Preparation of metallized GaN/sapphire cross sections for TEM analysis using wedge polishing

The tripod polisher has been used successfully in the past, in the preparation of difficult Si-based TEM cross-section specimens. Good TEM specimens, with large electron transparent areas, can be prepared in a relatively short time. In addition, wedge polishing considerably reduces the ion milling time because of the thinness of the final specimen. For metallized GaN on sapphire substrates, there are problems not inherent to Si-based materials: (1) sapphire is a difficult material to thin due to its high hardness and its mechanical instability when thinned below 20 m; (2) delamination of metal layers from the GaN can occur during polishing and/or ion milling; (3) markedly different ion milling rates for the metals and semiconductors. In this paper, wedge polishing has been modified to make it suitable for preparation of metallized GaN/sapphire samples or other metallized semiconductors and ceramics for TEM analysis. Using this method, TEM cross section specimens can be prepared with reasonably large thin areas.     

Removal of GaN film over AlGaN with inductively coupled BCl3/Ar atomic layer etch

Atomic layer etching(ALE)of thin film GaN(0001)is reported in detail using sequential surface modification by BCl₃ adsorption and removal of the modified surface layer by low energy Ar plasma exposure in a reactive ion etching system.The estimated etching rate of GaN is~0.74 nm/cycle.The GaN is removed from the surface of AlGaN after 135 cycles.To study the mechanism of the etching,the detailed characterization and analyses are carried out,including scanning electron microscope(SEM),x-ray photoelectron spectroscopy(XPS),and atomic force microscope(AFM).It is found that in the presence of GaCl_x after surface modification by BCl₃,the GaCl_x disappears after having exposed to low energy Ar plasma,which effectively exhibits the mechanism of atomic layer etch.This technique enables a uniform and reproducible fabrication process for enhancement-mode high electron mobility transistors with a p-GaN gate.     

A combined SNMS and EFTEM/EELS study on focused ion beam prepared vanadium nitride thin films

We investigated the diffusion profiles and core-loss fine-structures (ELNES) of thin vanadium nitride films by electron energy-loss spectroscopy (EELS) and energy filtering transmission electron microscopy (EFTEM). The nitride layers have been produced by rapid thermal processing in a NH₃ or N₂ atmosphere and have then been cross-sectioned with a focused ion beam instrument (FIB) under mild milling conditions to maintain crystallography. For the high-resolution electron energy-loss spectroscopy studies (HREELS), a recently developed TEM gun monochromator, implemented into a 200 kV field emission gun column was used in combination with a new post-column spectrometer. It was found that, dependent on substrate and atmosphere, layers with different vanadium and nitrogen content were formed, showing distinct differences in their ELNES. With an energy resolution at the 0.2 eV level and a TEM beam spot size of approximately 2 nm these layers could be unambiguously identified when compared to theoretical ELNES simulations from the literature.     

Determination of the linear attenuation range of electron transmission through film specimens

We have investigated the linear attenuation range of electron transmission through film specimens and its dependence on the electron energy, the acceptance half-angle of a detector or an objective aperture, and specimen properties, in the scanning transmission electron microscope (STEM) and the conventional transmission electron microscope (TEM). Electron transmission in the bright-field mode was calculated by the Monte Carlo simulation of electron scattering, and its range of the linear attenuation in film thickness was then determined by a linear least squares fit. The corresponding linear thickness range was shown to increase with the electron energy and the acceptance half-angle, although it decreased with the increase in the atomic number of specimen materials. Under the condition of a 300 kV STEM or a 3 MV ultra-high voltage electron microscope (ultra-HVEM), the linear attenuation range could extend to several microns for light specimen materials, and this was validated by experimental data in the ultra-HVEM. The presented results can be helpful for accurately measuring the specimen thickness or mass from electron transmission, and estimating the deviation of electron transmission from linearity when tilting a specimen in electron tomography.     

