Initial stages of GaN/GaAs (100) growth by metalorganic chemical vapor deposition

We have investigated the growth of GaN buffers by metalorganic chemical vapor deposition (MOCVD) on GaAs (100) substrates. Atomic force microscope (AFM) and reflection high-energy electron diffraction (RHEED) were employed to study the dependence of the nucleation on the growth temperature, growth rate, annealing effect, and growth time. A two-step growth sequence must be used to optimize and control the nucleation and the subsequent growth independently. The size and distribution of islands and the thickness of buffer layers have a crucial role on the quality of GaN layers. Based on the experimental results, a model was given to interpret the formation of hexagonal-phase GaN in the cubic-phase GaN layers. Using an optimum buffer layer, the strong near-band emission of cubic GaN with full-width at half maximum (FWHM) value as small as 5.6 nm was observed at room temperature. The background carrier concentration was estimated to be in the range of 10¹³ ∼ 10¹⁴ cm⁻³.     

Tri-Buffer Process: A New Approach to Obtain High-Quality ZnO Epitaxial Films on Sapphire Substrates

A tri-buffer method was applied to achieve layer-by-layer growth of high-quality ZnO films on sapphire (0001) substrates by rf plasma-assisted molecular beam epitaxy (MBE). After sufficient nitridation of the substrate, MgO and ZnO buffer layers were subsequently deposited on the resulting AlN layer. An atomically smooth ZnO surface with a roughness less than 1 nm in a 10 μm × 10 μm scanned area was obtained with this method. The crystal quality was also improved, as characterized by reflection high-energy electron diffraction (RHEED), x-ray diffraction (XRD), Raman spectroscopy, and transmission electron microscopy (TEM). The results indicate that the tri-buffer process could reduce the large lattice mismatch between ZnO and nitrided sapphire and facilitate the two-dimensional (2-D) growth of the ZnO epilayer. A model is proposed to understand the observations.     

Unintentional incorporation of B, As, and O impurities in GaN grown by molecular beam epitaxy

We have investigated systematically the effects of growth parameters upon the unintentional incorporation of B, As, and O impurities in GaN grown by molecular beam epitaxy with an RF-plasma activated nitrogen source. The prepared samples were analyzed using secondary ion mass spectrometry to determine the absolute concentration of the impurities. The boron background concentration in the unintentionally doped GaN was found to strongly correlate with the nitrogen plasma power used during the growth, indicating a decomposition of the pBN crucible in the plasma source. Due to previous GaAs growth in the same chamber, a considerably large amount of As contamination (≈3×10¹⁸ at/cm³) was also observed in the grown layer. The presence of Al in GaN is found to facilitate the incorporation of oxygen impurities in the layer. We determined an empirical formula, C_o ^t/C_o ^b 3.8×(C_Al/C_Al)^0.27, representing the correlation between O concentration and Al mole fraction (%) in the small range of Al content, 0.03≈1%, in the layer. The residual oxygen level was substantially reduced from 3.4×10¹⁹ to mid-10¹⁸ at/cm³ in the GaN layer when the buffer layer structure was changed from low temperature grown GaN single buffer to GaN/AlN double buffer layer. We ascribe this significantly lowered oxygen impurity level to improved crystalline quality of the layer due to the double buffer layer structure.     

Improvement in crystal quality of ZnO film on Si substrate by using a homo-buffer layer

ZnO thin films without and with a homo-buffer layer have been prepared on Si(1 1 1) substrates by pulsed laser deposition (PLD) under various conditions. Photoluminescence (PL) measurement indicates that the optical quality of ZnO thin film is dramatically improved by introducing oxygen into the growth chamber. The sample deposited at 60 Pa possesses the best optical properties among the oxygen pressure range studied. X-ray diffraction (XRD) results show that the films directly deposited on Si are of polycrystalline ZnO structures. A low-temperature (500 °C) deposited ZnO buffer layer was used to enhance the crystal quality of the ZnO film. Compared to the film without the buffer layer, the film with the buffer layer exhibits aligned spotty reflection high-energy electron diffraction (RHEED) pattern and stronger near-band-edge emission (NBE) with a smaller full-width at half-maximum (FWHM) of 98 meV. The structural properties of ZnO buffer layers grown at different temperatures were investigated by RHEED patterns. It is suggested that the present characteristics of the ZnO epilayer may be raised further by elevating the growth temperature of buffer layer to 600 °C.     

