GaN缓冲层对生长InN薄膜的影响

采用金属有机物化学气相沉积(MOCVD)方法生长六方相InN薄膜，利用氮化镓(GaN)缓冲层技术制备了高质量薄膜，得到了其能带带隙0.7eV附近对应的光致发光光谱(PL). 通过比较未采用缓冲层，同时采用低温和高温GaN缓冲层，以及低温GaN缓冲层结合高温退火三种生长过程，发现低温GaN缓冲层结合高温退火过程能够得到更优表面形貌和晶体质量的InN薄膜，同时表征了材料的电学性质和光学性质. 通过对InN薄膜生长模式的讨论，解释了薄膜表面形貌和晶体结构的差异.     

<Emphasis Type="Italic">In Situ</Emphasis> Stress Measurements During GaN Growth on Ion-Implanted AlN/Si Substrates

In situ wafer curvature measurements were used in combination with postgrowth structural characterization to study the evolution of film stress and microstructure in GaN layers grown by metalorganic chemical vapor deposition on N⁺ ion-implanted AlN/Si (111) substrates. The results were compared with growth on identical unimplanted substrates. In situ stress measurements revealed that, for the unimplanted sample, the GaN initiated growth under compressive stress of −1.41 GPa which arose due to lattice mismatch with the AlN buffer layer. In contrast, GaN growth on the ion-implanted sample began at lower compressive stress of −0.84 GPa, suggesting a reduction in epitaxial stress. In both cases, the compressive growth stress was fully relaxed after ~0.7 μm and minimal tensile stress was generated during growth. During post-growth cooling, tensile stress was introduced in the GaN layer of both samples due to thermal expansion mismatch. Post-growth optical microscopy characterization, however, demonstrated that the ion-implanted sample had lower density of channeling cracks compared with the unimplanted sample. Cross-sectional transmission electron microscopy images of the sample grown on ion-implanted Si with no post-implantation nitrogen annealing revealed the formation of horizontal cracks in the implanted region beneath the AlN buffer layer. The weakened layer acts to decouple the GaN film from the Si substrate and thereby reduces the density of channeling cracks in the film after growth.     

MOCVD Growth of InN on Si(111) with Various Buffer Layers

We report the growth of InN by metalorganic chemical vapor deposition on Si(111) substrates. It was found that the sharpest InN(002) x-ray diffraction peak could be achieved from the sample prepared on a complex buffer layer that consists of a low-temperature AlN, a graded Al _x Ga_1−x N (x = 1 → 0), and a high-temperature GaN. The resultant mobility of 275 cm²/V s thus obtained was 75% larger than that of the InN prepared on a single LT-AlN buffer layer only.     

Growth of zinc- blende GaN on GaAs (100) substrates at high temperature using low-pressure MOVPE with a Low V/lll molar ratio

Zinc-blende GaN films were grown on GaAs (100) substrates by low-pressure metalorganic vapor phase epitaxy using trimethylgallium or triethylgallium and NH₃. Films grown at lower temperatures contained considerable amounts of carbon, but the carbon concentration was reduced in high temperature growth. When the film was grown at 950°C using triethylgallium and NH₃, its carbon concentration was on the order of 10¹⁷ cm⁻³. The crystalline and optical quality of zinc-blende GaN crystal also improved with high-temperature growth at a low V/III ratio using a thin buffer layer. The films exhibited only one sharp photoluminescence peak at 3.20 eV with a full width at half maximum as low as 70 meV at room temperature.     

Correlation Between Threading Dislocations and Nonradiative Recombination Centers in InN Observed by IR Cathodoluminescence

The correlation between threading dislocations (TDs) and nonradiative recombination centers in InN films was investigated by infrared cathodoluminescence (CL). Samples were grown on nitridated (0001) sapphire substrates with a low-temperature-grown InN buffer layer by radio frequency molecular-beam epitaxy (RF-MBE). Panchromatic CL images of the InN films showed a high density of dark spots in a range of 10⁸ cm⁻² to 10⁹ cm⁻². The sample with a higher density of TDs had a higher density of CL dark spots. A depth-dependent CL measurement confirmed that CL dark spots aligned almost vertically in the film like TDs. Reasonable correlation between TDs and the nonradiative regions was also observed by a cross-sectional CL image of the InN film regrown on a microfaceted InN template, in which the TD density was dramatically reduced in part. These results suggest that threading dislocations act as nonradiative recombination centers in InN.     

