掺硼金刚石薄膜二次电子发射特性的研究

掺硼金刚石薄膜具有负电子亲和势和良好的电子运输性能且容易制备,作为冷阴极材料在图像显示技术和真空技术等方面都有着巨大的应用价值,引起人们的注意.从二次电子发射的机理以及影响二次电子发射系数的因素等方面,对如何利用MPCVD法制备出高二次电子发射系数的掺硼金刚石薄膜进行了综述.论述表明通过合适的工艺条件,对薄膜表面进行适当的处理,是可以制备出高二次电子发射系数的阴极用金刚石薄膜的.     

掺硼浓度对金刚石薄膜二次电子发射特性的影响

掺硼金刚石薄膜具有负电子亲和势和良好的电子运输性能且容易制备,作为冷阴极材料在图像显示技术和真空技术等领域都存在巨大的应用价值,引起人们的广泛关注。采用MPCVD法利用氢气、甲烷和硼烷的混合气体,制备出不同浓度的掺硼金刚石薄膜。结果表明,掺硼浓度影响金刚石薄膜的物相结构、组织形貌,进而影响其二次电子发射性能,当硼烷的流量为4mL/min时,制备的金刚石薄膜质量最好,二次电子发射系数约为90。     

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.     

低压气相生长金刚石薄膜

在低压下,以甲烷和氢的混和气为原料,应用热丝 CVD 法,在 Si 基片上生长出了金刚石薄膜。经 X 射线衍射、激光刺曼光谱和扫描电子显微镜分析,生长产物呈多晶金刚石结构。探讨了金刚石薄膜的生长机理。     

热丝CVD大面积金刚石薄膜的生长动力学研究

在传统工业型热丝化学气相沉积（HFCVD）反应腔内，相关工艺参数取模拟计算优化值的条件下，采用XRD，SEM及Raman光谱等分析手段研究了单晶Si（100）上较大面积金刚石薄膜的动力学生长行为，讨论了晶格取向的变化规律。结果表明：优化工艺参数条件下，在模拟计算的衬底温度和气体温度分布均匀的区域内，沉积的金刚石薄膜虽存在一定的内应力，但整体薄膜连续、均匀，几何晶形良好，质量较高，生长速率达1．8μm／h。薄膜生长过程中晶形显露面受衬底温度和活性生长基团浓度的影响较大。     

掺硼金刚石薄膜的电化学性能

利用循环伏安法,通过对比掺硼金刚石薄膜电极和铂／金刚石电极分别作为工作电极时的循环伏安曲线,分析了两种电极表现出的电化学性能差别,并利用能级理论进行了机理探讨。结果表明掺硼金刚石薄膜电极具有宽的电化学窗口（宽度约为3V）、良好的化学稳定性和极低的背景电流（接近0）,是一种较有潜力的电化学电极材料。     

硼硫共掺杂金刚石薄膜的研究

利用微波等离子体化学气相沉积(MPCVD)技术,以丙酮为碳源．用二甲基二硫和三氧化二硼作掺杂源．在硅衬底上制备了硼与硫共掺杂的金刚石薄膜。用俄歇谱分析金刚石薄膜中硫的含量．用傅里叶红外光谱(FTIR)分析了薄膜表面键结构．用扫描电子显微镜(SEM)观测薄膜的表面形貌．X射线衍射(XRD)和喇曼(Raman)光谱表征膜层的结构。结果表明：微量硼的加入促进硫在金刚石中的固溶度,使硫在金刚石中的掺杂率提高了近50％;随着薄膜中硫含量的增加．薄膜的导电性增加,当薄膜中硫含量达到0．15％(原子分数)时其导电激活能为0.39eV。     