Effects of annealing of MgO buffer layer on structural quality of ZnO layers grown by P-MBE on c-sapphire

We have investigated effects of annealing of MgO buffer layer on structural quality of ZnO layers grown by plasma assisted molecular beam epitaxy on c-sapphire. ZnO layers were characterized by atomic force microscopy, high resolution X-ray diffraction (HRXRD) and cross sectional transmission electron microscopy (TEM). AFM images show that annealing of a low temperature (LT)-MgO buffer at high temperatures enhanced the surface migration of adatoms, leading to the formation of larger terraces and smoother surface morphology, as indicated by the reduction of rms values of roughness from 0.6 to 0.3 nm. HRXRD and TEM experiments reveal that the dislocation density of ZnO layers is reduced from 5.3×10⁹ to 1.9×10⁹ cm⁻² by annealing a LT-MgO buffer. All of those features indicate the structural quality of ZnO layers was improved by annealing a LT-MgO buffer layer.     

The influence of composition and unintentional doping on the two-dimensional electron gas density in AlGaN/GaN heterostructures

We have studied the influence of Al content, AlGaN layer thickness, and unintentional background doping by oxygen on the two-dimensional electron gas (2DEG) density in AlGaN/GaN heterostructures. Hall measurements were made on samples grown with molecular beam epitaxy. The 2DEG densities in the range 2–3×10¹³ cm^?2 were measured. A one-dimensional Schrödinger-Poisson model was used to describe the heterostructure. The calculations gave two-dimensional electron densities in accordance with measured values. The electron density is very sensitive to the Al concentration in the AlGaN layer, whereas the sensitivity to layer thickness is small. Our simulations also showed that the two-dimensional concentration increased 50% when the free-carrier concentration changed from 10¹⁵ cm^?3 to 10¹⁸ cm^?3. The relation between donor concentration and free-carrier concentration was found to agree when using oxygen ionization energy as a parameter.     

ZnO and related materials: Plasma-Assisted molecular beam epitaxial growth, characterization and application

This paper will address features of plasma-assisted molecular beam epitaxial growth of ZnO and related materials and their characteristics. Two-dimensional, layer-by-layer growth is achieved both on c-plane sampphire by employing MgO buffer layer growth and on (0001) GaN/Al₂O₃ template by predepositing a low-temperature buffer layer followed by high-temperature annealing. Such two-dimensional growth results in the growth of high-quality heteroepitaxial ZnO epilayers. Biexciton emission is obtained from such high quality epilayers The polarity of heteroepitaxial ZnO epilayers is controlled by engineering the heterointerfaces. We achieved selective growth of Zn-polar and O-polar ZnO heteroepitaxial layers. The origin of different polarities can be successfully explained by an interface bonding sequence model. N-type conductivity in Gadoped ZnO epilayers is successfully controlled. High conductivity, enough to be applicable to devices, is achieved. Mg_xZn_1-xO/ZnO heterostructures are grown and emission from a ZnO quantum well is observed. Mg incorporation in a MgZnO alloy is determined by in-situ reflection high-energy electron diffraction intensity oscillations, which enables precise control of the composition. Homoepitaxy on commericial ZnO substrates has been examined. Reflection high-energy electron diffraction intensity oscillations during homoepitaxy growth are observed.     

Deposition of GaN Layers with a lowered dislocation density by molecular-beam epitaxy

The deposition of a multilayer buffer layer that includes a high-temperature AlN layer grown at a temperature above 1100°C has made it possible to reduce the dislocation density in a GaN layer by 1.5?C2 orders of magnitude to values in the range from 9 × 10⁸ to 1 × 10⁹ cm^?2, compared with the case of growth on a thin low-temperature AlN nucleation layer. The decrease in the dislocation density causes a substantial increase in the electron mobility in the GaN layers to 600?C650 cm² V^?1 s^?1, which is in agreement with the results of calculations and is indicative of the high crystalline perfection of the layers.     

