Formation of high quality gallium nitride thin films on Ga-diffused Si(1 1 1) substrate

High quality gallium nitride thin films have been successfully grown on the Ga-diffused Si(1 1 1) substrates through ammoniating Ga₂O₃ thin films deposited by r.f. magnetron sputtering. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), atomic force microscope (AFM) and photoluminescence (PL) were used to characterize the synthesized samples. The analyses reveal that the formed films are high quality polycrystalline hexagonal gallium nitride. The as-formed GaN films show a flat surface topography with RMS roughness varied from 29 to 48 Å. The strong near-band-edge-emission peak around 368 nm was observed at room temperature. This is a novel method to fabricate GaN thin films based on the direct reaction between Ga₂O₃ and NH₃ on the Ga-diffused Si(1 1 1) substrates.     

基于GaN同质衬底的高迁移率AlGaN/GaNHEMT材料

研究了表面预处理对GaN同质外延的影响,获得了高电子迁移率AlGaN/GaN异质结材料.通过NH_3/H_2混合气体与H_2交替通入反应室的方法对GaN模板和GaN半绝缘衬底进行高温预处理.研究结果表明,NH_3/H_2能够抑制GaN的分解,避免粗糙表面,但不利于去除表面的杂质,黄光带峰相对强度较高;H_2促进GaN分解,随时间延长GaN分解加剧,导致模板表面粗糙不平,AlGaN/GaN HEMT材料二维电子气迁移率降低.采用NH_3/H_2混合气体与H_2交替气氛模式处理模板或衬底表面,能够清洁表面,去除表面杂质,获得平滑的生长表面和外延材料表面,有利于提高AlGaN/GaN HEMT材料电学性能.在GaN衬底上外延AlGaN/GaN HEMT材料,2DEG迁移率达到2113 cm~2/V·s,电学性能良好.     

Dry etching characteristics of GaN using Cl2/BCl3 inductively coupled plasmas

ICP power/RF power, operating pressure, and Cl₂/BCl₃ gas mixing ratio are altered to investigate the effect of input process parameters on the etch characteristics of GaN films. The etch selectivity of GaN over SiO₂ and photoresist is studied. Although higher ICP/RF power can obtain higher GaN/photoresist etch selectivity, it can result in faceting of sidewall and weird sidewall profile due to photoresist mask erosion. Etch rates of GaN and SiO₂ decrease with the increase of operating pressure, and etch selectivity of GaN over SiO₂ increases with the increasing operating pressure at fixed ICP/RF power and mixture component. The highest etch selectivity of GaN over SiO₂ is 7.92, and an almost vertical etch profile having an etch rate of GaN close to 845.3 nm/min can be achieved. The surface morphology and root-mean-square roughness of the etched GaN under different etching conditions are evaluated by atomic force microscopy. The plasma-induced damage of GaN is analyzed using photoluminescence (PL) measurements. The optimized etching process, used for mesa formation during the LED fabrication, is presented. The periodic pattern can be transferred into GaN using a combination of Cl₂/BCl₃ plasma chemistry and hard mask SiO₂. Patterning of the sapphire substrate for fabricating LED with improved extraction efficiency is also possible using the same plasma chemistry.     

Characterization of hetero-interfaces between group III nitrides formed by PLD and various substrates

We have grown group III nitride epitaxial films on various substrates by pulsed laser deposition and investigated structural properties of the surfaces and the hetero-interfaces using grazing incidence angle X-ray reflectivity (GIXR) and atomic force microscopy (AFM). It has been found that hetero-interfaces between PLD AlN and conventional substrates such as Al₂O₃ and Si are quite abrupt (about 0.5 nm) probably due to a less reactive growth ambience. However, we observed a thin interfacial layer (less than 10 nm) at the hetero-interface between AlN and (Mn,Zn)Fe₂O₄. The surface roughness of AlN is mainly determined by the extent of the lattice mismatch. It has been also found that the roughness at the hetero-interface between GaN and AlN formed by PLD coincides with the surface roughness of the AlN layer.     

A study on the reaction between chlorine trifluoride gas and glass-like carbon

The reaction between glass-like carbon (GC) and chlorine trifluoride (ClF₃) gas was investigated with weight measurements, surface analysis, and gas desorption measurements, where the ClF₃ gas is used for the in situ cleaning of tubes in silicon-related fabrication equipment. From Auger electron spectroscopy and X-ray photoelectron spectroscopy measurements, a carbon mono-fluoride, –(CF)_n–, film near the surface of GC is considered to be grown onto the GC surface above 400 °C by the chemical reaction with ClF₃, and this thickness of the fluoride film depends on the temperature. The grown fluoride film desorbs by annealing in a vacuum up to 600 °C. Although GC is apparently etched by ClF₃ over 600 °C, the etch rate of GC is much lower than that of SiC and quartz.     

