氮气介质阻挡放电激发态氮的数值模拟研究

本文采用流体模型模拟了不同工作气体下N₂介质阻挡放电。并利N₂等离子体用发射光谱进行了实验对比。该模型考虑了10种反应物和28种反应。压力在1~5 atm之间,不同能级的N₂(C)分子是典型的活性物质。模拟结果表明,在等离子体中,随着压力的增加,反应物N₂(C)分子的数密度呈指数级下降。平均电子密度与压强的关系是复杂的,受中性粒子数密度和电子温度的影响。电子温度随压力范围的增大而降低。仿真结果可以描述等离子体参数的详细时空分布。由光谱计算得到的等离子体的平均电子温度、电子密度和N₂(C)的激发趋势与模拟结果一致。     

Chemical-reaction dependence of plasma parameter in reactive silane plasma

Electron temperature in a silane glow-discharge plasma, being an important plasma parameter for determining photo-induced instability in the resulting hydrogenated amorphous silicon (a-Si:H), has been studied under various film-preparation conditions. We have used an optical-emission-intensity ratio of Si^* to SiH^* (I_si*/I_siH^*) which corresponds to the high-energy-tail slope of the electron-energy-distribution function in the plasma as a measure of electron temperature in a reactive silane glow-discharge plasma. We have found quite differently from the conventional non-reactive glow-discharge plasma such as hydrogen plasma that the electron temperature in the silane plasma is strongly modified by the substrate temperature (gas temperature) especially under high silane-gas partial-pressure condition. This anomalous behavior of the electron temperature in the silane plasma has been explained by means of gas-phase-polymerization reaction and electron-attachment process to the polymers in the plasma. The electron temperature has been remarkably reduced when a hydrogen-dilution method and a cathode-heating method are used which are considered to control polymer-formation reactions in the silane plasma together with utilization of conventional electron-temperature-controlling methods such as a very high plasma-excitation frequency and an application of magnetic field for electron-confinement. As a consequence of the reduction of electron temperature in the silane plasma, highly stabilized a-Si:H has been successfully obtained even under high growth rate conditions of 1.5 nm s^-1.     

Effect of nitrogen addition on the properties and thermal stability of fluorinated amorphous carbon films

Continuous fluorinated amorphous carbon (a-C : F) films doped with nitrogen (a-C : F : N) were deposited by plasma enhanced chemical vapor deposition using CF₄ and C₂H₂ gases as precursors with the addition of N₂ gas. The surface morphologies, chemical compositions, deposition rates, thermal stability and mechanical properties of these films varied with the deposition parameters, including CF₄ and N₂ feed gas concentrations, processing pressure, plasma power and substrate temperature. With increasing N₂ feed gas concentration, the nitrogen content of the a-C : F : N films increased to about 6 at.% and contributed to higher mechanical properties. After thermal annealing, the a-C : F films with higher fluorine contents exhibited more obvious fluorine release and extensive film thickness shrinkage, whereas the a-C : F : N films with higher contents of nitrogen doping yielded less composition variations, smaller thickness shrinkages, higher mechanical properties, and conclusively better thermal stability.     

Preparation of strontium titanate thin films by mirror-confinement-type electron cyclotron resonance plasma sputtering

Using mirror-confinement-type electron cyclotron resonance (ECR) plasma sputtering method, strontium titanate (SrTiO₃) thin films have been prepared on Si and Pt/Ti/SiO₂/Si substrates at a low substrate temperature (below 450 K) in a low pressure (2.7×10⁻² Pa) environment of pure Ar and Ar/O₂ mixture. Prepared film surfaces were very smooth regardless of high deposition rate (8.5 nm/min). The composition ratio Sr/Ti of Sr to Ti in the films varied with the distance between the target and the substrate. All as-deposited films on Si substrates were found to be amorphous and were crystallized by post-deposition annealing using an electric furnace at 650 K, i.e. approximately 250 K lower than annealing for films obtained by conventional RF magnetron sputtering. Post-deposition annealing of these films using millimeter-wave radiation decreased the crystallization temperature to a value of 550 K. Furthermore, all as-deposited films on Pt/Ti/SiO₂/Si substrates by a plasma of Ar and O₂ gas mixture were found to be crystallized regardless of no substrate heating.     

