掺硼对超纳米金刚石薄膜的影响

采用微波等离子体化学气相沉积(MPCVD)技术,利用氩气、甲烷、二氧化碳混合气体,制备出平均晶粒尺寸在7.480 nm左右,表面粗糙度在15.72 nm左右的高质量的超纳米金刚石薄膜;在此工艺基础上以硼烷作为掺杂气体,合成掺硼的金刚石薄膜.表征结果显示在一定的浓度范围内随着硼烷气体的通入,金刚石薄膜的晶粒尺寸及表面粗糙度增大、结晶性变好,不再具有超纳米金刚石膜的显微结构和表面形态;同时膜材的物相组成也发生改变,金刚石组份逐渐增多,并且膜层内出现了更明显的应力以及更好的导电性能.     

掺氮类金刚石薄膜的制备与性能研究

利用空心阴极放电在玻璃基底表面沉积掺氮类金刚石(DLc)薄膜.拉曼光谱(Raman)分析表明,所制备的碳膜具有典型的类金刚石结构.扫描电镜(SEM)和原子力显微镜(AFM)分析了薄膜表面形貌和粗糙度;利用摩擦磨损仪测量膜的摩擦磨损性能.结果表明,氮的掺入使得薄膜中颗粒致密平整,改变了薄膜的表面微观形貌,进而改善了薄膜的摩擦磨损性能.     

正偏压对纳米金刚石薄膜结构和电阻率的影响

采用电子辅助热丝化学气相沉积工艺, 在1kPa反应气压和施加不同的偏流条件下, 沉积了纳米金刚石薄膜. 用X射线衍射, 场发射扫描电镜和半导体特性表征系统对该薄膜进行了表征和分析. 结果表明, 施加偏流可以使薄膜晶粒呈现明显的(110)晶面择优取向, 表面形貌发生较大变化. 当偏流为8A时, 薄膜晶粒达到最小值, 约为20nm, 薄膜表面也最光滑. 本文讨论了在低气压和电子轰击条件下(110)晶面择优取向的形成机制及其对薄膜显微形貌和电阻率的影响关系.     

掺硼金刚石/硬质合金膜基结合和摩擦磨损性能的研究

金刚石刀具涂层在碳纤维复合材料等难加工材料高效加工方面有着广阔的应用前景。在热丝化学气相沉积系统通过气体掺硼,在硬质合金表面制备了掺硼金刚石涂层。通过SEM、Raman以及压痕测试对涂层的表面形貌、成分和膜基结合性能进行了测试和分析;对涂层进行了摩擦磨损实验,研究了涂层不同环境温度下的摩擦系数及磨损率。结果表明,适量的硼掺杂可以细化金刚石晶粒,提高膜基结合力,降低摩擦系数并提高耐磨性,掺硼金刚石磨损率随温度的升高而增大,本文合适的掺硼浓度为3×10-3。     

掺硼金刚石膜的热敏特性

用微波ＰＣＶＤ法将掺硼金刚石膜淀积在Ｓｉ３Ｎ４基片上，用Ｔｉ薄膜作为欧姆接触电极蒸发在金刚石表面上，为防止Ｔｉ在高温下氧化，上面镀上了Ａｕ薄膜，从室温到６００℃范围内测试了这些金刚石膜样的电阻（Ｒ），发现Ｔ＾－１和Ｒ之间呈线性关系，若改变掺硼浓度以及热处理条件可以控制掺硼金刚石膜的热敏特性，结果表明掺硼金刚石膜显示了高的敏感性和好的稳定性，是一咱优良的热敏电阻材料。     

辅助气体压强比例对中频脉冲非平衡磁控溅射沉积类金刚石薄膜结构与性能的影响

以高纯石墨为靶材、氩气(Ar)和甲烷(CH4)为辅助气体,利用中频脉冲非平衡磁控溅射技术在不同气体压强比例下制备了类金刚石薄膜,采用原子力显微镜、拉曼光谱仪、傅立叶变换红外光谱仪、纳米压痕测试仪对所制备薄膜的表面形貌、微观结构、机械性能进行了分析.结果表明:当Ar气压强比例由17％增加到50％时,类金刚石薄膜的RMS表面粗糙度、sp3杂化键含量、纳米硬度、弹性模量随Ar气压强比例的增加而增加,当Ar气压强比例由50％增加到86％时,薄膜的RMS表面粗糙度、sp3杂化键含量、纳米硬度、弹性模量随Ar气压强比例的增加而减小.以上结果说明辅助气体压强比例对类金刚石薄膜的表面形貌、微观结构、机械性能有较大的影响.     

