电化学方法制备ZnO纳米颗粒掺杂类金刚石薄膜及其场发射性能研究

采用液相电化学沉积技术制备了ZnO纳米颗粒掺杂的类金刚石(DLC)薄膜, 研究了ZnO纳米颗粒掺杂对DLC薄膜场发射性能的影响. 利用X射线光电子能谱、透射电子显微镜、Raman光谱以及原子力显微镜分别对薄膜的化学组成、 微观结构和表面形貌进行了表征. 结果表明: 薄膜中的ZnO纳米颗粒具有纤锌矿结构, 其含量随着电解液中Zn源的增加而增加. ZnO纳米颗粒掺杂增强了DLC薄膜的石墨化和表面粗糙度. 场发射测试表明, ZnO纳米颗粒掺杂能提高DLC薄膜的场发射性能, 其中Zn与Zn+C的原子比为10.3%的样品在外加电场强度为20.7 V/μm时电流密度达到了1 mA/cm². 薄膜场发射性能的提高归因于ZnO掺杂引起的表面粗糙度和DLC薄膜石墨化程度的增加.     

N离子注入对金刚石膜场发射特性的影响

不同剂量的N离子被注入到化学气相沉积金刚石膜内，研究了表面结构及场发射特性的变化.Raman谱和x射线光电子能谱分析表明，N离子的注入破坏了金刚石膜表面原有的sp3结构，并在膜内形成大量的sp2 C—C 和sp2 C—N 键.样品的场发射测试显示N离子的注入显著提高了金刚石膜场发射特性，膜的场发射阈值电场从注入前的18 V/μm下降到注入后的4 V/μm.金刚石膜场发射特性的提高归因于N离子注入后膜内sp2 C键含量的增加和体内缺陷带的形成，这些变化能改变膜的表面功函数，提高Feimi能级，降低电子隧穿表面的能量势垒. 关键词： 场致电子发射 N离子注入 金刚石膜 热丝化学气相沉积     

Effect of nitrogen doping on nanomechanical and surface properties of silicon film

The effect of nitrogen ion implantation on the nanomechanical properties of single crystal Si was evaluated by means of a conventional Vickers indentation and nanoindentation tests. The images of Si surfaces before and after nitrogen implantation were observed and their average surface roughnesses were measured by an atomic force microscope (AFM), while the changes in the morphology and microstructure of the single crystal Si by N implantation were examined by field emission scanning electron microscope (SEM) and X-ray diffractometer (XRD). In addition, the hydrophilic/hydrophobic surface property of the N-doping Si film was determined from the measurement of water contact angle by the sessile drop technique. Furthermore, the effects of the doping energy on the surface contact angle and the surface roughness and the Vickers hardness of the film are also investigated.     

氮离子注入对类球状微米金刚石聚晶膜的影响

利用微波等离子体化学气相沉积法,在覆盖金属钛层的陶瓷衬底上制备出类球状微米金刚石聚晶膜,后对膜的表面进行氮离子的注入.通过扫描电子显微镜、拉曼光谱、X射线衍射谱及二级结构场发射测试,对膜进行了注入前后的分析.氮离子注入后场致电子发射的效果变强,这可能是氮离子的注入增加了类球状微米金刚石聚晶膜表面的缺陷度,从而增加了价带和导带间的缺陷能级,使电子更容易跃迁到高能级上,提高了场致电子的发射效果.     

Water vapor-induced structure modification of vertically-aligned carbon nanotube arrays and successive thin film coating for enhanced field emission properties

Vertically-aligned carbon nanotubes (VCNTs) are used as electron source in various field emission applications owing to its high aspect ratio, chemical inertness, mechanical strength and electrical conductivity. Here, we demonstrate that surface structure modification along with thin film coating enhances the field emission performance, such as turn-on voltage, emission site density, and stability. In the present study, VCNTs with different heights were grown on silicon wafers by thermal chemical vapor deposition followed by the structure modification of VCNTs using capillarity-driven water vapor condensation. We obtained various surface morphologies by varying the water vapor exposure time and heating temperature. In addition, the structure-modified VCNTs surfaces were coated with W and SiO₂ thin films using electron-beam evaporation. It was observed that W-coated VCNTs with modified surface morphology results in the best field emission performance.     

CVD金刚石中的氮对等离子体刻蚀的影响

采用非对称磁镜场电子回旋共振等离子体分别对沉积过程中掺氮和未掺氮的化学气相沉积金刚石膜进行了刻蚀研究, 结果表明: 掺氮制备的金刚石膜的刻蚀主要集中在晶棱处, 经过4h刻蚀后其表面粗糙度由刻蚀前的4.761 μm下降至3.701 μm, 刻蚀对金刚石膜的表面粗糙度的影响较小; 而未掺氮制备的金刚石膜的刻蚀表现为晶面的均匀刻蚀, 晶粒坍塌,刻蚀4h后其表面粗糙度由刻蚀前的3.061 μm下降至1.083 μm. 刻蚀导致表面粗糙度显著降低. 上述差别的主要原因在于金刚石膜沉积过程中掺氮导致氮缺陷在金刚石晶棱处富集, 晶棱处电子发射加强, 引导离子向晶棱运动并产生刻蚀, 从而加剧晶棱的刻蚀. 而未掺氮金刚石膜,其缺陷相对较少且分布较均匀 ,刻蚀时整体呈现为 (111) 晶面被均匀刻蚀继而晶粒坍塌的现象. 关键词： 掺氮 金刚石膜 刻蚀 非对称磁镜场     

