MLCROSTRUCTURE AND PROPERTIES OF C-Cu NANOSTRUCTURE THIN FILM

1. IntroductionTlle filnls of dial11ol1d-Iike carboll (DLC) llave a smooth, chemically inert sllrface withhigh hardness, a sluall fri.ti.,1 coefficiellt, and a low threshold fOr electron emissioll. Theyllaxv lIlall}' applicatioIls ill differellt fields. T…     

Improved Thermal Performance of Diamond-Copper Composites with Boron Carbide Coating

B₄C-coated diamond (diamond@B₄C) particles are used to improve the interfacial bonding and thermal properties of diamond/Cu composites. Scanning electron microscopy, x-ray diffraction, and x-ray photoelectron spectroscopy were applied to characterize the formed B₄C coating on diamond particles. It is found that the B₄C coating strongly improves the interfacial bonding between the Cu matrix and diamond particles. The resulting diamond@B₄C/Cu composites show high thermal conductivity of 665 W/mK and low coefficient of thermal expansion of 7.5 × 10^?6/K at 60% diamond volume fraction, which are significantly superior to those of the composites with uncoated diamond particles. The experimental thermal conductivity is also theoretically analyzed to account for the thermal resistance at the diamond@B₄C-Cu interface boundary.     

高取向低粗糙度金刚石薄膜生长的研究

目的研究热丝化学气相沉积(HFCVD)工艺对金刚石薄膜生长的影响,确定影响金刚石薄膜生长的因素。方法采用热丝CVD法,以丙酮为碳源,在不同晶面的Si衬底上沉积金刚石薄膜,通过金相显微镜、X射线衍射仪分析薄膜生长特性。结果不同沉积温度下生长的金刚石薄膜表面形貌差异很大。在高、低碳源浓度下分别获得了(400)和(111)晶面取向的金刚石薄膜。采用分步沉积法,改善了成膜的效率。结论气源浓度和生长温度是影响金刚石薄膜生长的重要因素,分步沉积法对于金刚石薄膜的生长有较大影响。     

并联导热结构的金刚石/铜基复合材料的制备

为提高金刚石/铜基复合材料的导热性能,在芯材表面预先化学气相沉积(CVD)高质量金刚石膜,获得柱状金刚石棒,再将其垂直排列,填充铜粉后真空热压烧结,制备并联结构的金刚石/铜基复合材料。分别采用激光拉曼光谱(Raman)与扫描电子显微镜(SEM)对CVD金刚石膜的生长进行分析,并通过数值分析讨论复合材料的热性能。结果表明:金刚石/铜基复合材料结构致密,密度为9.51g/cm3;CVD金刚石膜构成连续的导热通道,产生并联式导热,复合材料的热导率为392.78 W/(m·K)。     

预涂CuO的二氧化钛薄膜光催化性能与结构研究

载波片上浸涂一层CuO的TiO2薄膜会诱导金红石相生成，并有效提高其光催化活性，其中预涂一层含量1．0％（质量分数，下同）Cu（CH3COO）2水溶液其光催化活性增幅最大（提高53％）。结果表明：TiO2薄膜晶格畸变越大，金红石型TiO2含量越高，薄膜光催化性能就越好。扫描电镜显示预涂一层CuO的TiO2薄膜颗粒粒径较纯TiO2薄膜小。X射线光电子能谱研究表明，预涂一层CuO的TiO2薄膜中Ti^3＋含量较纯TiO2薄膜高。     

微波等离子体刻恂对WC—Co硬质合金基体金刚石薄膜附着力的影响

金刚石薄膜的附着力是影响CVD金刚石涂层刀具切削性能的关键因素,本文采用EACVD法在硬质合金（YG6）基体上沉积金刚石涂层;用Ar-H2微波等离子WC－C0衬底进行刻蚀处理,以改变基体表面与金刚石涂层间的界面结构,提高金刚石涂层的附着力;采用压痕法评估涂层附着力,借助SEM等观察刻蚀预处理方法对膜基界面的影响,并对此进行分析和讨论。     

基于内涨鼓泡实验的金刚石膜附着强度精确定量评价

根据内涨作用下薄膜发生鼓泡变形的原理，开发了1种新的适用于金刚石膜附着强度精确定量评价的测试系统。并在传统的硅平面加工工艺的基础上发展了1种新的在沉积好的基片上制备自支撑窗口试样的方法，该方法可以保证在刻蚀基底形成自支撑窗口的同时不会损坏到薄膜。通过实验，实现了对硅基底金刚石膜结合强度的定量检测，实验得到的薄膜结合强度为4．28726J／m^2。实验所测得的附着强度结果与有限元仿真结果类比的吻合，证实了该模型的有效性，从而为金刚石膜的制备工艺优化及其质量的评估提供了可靠的依据和标准，对促进金刚石膜材料的深度开发和工程应用将具有积极的意义。     