杆状氧化铍表面金刚石薄膜的生长

利用一种新型线形微波等离子体源以甲烷和氢气为反应气体在135 mm×1 mm×0.5 mm杆状氧化铍表面沉积金刚石膜。研究了氧化铍基底预处理对金刚石形核密度和膜的连续性,以及基底温度对金刚石质量的影响。通过扫描电镜、拉曼光谱对沉积的金刚石膜表面形貌以及质量进行表征。实验结果表明:600#砂纸与金刚石粉混合预处理可以大大提高氧化铍表面金刚石的形核密度,得到连续性较好的金刚石薄膜;同时,基底温度不仅影响着金刚石膜的表面形貌,也影响着金刚石膜的质量。基底温度较低时,金刚石膜在沉积过程中二次形核增强,非金刚石相含量较高;提高沉积温度后,等离子体中H原子浓度增加,有利于金刚石质量的提高。     

高气压下温度对金刚石膜择优取向的影响

采用自主改进的圆柱谐振腔式MPCVD装置,以H2-CH4为气源、反应腔压强30kPa、微波功率6kW、CH4浓度2%,在不同的沉积温度下进行了多晶金刚石膜的制备研究。采用扫描电镜、X-射线衍射技术对所制备样品的表面形貌、物相及晶面取向进行了分析。结果表明,在高气压条件下,沉积温度由800℃升高至900℃时,金刚石膜的表面形貌由(111)晶面择优取向逐渐转向(100)晶面择优取向;沉积温度由900℃升高至1050℃时,金刚石的表面形貌由(100)晶面择优取向逐渐转向(111)晶面择优取向。     

CO_2对金刚石膜结构的影响

采用微波等离子化学气相沉积法,使用甲烷、氢气和二氧化碳作为反应气氛进行金刚石膜的沉积研究。实验中通过添加并改变气体组分中CO_2/CH_4比值金刚石膜在高碳源浓度条件的可控性生长。通过Raman光谱、X射线衍射(XRD)及SEM对金刚石膜的沉积质量,生长取向及表面形貌进行表征。结果表明,在其他参数保持一致时,在高甲烷下,只改变CO_2/CH_4比值可明显改变金刚石膜的表面形貌并提高金刚石膜的质量,实现纳米、(111)面及(100)面微米金刚石膜的可控性生长。     

硼掺杂金刚石薄膜电极在酸碱盐中的电化学性质研究

通过热丝化学气相沉积技术,在P型单晶衬底上制备了掺硼金刚石薄膜电极。采用扫描电子显微镜和X射线衍射分析了丙酮流量对硼掺杂金刚石薄膜电极的表面形貌的影响,采用循环伏安法分析硼掺杂金刚石薄膜电极在不同浓度的酸碱盐电解液中的电化学特性。结果表明,硼掺杂金刚石薄膜质量随着丙酮流量的增加而先提高后下降的趋势,并且硼掺杂金刚石薄膜电极在不同电解质中存在不同的电化学窗口,中性溶液中的电化学窗口最宽在3.2 V以上,具有极强的电化学氧化性能。     

Ta/BDD薄膜材料电极在检测苯胺中的应用

制作钽衬底掺硼金刚石薄膜材料电极(Ta/BDD),并利用此薄膜材料电极为工作电极通过阴极溶出伏安法检测水中的苯胺.用热丝化学气相沉积(HFCVD)方法沉积Ta/BDD薄膜电极,扫描电镜和拉曼光谱表明电极具有良好的物理性质,循环扫描测试表明电极具有宽的电势窗口4.1V(-1.8～+2.3V vs SCE)和低背景电流,此特性对于电化学检测有着明显的优势.发现苯胺在氧化处理的Ta/BDD电极上有可逆的氧化还原峰,检测过程中未发生电极钝化现象.Ta/BDD电极在酸性介质中苯胺检测效果较明显,苯胺在1～40靘ol/L范围内浓度与溶出峰电流值有较好的线性关系.     

Fabrication of boron-doped diamond ultramicroelectrodes for use in scanning electrochemical microscopy experiments

Boron-doped diamond (BDD) ultramicroelectrode (UME) tips were fabricated by the growth of BDD films by chemical vapor deposition onto sharpened tungsten wires. Both nanocrystalline and microcrystalline forms of diamond coatings were examined. The diamond-coated wires were selectively insulated with nail varnish, electrophoretic paint, or fast-setting epoxy to form UME tips of critical dimensions of 1-25 microm. The geometry of the exposed electrode area was disk or hemispherical in most cases. Cyclic voltammetry and chronoamperometry were used to assess exposed electrode area and integrity of the insulation. BDD UMEs were used to obtain SECM approach curves to an insulating and a conducting substrate, which were fitted to the theory appropriate for the observed tip geometry. The tips were used to obtain SECM images of immobilized respiring E. coli, illustrating the suitability of BDD UMEs for electrochemical imaging in biological media.     