High contrast hollow-cone dark field transmission electron microscopy for nanocrystalline grain size quantification

In this paper, we describe hollow-cone dark field (HCDF) transmission electron microscopy (TEM) imaging, with a slightly convergent beam, as an improved technique that is suitable to form high contrast micrographs for nanocrystalline grain size quantification. We also examine the various factors that influence the HCDF TEM image quality, including the conditions of microscopy (alignment, focus and objective aperture size), the properties of the materials imaged (e.g., atomic number, strain, defects), and the characteristics of the TEM sample itself (e.g., thickness, ion milling artifacts). Sample preparation was found to be critical and an initial thinning by wet etching of the substrate (for thin film samples) or tripod polishing (for bulk samples), followed by low-angle ion milling was found to be the preferred approach for preparing high-quality electron transparent samples for HCDF imaging.     

Microstructural and compositional characteristics of GaN films grown on a ZnO-buffered Si (111) wafer

Polycrystalline GaN thin films have been deposited epitaxially on a ZnO-buffered (111)-oriented Si substrate by molecular beam epitaxy. The microstructural and compositional characteristics of the films were studied by analytical transmission electron microscopy (TEM). A SiO(2) amorphous layer about 3.5 nm in thickness between the Si/ZnO interface has been identified by means of spatially resolved electron energy loss spectroscopy. Cross-sectional and plan-view TEM investigations reveal (GaN/ZnO/SiO(2)/Si) layers exhibiting definite a crystallographic relationship: [111](Si)//[111](ZnO)//[0001](GaN) along the epitaxy direction. GaN films are polycrystalline with nanoscale grains ( approximately 100 nm in size) grown along [0001] direction with about 20 degrees between the (1l00) planes of adjacent grains. A three-dimensional growth mode for the buffer layer and the film is proposed to explain the formation of the as-grown polycrystalline GaN films and the functionality of the buffer layer.     

梯度掺杂与均匀掺杂GaN光电阴极的对比研究

为了提高负电子亲和势(NEA)GaN光电阴极的量子效率,利用金属有机化合物化学气相淀积(MOCVD)外延生长了梯度掺杂反射式GaN光电阴极,其掺杂浓度由体内到表面依次为1×10¹⁸ cm^-3,4×10¹⁷ cm^-3,2×10¹⁷ cm^-3和6×10¹⁶ cm^-3,每个掺杂浓度区域的厚度约为45 nm,总的厚度为180 nm.在超高真 关键词： NEA GaN光电阴极 梯度掺杂 量子效率 能带结构     

Influence of electron irradiation of the NOVER-1 vacuum resist on its resistance to ionbeam etching

The influence of electron irradiation on the resistance of the NOVER-1 resist to ion-beam etching is studied. Etching is carried out by argon ions with energies between 300 and 2500 eV. It is found that, depending on the energy and angle of incidence of the ions on the surface of the resist, electron irradiation may either speed up or slow down the NOVER-1 etching. A clear correlation is observed between the penetration depth of the ions in the resist and the influence of the electron irradiation on the resistance of the resist to etching. At ion energies higher than 500 eV (ion penetration depth ≳3.5 nm) the resistance decreases, passes through a minimum at low electron irradiation doses, and returns to the etching rate of the initial resist at high doses. For glancing etching angles (∼ 70° to the surface normal) and low ion energies (300 eV), i.e., small ion penetration depths (≲2.5 nm), an electron-irradiated resist is etched more slowly than the initial resist at all the electron irradiation doses studied. This effect may be used to enhance the resistance of resist structures whose height exceeds their width, which in this case is determined mostly by the rate of etching of the inclined facets. Zh. Tekh. Fiz. 68, 140–142 (January 1998)     

Synthesis of single crystalline GaN nanoribbons on sapphire (0001) substrates

Single crystalline GaN nanoribbons were synthesized through nitriding Ga₂O₃ thin films deposited on sapphire (0001) substrates by radio frequency magnetron sputtering. The component and structure of nanoribbons were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The flat and smooth ribbon-like nanostructures are high quality single crystalline hexagonal wurtzite GaN. The thickness and width-to-thickness ratio of the grown GaN nanoribbons are in the range of 8-15 nm and ∼5-10, respectively.     

