microscopy (AFM). We have shown that the structural quality of the CdTe epilayers improves significantly with increasing annealing temperature. The optimum annealing temperature resulting in the highest film quality has been found to be 500°C. Additionally, we have shown that the surface nucleation characterized by the island size distribution can be correlated with the crystalline quality of the film.     

Improved CdTe layers on GaAs and Si using atomic layer epitaxy

In this paper, we report on the atomic layer epitaxy (ALE) of CdTe on GaAs and Si by the organometallic vapor phase epitaxial process at atmospheric pressure. Self-limiting growth at one monolayer was obtained over the temperature range from 250°C to 320°C, under a wide range of reactant pressure conditions. A study of growth mechanism indicates that DMCd decomposes into Cd on the surface and the Te precursors react catalytically on the Cd covered surface. We have used this ALE grown layer to improve the crystal quality and the morphology of conventionally grown CdTe on GaAs. Improvement in the crystal quality was also observed when ALE CdTe nucleation was carried out on Si pretreated with DETe at 420°C. Atomic layer epitaxy grown ZnTe was used to obtain (100) oriented CdTe on (100) silicon.     

Effect of the Sapphire-Nitridation Level and Nucleation-Layer Enrichment with Aluminum on the Structural Properties of AlN Layers

The effect of atomic aluminum deposited onto sapphire substrates with different nitridation levels on the quality of AlN layers grown by ammonia molecular-beam epitaxy is investigated. The nitridation of sapphire with the formation of ~1 monolayer of AlN is shown to ensure the growth of layers with a smoother surface and better crystal quality than in the case of the formation of a nitrided AlN layer with a thickness of ~2 monolayers. It is demonstrated that the change in the duration of exposure of nitrided substrates to the atomic aluminum flux does not significantly affect the parameters of subsequent AlN layers.     

PVT法同质籽晶AlN晶体生长

为了获得高质量AlN晶体,通过物理气相传输(PVT)法,采用AlN籽晶进行AlN晶体生长,并通过双温区加热装置对衬底与原料之间的温差进行调节。研究结果表明,籽晶形核阶段,随着AlN籽晶与原料顶温差的减小,AlN的形核机制呈现三种模式,分别为岛生长模式、畴生长模式和螺旋位错生长模式;晶体生长阶段,通过增加AlN籽晶与原料顶温差来提高晶体生长速率,采用10℃/h的变温速率将温差从10℃增加为30℃时,AlN晶体生长模式不变,仍然保持螺旋位错生长模式,该生长模式下获得的AlN晶体结晶质量最高,(0002)面摇摆曲线半峰宽(FWHM)约为55 arcsec。     

GaN薄膜表面形貌与AlN成核层生长参数的关系

采用金属有机物化学气相淀积技术生长了以AlN为成核层的GaN薄膜,研究了成核层生长时三甲基铝(TMAl)流量对最终GaN薄膜表面形貌的影响.研究结果表明,高质量GaN薄膜只能在高TMAl流量下获得,采用充足的TMAl源才能形成满足需要的AlN成核点,这是生长高质量GaN薄膜的一个先决条件.     

AlN外延薄膜的生长和特征

文章研究了AlN薄膜的晶体质量、表面形貌、应力等性质与AlN生长工艺的依赖关系。通过对低温成核厚度、成核温度和高温生长AlN所用Ⅴ／Ⅲ比的研究，制备出了具有较好晶体质量的AlN薄膜。高分辨三晶X射线衍射给出AlN薄膜的(002)和(105)的半高宽分别为16．9arcsec和615arcsec，接近国际上报道的较好结果。原子力显微镜对表面形貌的分析表明AlN薄膜的粗糙度为5．7nm。拉曼光谱表明E2(high)模向高能方向移动，说明蓝宝石上外延的AlN薄膜处于压应变状态。光学吸收谱在204nm处具有陡峭的带边吸收，也表明了AlN外延薄膜具有较好地晶体质量。     

Spontaneous detachment of a sublimation-Grown AlN layer from a SiC-6H substrate

Growth of thick layers and bulk crystals of AlN is a topical problem for modern science and technology. The main way to solve the problem is to use the sublimation method in which AlN is evaporated at a temperature of about 2000°C and is epitaxially deposited onto a SiC substrate. A severe difficulty in this case is that the coefficients of thermal expansion of these materials are different, which leads to bending, cracking, and pronounced stresses in the AlN layer upon cooling to room temperature. This communication considers the case of a spontaneous detachment of a crack-free AlN layer from a SiC substrate, which points to the real possibility of developing a growth technology in which their separation becomes inevitable. The following reasons for spontaneous separation of the layer and the substrate are probable: (i) formation of a thin Al layer at the interface and (ii) occurrence of the initial growth stage by the previously described scheme, according to which, the layer and substrate are atomically bound only at separate comparatively sparse areas of nucleation of the growing crystal. Upon cooling, these areas disintegrate and the layer is detached from the substrate. It is unclear so far what specific features and anomalies of the growth process give rise to this result.

