大尺寸CVD金刚石厚膜的制备及应用

采用电子辅助化学气相沉积法（ＥＡＣＶＤ）制备了直径１２０ｍｍ、厚度１ｍｍ以上的大尺寸金刚石厚膜,这是国内已见报道的最大成膜尺寸．ＳＥＭ和Ｒａｍａｎ光谱分析表明它是一种纯晶质的多晶金刚石材料;其硬度接近天然金刚石,远高于聚晶金刚石．将这种材料加工成拉丝模具,现场拉丝结果表明其拉丝效果与天然金刚石和进口优质聚晶相当,优于国产聚晶．用这种金刚石制成的拉丝模具可广泛用于拉制钨、钼、铜和不锈钢丝．     

Plasma treatment effects on surface morphology and field emission characteristics of carbon nanotubes

In this study, electron field-emission properties of carbon nanotube films (CNTs) grown on silicon substrate before and after tetrafluoromethane (CF₄), hydrogen (H₂) and argon (Ar) plasma etchings were investigated. The CNTs were synthesized by thermal decomposition of methane in the presence of nickel catalyst. Our research results reveal that plasma treatment can modify the surface morphology and enhance the field-emission characteristics of CNTs regardless of the plasma used. The CNTs treated by both non-reactive and reactive plasmas have a higher density of defect and a smaller average diameter reflecting the etching effects of plasma treatments. In addition, higher emission currents and lower turn-on electric fields are also obtained for the CNTs after plasma treatment. As expected, reactive plasma treatment has a more pronounced effect on the surface morphology and field-emission characteristics of the synthesized CNTs than non-reactive plasma treatment. In particular, a huge increase in emission current (more than three orders of magnitude at high electric fields) and a substantial lower turn-on electric field are found for the CNTs after H₂ plasma treatment. This huge increase in the emitted current is primarily caused by the increase in the density of field-emission sites resulting from the change of surface morphology and the –CH _x nanoparticles redeposited on the CNTs.     

Production and characterization of pulsed large-area homogenous electron beams

The characteristics of electron beam pulses used for the annealing of ion implanted semiconductors and for silicon/metal reactions are given. Methods for the attainment of large area currents using different field-emission cathodes are discussed. Qualitative and quantitative systems for the evaluation of beam homogeneity (graphite films, thermoluminescent LiF crystal arrays, radiochromic films) are described together with results obtained by pulsed electron beam induced reaction in silicon/platinum systems.     

Boron-doped transparent conducting nanodiamond films

Boron-doped nanodiamond (ND) films on silica substrates have been obtained by the method of microwave plasma-enhanced chemical vapor deposition (MWPECVD). Using special technological regimes ensuring the growth of boron-doped ND films after the deposition of an initial ND nucleation layer with small roughness (<15 nm) and a large number of diamond phase nucleation centers per unit surface area (>10¹⁰ cm⁻²), it is possible to obtain conducting ND films transparent in the UV spectral range. Dependence of the transparency and conductivity of the obtained films on the boron concentration and methane content in the working methane-hydrogen mixture has been studied.     

Effects of potassium hydroxide post-treatments on the field-emission properties of thermal chemical vapor deposited carbon nanotubes

In this study, a simple potassium hydroxide treatment was applied to functionalize the surface and to modify the structure of multi-walled carbon nanotubes grown on silicon substrates by thermal chemical vapor deposition. Scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and energy dispersive spectrometry were employed to investigate the mechanism causing the modified field-emission properties of carbon nanotubes. From our experimental data, the emitted currents of carbon nanotubes after potassium hydroxide treatment are enhanced by more than one order of magnitude compared with those of untreated carbon nanotubes. The emitted current density of carbon nanotubes increases from 0.44 mA/cm2 to 7.92 mA/cm2 after 30 minutes KOH treatment. This technique provides a simple, economical, and effective way to enhance the field-emission properties of carbon nanotubes.     