Real-time monitoring of SiO2/Si(1 1 1) interlayer etching by Brewster-angle reflectometry

A transitory etching regime after SiO₂ dissolution and before bulk Si(1 1 1) etching in neutral NH₄F solutions was monitored by in situ Brewster-angle reflectometry (BAR). An observed intermediate increase of the BAR reflectance signal is attributed to a fast dissolution of a stressed/strained interlayer beneath the SiO₂/Si(1 1 1) interface. Similar effects were observed on thin thermal oxides (18.2 nm), grown on float zone silicon, as well as on ultra-thin native oxides (1.2 nm) on Czochralsky silicon. Native oxide covered samples showed an increased surface roughness in the course of interlayer dissolution while the surface is progressively covered with compounds of fluorinated silicon. The etch rate, determined by atomic force microscopy (AFM) and compared to the etch rate of bulk silicon, is increased by a factor of four. In the limit of extended etching, the known low etch rates for silicon in 40% NH₄F are observed. Structural and chemical properties of the interfacial layer were analyzed by synchrotron radiation photoelectron spectroscopy (SRPES) which confirmed the presence of Si^3+/4+ valence states throughout the interlayer and by near open-circuit potential (N-OCP) dark current measurements. As a result, oxide etch rates in NH₄F in the pH-range 7–8 as well as the silicon interlayer depth can be assessed by in situ BAR.     

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N2-Ar射频放电等离子体广泛应用于微电子工业的刻蚀、氮化物薄膜的制备及金属表面氮化等技术领域。开发了N2-Ar混合气体容性耦合射频放电PIC/MC自洽模型,模型主要描述了e-,N2+,N+,Ar+等主要带电粒子的行为分布。等离子体的碰撞过程分别考虑了带电粒子(e-,N2+,N+,Ar+)与基态中性N2分子和Ar原子的21种碰撞反应过程。模拟结果表明,在纯N2及N2-Ar混合气体容性耦合射频放电中,各种带电粒子的数密度都在等离子体区达到最大值,且氮分子离子为主要粒子;在N2容性耦合射频放电中,加入10%氩气时,N+平均能量有所增加,在射频电极处两种氮离子(N2+,N+)高能粒子所占比例增加。本研究对认识N2-Ar射频放电等离子体过程微观机理具重要意义。     

蓝光激光器结构中InGaN/GaN多量子阱界面效应的精细光致发光光谱研究

金属有机化学气相沉积(MOCVD)方法制备InGaN/GaN多量子阱结构时,在GaN势垒层生长的N2载气中引入适量H2,能够有效改善阱/垒界面质量从而提升发光效率.本工作利用光致发光(PL)光谱技术,对蓝光激光器结构中的InGaN/GaN多量子阱的发光性能进行了精细的光谱学测量与表征,研究了通H2生长对量子阱界面的调控...     

Increased surface roughness by oxygen plasma treatment of graphite/polymer composite

The technology of selective plasma etching was applied to increase the surface roughness of graphite/polymer composite. Etching was performed with a low pressure weakly ionised oxygen plasma created with a RF generator of the output power of 200 W and frequency of 27.12 MHz. The density of charged particles, density of neutral oxygen atoms and the electron temperature was about 1×10¹⁶ m⁻³, 4×10²¹ m⁻³, and 5 eV, respectively. The effects of plasma treatment were observed by scanning electron microscope (SEM), electron microprobe (EMPA) and Talysurf. It was found that the surface roughness was increased by approximately 15 times, from a virgin sample at the roughness of R_a=0.27 μm to a very rough surface with R_a=4 μm. The roughness increased with increasing plasma exposure time. The EMPA results showed that the amount of sulphur in the surface layer decreased with increasing etching time indicating that PPS polymer was the material etched preferentially.     

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.     

Active species in microwave postdischarge for steel-surfacenitriding

Production of nitrogen atoms has been studied in a 2.45-GHz flowing postdischarge in N₂ and N₂-H₂ gas mixtures with Ar as a buffer gas in the high-pressure regime (5×10³ to 6.5×10⁴ Pa). N atom densities have been measured by NO titration in the 10¹⁴-10 ¹⁵ cm³ range and monitored by the first positive emission resulting from the N atom recombination. The rate coefficient of the N+N+N₂ recombination has been found to be _k=6×10^-33 cm⁶ atom^-2 s ^-1 at T₀=300 K, which agrees with previously published data. The N atom production (or degree of N/N₂ dissociation) in front of an Fe-0.1%C substrate correlates well with the thickness of a γ' Fe₄N layer produced by the postdischarge treatment. The H₂ gas was first introduced in the initial phase of treatment to remove surface oxidizing and then was cut off to keep high densities of N atoms. It is deduced that N atoms are more active nitriding species than NH-type radicals     