Large-scale synthesis of GaN nanorods and their photoluminescence

Large quantities of gallium nitride (GaN) nanorods have been synthesized via direct reaction of metallic gallium vapor with flowing ammonia at 970 °C in a quartz tube. The nanorods have been confirmed as crystalline wurzite GaN by powder X-ray diffraction, selected-area electron diffraction and X-ray photoelectron spectrometry. Transmission electron microscopy and scanning electron microscopy reveal that the nanorods are straight and uniform, with diameters ranging from 40 nm to 150 nm and lengths up to hundreds of micrometers. The growth mechanism is discussed briefly. Photoluminescence measurements on bulk GaN nanorods at room temperature show two strong peaks at 377 nm (3.28 eV) and 360 nm (3.44 eV) attributed to the zero-phonon donor-acceptor pair transition and the donor-bound exciton, respectively. Received: 19 April 2001 / Accepted: 10 May 2001 / Published online: 20 June 2001     

Inelastic electron scattering observation using energy filtered transmission electron microscopy for silicon -- germanium nanostructures imaging

This paper presents a new technique using energy filtered TEM (EFTEM) for inelastic electron scattering contrast imaging of Germanium distribution in Si-SiGe nanostructures. Comparing electron energy loss spectra (EELS) obtained in both SiGe and Si single crystals, we found a spectrum area strongly sensitive to the presence of Ge in the range [50-100 eV]. In this energy loss window, EELS spectrum shows a smooth steeply shaped background strongly depending on Ge concentration. Germanium mapping inside SiGe can thus be performed through imaging of the EELS background slope variation, obtained by processing the ratio of two energy filtered TEM images, respectively, acquired at 90 and 60 eV. This technique gives contrasted images strongly similar to those obtained using STEM Z-contrast, but presenting some advantages: elastic interaction (diffraction) is eliminated, and contrast is insensitive to polycrystalline grains orientation or specimen thickness. Moreover, since the extracted signal is a spectral signature (inelastic energy loss) we demonstrate that it can be used for observation and quantification of Ge concentration depth profile of SiGe buried layers.     

The synthesis of highly oriented GaN nanowire arrays

Highly oriented GaN nanowire arrays have been achieved by the catalytic reaction of gallium with ammonium. The resulting materials were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM) and selected-area electron diffraction (SAED). SEM images show that the resulting materials are nanowire arrays with a uniform length of about 10 μm. XRD, EDS, TEM and SAED indicate that the nanowire arrays are single-crystal hexagonal GaN with a wurtzite structure. They have diameters of 10 to 20 nm. Received: 2 October 2002 / Accepted: 7 October 2002 / Published online: 17 December 2002 RID="*" ID="*"Corresponding author. E-mail: wwwangjc@sina.com     

Spectroscopic characterizations of individual single-crystalline GaN nanowires in visible/ultra-violet regime

Spectroscopic investigations of individual single-crystalline GaN nanowires with a lateral dimensions of ～30–90 nm were performed using the spatially resolved technique of electron energy-loss spectroscopy in conjunction with scanning transmission electron microscope showing a 2-Å electron probe. Positioning the electron probe upon transmission impact and at aloof setup with respect to the nanomaterials, we explored two types of surface modes intrinsic to GaN, surface exciton polaritons at ～8.3 eV (～150 nm) and surface guided modes at 3.88 eV (～320 nm), which are in visible/ultra-violet spectral regime above GaN bandgap of ～3.3 eV (～375 nm) and difficult to access by conventional optical spectroscopies. The explorations of these electromagnetic resonances might expand the current technical interests in GaN nanomaterials from the visible/UV range below ～3.5 eV to the spectral regime further beyond.     

离子源工艺参数对BCB胶刻蚀速率和表面粗糙度的影响

为了研究离子束刻蚀抛光过程中离子源工艺参数对刻蚀速率及表面粗糙度的影响,采用微波离子源为刻蚀离子源,以BCB胶为主要研究对象,研究了离子束能量、离子束电流、氩气流量、氧气流量对BCB胶刻蚀速率及表面粗糙度的影响,获得了离子源工艺参数与刻蚀速率及表面粗糙度演变的关系。研究结果表明,离子束能量在从400 eV增大到800 eV的过程中,刻蚀速率不断增大,从3.2 nm/min增大到16.6 nm/min;离子束流密度在从15 mA增大到35 mA的过程中,刻蚀速率不断增大,从1.1 nm/min增大到2.2 nm/min;工作气体中氧气流量从2 mL/min增大到10 mL/min的过程中,刻蚀速率会整体增大,在8 mL/min处略有下降。表面粗糙度变化不大,可以控制在1.8 nm以下。     