Chemical-reaction dependence of plasma parameter in reactive silane plasma

Electron temperature in a silane glow-discharge plasma, being an important plasma parameter for determining photo-induced instability in the resulting hydrogenated amorphous silicon (a-Si:H), has been studied under various film-preparation conditions. We have used an optical-emission-intensity ratio of Si¹ to SiH¹ (I_Si¹/I_SiH¹) which corresponds to the high-energy-tail slope of the electron-energy-distribution function in the plasma as a measure of electron temperature in a reactive silane glow-discharge plasma. We have found quite differently from the conventional non-reactive glow-discharge plasma such as hydrogen plasma that the electron temperature in the silane plasma is strongly modified by the substrate temperature (gas temperature) especially under high silane-gas partial-pressure condition. This anomalous behavior of the electron temperature in the silane plasma has been explained by means of gas-phase-polymerization reaction and electron-attachment process to the polymers in the plasma. The electron temperature has been remarkably reduced when a hydrogen-dilution method and a cathode-heating method are used which are considered to control polymer-formation reactions in the silane plasma together with utilization of conventional electron-temperature-controlling methods such as a very high plasma-excitation frequency and an application of magnetic field for electron-confinement. As a consequence of the reduction of electron temperature in the silane plasma, highly stabilized a-Si:H has been successfully obtained even under high growth rate conditions of 1.5 nm s⁻¹.     

压力对PbTiO3结构和热物性质影响的第一性原理研究

PbTiO₃是一种重要的铁电功能材料, 但压力对其结构、稳定性、力学和热力学性能的影响尚不明确, 从而限制了其在电子通讯领域的应用。本研究采用基于密度泛函理论的第一性原理方法, 研究了压力下四方铁电相钛酸铅(TP-PTO)、立方顺电相钛酸铅(CP-PTO)、四方前驱体相钛酸铅(PP-PTO)结构和热物性质。研究发现, 三种结构可压缩性由大到小依次为PP-PTO>TP-PTO>CP-PTO。能带结构和态密度均表明PTO在研究的压力范围内未发生相变。PTO带隙随着压力增大逐渐降低, TP-PTO在20 GPa由间接带隙半导体转变为直接带隙半导体, 其余两相在压力下恒为直接带隙半导体。PTO在0~30 Gpa范围力学稳定, 且具有各向异性, 其综合力学性能随着压力的增加而增强, 各向异性则是先降低后升高。通过准谐德拜近似理论研究了温度和压力对PTO德拜温度、熵、热容的影响, 结果表明德拜温度随着温度上升而下降, 随着压力增大而上升, 反映出共价键强度依次为CP-PTO>TP-PTO> PP-PTO。熵和热容随着温度上升而上升, 随着压力的增大而下降。     

Mass flow limitations in reactive sputtering

Reactive sputtering may be accomplished by mixing the inert gas argon with some reactive gas during sputtering. To form ZrN, sputtered zirconium atoms must react with nitrogen. At a specific deposition rate, a certain number F_N0 of nitrogen atoms must arrive at the substrate. This requirement is fulfilled at the partial pressure P_N = P_N0. The minimum partial pressure P_N0 to obtain a nitride is often detected by a sharp decrease in sputtering rate at a specific N₂ partial pressure. However, during reactive sputtering of for example ZrN we found that the value of P_N0 was strongly dependent on the total gas throughout in the vacuum system. An increase in total gas throughput causes a decrease in the value of P_N0.

The decrease in sputtering rate has indirectly been measured by optical emission spectroscopy from the sputtering plasma.     

Effect of substrate temperature on the deposition of C–N films by pulsed high-temperature C–H–N Plasma CVD

Rather than using conventional low-temperature plasma, the pulsed high-temperature plasma was used to synthesize C–N films. CH₄+N₂ mixture was used as the gas source. The effect of substrate temperature on the deposition was studied. It was found that with the increase of substrate temperature, the deposition rate dropped drastically, the content of H in the films decreased and the hardness of the films was improved; The N/C ratio, however, changed only by a small degree, suggesting that the C and N has been well combined by using high-temperature plasma.     