Growth and characterization of GaN thin films on SiC SOI substrates

SiC semiconductor-on-insulator (SOI) structures have been investigated as substrates for the growth of GaN films. The SiC SOI was obtained through the conversion of Si SOI wafers by reaction with propane and H₂. (111) SiC SOI have been produced by this carbonization process at temperatures ranging from 1200 to 1300°C. X-ray diffraction (XRD) and infrared spectroscopy (FTIR) are used to chart the conversion of the Si layer to SiC. Under our conditions, growth time of 3 min at 1250°C is sufficient to completely convert a 1000? layer. XRD of the SiC SOI reveals a single SiC peak at 2θ = 35.7° corresponding to the (111) reflection, with a corrected full width at half-maximum (FWHM) of ~590±90 arc-sec. Infrared spectroscopy of SiC SOI structures obtained under optimum carboniza-tion conditions exhibited a sharp absorption peak produced by the Si-C bond at 795 cm⁻¹, with FWHM of ∼ 20–25 cm⁻¹. Metalorganic CVD growth of GaN on the (111) SiC SOI was carried out with trimethylgallium and NH₃. The growth of a thin (≤200?), low temperature (500°C) GaN buffer layer was followed by the growth of a thick (∼2 μm) layer at 1050°C. Optimum surface morphology was obtained for zero buffer layer. XRD indicates highly oriented hexagonal GaN, with FWHM of the (0002) peak of ~360±90 arc-sec. Under high power excitation, the 300°K photoluminescence (PL) spectrum of GaN films exhibits a strong near band-edge peak (at λ_p~371 nm, with FWHM = 100–150 meV) and very weak yellow emission. Under low power excitation, the 370 nm PL emission from the GaN/SiC SOI structure increases rapidly with SiC carbonization temperature, while the yellow band (∼550–620 nm) correspondingly decreases.     

MBE growth and properties of GaN and AlxGa1−xN on GaN/SiC substrates

The growth of GaN and AlGaN by molecular beam epitaxy (MBE) has been studied using GaN/SiC substrates. The GaN/SiC substrates consisted of ∼3 μm thick GaN buffer layers grown on 6H-SiC wafers by metalorganic vapor phase epitaxy (MOVPE) at Crée Research, Inc. The MBE-grown GaN films exhibit excellent structural and optical properties—comparable to the best GaN grown by MOVPE. Al_xGa_1−xN films (x ∼ 0.06-0.08) and Al_xGa_1−xN/GaN multi-quantum-well structures which display good optical properties were also grown by MBE on GaN/SiC substrates.     

The impact of nitridation and nucleation layer process conditions on morphology and electron transport in GaN epitaxial films

A systematic study has been performed to determine the characteristics of an optimized nucleation layer for GaN growth on sapphire. The films were grown during GaN process development in a vertical close-spaced showerhead metalorganic chemical vapor deposition reactor. The relationship between growth process parameters and the resultant properties of low temperature GaN nucleation layers and high temperature epitaxial GaN films is detailed. In particular, we discuss the combined influence of nitridation conditions, V/III ratio, temperature and pressure on optimized nucleation layer formation required to achieve reproducible high mobility GaN epitaxy in this reactor geometry. Atomic force microscopy and transmission electron microscopy have been used to study improvements in grain size and orientation of initial epitaxial film growth as a function of varied nitridation and nucleation layer process parameters. Improvements in film morphology and structure are directly related to Hall transport measurements of silicon-doped GaN films. Reproducible growth of silicon-doped GaN films having mobilities of 550 cm²/Vs with electron concentrations of 3 × 10¹⁷ cm⁻³, and defect densities less than 10⁸ cm⁻² is reported. These represent the best reported results to date for GaN growth using a standard two-step process in this reactor geometry.     