蓝宝石衬底上GaN/AlxGa1-xN超晶格插入层对AlxGa1-xN外延薄膜应变及缺陷密度的影响

室温300K下,由于Al_xGa_1-xN的带隙宽度可以从GaN的3.42eV到AlN的6.2eV之间变化,所以Al_xGa_1-xN是紫外光探测器和深紫外LED所必需的外延材料.高质量高铝组分Al_xGa_1-xN材料生长的一大困难就是Al_xGa_1-xN与常用的蓝宝石衬底之间大的晶格失配和热失配.因而采用MOCVD在GaN/蓝宝石上生长的Al_xGa_1-xN薄膜由于受张应力作用非常容易发生龟裂.GaN/Al_xGa_1-xN超晶格插入层技术是释放应力和减少Al_xGa_1-xN薄膜中缺陷的有效方法.研究了GaN/Al_xGa_1-xN超晶格插入层对GaN/蓝宝石上Al_xGa_1-xN外延薄膜应变状态和缺陷密度的影响.通过拉曼散射探测声子频率从而得到材料中的残余应力是一种简便常用的方法,Al_xGa_1-xN外延薄膜的应变状态可通过拉曼光谱测量得到.Al_xGa_1-xN外延薄膜的缺陷密度通过测量X射线衍射得到.对于具有相同阱垒厚度的超晶格,例如4nm/4nm,5nm/5nm,8nm/8nm的GaN/Al_0.3Ga_0.7N超晶格,研究发现随着超晶格周期厚度的增加Al_xGa_1-xN外延薄膜缺陷密度降低,Al_xGa_1-xN外延薄膜处于张应变状态,且5nm/5nmGaN/Al_0.3Ga_0.7N超晶格插入层Al_xGa_1-xN外延薄膜的张应变最小.在保持5nm阱宽不变的情况下,将垒宽增大到8nm,即十个周期的5nm/8nmGaN/Al_0.3Ga_0.7N超晶格插入层使Al_xGa_1-xN外延层应变状态由张应变变为压应变.由X射线衍射结果计算了Al_xGa_1-xN外延薄膜的刃型位错和螺型位错密度,结果表明超晶格插入层对螺型位错和刃型位错都有一定的抑制效果.透射电镜图像表明超晶格插入层使位错发生合并、转向或是使位错终止,且5nm/8nmGaN/Al_0.3Ga_0.7N超晶格插入层导致Al_xGa_1-xN外延薄膜中的刃型位错倾斜30°左右,释放一部分压应变.     

Optimization of inductively coupled plasma deep etching of GaN and etching damage analysis

Inductively coupled plasma (ICP) etching of GaN with an etching depth up to 4 μm is systemically studied by varying ICP power, RF power and chamber pressure, respectively, which results in etch rates ranging from ∼370 nm/min to 900 nm/min. The surface morphology and damages of the etched surface are characterized by optical microscope, scanning electron microscope, atomic force microscopy, cathodoluminescence mapping and photoluminescence (PL) spectroscopy. Sub-micrometer-scale hexagonal pits and pillars originating from part of the structural defects within the original GaN layer are observed on the etched surface. The density of these surface features varies with etching conditions. Considerable reduction of PL band-edge emission from the etched GaN surface indicates that high-density non-radiative recombination centers are created by ICP etching. The density of these non-radiative recombination centers is found largely dependent on the degree of physical bombardments, which is a strong function of the RF power applied. Finally, a low-surface-damage etch recipe with high ICP power, low RF power, high chamber pressure is suggested.     