纳米孔隙内混合气体流动特性的分子动力学模拟

纳米孔隙内气体流动的理论预测对气体微流控器件的设计和制造具有重要的理论指导作用,文章采用分子动力学方法研究了氮气、氧气和二氧化碳混合气体在平行壁纳米孔隙内的剪切流动特性和边界滑移特性.研究结果表明:随着加入二氧化碳比例的不断增加,混合气体滑移速度不断增大,并且当二氧化碳的比例低于20%时,混合气体流动速度沿孔隙宽度方向呈线性分布;而当比例达到40%后,其速度轮廓将呈现非线性趋势.当二氧化碳所占比例为20%时,随着孔隙宽度的增加,混合气体的整体边界滑移随之减小.探究了混合气体密度和气-固耦合强度对混合气体流动及边界滑移的影响机理.发现随着混合气体密度的减小,气流边界滑移增大;随着气-固界面耦合强度的增强,边界气体分子易被吸附而出现黏滑运动,气体分子在边界处的积聚现象增强,剪切应变率增大,边界滑移减小.      

Femtosecond laser micro-structuring of aluminium under helium

The interaction of 180 fs, 775 nm laser pulses with aluminium under a flowing stream of helium at ambient pressure have been used to study the material re-deposition, ablation rate and residual surface roughness. Threshold fluence F_th0.4 J cm⁻² and the volume ablation rate was measured to be 30<V<450 μm³ per pulse in the fluence range 1.4<F<21 J cm⁻². The presence of helium avoids gas breakdown above the substrate and leads to improved surface micro-structure by minimising surface oxidation and debris re-deposition. At 1 kHz rep. rate, with fluence F>7 J cm⁻² and >85 W cm⁻² average power density, residual thermal effects result in melt and debris formation producing poor surface micro-structure. On the contrary, surface micro-machining at low fluence F1.4 J cm⁻² with low power density, 3 W cm⁻² produces much superior surface micro-structuring with minimum melt and measured surface roughness R_a1.1±0.1 μm at a depth D50 μm. By varying the combination of fluence/scan speed during ultra-fast ablation of aluminium at 1 kHz rep. rate, results suggest that maintaining average scanned power density to <5 W cm⁻² combined with single pulse fluence <4 J cm⁻² produces near optimum micro-structuring. The debris under these conditions contains pure aluminium nanoparticles carried with the helium stream.     

Studies of sol–gel TiO2 and Pt/TiO2 catalysts for NO reduction by CO in an oxygen-rich condition

The textural properties, morphological features, surface basicity and oxygen reduction behaviours of titania and Pt supported titania catalysts synthesized via a sol–gel method were studied by means of N₂ physisorption, SEM, TEM, CO₂-TPD and H₂-TPR techniques. Mesostructured TiO₂ shows a very narrow pore size distribution that uniformly centred at about 4 nm. High resolution TEM images confirmed that most of Pt particles on Pt/TiO₂-SG had a size smaller than 2 nm. Both the titania support and Pt loaded catalysts chiefly contained weak basic sites with small amount of strong basic sites. Loading Pt did not significantly alter the surface reduction characters of titania, indicating a weak interaction between Pt metals and titania support. Catalytic evaluation revealed that the selectivity of NO reduction over titania was insensitive to variation of textural property. On the bare titania, low NO conversion but high selectivity to N₂O was obtained. However, the Pt/TiO₂-SG catalysts exhibited high NO conversion and high selectivity to N₂, which is assumed to relate to NO dissociation catalysed by the metallic Pt clusters. In addition, when the reaction temperature was above 200 °C, 3–11% NO₂ was yielded over the Pt/TiO₂-SG catalysts, which was discussed on a basis of reaction competition, metal-support interaction and NO dissociation.     

Effects of surface treatments and annealing on carbon-based molecular sieve membranes for gas separation

A new method in preparing carbon-based molecular sieve (CMS) membranes for gas separation has been proposed. Carbon-based films are deposited on porous Al₂O₃ disks using hexamethyldisiloxane (HMDSO) by remote inductively coupled plasma (ICP) chemical vapor deposition (CVD). After treating the film with ion bombardment and subsequent pyrolysis at a high temperature, carbon-based molecule sieve membranes can be obtained, exhibiting a very high H₂/N₂ selectivity around 100 and an extremely high permeance of H₂ around 1.5 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ at 298 K. The O₂/N₂ selectivity could reach 5.4 with the O₂ permeance of 2 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ at 423 K.