HFCVD金刚石膜过程的气氛模拟与分析

对热丝法化学气相沉积金刚石膜过程的气氛进行了模拟与分析。使用GRI－Mech3.0甲烷燃烧过程C／H／O／N四元体系热化学反应机理和动力学数据，模拟并分析了HFCVD金刚石膜的C／H气相化学反应，通过对反应流的简单模拟得到了衬底位置气相组成，结果与前人实验数据吻合，探讨了灯丝温度、碳源浓度和碳源种类等因素变化对衬底位置气相组成的影响。结果表明甲基是金刚石膜生长最主要的前驱基团，其作用远高于乙炔，而超平衡态原子氢的存在对金刚石膜的质量至关重要。     

Anodic oxidation of wastewater containing the Reactive Orange 16 Dye using heavily boron-doped diamond electrodes

Boron-doped diamond (BDD) films grown on the titanium substrate were used to study the electrochemical degradation of Reactive Orange (RO) 16 Dye. The films were produced by hot filament chemical vapor deposition (HFCVD) technique using two different boron concentrations. The growth parameters were controlled to obtain heavily doped diamond films. They were named as E1 and E2 electrodes, with acceptor concentrations of 4.0 and 8.0 × 10²¹ atoms cm⁻³, respectively. The boron levels were evaluated from Mott-Schottky plots also corroborated by Raman's spectra, which characterized the film quality as well as its physical property. Scanning Electron Microscopy showed well-defined microcrystalline grain morphologies with crystal orientation mixtures of (1 1 1) and (1 0 0). The electrode efficiencies were studied from the advanced oxidation process (AOP) to degrade electrochemically the Reactive Orange 16 azo-dye (RO16). The results were analyzed by UV/VIS spectroscopy, total organic carbon (TOC) and high-performance liquid chromatography (HPLC) techniques. From UV/VIS spectra the highest doped electrode (E2) showed the best efficiency for both, the aromaticity reduction and the azo group fracture. These tendencies were confirmed by the TOC and chromatographic measurements. Besides, the results showed a direct relationship among the BDD morphology, physical property, and its performance during the degradation process.     

沉积参数对化学气相沉积纳米金刚石薄膜的影响

用强电流直流伸展电弧化学气相沉积金刚石薄膜装置,在CH4-Ar和CH4-H2-Ar气氛中沉积了纳米金刚石薄膜,研究了沉积气氛中H2加入量和沉积压力对金刚石薄膜显微组织和生长机制的影响.沉积气氛中H2含量对金刚石薄膜的表面形貌、晶粒尺寸和生长速度有显著影响,随着H2含量增加,金刚石晶粒尺寸增大,薄膜生长速度提高.在1%CH4-Ar气氛中沉积的纳米金刚石薄膜,晶粒尺寸细小,薄膜表面形貌光滑平整.在1%CH4-少量H2-Ar气氛中沉积的金刚石薄膜,晶粒尺寸小于100nm,薄膜表面形貌较平整.随着沉积压力提高,金刚石薄膜的生长速度增大.用激光Ram an对金刚石薄膜进行了表征.     

金刚石基燃料电池催化剂的研究进展

金刚石是由共价键方式连接的sp³杂化碳原子组成, 具有极强的稳定性。含硼金刚石(BDD)薄膜、BDD颗粒、非掺杂纳米金刚石(ND)等新型金刚石又兼具一定的导电性, 因此成为高稳定性燃料电池催化剂的理想载体材料。研究者进一步发现通过对上述新型金刚石进行适当功能化处理, 可以进一步提高催化剂的催化活性和稳定性。对金刚石进行掺杂处理, 既包括向金刚石晶格中掺杂, 也包括向金刚石衍生的石墨结构中进行掺杂, 能够得到新型高稳定性燃料电池非铂催化剂, 且金刚石sp³结构在提高非铂催化剂稳定性方面作用独特。本文总结介绍了相关研究成果, 希望能为后续研究提供参考借鉴。     

Low Resistance Polycrystalline Diamond Thin Films Deposited by Hot Filament Chemical Vapour Deposition