Generation of nanostructured CuO by electrochemical method and its Zn–Ni–CuO composite thin films for corrosion protection

Nanocrystalline copper oxide (CuO) powder of varying sizes (22, 25, 28 and 36 nm) have been successfully synthesized by hybrid electrochemical method using aqueous sodium nitrate electrolyte with Cu electrodes under galvanostatic mode at room temperature. The as‐synthesized CuO sample was calcined for an hour at temperatures ranging from 60 to 900 °C. The crystallite size, morphology, and chemical state of the synthesized powders were characterized by powder XRD, XPS, SEM/EDAX, TEM, and UV–Vis spectral methods. The effect of calcination temperature on crystallite size and morphology was studied. The TEM result revealed that, the particles are hexagonal and the sizes are in 30–50 nm in diameter and 120–200 nm in length. The band gap values are 5.60 and 5.54 eV. The crystallite size increased with increase of calcination temperature. The CuO nanopowder is used to fabricate Zn–Ni–CuO composite thin films and its corrosion behaviour was analysed by Tafel extrapolation and electrochemical impedance spectroscopy. The results indicate that the Zn–Ni–CuO composite thin films provided good corrosion protection.     

甲烷体积分数对纳米金刚石薄膜形貌的影响

目的研究不同甲烷体积分数对纳米金刚石(NCD)薄膜生长的影响,实现较小晶粒尺寸、高平整度的NCD薄膜的制备。方法采用微波等离子体增强化学气相沉积的方法制备NCD薄膜,以CH4/H2为气源,在生长阶段控制其他条件不变的前提下,探讨不同甲烷体积分数对NCD晶粒尺寸、表面形貌以及表面粗糙度的影响。采用SEM、XRD等观测NCD薄膜的表面形貌和晶粒尺寸大小,并利用Raman对NCD薄膜的不同散射峰进行分析。结果随着甲烷体积分数的增加,薄膜晶粒尺寸有减小的趋势。甲烷体积分数较低时,晶形比较完整,但致密度较小;甲烷体积分数较高时,晶形杂乱无章,但致密度较好。当甲烷体积分数为9%时NCD薄膜平均粒径达到最小,为21.3 nm,表面粗糙度较好,但非晶金刚石成分开始大量生成,NCD薄膜质量开始变差;当甲烷体积分数为8%时其形貌最好,且此时最小表面粗糙度小于20 nm。通过Raman分析可知NCD薄膜中出现了硅峰和石墨烯特征峰。结论甲烷体积分数对NCD薄膜形貌有较大影响,甲烷体积分数为8%时是表面平整度由较差变好再逐渐变差的分界点,且平均晶粒尺寸为23.6 nm,薄膜表面具有较好的平整度。     

泡沫铜表面改性对化学气相沉积高质量泡沫金刚石的影响

目的选择合适的过渡层材料改善三维连通泡沫铜衬底与金刚石之间的结合性,制备出三维连通结构的泡沫金刚石。方法选择三维连通的泡沫铜作为衬底,使用磁控溅射技术在其表面沉积Ti、Cr过渡层,然后通过热丝化学气相沉积技术(HFCVD)在表面改性后的泡沫铜衬底上沉积金刚石涂层。通过扫描电子显微镜(SEM)、能谱分析仪(EDS)、拉曼光谱仪及红外热成像仪等仪器,对样品的表面/截面形貌、成分结构及热扩散性能进行检测与分析。结果经过Ti、Cr过渡层改性后,泡沫铜表面均能沉积出连续致密的高质量金刚石涂层,在相同的CVD沉积参数下,Cr过渡层泡沫金刚石(Cu-Cr/Dia)的晶粒尺寸更大(~5μm),晶粒质量更高,且膜层厚度大于Ti过渡层泡沫金刚石(Cu-Ti/Dia),Cu-Ti/Dia与铜衬底的结合性要优于Cu-Cr/Dia。Cu-Cr/Dia和Cu-Ti/Dia的热扩散性能均优于泡沫铜,其中Cu-Cr/Dia的热扩散能力略高于Cu-Ti/Dia。结论镀覆Ti、Cr过渡层有效增强了金刚石与泡沫铜衬底之间的界面结合,成功制备了三维连通结构的泡沫金刚石。     

Formation of CIGS thin absorption layer by sequential sputtering of CuGa/In/CuGa precursor on Mo/SLG with post selenization