Dependence of field-emission threshold in diamond-like carbon films grown by various techniques

In this paper, we report field-emission measurements from ∼0.5-μm-thick hydrogenated amorphous carbon (diamond-like carbon (DLC)) films. These films were grown by a variety of easily implementable plasma-enhanced chemical vapor deposition (PECVD) based techniques and also by a method that uses a saddle-field fast atom beam source. Field-emission behavior in these materials has been discussed in light of residual stress, hardness, optical band gap, and characteristic energy of band tails (Urbach energy). Onset emission-fields as low as ∼6 V/μm, together with low residual stress of 0.25 GPa, hardness of 17.5 GPa, optical band gap of 1.5 eV, and Urbach energy of 165 meV, have been obtained in DLC films grown by pulsed-PECVD at 13.56 MHz. DLC films of comparable quality could also be grown using a saddle-field fast atom beam source, which operates on modest dc power supply and with no heated filaments or magnets.     

Nanocrystalline diamond growth on different substrates

Nanocomposite films consisting of diamond nanoparticles of 3-5 nm diameter embedded in an amorphous carbon matrix have been deposited by means of microwave plasma chemical vapour deposition (MWCVD) from CH₄/N₂ gas mixtures. Si wafers, Si coated with TiN, polycrystalline diamond (PCD) and cubic boron nitride films, and Ti-6Al-4V alloy have been used as substrates. Some of the substrates have been pretreated ultrasonically with diamond powder in order to enhance the nucleation density n_nuc. It turned out that n_nuc depends critically on the chemical nature of the substrate, its smoothness and the pretreatment applied. No differences to the nucleation behaviour of CVD PCD films were observed. On the other hand, the growth process seems to be not affected by the substrate material. The crystallinity (studied by X-ray diffraction) and the bonding environment (investigated by Raman spectroscopy) show no significant differences for the various substrates. The mechanical and tribological properties, finally, reflect again the influence of the substrate material: on TiN, a lower hardness was measured as compared to Si, PCD and c-BN, whereas the adhesion of c-BN/nanocrystalline diamond (NCD) system was determined by that of the c-BN film on the underlying Si substrate.     

Screen-printed single-walled carbon nanotube networks and their use for dimethyl methylphosphonate detection

Single-walled carbon nanotube (SWNT) films were prepared on silicon/silica substrates by screen-printed technique at a wafer scale, and their sensing properties to dimethyl methylphosphonate (DMMP) were studied. The SWNT networks were characterized by field-emission scanning electron microscope. The resistance responses to different concentrations of DMMP vapors were investigated at room temperature. The results showed that the resistance changes of the screen-printed SWNT films increased rapidly in varying concentrations ranging from 20 to 200?ppm. The sensor exhibited high resistance responses, good reproducibility and excellent long-term stability for DMMP vapor detection. The screen-printed SWNT networks would be potentially extended to large-scale, low cost and simple manufacturing sensor applications.     

Growth of polycrystalline and nanocrystalline diamond films on pure titanium by microwave plasma assisted CVD process

Well-faceted polycrystalline diamond (PCD) films were deposited along with nanocrystalline diamond (NCD) films on the pure titanium substrate by a microwave plasma assisted chemical vapor deposition (MWPCVD) system in the environment of CH₄ and H₂ gases at a moderate temperature. Diamond film deposition on pure titanium and Ti alloys is always extremely hard due to the high diffusion coefficient of carbon in Ti, the big mismatch in their thermal expansion coefficients, the complex nature of the interlayer formed during diamond deposition, and the difficulty of attaining very high nucleation density. A well-faceted PCD film and a smooth NCD film were successfully deposited on pure Ti substrate by using a simple two-step deposition technique. Both films adhered well. Detailed experimental results on the preparation, characterization and successful deposition of the diamond coatings on pure Ti are discussed. Lastly, it is shown that smooth NCD film can be deposited at moderate temperature with sufficient diamond quality for mechanical and tribological applications.     