MBE growth and properties of ZnO on sapphire and SiC substrates

Molecular beam epitaxy (MBE) of ZnO on both sapphire and SiC substrates has been demonstrated. ZnO was used as a buffer layer for the epitaxial growth of GaN. ZnO is a würtzite crystal with a close lattice match (<2% mismatch) to GaN, an energy gap of 3.3 eV at room temperature, a low predicted conduction band offset to both GaN and SiC, and high electron conductivity. ZnO is relatively soft compared to the nitride semiconductors and is expected to act as a compliant buffer layer. Inductively coupled radio frequency plasma sources were used to generate active beams of nitrogen and oxygen for MBE growth. Characterization of the oxygen plasma by optical emission spectroscopy clearly indicated significant dissociation of O₂ into atomic oxygen. Reflected high energy electron diffraction (RHEED) of the ZnO growth surface showed a two-dimensional growth. ZnO layers had n-type carrier concentration of 9 × 10¹⁸ cm⁻³ with an electron mobility of 260 cm²/V-s. Initial I-V measurements displayed ohmic behavior across the SiC/ZnO and the ZnO/GaN heterointerfaces. RHEED of GaN growth by MBE on the ZnO buffer layers also exhibited a two-dimensional growth. We have demonstrated the viability of using ZnO as a buffer layer for the MBE growth of GaN.     

Spontaneous growth of III-nitride nanowires on Si by molecular beam epitaxy

In this paper, we report on the catalyst-free growth and the optoelectronic properties of GaN and InN nanowires (NWs) grown on Si(1 1 1) substrates by nitrogen RF plasma source molecular beam epitaxy (RF-MBE) without the use of intermediate GaN or AlN buffer layer. The growth conditions were optimized in order to fabricate well-aligned, stress-free single crystalline nanowires. In both cases, the III-nitride NWs were generated from the lattice mismatch strain of the materials on Si and the high surface energy of their nitrogen stabilized surfaces. Both PL and Raman spectroscopy revealed that the NWs were fully relaxed. XRD results further assert the single crystallinity of the nanowires.     

Growth and characterization of indium arsenide thin films

The growth and characterization of indium arsenide films grown on indium phosphide substrates by the metal organic chemical vapor deposition (MOCVD) process is reported. Either ethyl dimethyl indium or trimethyl indium were found to be suitable in combination with arsine as source compounds. The highest electron mobilities were observed in films nucleated at reduced growth temperature. Scanning electron microscopy studies show that film nucleation at low temperature prevents thermal etch pits from forming on the InP surface before growth proceeds at an elevated temperature. Electron mobilities as high as 21,000 cm²V⁻¹ sec⁻¹ at 300 K were thus obtained for a film only 3.4 μm thick. This mobility is significantly higher than was previously observed in InAs films grown by MOCVD. From the depth dependence of transport properties, we find that in our films electrons are accumulated near the air interface of the film, presumably by positive ions in the native oxide. The mobility is limited by electrons scattering predominantly from ionized impurities at low temperature and from lattice vibrations and dislocations at high temperature. However, scattering from dislocations is greatly reduced in the surface accumulation layer due to screening by a high density of electrons. These dislocations arise from lattice mismatch and interface disorder at the film-substrate interface, preventing these films from obtaining mobility values of bulk indium arsenide.     

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).     

Growth of thick gan films on rf sputtered ain buffer layer by hydride vapor phase epitaxy

High crystalline quality thick GaN films were grown by vapor phase epitaxy using GaCl₃ and NH₃. The growth rate was in the range of 10~15 Μm/h. GaN films grown at higher temperatures (960~ 1020?C) were single crystalline with smooth surface morphologies. No chlorine impurity was incorporated in these films during growth. The best crystalline quality and surface morphology of grown films was achieved by sputtering a thin A1N buffer layer, prior to growth. According to reflection high energy electron diffraction and atomic force microscopy measurements, as-sputtered A1N buffer layer was amorphous with root means square roughness of 0.395 nm and then crystallized during the GaN growth. This improved the GaN growth due to more uniform distribution of GaN nucleation. Rutherford backscattering channeling experiments produced the lowest value from the GaN film grown on a-Al₂O₃ with a 500å A1N buffer layer at 1020?C.     

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.     

A new buffer layer for MOCVD growth of GaN on sapphire

High quality GaN films have been grown on sapphire substrates (C face and A face) by atmospheric pressure metalorganic chemical vapor deposition (MOCVD) using a new buffer layer. With our reactor configuration and growth parameters, a GaN film grown on a single GaN buffer layer appears opaque with high density of hexagonal pits. Using a single A1N buffer layer results in extremely nonuniform morphology with mirror-like areas near the edge of the substrates and opaque areas in the center. The double buffer layer we report here, with GaN as the first layer and A1N as the second, each with an optimized thickness, leads to mirror-like films across the entire substrate. Scanning electron microscopy, photoluminescence, x-ray diffraction, and van der Pauw geometry Hall measurement data are presented to establish the quality of our films. The mechanism for this new buffer layer is also discussed.     