Precursor structures of CuGa/In/CuGa stacking layers were prepared on Mo/soda-lime glass by sequential sputtering using intermetallic CuGa and metal In targets, with post selenization by Se evaporation at substrate temperature 500 °C. The selenized CIGS thin films were characterized by X-ray photo electron spectroscopy, X-ray diffraction, energy dispersive spectroscopy, Field emission scanning electron microscopy (FE-SEM), and Photoluminescence (PL). XPS survey spectra show that the constituent elements such as Cu, Ga, In, and Se appeared on the surface composition with corresponding photoelectron lines and a detailed study of the Se 3d signal in the CIGS absorption layer was discussed. The X-ray diffractograms of the CIGS films exhibited peaks revealing that the films are crystalline in nature with tetragonal chalcopyrite structure. FESEM images reveal that CIGS thin films yield granular nanostructure and a Mo back contact with a columnar structure. The CIGS thin films demonstrated intense near-band-edge PL and free-to-bound transitions were found and reported.     

氮化铀薄膜的制备及性能研究

开展了氮化铀薄膜射频制备及薄膜性能研究,通过优化氮化铀薄膜的制备工艺条件,成功在Si基片上制备了氮化铀薄膜,并利用扫描电镜、原子力显微镜、X射线电子衍射、俄歇电子能谱仪和X射线光电子能谱对氮化铀薄膜进行了表面形貌和结构组分分析。结果表明:利用射频磁控沉积法制备的氮化铀薄膜为比较平整和致密的U2N3和UNxOy的混合相组成,具有一定的抗氧化腐蚀性能。     

碳化硼薄膜的电子束蒸发制备及表面分析

采用电子束蒸发技术制备碳化硼薄膜,利用X射线衍射(XRD)分析了薄膜的结构,测量了薄膜的X射线光电子能谱(XPS),并利用原子力显微镜(AFM)对薄膜进行表面分析.XRD结果表明:薄膜的结晶性随着衬底温度的升高逐渐转好,在较低的衬底温度下制备出多晶碳化硼薄膜.XPS分析得到了碳化硼薄膜表面的化学成分和结构特性,其主要成分为B_4C.AFM结果表明,薄膜表面光滑平整、均匀致密,随着衬底温度的升高薄膜均方根(RMS)粗糙度逐渐增大.     

衬底位置对制备（100）面金刚石薄膜的影响

本文利用5kW微波等离子体装置,在直径22mm的石英上沉积金刚石薄膜。实验研究了衬底在不同位置对沉积金刚石薄膜的质量产生的影响。实验中将2块石英衬底编号为A和B,样品A被放在偏离钼基片台中心5mm的位置,使石英的中间区域偏离等离子体球,而边缘区域处于等离子体球的下方。通过SEM和拉曼光谱表征所沉积的金刚石膜,对比样品A的中间和边缘区域发现中间的区域金刚石膜的质量差且不均匀,边缘区域则长出取向一致的（100）面金刚石。通过分析认为,较高的温度、大的等离子体密、合适的碳源浓度度等条件有利于（100）面金刚石薄膜的沉积。随后改进工艺,将样品B放在基片台中心使其处于等离子体的正下方,并调整生长温度和甲烷浓度,成功的获得了高质量均匀的（100）面金刚石薄膜。     

不同气体流量比对Cu/a-C∶H复合薄膜结构及摩擦学性能的影响

采用磁控溅射技术结合等离子体气相沉积技术,通过调节CH₄与Ar的气体流量比例,获得了不同Cu含量的Cu/a-C∶H复合薄膜。采用XPS、Raman等表征方法分析了不同气体流量比对Cu在复合薄膜中的存在形式及薄膜结构的影响,利用纳米压痕仪测量了复合薄膜的硬度与弹性模量,采用往复式摩擦磨损试验机、白光干涉仪、FESEM等分析了复合薄膜在空气中的摩擦学性能及相关机理。结果表明:随着CH₄在混合气体中所占比例增加,复合薄膜中sp²C含量升高,Cu含量降低,Cu晶粒的尺寸变小,复合薄膜的硬度逐渐升高,韧性降低。CH₄气体流量比为60%、Cu含量为 6.68at%的复合薄膜具有较高的硬度、良好的韧性以及在空气中最低的摩擦因数(0.091)与磨损率(1.77×10^-6 mm³·N^-1·m^-1),这与复合薄膜中sp²C含量及Cu纳米粒子的尺寸和含量有关。     

石英玻璃管外表面抗腐蚀纳米金刚石薄膜的制备

在具有新型谐振腔的微波等离子体CVD装置上,利用乙醇和氢气为工作气体在石英玻璃管外表面沉积了均匀、致密的纳米金刚石薄膜。采用扫描电子显微镜、Raman光谱及X射线衍射表征了金刚石薄膜的质量;设计腐蚀实验检验了金刚石薄膜的抗腐蚀效果。结果表明:在反应气压为5.5 kPa、碳源浓度为8vol%、石英玻璃管温度为500℃的条件下,得到的纳米金刚石薄膜能有效增强石英玻璃管的抗腐蚀性能。     