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.     

The role of the low temperature buffer layer and layer thickness in the optimization of OMVPE growth of GaN on sapphire

In agreement with previous work,¹² a thin, low temperature GaN buffer layer, that is used to initiate OMVPE growth of GaN growth on sapphire, is shown to play a critical role in determining the surface morphology of the main GaN epilayer. X-ray analysis shows that the mosaicity of the main GaN epilayer continues to improve even after several μm of epitaxy. This continuing improvement in crystal perfection correlates with an improvement in Hall mobility for thicker samples. So far, we have obtained a maximum mobility of 600 cm²/V-s in a 6 μm GaN epilayer. Atomic force microscopy (AFM) analysis of the buffer layer and x-ray analysis of the main epilayer lead us to conclude that the both of these effects reflect the degree of coherence in the main GaN epitaxial layer. These results are consistent with the growth model presented by Hiramatsu et al., however, our AFM data indicates that for GaN buffer layers partial coherence can be achieved during the low temperature growth stage.     

Correlation of biaxial strains, bound exciton energies, and defect microstructures in gan films grown on AlN/6H-SiC(0001) substrates

Biaxial strains resulting from mismatches in thermal expansion coefficients and lattice parameters in 22 GaN films grown on A1N buffer layers previously deposited on vicinal and on-axis 6H-SiC(0001) substrates were measured via changes in the c-axis lattice parameter. A Poisson’s ratio of ν = 0.18 was calculated. The bound exciton energy (E_BX) was a linear function of these strains. The shift in E_BX with film stress was 23 meV/GPa. Threading dislocations densities of ~10¹⁰/cm² and ~10⁸/em² were determined for GaN films grown on vicinal and on-axis SiC, respectively. A 0.9% residual compressive strain at the GaN/AIN interface was observed by high resolution transmission electron microscopy (HRTEM).     

Effects of high-temperature AIN buffer on the microstructure of AlGaN/GaN HEMTs

Effects on AlGaN/GaN high-electron-mobility transistor structure of a high-temperature AlN buffer on sapphire substrate have been studied by high-resolution x-ray diffraction and atomic force microscopy techniques. The buffer improves the microstructural quality of GaN epilayer and reduces approximately one order of magnitude the edge-type threading dislocation density. As expected, the buffer also leads an atomically flat surface with a low root-mean-square of 0.25 nm and a step termination density in the range of 10⁸ cm^?2. Due to the high-temperature buffer layer, no change on the strain character of the GaN and AlGaN epitaxial layers has been observed. Both epilayers exhibit compressive strain in parallel to the growth direction and tensile strain in perpendicular to the growth direction. However, an high-temperature AlN buffer layer on sapphire substrate in the HEMT structure reduces the tensile stress in the AlGaN layer.     

Optical and electrical characterization of GaN layers grown on silicon and sapphire substrates

Characterization of the structural, optical and electrical properties of GaN layers grown by two epitaxial techniques (ECR-MBE and MOCVD) using different substrates (vicinal Si111 and sapphire) has been performed. The quality of the samples grown by MOCVD seems to be influenced by the nitrogen source used for the growth. Unintentionally doped MBE samples with n-type concentrations around 10¹⁸ cm⁻³ and Hall mobility of 15 cm² (V s)⁻¹ were studied. GaN films doped with Mg and grown using AlN buffer layers have also been analyzed to study the influence of the thickness of the buffer layer on the optical properties of the GaN epilayer. In the samples with low Mg doping, a thin AlN buffer layer improved the optical quality of the film. In general, all the MBE samples doped with Mg were highly resistive, probably due to a low activation or high ionization energy of the Mg acceptors. Technological issues related to the formation of ohmic contacts on GaN layers are also presented.     