CO2/O2环境下L320钢在不同流速下的腐蚀行为研究

为了确定L320钢在CO₂/O₂环境中不同流速下的腐蚀行为,通过多相流瞬态模拟仿真软件,模拟目标管道的流动状态,确定室内模拟试验的流速范围,选择L320钢进行CO₂/O₂共存体系下不同流速的高温高压动态反应釜试验,采用扫描电镜、X射线衍射仪对腐蚀产物进行微观形貌表征和成分分析。结果表明:温度和压力随着里程的增加呈现下降的趋势;管道气体流速和壁面剪切力随着里程的增加呈现逐渐上升的趋势。基于Pearson相关系数法,确定了流速是影响腐蚀速率的主控因素。随着流速的增加,L320在CO₂/O₂共存条件下的均匀腐蚀速率逐渐增大。CO₂/O₂共存体系的腐蚀产物为Fe 2 O₃、FeOOH、Fe(OH)3、Fe 3 O 4、FeCO₃等。研究结论可为不同流速下的L320钢在CO₂/O₂共存环境中的防护提供借鉴。     

Influence of Substrate Temperature and Plasma Power Density on the Properties of Plasma-Assisted Chemical Vapor Deposited Titanium Nitride

Titanium nitride films deposited onto high speed steel substrates by plasma-assisted chemical vapor deposition (PACVD) from TiCl₄, H₂, N₂, and Ar gas mixtures have been investigated. The substrate temperature was varied between 250 and 550^° C via the plasma power density or via an additional electrical heater. The influence of temperature and plasma power density on the morphology, chemical composition, hardness and adhesion of the coatings was studied. At a temperature of 500^° C different plasma power densities caused changes of the morphology of the coatings. At low plasma power densities fine grained polycrystalline layers were observed. A significant change from coarse to fine grained structures was also observed with decreasing deposition temperature. Scratch test results indicate that coatings deposited at a given substrate temperature with lower plasma power density showed increased values of the critical load.     

R.f. plasma deposition from hexamethyldisiloxane-oxygen mixtures

Hexamethyldisiloxane (HMDSO) has been used as a precursor for the deposition of silicon dioxide films at low substrate temperature (25–400°C) by plasma enhanced chemical vapour deposition processing. Effects of the partial pressure of oxygen in the discharge on the deposition rate and the composition of the films are investigated. The deposition rate is found to decrease with increasing oxygen concentration in the HMDSO/O₂ mixture. The chemical composition of the formed films was characterized by X-ray photoelectron spectroscopy and infrared spectroscopy. Over 40% of the oxygen in the gas phase the carbon content of films deposited from HMDSO/O₂ mixtures is less than 5%.     

热处理对Zr-B-N纳米复合涂层显微结构的影响

利用高功率脉冲和脉冲直流复合磁控溅射技术制备Zr-B-N涂层, 研究沉积过程中的氮气流量和热处理温度对涂层显微结构的影响。采用电子探针显微分析仪、扫描电镜和X射线衍射仪对涂层的成分、断面形貌及结构进行观察和分析。结果表明:热处理温度为600℃时, 涂层表面开始形成氧化膜, 部分锆离子与氧反应生成 (116) 晶面取向的Zr₃O;在N₂流量为6 m L/min (标准状态) 时, 经热处理后涂层结构仍以非晶相为主;当氮气流量为10 m L/min时, 随着热处理温度升高, 涂层结构逐渐变得疏松, 氧化反应加剧。氮分压越高制备的涂层结构越致密, 抗氧化能力越强;当热处理温度达800℃时, 涂层表面开始出现裂纹, 部分涂层脱离基体, 严重失效。     

Effect of process parameter changes on the composition of magnetron sputtered and evaporated TiN and AlN films measured by UHV in-situ techniques

TiN and AlN films are deposited on HSS steel substrates in an ultrahigh vacuum magnetron system equipped with in-situ Auger electron spectroscopy (AES) and mass spectrometric sensors for plasma diagnostics. The composition of TiN_x coatings is measured by AES as a function of the N₂ pressure, the bias voltage, and the d.c. power. The flux of ionic particles impinging on the substrate surface and their energies are determined by a quadruple mass analyzer mounted behind a hole in the substrate. In addition, the reactivity of neutral nitrogen molecules in a reactive evaporation process is measured by a quartz crystal microbalance.     