Optical and Photocatalytic Properties of Cu-Cu2O/TiO2 Two-Layer Nanocomposite Films on Si Substrates

通过磁控溅射法在TiO2薄膜上生长Cu-Cu2O复合层,从而制备新型Cu-Cu2O/TiO2双层纳米复合薄膜。并采用X射线衍射（XRD）,扫描电子显微镜（SEM）,荧光光谱（PL）,X射线光电子能谱（XPS）和紫外可见漫反射光谱（DRS）等方法对膜的结构,形态和光学性能进行了研究。X射线衍射谱表明,Cu-Cu2O混合物层和Cu2O层都没有影响TiO2的结晶相。XPS结果表明,Cu的存在抑制了Cu2O表面在空气中的氧化。SEM分析表明,结晶良好的Cu-Cu2O混合物微小纳米颗粒均匀分散于TiO2表面。由于紫外可见漫反射光谱的Cu-Cu2O/TiO2复合薄膜的吸收边发生红移。PL光谱证实了在Cu的存在下,激发电子和空穴的复合率降低。光催化实验表明,与纯Cu2O/TiO2相比,所制备的Cu-Cu2O/TiO2-8显示出更高的光生载流子效率,其光催化性能也显著提高。此外,还对Cu-Cu2O/TiO2-8光催化活性增强的原因进行了讨论     

High-temperature oxidation behavior of nanocrystalline diamond films

In this study, high-temperature stability of nanocrystalline diamond films prepared by hot filament chemical vapor deposition (HFCVD) was investigated through differential thermal analysis/thermal gravimetric analysis (DTA/TGA), thermal analyses, visible and UV Raman analysis, and XPS analysis. Nanocrystalline diamond films with crystalline size of about 25 nm were obtained, which possess high density of grain boundaries with a high sp²-bonding of non-diamond carbon. In the initial stage of oxidation, grain boundaries with non-diamond carbon and graphite phase were preferentially etched away by oxygen, which carries on with a faster rate. Then, a slower oxidation rate was continued through reacting the carbon atoms in rigid diamond structure with oxygen. The activation energies for former and the latter, calculated from the thermal analysis, are 195 and 217 kJ/mol, respectively. Both the results of in-situ Raman spectra and XPS spectra indicate that the carbon with sp²-bonding significantly decreased with increasing temperature and soaking time.     

退火对氧化钒薄膜成分及热敏性能的影响

在衬底上溅射沉积一层金属钒膜,然后对其退火制备氧化钒薄膜.研究了原位退火热处理和后续退火热处理对氧化钒薄膜成分及其热敏性能的影响.XPS分析表明,原位380 ℃退火处理得到的氧化钒薄膜中4价态和5价态钒的比例为1.097:1,经后续退火处理后,该比例变为0.53:1;同时,原位退火处理得到的氧化钒薄膜的V/O比为1:2.24,经后续退火处理变为1:2.33.AFM分析后显示,经后续退火处理的薄膜晶粒尺寸有所增大.测试了薄膜方阻随温度的变化,结果显示,生成的薄膜具有明显的金属-半导体相变;原位退火热处理后的薄膜方阻(R)为5.46 kΩ/□(25 ℃),方阻温度系数(TRC)为-1.5%/℃(25 ℃);后续退火热处理后,薄膜方阻增大到231 kΩ/□(25 ℃),方阻温度系数升高为-2.74%/℃(25 ℃).此外,就氧化钒薄膜的成分、热敏性能与退火处理之间的关系进行了讨论.     

Cu靶功率和衬底温度对Cu-SiO_2纳米复合膜的相结构与光吸收性能影响

实验利用直流和射频磁控溅射方法交替沉积Cu-SiO2纳米复合膜,研究不同Cu靶功率和衬底温度对纳米复合膜的相结构和光吸收性能的影响。结果表明:随着Cu靶功率的增加,金属Cu纳米颗粒尺寸增大,导致光吸收峰峰位发生红移;随着衬底温度的升高,由于Cu再蒸发效应致使金属Cu纳米颗粒尺寸减小,引起光吸收峰峰位发生蓝移;与室温下沉积态Cu-SiO2纳米复合膜相比,在衬底加热条件下沉积的纳米复合膜在可见光波段出现了明显的表面等离子体共振吸收峰。因此,Cu靶功率和衬底温度对Cu-SiO2纳米复合薄膜的结晶状况和光吸收性能有显著影响。