Method for HVPE growth of thick crack-free GaN layers

Twenty-five micrometer thick GaN was grown with hydride vapor phase epitaxy (HVPE) on metal-organic chemical vapor deposition (MOCVD) grown templates on sapphire substrates with the gallium treatment step (GTS) technique with varying buffer layer thickness. The samples are studied with atomic force microscopy (AFM), etching and scanning electron microscopy (SEM), photo-luminescence (PL), X-ray diffraction (XRD) and optical microscopy. The results show that the thickness of the buffer layer is not important for the layer quality once the growth in MOCVD starts to make the transition from 3D growth to 2D growth and HVPE continues in the same growth mode. We show that the MOCVD templates with GTS technique make excellent templates for HVPE growth, allowing growth of GaN without cracks in either sapphire or GaN.     

Hydride vapor phase epitaxy of GaN boules using high growth rates

The boule-like growth of GaN in a vertical AIXTRON HVPE reactor was studied. Extrinsic factors like properties of the starting substrate and fundamental growth parameters especially the vapor gas composition at the surface have crucial impact on the formation of inverse pyramidal defects. The partial pressure of GaCl strongly affects defect formation, in-plane strain, and crystalline quality. Optimized growth conditions resulted in growth rates of 300–500 μm/h. GaN layers with thicknesses of 2.6 and of 5.8 mm were grown at rates above 300 μm/h. The threading dislocation density reduces with an inverse proportionality to the GaN layer thickness. Thus, it is demonstrated that growth rates above 300 μm/h are promising for GaN boule growth.     

Fabrication of a freestanding GaN layer by direct growth on a ZnO template using hydride vapor phase epitaxy

A new hydride vapor phase epitaxy (HVPE)-based approach for the fabrication of freestanding GaN (FS-GaN) substrates was investigated. For the direct formation of low-temperature GaN (LT-GaN) layers, the growth parameters were optimized: the polarity of ZnO, the growth temperature, and the V/III ratio. The FS-GaN layer was achieved by gas etching in an HVPE reactor. A fingerprint of Zn out-diffusion was detected in the photoluminescence measurements, especially for the thin (80 μm) FS-GaN film; however, a thicker film (400 μm) was effectively reduced by optimization of GaN growth.     

衬底温度对电子辅助增强化学气相沉积金刚石膜的影响

本工作采用蒙特卡罗(Monte Carlo)方法,对以CH4/H2为源气体的电子助进化学气相沉积(EACVD)金刚石薄膜的气相动力学过程进行了模拟.提出了衬底温度的空间梯度变化模型,研究了衬底温度对EACVD气相过程中的电子群行为以及H2和CH4分解过程的影响.结果表明:电子平均温度随着衬底温度的升高而升高;当气压较低时,分解得到的成膜关键粒子H、CH3数量随衬底温度的增大而减少;而当气压较高时,H、CH3数目随衬底温度的增大而增大;衬底温度主要改变了衬底表面附近的化学反应动力学过程,从而对薄膜质量产生了决定性的影响.     

Modelling the growth of nitrides in ammonia‐rich environment

Surface properties and the principal processes at the growth of gallium nitride on GaN (0001) face in ammonia‐based are modeled using DFT (density functional theory – SIESTA code) ab initio calculations and 2‐d diffusion analysis. The GaN growth methods are: ammonia‐source MBE, MOVPE, and also HVPE. The adiabatic trajectories, calculated for hydrogen‐rich and hydrogen‐free state of the GaN(0001) surface, include the adsorption of NH₃, GaCl and HCl molecules and the desorption of Ga atoms. The adsorption of ammonia and GaCl has no energy barrier. Thus, in contrast to the results concerning Plasma‐Assisted Molecular Beam Epitaxy (PA MBE), proving that the GaN(0001) surface remains in metal‐rich state, these results indicate that, in the ammonia‐rich environment, typical for HVPE and MOVP growth, the GaN(0001) surface remains in the nitrogen‐rich state. In the case of HCl adsorption, the energy barrier depends on the surface coverage, and could reach 2.0 eV. The direct desorption of single Ga atom has the energy barrier, close to 7 eV. This indicates that Ga surface diffusion (growth controlling process) length is very large, leading to strong interaction of the step kinetics and the diffusion on the terraces. This interaction leads to double–step intertwined structures both in the case of dislocation‐mediated spiral growth and in the step flow growth mode. These morphologies, proposed by the geometric arguments, are observed in the atomic force microscopy (AFM) scans of the GaN(0001) surface. Additionally we have compared the interaction energy of two hydrogen atoms obtained in the DFT SIESTA and the high precision Gaussian in coupled cluster singles, double and perturbation triples CCSD(T) approximation. Both approaches yielded virtually identical interaction energy confirming the validity of DFT analysis of ammonia‐rich growth of GaN. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Selective area growth of GaN microstructures on patterned (1 1 1) and (0 0 1) Si substrates