硼掺杂金刚石薄膜电极电化学特性的研究

本文用未经任何表面处理的硼掺杂金刚石薄膜为电极材料，采用循环伏安法和计时电流法检测含Ｋ３Ｆｅ（ＣＮ）６的ＫＣｌ和ＨＣｌ－ＫＣｌ溶液的响应电流，对电极的基本特性，如响应时间，稳定性等进行了研究；同坟也对溶液ｐＨ值变化与因而造成的响应电流变化进行了研究。从与玻碳电极比较的角度出发，分别在含汞的酸性ＫＣｌ－ＨＮＯ３和中性ＫＣｌ体系中，在一定电位下预富集铅，而后用阳极扫描法检测Ｐｂ－Ｈｇ的溶出峰电流，对金     

热丝法化学气相沉积金刚石系统温度分布与薄膜生长关系研究

对热丝化学气相沉积金刚石薄膜系统内的三种传热方式（传导、对流和辐射）进行了比较分析,数值计算了气相空间温度分布和衬底表面二维温度分布。采用热丝化学气相沉积工艺制备了金刚石薄膜,扫描电镜结果显示金刚石薄膜在不同生长区域呈现出与温度分布相关的微观结构与形貌。     

Effect of oxygen terminated surface of boron-doped diamond thin-film electrode on seawater salinity sensing

Tremendous demands for highly sensitive and stable seawater salinometers have motivated intensive research on advanced electrode materials.Boron-doped diamond(BDD)is attractive in terms of its high mechanical stability and chemical inertness,but is usually hindered by its low double-layer capacitance(Cdl)for seawater salinity detection.Here,inspired by the principle of oxygen-terminated BDD electrode endowing higher Cdl than hydrogen-terminated surface,we introduce the oxygen terminated surface by oxygen plasma or reactive ion etch(RIE),and the fabricated oxygen terminated BDD electrodes demon-strate high sensitivity and long-term stability in seawater salinity detection comparing with the hydrogen terminated BDD electrodes.Significantly,the as-fabricated O-BDD-RIE electrodes not only show remark-able enhanced response even better than the commercial platinum black electrodes but also display long-time stability which is weekly verified by continuous monitor for 90 days.The outstanding per-formance of the oxygen terminated BDD electrodes can be ascribed to the enhancement of C-0 surface functional group on Cdl.In addition,a comprehensive analysis of effective electroactive surface area(EASA)and Cdl proves that the surface oxygen is the major factor for the improved Cdl.In summary,the excellent oxygen terminated BDD electrodes promise potential application in seawater salinity detection.     

Standard electrochemical behavior of high-quality, boron-doped polycrystalline diamond thin-film electrodes

Standard electrochemical data for high-quality, boron-doped diamond thin-film electrodes are presented. Films from two different sources were compared (NRL and USU) and both were highly conductive, hydrogen-terminated, and polycrystalline. The films are acid washed and hydrogen plasma treated prior to use to remove nondiamond carbon impurity phases and to hydrogen terminate the surface. The boron-doping level of the NRL film was estimated to be in the mid 1019 B/cm3 range, and the boron-doping level of the USU films was approximately 5 x 10(20) B/cm(-3) based on boron nuclear reaction analysis. The electrochemical response was evaluated using Fe-(CN)6(3-/4-), Ru(NH3)6(3+/2+), IrCl6(2-/3-), methyl viologen, dopamine, ascorbic acid, Fe(3+/2+), and chlorpromazine. Comparisons are made between the apparent heterogeneous electron-transfer rate constants, k0(app), observed at these high-quality diamond films and the rate constants reported in the literature for freshly activated glassy carbon. Ru(NH3)6(3+/2+), IrCl6(2-/3-), methyl viologen, and chlorpromazine all involve electron transfer that is insensitive to the diamond surface microstructure and chemistry with k0(app) in the 10(-2)-10(-1) cm/s range. The rate constants are mainly influenced by the electronic properites of the films. Fe(CN)6(3-/4-) undergoes electron transfer that is extremely sensitive to the surface chemistry with k0(app) in the range of 10(-2)-10(-1) cm/s at the hydrogen-terminated surface. An oxygen surface termination severely inhibits the rate of electron transfer. Fe(3+/2+) undergoes slow electron transfer at the hydrogen-terminated surface with k0(app) near 10(-5) cm/s. The rate of electron transfer at sp2 carbon electrodes is known to be mediated by surface carbonyl functionalities; however, this inner-sphere, catalytic pathway is absent on diamond due to the hydrogen termination. Dopamine, like other catechol and catecholamines, undergoes sluggish electron transfer with k0(app) between 10(-4) and 10(-5) cm/s. Converting the surface to an oxygen termination has little effect on k0(app). The slow kinetics may be related to weak adsorption of these analytes on the diamond surface. Ascorbic acid oxidation is very sensitive to the surface termination with the most negative Ep(ox) observed at the hydrogen-terminated surface. An oxygen surface termination shifts Ep(ox) positive by some 250 mV or more. An interfacial energy diagram is proposed to explain the electron transfer whereby the midgap density of states results primarily from the boron doping level and the lattice hydrogen. The films were additionally characterized by scanning electron microscopy and micro-Raman imaging spectroscopy. The cyclic voltammetric and kinetic data presented can serve as a benchmark for research groups evaluating the electrochemical properties of semimetallic (i.e., conductive), hydrogen-terminated, polycrystalline diamond.     