Synthesis, characterization, growth mechanism, photoluminescence and field emission properties of novel dandelion-like gallium nitride

Dandelion-like gallium nitride (GaN) microstructures were successfully synthesized via Ni catalyst assisted chemical vapor deposition method at 1200 °C under NH₃ atmosphere by pre-treating precursors with aqueous ammonia. The as-synthesized product was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). X-ray diffraction analysis revealed that as-synthesized dandelion-like GaN was pure and has hexagonal wurtzite structure. SEM results showed that the size of the dandelion-like GaN structure was in the range of 30-60 μm. Dandelion-like GaN microstructures exhibited reasonable field emission properties with the turn-on field of 9.65 V μm⁻¹ (0.01 mA cm⁻²) and threshold field of 11.35 V μm⁻¹ (1 mA cm⁻²) which is sufficient for applications of electron emission devices, field emission displays and vacuum micro electronic devices. Optical properties were studied at room temperature by using fluorescence spectrophotometer. Photoluminescence (PL) measurements of dandelion-like GaN showed a strong near-band-edge emission at 370.2 nm (3.35 eV) with blue band emission at 450.4 nm (2.75 eV) and 465.2 nm (2.66 eV) but with out yellow band emission. The room-temperature photoluminescence properties showed that it has also potential application in light-emitting devices. The tentative growth mechanism for the growth of dandelion-like GaN was also described.     

Influence of AlN Buffer Thickness on GaN Grown on Si(111) by Gas Source Molecular Beam Epitaxy with Ammonia

Hexagonal GaN is grown on a Si(111) substrate with AlN as a buffer layer by gas source molecular beam epitaxy (GSMBE) with ammonia. The thickness of AlN buffer is changed from 9 to 72nm. When the thickness of AlN buffer is 36nm, the surface morphology and crystal quality of GaN is optimal. The in-situ reflection high energy electron diffraction (RHEED) reveals that the transition to a two-dimensional growth mode of AlN is the key to the quality of GaN. However, the thickness of AlN buffer is not so critical to the residual in-plane tensile stress in GaN grown on Si(111) by GSMBE for AlN thickness between 9 to 72nm.     

Observation of Undamped 3D Brownian Motion of Nanoparticles Using Liquid-Cell Scanning Transmission Electron Microscopy

In theory, liquid-cell (scanning) transmission electron microscopy (LC(S)TEM) is the ideal method to measure 3D diffusion of nanoparticles (NPs) on a single particle level, beyond the capabilities of optical methods. However, particle diffusion experiments have been especially hard to explain in LC(S)TEM as the observed motion thus far has been slower than theoretical predictions by 3–8 orders of magnitude due to electron beam effects. Here, direct experimental evidence of undamped diffusion for two systems is shown; charge-neutral 77 nm gold nanoparticles in glycerol and negatively charged 350 nm titania particles in glycerol carbonate. The high viscosities of the used media and a low electron dose rate allow observation of Brownian motion that is not significantly altered by the electron beam. The resulting diffusion coefficient agrees excellently with a theoretical value assuming free diffusion. It is confirmed that the particles are also moving in the direction parallel to the electron beam by simulating STEM images using Monte Carlo simulations. Simulations and experiments show blurring of the particles when these move out of focus. These results make clear that direct observation of 3D diffusion of NPs is possible, which is of critical importance for the study of interparticle interactions or in situ colloidal self-assembly using LC(S)TEM.     

U型槽刻蚀工艺对GaN垂直沟槽型金属-氧化物-半导体场效应晶体管电学特性的影响

U型槽的干法刻蚀工艺是GaN垂直沟槽型金属-氧化物-半导体场效应晶体管(MOSFET)器件关键的工艺步骤,干法刻蚀后GaN的侧壁状况直接影响GaN MOS结构中的界面态特性和器件的沟道电子输运.本文通过改变感应耦合等离子体干法刻蚀工艺中的射频功率和刻蚀掩模,研究了GaN垂直沟槽型MOSFET电学特性的工艺依赖性.研究结果表明,适当降低射频功率,在保证侧壁陡直的前提下可以改善沟道电子迁移率,从35.7 cm^2/(V·s)提高到48.1 cm^2/(V·s),并提高器件的工作电流.沟道处的界面态密度可以通过亚阈值摆幅提取,射频功率在50 W时界面态密度降低到1.90×10^12 cm^-2·eV^-1,比135 W条件下降低了一半.采用SiO2硬刻蚀掩模代替光刻胶掩模可以提高沟槽底部的刻蚀均匀性.较薄的SiO2掩模具有更小的侧壁面积,高能离子的反射作用更弱,过刻蚀现象明显改善,制备出的GaN垂直沟槽型MOSFET沟道场效应迁移率更高,界面态密度更低.