Characterization of AlGaN/GaN structures on various substrates grown by radio frequency-plasma assisted molecular beam epitaxy

The structural properties and surface morphology of AlGaN/GaN structures grown on LiGaO₂ (LGO), sapphire, and hydride vapor phase epitaxy (HVPE)-grown GaN templates are compared. AlGaN grown on LGO substrates shows the narrowest x-ray full width at half maximum (FWHM) for both symmetric 〈00.4〉 and asymmetric 〈10.5〉 reflections. Atomic force microscopy (AFM) analysis on AlGaN surfaces on LGO substrates also show the smoothest morphology as determined by grain size and rms roughness. The small lattice mismatch of LGO to nitrides and easily achievable Ga-polarity of the grown films are the primary reasons for the smoother surface of AlGaN/GaN structure on this alternative substrate. Optimizations of growth conditions and substrate preparation results in step flow growth for an AlGaN/GaN structure with 300 Å thick Al_0.25Ga_0.75N on 2.4 μm thick GaN. A high III/V flux ratio during growth and recently improved polishing of LGO substrates aids in promoting two dimensional step flow growth. The GaN nucleation layer directly on the LGO substrate showed no evidence of mixed phase cubic and hexagonal structure that is typically observed in the nucleation buffer on sapphire substrates. Cross-sectional high-resolution transmission electron microscopy (HRTEM) was performed on an AlGaN/GaN heterostructure grown on LGO. The atomic arrangement at the AlGaN/GaN interface was sharp and regular, with locally observed monolayer and bilayer steps.     

Growth Optimization of an Electron Confining InN/GaN Quantum Well Heterostructure

The molecular beam epitaxy of In-face InN (0001) epilayers with optimized surface morphology, structural quality, and electrical properties was investigated. Namely, compact InN epilayers with atomically flat surfaces, grown in a step-flow mode, were obtained using stoichiometric fluxes of In and N and substrate temperatures in the range from 400°C to 435°C. Typical values for the electron concentration and the Hall mobility at 300 K were 4.3 × 10¹⁸ cm⁻³ and 1210 cm²/Vs, respectively. The growth mode of InN during the very first stage of the nucleation was investigated analytically, and it was found that the growth proceeds through nucleation and fast coalescence of two-dimensional (2-D)–like InN islands. The preceding conditions were used to grow an InN/GaN quantum well (QW) heterostructure, which exhibited well-defined interfaces. Schottky contacts were successfully fabricated using a 15-nm GaN barrier enhancement cap layer. Capacitance-voltage measurements revealed the confinement of electrons within the InN QW and demonstrated the capability to modulate the electron density within an InN channel. The sheet concentration of the confined electrons (1.5 × 10¹³ cm⁻²) is similar to the calculated sheet polarization charge concentration (1.3 × 10¹³ cm⁻²) at the InN/GaN interface. However, electrons may also originate from ionized donors with a density of 8 × 10¹⁸ cm⁻³ within the InN layer.     

Growth optimization and doping with Si and Be of high quality GaN on Si(111) by molecular beam epitaxy

GaN layers have been grown by plasma-assisted molecular beam epitaxy on AlN-buffered Si(111) substrates. An initial Al coverage of the Si substrate of aproximately 3 nm lead to the best AlN layers in terms of x-ray diffraction data, with values of full-width at half-maximum down to 10 arcmin. A (2×2) surface reconstruction of the AlN layer can be observed when growing under stoichiometry conditions and for substrate temperatures up to 850°C. Atomic force microscopy reveals that an optimal roughness of 4.6 nm is obtained for AlN layers grown at 850°C. Optimization in the subsequent growth of the GaN determined that a reduced growth rate at the beginning of the growth favors the coalescence of the grains on the surface and improves the optical quality of the film. Following this procedure, an optimum x-ray full-width at half-maximum value of 8.5 arcmin for the GaN layer was obtained. Si-doped GaN layers were grown with doping concentrations up to 1.7×10¹⁹ cm⁻³ and mobilities approximately 100 cm²/V s. Secondary ion mass spectroscopy measurements of Be-doped GaN films indicate that Be is incorporated in the film covering more than two orders of magnitude by increasing the Be-cell temperature. Optical activation energy of Be acceptors between 90 and 100 meV was derived from photoluminescence experiments.     