Selective MOVPE growth of GaN microstructure on silicon substrates has been investigated using SiO₂ mask having circular or stripe window. In case of (0 0 1)substrate, grooves with (1 1 1) facets at the sides were made by using the etching anisotropy of a KOH solution. On the (1 1 1) facets of patterned silicon substrate (or on the as opened window region of (1 1 1) substrate), growth of wurtzite GaN was performed, of which the c-axis is oriented along the 1 1 1 axis of silicon. The photoluminescence and X-ray diffraction analysis were performed to characterize the single crystal to reveal the effect of the growth conditions of the intermediated layer and the microstructure.     

Hydrogen and nitrogen ambient effects on epitaxial growth of GaN by hydride vapour phase epitaxy

This study presents the influence of the composition of the carrier gas on the growth of GaN by HVPE. Since no hydrogen is introduced in the vapour phase, the deposition is expected to be controlled by Cl desorption in the form of GaCl₃, as has been proposed for GaAs. However, our published model predicts much lower growth rates than those observed. We can account for both the observed parasitic deposition and GaN growth rate if we assume that GaCl₃ is not at its equilibrium pressure in the deposition zone and where nucleation takes place on the walls as well as on the substrate. This yields a high rate of parasitic nucleation even though the nominal supersaturation is vanishing small. Very little growth takes place on the substrate where the equilibrium pressure of GaCl₃ is reached. We describe similar experiments performed with a H₂/N₂ mixture as the carrier gas. In this case, we expect GaN deposition to be controlled by desorption of Cl as HCl, which is known as the H₂ mechanism. It is speculated that the results show the existence of a new growth mechanism.     

Cross‐sectional and surface Raman mapping of thick GaN layers

Raman scattering spectroscopy was utilized for investigation of the structural properties of thick GaN layers. These layers with thickness ∼ 40 μm have been grown by HVPE technique on the sapphire substrates. The investigations have been focused on the strain distribution in GaN layer cross‐section as a function of distance from an interface sapphire/GaN and mapping of the surface and of the inner layer, near the sapphire/GaN interface. From the observed phonon shifts in the Raman spectra strain differences lower than 6.4×10^–4 corresponding to stress differences of 240 MPa were estimated across the thick GaN epitaxial layer. The measurements exhibit that strain in the layer causes changes in the Raman spectra and allow determining the relaxation process in the crystal. The obtained results confirmed, that the mode frequencies in the measured Raman spectra in both directions (parallel or perpendicular to the growth direction) for layer thicknesses over 30 µm are comparable with typical values for bulk material and match the low strain in the structure due to relaxation processes. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The impact of an intermediate temperature buffer on the growth of GaN on an AlN template by hydride vapor phase epitaxy

The present study focused on the effect of an intermediate-temperature (IT; ∼900 °C) buffer layer on GaN films, grown on an AlN/sapphire template by hydride vapor phase epitaxy (HVPE). In this paper, the surface morphology, structural quality, residual strain, and luminescence properties are discussed in terms of the effect of the buffer layer. The GaN film with an IT-buffer revealed a relatively lower screw-dislocation density (3.29×10⁷ cm⁻²) and a higher edge-dislocation density (8.157×10⁹ cm⁻²) than the GaN film without an IT-buffer. Moreover, the IT-buffer reduced the residual strain and improved the luminescence. We found that the IT-buffer played an important role in the reduction of residual strain and screw-dislocation density in the overgrown layer through the generation of edge-type dislocations and the spontaneous treatment of the threading dislocation by interrupting the growth and increasing the temperature.     