Nanodimensional carbon materials formed in a gas discharge plasma

We have experimentally studied the formation of nanodimensional carbon materials from a methane-hydrogen gas mixture activated by a dc discharge. The range of discharge voltages and currents ensuring stable deposition of carbon films was determined. Data on the carbon-containing components of the activated gas phase were obtained by in situ optical emission spectroscopy of the gas discharge plasma. It is shown that the formation of nanodiamond and nanographite particles, as well as carbon nanotubes, in the deposited films is correlated with the presence of C₂ carbon dimers in the gas phase. A mechanism of the noncatalytic formation of carbon nanotubes from platelike graphite nanoparticles is proposed.     

Electron field emission from the carbon-doped TiO2 nanotube arrays

The field-emission characteristics of the carbon-doped TiO₂ nanotube arrays (TNAs), which can be obtained by a heat treatment of the as-fabricated TNAs under a continuous argon and acetylene flux, were investigated. The morphology, crystalline structure, and composition of the as-grown specimens were characterized by the use of field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. It was found that the samples' turn-on electric field is reduced from 21.9 to 5.0 V/μm and the field-emission current density rapidly reaches about 9.0 mA/cm² at 11.8 V/μm after carbon doping. The dramatically improved field-emission characteristics would be mainly attributed to the reduced work function and the enhanced conductivity due to the carbon doping into TNAs.     

Surface etching effects of amorphous C:H and CNx:H films formed by supermagnetron plasma for field emission use

Supermagnetron plasma was used to deposit amorphous hydrogenated carbon (a-C:H) and hydrogenated carbon nitride (a-CN_x:H) films for field-emission devices using i-C₄H₁₀/(H₂ or N₂). It was also used to improve the field-emission characteristics by surface etching using N₂/H₂ plasma. The best emission threshold electric field (E_TH) was 13 and 12 V/μm for devices using as-deposited a-C:H and as-deposited a-CN_x:H films, respectively, while they were remarkably improved to 11 and 8 V/μm by surface etching using N₂/H₂ (120/40 sccm) gas, though surface roughness was slightly increased by the surface etching. The hardness of as-deposited films was higher than 22 GPa.     

Temperature dependence of current-voltage characteristics of polycrystalline diamond FETs: modelling and experiment

For the first time, a theoretical model for polycrystalline diamond (PCD) field effect transistors is proposed. The model is accompanied by an investigation of the single crystalline diamond (SCD) FET for the verification of material parameters employed in the simulation. The model runs on a device simulator, PISCES-IIB, and correctly accounts for the temperature-dependent shift of the I–V characteristics from pentode-like to triode-like behaviour as well as the temperature dependent pinch-off and saturation. Agreement between simulated and measured currents is obtained with a higher value of the activation energy for the dopant in PCD than in SCD, as has been reported for silicon.     

Enhanced field-emission from a mixture of carbon nanotubes, ZnO tetrapods and conductive particles

We report the enhancement of field-emission current from a mixture of carbon nanotubes, ZnO tetrapod-like nano structures, and conductive particles. Carbon nanotubes are deposited on the electrode as the field emitters. A MgO layer is printed around the cathode electrode, and ZnO tetrapod-like nano structures are deposited on this layer for the generation of secondary emission electrons. A few conductive particles are also distributed on the MgO layer by spraying or screen-printing. These conductive particles enhance the transverse electric field around the cathode electrode. Consequently, more primary electrons emitted from the carbon nanotubes bombard on the ZnO tetrapods, and secondary emission electrons and scattered electrons are yielded. Finally, the field-emission current is enhanced obviously. As experimental results shown, a high field-emission current about 32 mA in a direct current emission mode has been obtained from a 0.5 cm2 emission site when an electric field of 9 V/microm is applied between cathode and anode. Compared with a conventional carbon nanotube cathode, the field-emission current has been improved about 80%.     

Mo电极形貌对AIN薄膜择优取向生长的影响

采用射频磁控溅射方法在不同形貌的Mo电极上制备了(002)择优取向的AlN薄膜。采用XRD、FESEM表征了Mo电极及AlN薄膜的结构、表面形貌及择优取向。结果表明,Mo电极的形貌影响AlN薄膜的择优取向生长,在较高溅射气压下沉积的Mo电极晶粒细小、分布均匀,有助于AlN薄膜(002)择优取向生长。     

Preparation of Oriented Barium Titanate Thin Films by Combination of Electrophoretic Deposition with Hydrothermal Treatment

Highly oriented barium titanate (BaTiO 3) thin films on Pt substrate were fabricated by combination of electrophoretic deposition with hydrothermal treatment.The structure and morphology of thin films were characterized by X-ray diffraction and field-emission scanning electron microscopy.It is found that the titania precursor film,Ba(OH)2 concentration and hydrothermal temperature play crucial roles in the film morphology and orientation.The BaTiO3 thin films with highly (110) preferred orientation can be f...     