Si_3N_4原位增强Cu基复合材料的制备

采用感应炉熔炼及水雾化工艺制得了Cu-Si合金粉末,经N2、H2混合气体选择氮化和真空放电等离子烧结(SPS)成型,制备得到了Si3N4原位增强Cu基复合材料(Si3N4/Cu),利用萃取法研究了选择性氮化产物及其晶体结构。结果表明:复合粉末中N含量随氮化温度的升高和氮化时间的延长而增大。在1 000℃下氮化,持续时间大于60h时,粉末中的N含量明显提高;Cu的衍射峰出现整体向大角度方向的明显偏移,同时晶格常数变小,表明Si从Cu基体中脱溶,与N反应生成Si3N4;Si3N4/Cu复合材料的增强体以β-Si3N4为主;随着氮化温度的升高和氮化时间的延长,Si3N4/Cu复合材料的电导率和硬度逐步提高。     

基体表面粗糙度对MoS_(2)/Ti薄膜摩擦磨损性能的影响EI北大核心CSCD

为揭示基体表面粗糙度对MoS_(2)/Ti固体润滑薄膜摩擦磨损性能的影响规律,并探究其摩擦磨损机理,采用磁控溅射方法,在不同表面粗糙度的轴承钢基体上沉积MoS_(2)/Ti薄膜。通过划痕测试仪、X射线衍射仪、场发射扫描电子显微镜和粗糙度轮廓仪,分别评价MoS_(2)/Ti薄膜的膜基结合力、物相成分、表面微观形貌以及表面粗糙度,并采用球-盘摩擦磨损实验研究干摩擦、固体-油复合润滑和固体-脂复合润滑条件下,MoS_(2)/Ti薄膜的摩擦磨损性能。结果表明:随着基体表面粗糙度的增加,MoS_(2)/Ti薄膜的表面粗糙度逐渐增加;薄膜中(002)_(MoS_(2))和(100)_(MoS_(2))衍射峰的强度先减弱后增加;薄膜与基体的结合性能降低。当基体表面粗糙度为0.01μm时,干摩擦条件下MoS_(2)/Ti薄膜具有良好的润滑特性,平均摩擦因数为0.101,磨痕浅且小;随基体粗糙度的升高,样品的平均摩擦因数和磨损率均是先增大后减小,薄膜的主要磨损机制由磨粒磨损转变为屑片形成和破碎。当基体粗糙度较大时(R_(a)=0.26μm),分子间相互作用的影响大于机械啮合作用。采用固体-油复合润滑,高基体粗糙度的薄膜磨损表面不再出现片层剥落现象,磨痕较浅,平均摩擦因数最高可减小19%。固体-脂复合润滑条件下,样品摩擦磨损性能较差,基体粗糙度对摩擦因数的影响不显著。     

Thin anodic oxides on n-InP studied by photocurrent transients and surface analysis

Surface reactions induced by fluorocarbon plasmas were studied on Si substrates with SiO₂ and photo-resist overlayers using an inductively coupled plasma source. As source gases, C₄F₈ and C₅F₈ were employed to investigate their differences in the etching performance and the selectivity between SiO₂ and photo-resist. Deposition of fluorocarbon polymer was noticed in both gases by Fourier-transform infrared ellipsometric measurements when substrate bias was not applied. With the bias application, etching started on both substrate from certain threshold values of the bias voltage and the rate increased with increase of the voltage. However, in C₅F₈ plasma the increasing tendency on photo-resist was much less than on SiO₂, while in C₄F₈ plasma the difference is small. This difference is attributed to a larger deposition ability of C₅F₈ plasma with higher content of fluorine atoms in the polymer than that of C₄F₈ plasma as confirmed by X-ray photoelectron spectroscopy.     

Ti-content and annealing temperature dependence of transformation behavior of TiXNi(92-XCu8 shape memory alloys

Ti-content and annealing temperature dependence of the transformation behavior of Ti_XNi_(92-X)Cu_8.0 (at,%) (X = 49.0–5l.0) alloys was investigated by varying the annealing temperature from 573 to 1273 K. It was found that the peak temperature of B2–B19 transformation (O^*) increases with increasing annealing temperature from 673 to 873 K for all of the alloys. With annealing at temperatures above 873 K, the influence of annealing on O^* depends on Ti-content. In the range of 50.4–51.0 at.% Ti, O^* shows little dependence on annealing temperature. In the range of 49.3–50.2 at.% Ti, O^* firstly decreases and then keeps constant with increasing annealing temperature. For the alloy of 49.0 at.% Ti, O^* continuously decreases with increasing annealing temperature from 873 to 1273 K. On the basis of the above data, a partial phase diagram of Ti-Ni-8.0Cu (at.%) was proposed. The transformation hysteresis also showed unique Ti-content and annealing temperature dependence.     