     

基于AlN和GaN形核层的AlGaN/GaN HEMT外延材料和器件对比

使用金属有机物化学气相淀积(MOCVD)方法在蓝宝石衬底上分别采用AlN和GaN作为形核层生长了AlGaN/GaN高电子迁移率晶体管(HEMT)外延材料,并进行了器件制备和性能分析.通过原子力显微镜(AFM)、高分辨率X射线双晶衍射仪(HR-XRD)和二次离子质谱仪(SIMS)等仪器对两种样品进行了对比分析,结果表明采用AlN形核层的GaN外延材料具有更低的位错密度,且缓冲层中氧元素的拖尾现象得到有效地抑制.器件直流特性显示,与基于GaN形核层的器件相比,基于AlN形核层的器件泄漏电流低3个数量级.脉冲Ⅰ-Ⅴ测试发现基于GaN形核层的HEMT器件受缓冲层陷阱影响较大,而基于AlN形核层的HEMT器件缓冲层陷阱作用不明显.     

Atomic layer epitaxy of InAs using tertiarybutylarsine

Tertiarybutylarsine and trimethylindium were used as precursors for atomic layer epitaxy of InAs. Self-limiting growth has been observed for a large temperature range between 350–410°C. In-situ reflectance difference spectroscopy was used to study the difference between the As and In self-limiting mechanisms on the InAs surface and also to optimize the growth parameters. Optical and transport properties of InAs grown epilayers show that high purity material can be achieved by atomic layer epitaxy.     

Comparative Study on MOCVD Growth of a-Plane GaN Films on r-Plane Sapphire Substrates Using GaN, AlGaN, and AlN Buffer Layers

In this work, we have comparatively investigated the effects of the GaN, AlGaN, and AlN low-temperature buffer layers (BL) on the crystal quality of a-plane GaN thin films grown on r-plane sapphire substrates. Scanning electron microscopy images of the a-plane GaN epilayers show that using an AlGaN BL can significantly reduce the density of surface pits. The full-width at half-maximum values of the x-ray rocking curve (XRC) are 0.19°, 0.36°, and 0.48° for the films grown using Al_0.15Ga_0.85N, GaN, and AlN BLs, respectively, indicating that an AlGaN BL can effectively reduce the mosaicity of the films. Room-temperature photoluminescence shows that the AlGaN BL results in lower impurity incorporation in the subsequent a-plane GaN films, as compared with the case of GaN and AlN BLs. The higher crystal quality of a-plane GaN films produced by the Al_0.15Ga_0.85N BL could be due to improvement of BL quality by reducing the lattice mismatch between the BL and r-sapphire substrates, while still keeping the lattice mismatch between the BL and epitaxial a-plane GaN films relatively small.     

Seeded growth of AlN crystals on nonpolar seeds via physical vapor transport

Seeded growth of AlN single crystals was demonstrated in an induction-heated, high-temperature reactor via a physical vapor transport (PVT) process. AlN seeds were prepared from a self-seeded boule containing large single-crystalline grains. Seeded growth was interrupted several times in order to refill the AlN powder source, and a dedicated process scheme was used to ensure epitaxial growth on the seed surface, after prior exposure to air. The growth temperatures were in the range of 2200–2300°C, and the reactor pressure was in the range of 500–900 torr of UHP-grade nitrogen during each growth run. Under these growth conditions, a seed (10 mm diameter) expanded at an angle of 45°, and a larger single crystal up to 18 mm in diameter was obtained. The as-grown surface had three facets, of which facet (1120) was smooth and featureless while the other two, (4150) and (2570), showed serrated morphologies. The double-crystal x-ray rocking curve and glow discharge mass spectroscopy analysis confirmed that the grown crystal was of high crystalline quality with low impurity incorporation.     

Investigations of GaN growth on the sapphire substrate by MOCVD method with different AlN buffer deposition temperatures

The effects of different AlN buffer deposition temperatures on the GaN material properties grown on sapphire substrate was investigated. At relatively higher AlN buffer growth temperature, the surface morphology of subsequent grown GaN layer was decorated with island-like structure and revealed the mixed-polarity characteristics. In addition, the density of screw TD and leakage current in the GaN film was also increased. The occurrence of mixed-polarity GaN material result could be from unintentional nitridation of the sapphire substrate by ammonia (NH₃) precursor at the beginning of the AlN buffer layer growth. By using two-step temperature growth process for the buffer layer, the unintentional nitridation could be effectively suppressed. The GaN film grown on this buffer layer exhibited a smooth surface, single polarity, high crystalline quality and high resistivity. AlGaN/GaN high electron-mobility transistor (HEMT) devices were also successfully fabricated by using the two-step AlN buffer layer.     