Kinetic studies of hydroquinone_quinone at the boron-doped diamond electrode by cyclic voltammetry

Abstracts are not published in this journal This revised version was published online in November 2006 with corrections to the Cover Date.     

Electrochemical oxidation of chlorophenols at a boron-doped diamond electrode and their determination by high-performance liquid chromatography with amperometric detection

Anodically pretreated diamond electrodes have been used for the detection of chlorophenols (CPs) in environmental water samples after high-performance liquid chromatographic (HPLC) separation. The anodization of as-deposited boron-doped polycrystalline diamond thin-film electrodes has enabled the stable determination of phenols over a wide concentration range. Prior to the HPLC analysis, a comparative study with ordinary glassy carbon, as-deposited diamond, and anodized diamond was made to examine the oxidative behavior of phenols by cyclic voltammety and flow injection analysis with amperometric detection. At anodized diamond electrodes, reproducible, well-defined cyclic voltammograms were obtained even at high CP concentration (5 mM), due to a low proclivity for adsorption of the oxidation products on the surface. In addition, after prolonged use, the partially deactivated diamond could be reactivated on line by applying a highly anodic potential (2.64 Vvs SCE) for 4 min, which enabled the destruction of the electrodeposited polymer deposits. Hydroxyl radicals produced by the high applied potential, in which oxygen evolution occurs, are believed to be responsible for the oxidation of the passivating layer on the surface. When coupled with flow injection analysis (FIA), anodized diamond exhibited excellent stability, with a response variability of 2.3% (n = 100), for the oxidation of a high concentration (5 mM) of chlorophenol. In contrast, glassy carbon exhibited a response variability of 39.1%. After 100 injections, the relative peak intensity, for diamond decreased by 10%, while a drastic decrease of 70% was observed for glassy carbon. The detection limit obtained in the FIA mode for 2,4-dichlorophenol was found to be 20 nM (S/N = 3), with a linear dynamic range up to 100 microM. By coupling with the column-switching technique, which enabled on-line preconcentration (50 times), the detection limit was lowered to 0.4 nM (S/N = 3). By use of this technique, anodized diamond electrodes were demonstrated for the analysis of CPs in drainwater that was condensed from the flue gas of waste incinerators.     

Label-free DNA sensor by boron-doped diamond electrode using an ac impedimetric approach

An electrochemical biosensor using a boron-doped diamond (BDD) electrode is described for differentiating between gene sequences according to DNA hybridization events using an ac impedimetric approach. BDD electrodes were dipped into a 1% solution of polyethylenimine (PEI) to adsorb a thin layer of positively charged PEI on the surface of BDD, then PEI-modified BDD electrodes were used to immobilize negatively charged single-stranded PCR fragments from Exon 7 of human p53 gene. Alternating current impedimetric measurements were first performed on these systems in phosphate buffered saline (PBS) and then upon exposure to single-stranded DNA (ssDNA). When the ssDNA-immobilized BDD electrode and solution ssDNA were completely complementary, a large drop in impedance was measured. Complementary DNA could be clearly detected at concentrations down to 10 (-19) g mL (-1) at a fixed frequency (10 Hz). Higher concentrations of DNA gave faster hybridization with saturation occurring at levels above 1.0 pg mL (-1.) Responses were much lower upon exposure to noncDNA, even at higher concentrations. The results show it is possible to directly detect target DNA at a fixed frequency and without additional labeling.     