Surface chemistry and transport effects in GaN hydride vapor phase epitaxy

A simple quasi-thermodynamic model of surface chemistry in GaN hydride vapor phase epitaxy (HVPE) is presented. The model is coupled with the detailed 3D simulations of species transport in a horizontal-tube reactor and validated by the comparison with the data on the GaN growth rate obtained by laser reflectometry. Parametric study of the growth rate as a function of temperature and species flow rates has been performed over a wide range of growth conditions. The important role of species transport in an HVPE reactor is demonstrated. In particular, a strong effect of the natural concentration convection resulting in the formation of recirculation zones and in a non-uniform vapor composition is revealed by modeling. The impact of these effects on the GaN growth rate and V/III ratio on the growth surface is discussed in detail.     

Experimental and theoretical investigations of the electrical properties of undoped and magnesium-doped GaN layers

The ac characteristics of GaN : Mg and undoped GaN layers, grown by MOVPE on sapphire substrates, are measured for a wide range of temperature and bias conditions, in order to investigate the effect of the magnesium-related level on the transport properties. Two peaks, whose height and position depend on the measurement temperature, are observed in the admittance curves (G/ω versus frequency) of the Mg-doped samples, whereas only one peak appears in undoped samples. The study of the frequency dependence of the impedance, with a model including the two metallic Au/GaN junctions, the GaN layer itself, shows that, besides the effect of the differential resistance of the layer which plays a role in both sample types, the presence of a Mg-related deep level contributes to the observed variations of the peaks in the admittance curves of the p-doped samples. Results of a theoretical steady-state and small-signal analysis based on numerical modelling of the Au/GaN/Au heterostructure complete our analysis.     

化学气相沉积单层VIB族过渡金属硫化物的研究进展

2004年以来,石墨烯因其优异的光学、电学性质而被广泛地研究,但由于其零带隙的特性极大地限制了它的应用前景.单层的VIB族过渡金属硫化物(TMDs)拥有类似石墨烯的晶体结构及可控的能带结构,是一类理想的二维直接带隙半导体材料,不仅可用于探索如谷极化等一些基础和前沿的物理问题,也可以广泛应用于纳米器件、光电子学和光催化的研究.近年来,化学气相沉积(CVD)技术作为一种相较于传统化学合成或物理剥离更加有效的制备方法被引入此类材料的生长,能够合成出拥有大面积连续的、厚薄均匀和较高晶体质量的单层TMDs.基于此,重点介绍了利用CVD技术生长单层TMDs所取得的进展,讨论了各工艺条件(如反应温度、载流气体、衬底、前驱物与衬底之间的距离等)对单层TMDs的生长及性质的影响.最后,探讨了利用CVD技术实现调控单层TMDs的尺寸、覆盖度和层厚均匀性的途径和方法.     

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.     

Epitaxial growth of ZnO films

After summing up the main physical properties of ZnO and its subsequent applications the aim of this article is to review the growth of ZnO epitaxial films by PLD, MBE, MOCVD and sputtering under their various aspects, substrates, precursors, reaction chemistry, assessment of the layers etc. …, keeping constantly in mind some key issues for the device applications of ZnO in optoelectronics, surface acoustic filters and spintronics, amongst which the growth of high quality epitaxial layers of both n- or p-type conductivity, the possibility of dissolving transition elements in the layers, the growth of ZnO related alloys and heterostructures are of major significance.     

金属有机物气相外延生长InAlGaN薄膜及其性能表征

在不同的生长温度和载气的条件下,采用低压金属有机物气相外延方法生长了系列的InAlGaN薄膜,通过能量色散谱(EDS),高分辨X射线衍射(HRXRD)和光致发光谱(PL)对样品进行表征与分析,研究了生长工艺对InAlGaN外延层结构和光学性能的影响.发现当以氮气做载气时,样品的发光很弱并且在550nm附近存在一个很宽的深能级发光峰;当采用氮气和氢气的混合气做载气时,样品中的深能级发光峰消失且发光强度明显提高.以混合气做载气,InAlGaN薄膜中铟的组分随生长温度的升高而降低,而薄膜的结构和光学性能却提高.结合PL和HRXRD的测试结果得到了较佳的生长参数:即载气为氢气和氮气的混合气以及生长温度在850℃到870℃.     