Polycrystalline diamond thin films with outgrowing diamond (OGD) grains were deposited onto silicon wafers using a hydrocarbon gas (CH4) highly diluted with H2 at low pressure in a hot filament chemical vapour deposition (HFCVD) reactor with a range of gas flow rates. X-ray diffraction (XRD) and SEM showed polycrystalline diamond structure with a random orientation. Polycrystalline diamond films with various textures were grown and (111) facets were dominant with sharp grain boundaries. Outgrowth was observed in flowerish character at high gas flow rates. Isolated single crystals with little openings appeared at various stages at low gas flow rates. Thus, changing gas flow rates had a beneficial influence on the grain size, growth rate and electrical resistivity. CVD diamond films gave an excellent performance for medium film thickness with relatively low electrical resistivity and making them potentially useful in many industrial applications.     

Examination of the spatially heterogeneous electroactivity of boron-doped diamond microarray electrodes

Spatial variations in the electrical and electrochemical activity of microarray electrodes, fabricated entirely from diamond, have been investigated. The arrays contain approximately 50-mum-diameter boron-doped diamond (BDD) disks spaced 250 mum apart (center to center) in insulating intrinsic diamond supports, such that the BDD regions are coplanar with the intrinsic diamond. Atomic force microscopy (AFM) imaging of the surface reveals a roughness of no more than +/-10 nm over the array. Each BDD microdisk within the array contains polycrystalline BDD with a variety of different grains exposed. Using conducting-AFM, the conductivity of the different grains was found to vary within a BDD microdisk. Electrochemical imaging of the electroactivity of the microdisk electrodes using scanning electrochemical microscopy operating in substrate generation-tip collection mode revealed that, under apparently diffusion-limited steady-state conditions, there was a small variation in the response between electrodes. However, the majority of electrodes in the array appeared to show predominantly metallic behavior. For the electrodes that showed a lower activity, all grains within the microdisk supported electron transfer, albeit at different rates, as evidenced by studies on the electrodeposition of metallic silver, at potentials far negative of the flat band potential of oxygen-terminated polycrystalline diamond. The possibility of using these array electrodes for steady-state diffusion-limited measurements in electroanalytical applications is far-reaching. However, caution should be exercised in the kinetic analysis of voltammetric measurements, since wide variations in the electroactivity of individual grains are apparent when the potential is below the diffusion-limited value.     

The oxygenated phenomena of the undoped large-grain and small-grain polycrystalline diamond films

The polycrystalline diamond films in this research were deposited using a methane/hydrogen gas mixture in a microwave plasma assisted chemical vapor deposition system. Large-grain, several μm size crystallite, diamond films and small-grain, sub-micron size crystallite, diamond films were prepared by diamond paste and diamond powder nucleation method, respectively. It is found that there is no oxygen incorporated into the diamond films during the microwave plasma chemical vapor deposition process at the synthesis temperature between 900°C and 1000°C. However, the oxygenated phenomena did appear for both of the large-grain and the small-grain polycrystalline diamond films after the films were exposed to air for a period of time. It was shown that the large-grain diamond films are oxygenated more than the small-grain diamond films as the samples were exposed to air for a period of time and also after the chemical cleaning treatment. It is indicated that the oxygenated phenomena of the diamond films come from two contributors, the diamond crystallite surfaces and the diamond grain boundaries. The reaction between the diamond grain boundaries and the air is fast and the oxidized dangling bonds are hard to remove. However, the oxidized dangling bonds on the diamond crystallite surfaces are gradually formed and are easily etched away by the hydrogen plasma.     

Cyclic voltammetry and impedance studies of undoped diamond films

The undoped, polycrystalline diamond films were deposited on tungsten wire substrates by hot filament chemical vapor deposition (HF CVD), using a precursor gas mixture of methanol with excess of hydrogen. The morphology and quality of the as-deposited films were monitored by scanning electron microscopy (SEM) and Raman spectroscopy. The surface morphology analyzed by SEM resembles a continuous and well faceted diamond film. Raman results showed essential differences in qualities of diamond films grown at different hydrocarbon concentrations. The electrochemical properties of diamond electrodes were examined with cyclic voltammetry (CV) and the electrochemical impedance spectroscopy (EIS). The CV experiments revealed a large chemical window (>～4.3 V) of undoped diamond. Analysis of the ferrocyanide-ferricyanide couple at a diamond electrode suggests some extent of electrochemical quasi-reversibility, but the rates of charge transfer across the diamond substrate interface vary with diamond quality.