Applicability of boron-doped diamond electrode to the degradation of chloride-mediated and chloride-free wastewaters

The degradation of diphenylamine (DPA) in aqueous solution by persulfate is investigated. Effects of pH, persulfate concentration, ionic strength, temperature and catalytic ions Fe(3+) and Ag(+) on the degradation efficiency of DPA by persulfate are examined in batch experiments. The degradation of DPA by persulfate is found to follow the pseudo-first-order kinetic model. Increasing the reaction temperature or persulfate concentration may significantly accelerate the DPA degradation. Fe(3+) and Ag(+) ions can enhance the degradation of DPA, and Ag(+) ion is more efficient than Fe(3+) ion. However, the increase of either the pH value or ionic strength will decrease the rate of DPA degradation. N-Phenyl-4-quinoneimine, N-carboxyl-4-quinoneimine, 4-quinoneimine and oxalic acid are identified as the major intermediates of DPA degradation, and a primary pathway for the degradation of DPA is proposed. The degradation of DPA in surface water, groundwater and seawater is also tested by persulfate, and more than 90% of DPA can be degraded at room temperature in 45min at an initial concentration of 20mgL(-1).     

Applicability of boron-doped diamond electrode to the degradation of chloride-mediated and chloride-free wastewaters

The electrochemical degradation of chloride-mediated and chloride-free dye wastewaters was investigated on a boron-doped diamond (BDD) electrode in comparison with that on a dimensionally stable anode (DSA), and the applicability of BDD electrode to the degradation of these two kinds of wastewaters was explored. In chloride-free wastewater, the electrochemical degradation efficiency of dye on BDD electrode was much higher than that on DSA, with a chemical oxygen demand (COD) removal of 100% and 26% for BDD and DSA, respectively. In chloride-mediated dye wastewater, COD removal was faster than that in chloride-free wastewater on both BDD and DSA electrodes with COD removal efficiencies higher than 95%, whereas the rate of COD removal on DSA was faster than that on BDD electrode. The investigation indicates that DSA is more suitable than BDD electrode in degradation of originally chloride contained dye wastewaters for the sake of energy and time saving. However, for chloride-free dye wastewaters, with the aim of environmental protection, BDD electrode is more appropriate to realize complete mineralization. At the same time, the secondary pollution can be avoided.     

Differential pulse voltammetry of toxic metal ions at the boron-doped CVD diamond electrode

Boron-doped polycrystalline diamond films were grown over a molybdenum substrate by a microwave plasma CVD process using a methane and hydrogen gas mixture at a pressure of 35 ± 1 Torr. Boron doping of diamond was achieved in situ by using a solid boron source while growing diamond in the CVD processxu. We have observed a negligible background current (l) for diamond by differential pulse voltammetry in 0.5 M NaCl, 0.5 M H₂SO₄, and 0.5 M HNO₃ solutions over a wide potential range. Therefore, diamond will certainly have a use as an electrode material in electroanalytical applications to detect trace toxic/nontoxic metal ions such as cadmium, lead, copper, and silver. Differential pulse voltammetry was used to detect and evaluate the presence of lead ions in 0.5 M NaCl and cadmium ions in 0.5 M H₂SO₄ supporting electrolyte solution using highly conducting boron-doped diamond coated molybdenum electrode material. Furthermore, reverse differential pulse voltammetry was used to evaluate the presence of copper and silver ions in 0.5 M H₂SO₄ and 0.5 M HNO₃ solution, respectively. Diamond electrode has been used in this study to detect metallic ions in the solution over a wide potential range that covers + 0.8 V to –0.4 V vs., SHE.