During surface treatments, HMDSO ions were found to be more effective than CH₄, Ar, O₂ and N₂ ions to improve the selectivity and permeance. Short and optimized surface treatment periods were required for high efficiency. Without pyrolysis, surface treatments alone greatly reduced the H₂ and N₂ permeances and had no effect on the selectivity. Besides, without any surface treatment, pyrolysis alone greatly increased the H₂ and N₂ permeances, but had no improvement on the selectivity, owing to the creation of large pores by desorption of carbon. A combination of surface treatment and pyrolysis is necessary for simultaneously enhancing the permeance and the selectivity of CMS membranes, very different from the conventional pore-plugging mechanism in typical CVD.     

Deposition and characterization of carbon nitride films from hexamethylenetetramine/N2 by microwave plasma-enhanced chemical vapor deposition

Carbon nitride thin films were deposited on Si(1 0 0) substrate by microwave plasma-enhanced chemical vapor deposition (PECVD). Hexamethylenetetramine (HMTA) was used as carbon and nitrogen source while N₂ gas was used as both nitrogen source and carrier gas. The sp³-bonded C---N structure in HMTA was considered significantly in the precursor selection. X-ray diffraction analysis indicated that the film was a mixture of crystalline - and β-C₃N₄ as well as graphitic-C₃N₄ and β-Si₃N₄ which were not easily distinguished. Raman spectroscopy also suggested the existence of - and β-C₃N₄ in the films. X-ray photoelectron spectroscopy study indicated the presence of sp²- and sp³-bonded C---N structures in the films while sp³C---N bonding structure predominated to the sp² C---N bonding structure in the bulk composition of the films. N was also found to be bound to Si atoms in the films. The product was, therefore, described as CN_x:Si, where x depends on the film depth, with some evidences of crystalline C₃N₄ formation.     

Synthesis and optical characterization of c-axis oriented GaN thin films on amorphous quartz glass via sol–gel process

c-Axis oriented GaN nanocrystalline thin films were fabricated by nitridation of three different thin films of -GaO(OH), -Ga₂O₃ or β-Ga₂O₃ obtained by sol–gel technique on amorphous quartz glass substrates. All these GaN thin films showed near band edge emission at 390 nm and yellow luminescence at 570 nm. The crystalline nature and c-axis orientation as well as luminescence properties of the GaN thin films increased by several times by using a buffer layer of GaN on the substrate.     

Picosecond nonlinear optical response of Ba0.5Sr0.5TiO3 thin films fabricated by pulsed laser deposition

Well-crystallized Ba_0.5Sr_0.5TiO₃ thin films with good surface morphology were prepared on MgO(1 0 0) substrates by pulsed laser deposition technique at a deposition temperature of 800 °C under the oxygen pressure of 2 × 10⁻³ Pa. X-ray diffraction and atomic force microscopy were used to characterize the films. The full width at half maximum of the (0 0 2) Ba_0.5Sr_0.5TiO₃ rocking curve and the root-mean-square surface roughness within the 5 μm × 5 μm area were 0.542° and 0.555 nm, respectively. The nonlinear optical properties of the films were determined by a single beam Z-scan method at a wavelength of 532 nm with laser duration of 55 ps. The results show that Ba_0.5Sr_0.5TiO₃ thin films exhibit a fast third-order nonlinear optical response with the nonlinear refractive index and nonlinear absorption coefficient being n₂ = 5.04 × 10⁻⁶ cm²/kW and β = 3.59 × 10⁻⁶ (m/W), respectively.     

GaN外延片中载流子浓度的纵向分布

采用适合宽禁带半导体材料的电化学电容电压(ECV)分析仪,对掺硅GaN外延片用硫酸逐层进行了精密腐蚀后,在此基础上得到了在进口MOCVD设备上生产的GaN基外延片的载流子浓度纵向分布.探讨了该分布与晶体生长过程及晶体质量的关系,测量分析结果可为生长工艺参数的优化提供参考.还采用主扩散模型对测量结果进行高斯拟合,得出了高温时(1030℃)硅在GaN中的扩散系数,并由此估算了硅在GaN外延片中的扩散宽度.该结果可为GaN外延层结构设计提供参考.     

高阻GaN的MOCVD外延生长

利用金属有机化合物气相沉积(MOCVD)在蓝宝石衬底上生长了高阻GaN薄膜。对GaN成核层生长的反应室压力、生长时间和载气类型对GaN缓冲层电学特性的影响进行了分析。实验结果表明,延长GaN成核层的生长时间,降低成核层生长时的反应室压力,载气由H₂换为N₂都会得到高阻的GaN缓冲层。样品的方块电阻R_s最高为2.49×10¹¹ Ω/□。以高阻GaN样品为衬底制备了AlGaN/AlN/GaN结构HEMT器件,迁移率最高达1 230 cm²/(V·s)。