Hot-filament CVD synthesis and application of carbon nanostructures

We have reported the catalyst-assisted hot-filament chemical vapor deposition (HFCVD) of various carbon nanostructures, such as carbon nanotube (CNT), nanoparticle (CNP), and nanofiber (CNF), and their application examples. In the case of CNT, vertically aligned high-density growth has been investigated in detail using in-situ optical reflectivity measurement. For CNF showing large field-emission currents, adsorbate-related emission behavior and the emission from patterned cathodes have been studied. Regarding CNP, the performances of a series of triode field emitters with CNP cathodes have been compared, and the application of CNP triode to miniature time-of-flight mass spectrometer has been discussed.     

纳米ZnO镶嵌SiO2薄膜的光学特性研究

采用射频反应磁控溅射法在玻璃衬底上成功制备出纳米ZnO镶嵌SiO2非晶薄膜,利用X射线衍射仪、场发射扫描电子显微镜、X射线光电子能谱仪和紫外-可见分光光度计研究了纳米Zn0镶嵌SiO2薄膜相比纯ZnO纳米薄膜结构的变化及镶嵌结构对其光学特性的影响.研究发现与纯ZnO纳米薄膜相比,纳米ZnO镶嵌SiO2薄膜结构样品呈非晶结构,在紫外区光吸收系数以及光学带隙明显增大,光吸收以及光学带隙的变化与样品制备的衬底温度有关.研究结果表明,由于SiO2的特殊结构实现了对纳米ZnO的束缚,减少了ZnO纳米粒子的集聚,使得量子限制效应变得显著,导致复合膜光学带隙的明显增大以及吸收边的蓝移.     

GOX-functionalized nanodiamond films for electrochemical biosensor

The importance of nanodiamond in biological and technological applications has been recognized recently, and applied in drug delivery, biochip, sensors and biosensors. Under this investigation, nanodiamond (ND) and nitrogen doped nanodiamond (NND) were deposited on n-type silicon films, and later functionalized with enzyme Glucose oxidase (GOX). The GOX functionalized doped and undoped ND films were characterized using combination of several techniques; i.e. FTIR spectroscopy, Raman spectroscopy, atomic force microscopy (AFM) and electrochemical techniques. ND/GOX and NND/GOX thin films on n-type silicon have been found to provide sensitive glucose sensor. GOX has been chosen as a model enzyme system to functionalize with ND at molecular level to understand the glucose biosensor.     

Direct electron transfer of cytochrome P450 2B4 at electrodes modified with nonionic detergent and colloidal clay nanoparticles

A method for construction of biosensors with membranous cytochrome P450 isoenzymes was developed based on clay/detergent/protein mixed films. Thin films of sodium montmorillonite colloid with incorporated cytochrome P450 2B4 (CYP2B4) with nonionic detergent were prepared on glassy carbon electrodes. The modified electrodes were electrochemically characterized, and bioelectrocatalytic reactions were followed. CYP2B4 can be reduced fast on clay-modified glassy carbon electrodes in the presence of the nonionic detergent Tween 80. In anaerobic solutions, reversible oxidation and reduction is obtained with a formal potential between -0.292 and -0.305 V vs Ag/AgCl 1 M KCl depending on the preparation of the biosensor. In air-saturated solution, bioelectrocatalytic reduction currents can be obtained with the CYP2B4-modified electrode on addition of typical substrates such as aminopyrine and benzphetamine. This reaction was suppressed when methyrapone, an inhibitor of P450 reactions, was present. Measurement of product formation also indicates the bioelectrocatalysis by CYP2B4.