溅射AlN技术对GaN基LED性能的影响

研究了在图形蓝宝石衬底(PSS)上利用磁控溅射制备AlN薄膜的相关技术,随后通过采用金属有机化学气相沉积(MOCVD)在相关AlN薄膜上生了长GaN基LED.通过一系列对比实验,分析了AlN薄膜的制备条件对GaN外延层晶体质量的影响,研究了AlN薄膜溅射前N2预处理功率和溅射后热处理温度对GaN基LED性能的作用机制.实验结果表明:AlN薄膜厚度的增加,导致GaN缓冲层成核密度逐渐升高和GaN外延膜螺位错密度降低刃位错密度升高;N2处理功率的提升会加剧衬底表面晶格损伤,在GaN外延膜引入更多的螺位错;AlN热处理温度的升高粗化了表面并提高了GaN成核密度,使得GaN外延膜螺位错密度降低刃位错密度升高;而这些GaN外延膜位错密度的变化又进一步影响到LED的光电特性.     

通过双中温AlN插入层提高半极性(1122)面AlN薄膜的表面形貌和晶体质量

利用金属有机化学气相沉积方法在蓝宝石衬底上生长了一系列具有双中温AlN插入层(MTG-AlN)的半极性AlN薄膜样品。中温生长的AlN插入层具有较大的表面粗糙度,形成了类似纳米级图形化衬底结构,能够有效阻断高温生长的半极性AlN样品中堆垛层错的传播,从而提高半极性AlN样品的表面形貌和晶体质量。通过原子力显微镜和X射线衍射仪的表征,研究了MTG-AlN插入层厚度在20～100 nm之间的变化对半极性AlN样品的表面形貌和晶体质量的影响。结果表明,所有半极性AlN样品都具有■取向。当插入的MTG-AlN中间层厚度约为80 nm时,半极性AlN样品表面粗糙度显著降低,晶体质量明显改善。     

Influence of Substrate Temperature on Structural Properties and Deposition Rate of AlN Thin Film Deposited by Reactive Magnetron Sputtering

Aluminum nitride (AlN) thin films with c-axis preferred orientation have been prepared by reactive direct-current (DC) magnetron sputtering. The degree of preferred crystal orientation, the cross-sectional structure, and the surface morphology of AlN thin films grown on Si (100) substrates at various substrate temperatures from 60°C to 520°C have been investigated by x-ray diffraction, scanning electron microscopy, and atomic force microscopy. Results show that the substrate temperature has a significant effect on the structural properties, such as the degree of c-axis preferred orientation, the full-width at half-maximum (FWHM) of the rocking curve, the surface morphology, and the cross-sectional structure as well as the deposition rate of the AlN thin films. The optimal substrate temperature is 430°C, with corresponding root-mean-square surface roughness (R _rms) of 1.97?nm, FWHM of AlN (002) diffraction of 2.259°, and deposition rate of 20.86?nm/min. The mechanisms behind these phenomena are discussed. Finally, film bulk acoustic resonators based on AlN films were fabricated; the corresponding typical electromechanical coupling coefficient (k _t ² ) is 5.1% with series and parallel frequencies of 2.37?GHz and 2.42?GHz, respectively.     

HVPE法生长AlN薄膜材料

利用自制立式HVPE设备,在蓝宝石衬底上进行了不同载气情况下AlN的生长试验,生长温度1 000℃。在采用H2作载气情况下,由于预反应严重,没能生长出AlN薄膜,只得到一些白色AlN粉末;而在分别采用Ar和N2作载气的情况下,则成功生长出AlN薄膜,但由于生长温度低,AlN生长均为岛状生长模式。在生长速率较快时,AlN薄膜是以〈0001〉AlN为主的AlN多晶;而在较低生长速率下,得到的AlN薄膜由为〈0001〉取向的AlN岛组成。试验还发现:用Ar作载气更有利于AlN晶核的横向生长,用N2作载气则有相对高得多的AlN成核密度。     

原子层沉积超薄氮化铝薄膜的椭圆偏振光谱法表征

采用原子层沉积(ALD)工艺在硅衬底上生长了35 nm以下不同厚度的超薄氮化铝(AlN)晶态薄膜。利用椭圆偏振光谱法在波长275~900 nm内测量并拟合薄膜的厚度及折射率和消光系数等光学参数。利用原子力显微镜(AFM)表征AlN晶粒尺寸随生长循环次数的变化,计算得到薄膜表面粗糙度并用于辅助椭偏模型拟合。针对ALD工艺特点建立合适的椭偏模型,可获得AlN超薄膜的生长速率为0.0535 nm/cycle,AlN超薄膜的折射率随着生长循环次数的增加而增大,并逐渐趋于稳定,薄膜厚度为6.88 nm时,其折射率为1.6535,薄膜厚度为33.01 nm时,其折射率为1.8731。该模型为超薄介质薄膜提供了稳定、可靠的椭圆偏振光谱法表征。