Enhanced growth rates and reduced parasitic deposition by the substitution of Cl2 for HCl in GaN HVPE

The main limitation in the application of hydride vapor phase epitaxy for the large scale production of thick free-standing GaN substrates is the so-called parasitic deposition, which limits the growth time and wafer thickness by blocking the gallium precursor inlet. By utilizing Cl₂ instead of the usual HCl gas for the production of the gallium chlorine precursor, we found a rapid increase in growth rate from ∼80 to ∼400 μm/h for an equally large flow of 25 sccm. This allowed us to grow, without any additional optimization, 1.2 mm thick high quality GaN wafers, which spontaneously lifted off from their 0.3° mis-oriented GaN on sapphire HCl-based HVPE templates. These layers exhibited clear transparencies, indicating a high purity, dislocation densities in the order of 10⁶ cm⁻², and narrow rocking curve XRD FWHMs of 54 and 166 arcsec in for the 0002 and 101−5 directions, respectively.     

Properties of Ge-doped,high-quality bulk GaN crystals fabricated by hydride vapor phase epitaxy

We investigated the properties of Ge-doped, high-quality bulk GaN crystals with Ge concentrations up to 2.4×10¹⁹ cm⁻³. The Ge-doped crystals were fabricated by hydride vapor phase epitaxy with GeCl₄ as the dopant source. Cathodoluminescence imaging revealed no increase in the dislocation density at even the highest Ge concentration, with values as low as 3.4×10⁶ cm⁻². The carrier concentration, as determined by Hall measurement, was almost identical to the combined concentration of Ge and unintentionally incorporated Si. The electron mobilities were 260 and 146 cm² V⁻¹ s⁻¹ for n=3.3×10¹⁸ and 3.35×10¹⁹ cm⁻³, respectively; these values are markedly larger than those reported in the past for Ge-doped GaN thin films. The optical absorption coefficient was quite small below the band gap energy; it slightly increased with increase in Ge concentration. Thermal conductivity, estimated by the laser-flash method, was virtually independent of Ge concentration, maintaining an excellent value around 2.0 W cm⁻¹ K⁻¹. Thermal expansion coefficients along the a- and m-axes were approximately constant at 5.0×10⁻⁶ K⁻¹ in the measured doping concentration range.     

Subtle interplay between polytypism and preferred growth direction alignment in GaN nanorods non-catalytically grown on Si(1 1 1) substrates by using hydride vapor phase epitaxy

GaN nanorods were grown on Si(1 1 1) substrates by using hydride vapor phase epitaxy, and the crystallographic characteristics associated with their preferred growth directions were investigated by utilizing synchrotron X-ray reciprocal space mapping in a grazing incidence geometry and scanning electron microscopy. Crystallographic analysis reveals that the nanorods containing both wurtzite and zinc blende phase tend to have narrower distribution of the preferred growth directions than those containing only wurtzite phase. This tendency is partly attributed to the subtle interplay between polytypism and the preferred growth directions of GaN nanorods.     

Role of vapor-phase diffusion in selective-area MOVPE of InGaN/GaN MQWs

Selective-area growth (SAG) of InGaN/GaN multiple quantum wells (MQWs) was performed by metalorganic vapor phase epitaxy (MOVPE). The layers of a blue light-emitting diode (LED), that includes five InGaN quantum wells, were grown on a patterned GaN template on a sapphire substrate. In order to elucidate the contribution of vapor-phase diffusion of group-III precursors to the in-plane modulation of luminescence wavelength, the width of a stripe selective growth area was 60 μm that is sufficiently larger than the typical surface diffusion length, with the mask width varied stepwise between 30 and 240 μm. The distribution of the luminescence wavelength from the MQWs was measured with cathode luminescence (CL) across the stripe growth area. The peak wavelength ranged between 420 and 500 nm. The peak shifted to longer wavelengths and became broader as the measured point approached to the mask edge. Such a shift in the peak wavelength exhibited parabolic profile in the growth area and the wider mask shifted the entire peak positions to longer wavelengths. These trends clearly indicate that the vapor-phase diffusion play a dominant role in the in-plane modulation of the luminescence wavelength in the SA-MOVPE of InGaN MQWs, when the size of a growth area and/or the mask width exceeds approximately 10 μm.