Epitaxial GaN layers formed on langasite substrates by the plasma-assisted MBE method

In this publication, the results of development of the technology of the epitaxial growth of GaN on single-crystal langasite substrates La₃Ga₅SiO₁₄ (0001) by the plasma-assisted molecular-beam epitaxy (PA MBE) method are reported. An investigation of the effect of the growth temperature at the initial stage of deposition on the crystal quality and morphology of the obtained GaN layer is performed. It is demonstrated that the optimal temperature for deposition of the initial GaN layer onto the langasite substrate is about ~520°C. A decrease in the growth temperature to this value allows the suppression of oxygen diffusion from langasite into the growing layer and a decrease in the dislocation density in the main GaN layer upon its subsequent high-temperature deposition (~700°C). Further lowering of the growth temperature of the nucleation layer leads to sharp degradation of the GaN/LGS layer crystal quality. As a result of the performed research, an epitaxial GaN/LGS layer with a dislocation density of ~10¹¹ cm^–2 and low surface roughness (<2 nm) is obtained.     

Low-temperature growth of silicon epitaxial layers codoped with erbium and oxygen atoms

The fabrication technology and properties of light-emitting Si structures codoped with erbium and oxygen are reported. The layers are deposited onto (100) Si by molecular beam epitaxy (MBE) using an Er-doped silicon sublimation source. The partial pressure of the oxygen-containing gases in the growth chamber of the MBE facility before layer growth is lower than 5 × 10^?10 Torr. The oxygen and erbium concentrations in the Si layers grown at 450°C is ～1 × 10¹⁹ and 10¹⁸ cm^?3, respectively. The silicon epitaxial layers codoped with erbium and oxygen have high crystal quality and yield effective photoluminescence and electroluminescence signals with the dominant optically active Er-1 center forming upon postgrowth annealing at a temperature of 800°C.     

Anti-phase domain-free growth of GaAs on offcut (001) Ge wafers by molecular beam epitaxy with suppressed Ge outdiffusion

The nucleation and growth of GaAs films on offcut (001) Ge wafers by solid source molecular beam epitaxy (MBE) is investigated, with the objective of establishing nucleation conditions which reproducibly yield GaAs films which are free of antiphase domains (APDs) and which have suppressed Ge outdiffusion into the GaAs layer. The nucleation process is monitored by in-situ reflection high energy electron diffraction and Auger electron spectroscopy. Several nucleation variables are studied, including the state of the initial Ge surface (single-domain 2×1 or mixed-domain 2×1:1×2), the initial prelayer (As, Ga, or mixed), and the initial GaAs growth temperature (350 or 500°C). Conditions are identified which simultaneously produce APD-free GaAs layers several microns in thickness on Ge wafers with undetectable Ge outdiffusion and with surface roughness equivalent to that of GaAs/GaAs homoepitaxy. APD-free material is obtained using either As or Ga nucleation layers, with the GaAs domain dependent upon the initial exposure chemical species. Key growth steps for APD-free GaAs/Ge growth by solid source MBE include an epitaxial Ge buffer deposited in the MBE chamber to bury carbon contamination from the underlying Ge wafer, an anneal of the Ge buffer at 640°C to generate a predominantly double atomic-height stepped surface, and nucleation of GaAs growth by a ten monolayer migration enhanced epitaxy step initiated with either pure As or Ga. We identify this last step as being responsible for blocking Ge outdiffusion to below 10¹⁵ cm⁻³ within 0.5 microns of the GaAs/Ge interface.     

外延GaN基薄膜表面应变演变RHEED分析

介绍了反射式高能电子衍射仪(RHEED)衍射原理以及半导体薄膜表面原子间距与其衍射图像间距成反比例关系。分析了采用ECR-PEMOCVD生长技术,在α-Al2O3衬底上低温外延GaN基薄膜(氮化层、缓冲层、外延层)工艺过程。通过对RHEED图像分析软件获取不同工艺过程中的外延薄膜衍射条纹间距的数据分析、计算、比较,得到薄膜表面衍射图像间距的大小,依据RHEED衍射图像与原子面间距之间的对应关系,分析薄膜表面的应变状态演变情况。分析计算结果表明生长20min氮化层、20min缓冲层的表面原子层处于压应变状态,而生长180min的AlN外延层,表面则处于完全弛豫状态。