Nanohomojunction (GaN) and Nanoheterojunction (InN) Nanorods on One‐Dimensional GaN Nanowire Substrates

The formation of homojunctions and heterojunctions on two‐dimensional (2D) substrates plays a key role in the device performance of thin films. Accelerating the progress of device fabrication in nanowires (NWs) also necessitates a similar understanding in the one‐dimensional (1D) system. Nanohomojunction (GaN on GaN) and nanoheterojunction (InN on GaN) nanorods (NRs) were formed in a two‐step growth process by a vapor–liquid–solid (VLS) mechanism. Ga₂O₃ nanoribbons were formed using Ni as catalyst in a chemical vapor deposition (CVD) technique and then completely converted to GaN NWs with NH₃ as reactant gas. An Au catalyst is used in the second step of the VLS process to grow GaN and InN NRs on GaN NWs using CVD techniques. A morphological study showed the formation of nanobrushes with different structural symmetries and sub‐symmetries in both homogeneous and heterogeneous systems. Structural characterizations showed nearly defect‐free growth of nanohomojunction (GaN) and nanoheterojunction (InN) NRs on 1D GaN NW substrates.     

Growth and microstructure of InxGa1−xN films grown on SiC substrates via low pressure metalorganic vapor phase epitaxy

The growth and microstructures of In_xGa_1−xN films (x≤0.23) grown on α(6H)–SiC(0001) wafer/AIN buffer layer/GaN heterostructures by low pressure metalorganic vapor phase epitaxy have been investigated. The system deposition pressure limited the InN content in these films. The maximum InN contents achievable at the deposition pressures of 45 and 90 torr were ∼13 and ∼23%, respectively. Kinetic phenomena based on the rates of adsorption and desorption of the In growth species off the growth surface are presented to explain the film composition dependence on the system pressure. The surface morphologies and microstructures of the In_xGa_1−xN films were analyzed using several techniques, and the formation of pinhole defects in the films was investigated. Most of the pinhole defects were associated with threading dislocations with a c-component Burgers vector. Edge-type dislocations were never observed to terminate in pinholes in the samples observed here. Indium segregation to areas around the defect areas was observed, as was an In compositional gradient in the growth direction. Based on experimental observations, the strain field around dislocations with a c-component Burgers vector could result in the increase of In atoms at the dislocation sites in the film, which result in a change to the local growth mode of the film and causes the pinhole defects to form.     

A comparative study on the growth of InAlN films on different substrates

This work investigates the growth of InAlN films on Si (111), sapphire (001), GaAs (100) and glass substrates and compares the structural, morphological, electrical and optical properties of these films. One micron thick InAlN films were synthesized on these substrates at 300 °C by using reactive magnetron co-sputtering system. The structural analysis showed the formation of polycrystalline InAlN films on all the substrates having preferred orientation along (101) plane. The films grown on sapphire and silicon displayed better structural quality than the films grown on GaAs and glass. The morphological results revealed identical granular features on all the substrates with small variation in the grain size. The electrical resistivity of InAlN film on sapphire was the lowest one (8×10⁻³ Ω-cm) whereas the highest carrier concentration (8×10²⁰ cm⁻³) was obtained for the film deposited on glass. The energy band gap of InAlN films was determined through UV–vis absorption and reflectance spectroscopy. The band gap value obtained on the glass was slightly higher as compared to its value on the other substrates. The changes in InAlN properties on different substrates were explained on the basis of lattice mismatch, crystallite size, residual strain and orientation of the 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.     

引入GaN过渡层对Si（111）衬底上生长GaN外延的影响

本文研究了在Si(111)衬底上生长GaN外延层的方法。相比于直接在AlN缓冲层上生长GaN外延层,引入GaN过渡层显著地提高了外延层的晶体质量并降低了外延层的裂纹密度。使用X射线双晶衍射仪、光学显微镜以及在位监测曲线分析了GaN过渡层对外延层的晶体质量以及裂纹密度的影响。实验发现,直接在AlN缓冲层上生长外延层,晶体质量较差, X射线(0002)面半高宽最优值为0.686°,引入GaN过渡层后,通过调整生长条件,控制岛的长大与合并的过程,从而控制三维生长到二维生长过渡的过程,外延层的晶体质量明显提高, (0002)面半高宽降低为0.206°,并且裂纹明显减少。研究结果证明,通过生长合适厚度的GaN过渡层,可以得到高质量、无裂纹的GaN外延层。