Investigation of stress behaviors and mechanism of void formation in sputtered TiSix films

We have investigated the stress behaviors and a mechanism of void formation in TiSi_x films during annealing. TiSi_x thin films were prepared by DC magnetron sputtering using a TiSi_2.1 target in the substrate temperature range of 200–500 °C. The as-deposited TiSi_x films at low substrate temperature (<300 °C) have an amorphous structure with low stress of 1×10⁸ dynes/cm². When the substrate temperature increases to 500 °C, the as-deposited TiSi_x film has a mixture of C49 and C54 TiSi₂ phase with stress of 8×10⁹ dynes/cm². No void was observed in the as-deposited TiSi_x film. Amorphous TiSi_x film transforms to C54 TiSi₂ phase with a random orientation of (311) and (040) after annealing at 750 °C. The C49 and C54 TiSi₂ mixture phase transforms to (040) preferred C54 TiSi₂ phase after annealing over 650 °C. By increasing substrate temperature, the transformation temperature for C54 TiSi₂ can be reduced, resulting in relieved stress of TiSi₂ film. The easy nucleation of the C54 phase was attributed to an avoidance of amorphous TiSi_x phase. We found that amorphous TiSi_x→C54 TiSi₂ transformation caused higher tensile stress of 2×10¹⁰ dynes/cm², resulting in more voids in the films, than C49→C54 transformation. It was observed that void formation was increased with thermal treatment. The high tensile stress caused by volume decreases in the silicide must be relieved to retard voids and cracks during C54 TiSi₂ formation.     

On the influence of residual stresses on the fracture behavior of a structural steel in the KIc temperature range

The increase with increasing temperature of K_Ic, measured with 2CT and 1'CT specimens, from about 10³N mm at 77 K to about 2.10³ N mm at about 170 K is attributed to the increasing proportion of dimple to cleavage fracture as revealed by scanning electron microscope investigation.

The specimens were prestrained to different partial scale yielding states by the same kind of loading, performed at 298 K, as in the later K_Ictests, performed at 77 K. After pretension K_Ic = K^*_Ic is increased by a maximum amount of about half of the value K⁰_Icof nonprestrained specimens, after precompression it is reduced by the same amount if this value is evaluated from the load at which a pop-in occurs. The value K_Ic = K^**_Ic for the final fracture lies between K^*_Ic and K⁰_Ic. These results are interpretated in terms of the residual stress states due to prestraining.     

Molybdenum oxide as a molecular sieve towards nitrogen containing molecules: synthesis and characterization of MoO3 intercalation compounds with nicotinamide and hexamethylenetetramine

MoO₃ intercalation compounds with nicotinamide (nic) and hexamethylenetetramine (hmta) were synthesized at room temperature, by suspending -MoO₃ in a water–ethanol solution of nic or hmta. Six intercalation compounds of the formula MoO₃·(nic)_0.20, MoO₃·(nic)_0.40, MoO₃·(nic)_0.56, MoO₃·(hmta)_0.4, MoO₃·(hmta)_0.60 and MoO₃·(hmta)_1.12, named as Mo1, Mo2, Mo3, Mo4, Mo5 and Mo6, respectively, were prepared. The obtained hybrid matrices were characterized by elemental analysis, infrared spectroscopy, thermogravimetry, X-ray diffractometry and scanning electron microscopy. The obtained X-ray data, as well as molecular lengths of nic and hmta calculated by using Spartan-Pro 1.0.3 package shows that the total amount of intercalated nic molecules, as well as the orientation of the organic specie into the inorganic interlayer space (interaction with the acidic Lewis sites on the surface) is dependent on the organic moiety/oxide ratio. Comparing nic with hmta results, can be verified that MoO₃ exhibits a higher affinity towards nic than hmta, since for nic an increase of the organic moiety/inorganic substrate ratio increases the total amount of intercalated molecules, whereas for hmta an opposite behavior is observed, with substitution of hmta by water molecules into the interlayer space.