Optoelectronics and formaldehyde sensing properties of tin-doped ZnO thin films

Sn-doped ZnO thin films were deposited on clean glass substrates using the chemical spray pyrolysis technique. XRD analyses confirm stable ZnO hexagonal wurtzite structure of the films with crystallite size in the range of 20–28 nm. The surface roughness of the films increases on Sn doping, which favors to higher adsorption of oxygen species on the film surface, resulting in higher gas response. Optical studies reveal that the band gap decreases on Sn doping. All the films show near band edge emission, and on Sn doping the luminescence peak intensity has been found to increase. Photocurrent in the 1.5 at.% doped film enhances about three times to that observed in the undoped ZnO film. Among all the films examined, the 1.5 at.% Sn-doped film exhibits the maximum response (～94.5 %) at the operating temperature of 275?°C for 100 ppm concentration of formaldehyde, which is much higher than the response (～35 %) in the undoped film. The gas response of the film is attributed to the chemisorption of oxygen on the film surface and the subsequent reaction between the adsorbed oxygen species and the formaldehyde molecules.     

氮流量在高氢氛围中对富硅氮化硅薄膜材料结构及其发光特性的影响

采用等离子体增强化学气相沉积技术,以N₂掺入到SiH₄和H₂的沉积方式,分别在玻璃和N型单晶硅片(100)衬底上制备富硅氮化硅薄膜。通过紫外-可见光吸收光谱、傅里叶变换红外吸收光谱(FTIR光谱)、拉曼光谱和光致发光谱(PL谱)分别表征掺氮硅薄膜材料的带隙、结构及其发光特性的变化。结果表明：在氢气的氛围中,随着氮气流量的增加,氢原子能够对薄膜缺陷起到抑制作用,并使较低的SiH₄/N₂流量比下呈现富硅态,但却不利于硅团簇的形成。随着氮原子的掺入,Si—N键的含量增大,带隙增大,薄膜内微结构的无序度也增大,薄膜出现了硅与氮缺陷相关的缺陷态发光;随着氮原子进一步增加,出现了带尾态发光,进一步讨论了发光与结构之间的关联。这些结果有助于采用PECVD制备富硅氮化硅对材料发光与结构特性的优化。     

硅掺杂铝镓氮薄膜场发射性能研究

利用脉冲激光沉积,分别制备了一系列不同Si掺杂浓度的铝镓氮(AlGaN)薄膜.对此薄膜进行场致电子发射测试表明,Si掺杂浓度为1％的AlGaN薄膜具有最好的场发射特性.相对于非掺杂样品,其场发射电流明显增加,场发射开启电场显著降低.掺杂带来载流子浓度的提升,为场发射提供足够的电子源,使样品的场发射性能提升.但掺杂浓度的进一步提高,薄膜缺陷增加,电子迁移率降低,其薄膜内部电子输运能力降低大于电子浓度的增加对场电子发射的贡献,导致场发射性能开始变差.     

生长条件对Ga掺杂ZnO薄膜微观结构及光致发光性能的影响

利用热氧化法在不同参数条件下生长了Ga掺杂范围较宽的ZnO薄膜, 研究了ZnO薄膜的表面微观结构和光致发光性能. 研究表明: Ga以Ga³⁺存在并掺入ZnO晶格取代Zn²⁺, Ga的掺入改变了ZnO薄膜中的缺陷类型及浓度、化学计量比、薄膜表面结晶质量, 进而影响了薄膜的光致发光性能. 随着热氧化温度升高, Ga掺杂量增大, ZnO薄膜的晶粒尺寸增大, 尺寸更均一, 紫外光与可见光强度比增大. 随着热氧化时间延长, Ga掺杂量降低, ZnO薄膜的晶粒尺寸均一性变差, 紫外光与可见光强度比减小.     

Field emissions of graphene films deposited on different substrates by CVD system

<正>Graphene films are deposited on copper(Cu) and aluminum(Al) substrates,respectively,by using a microwave plasma chemical vapour deposition technique.Furthermore,these graphene films are characterized by a field emission type scanning electron microscope(FE-SEM),Raman spectra,and field emission(FE) I-V measurements.It is found that the surface morphologies of the films deposited on Cu and Al substrates are different:the field emission property of graphene film deposited on the Cu substrate is better than that on the Al substrate,and the lowest turn-on field of 2.4 V/μm is obtained for graphene film deposited on the Cu substrate.The macroscopic areas of the graphene samples are all above 400 mm~2.     

Electron field emission from boron doped microcrystalline diamond

Field emission properties of hot filament chemical vapor deposited boron doped polycrystalline diamond have been studied. Doping level (N_B) of different samples has been varied by the B/C concentration in the gas feed during the growth process and doping saturation has been observed for high B/C ratios. Threshold field (E_th) for electron emission as function of B/C concentration has been measured, and the influences of grain boundaries, doping level and surface morphology on field emission properties have been investigated. Carrier transport through conductive grains and local emission properties of surface sites have been figured out to be two independent limiting effects in respect of field emission. Emitter current densities of 500 nA cm⁻² were obtained using electric fields less than 8 V/μm.     

Microstructure and optical properties of nitrogen-doped ZnO film

The nitrogen doping of ZnO film deposited by the magnetron sputtering method is subsequently realized by the hydrothermal synthesis method.The nitrogen-doped ZnO film is preferably(002) oriented.With the increase of hexamethylenetetramine(HMT) solution concentration,the average grain size of the film along the 002 direction almost immediately decreases and then monotonously increases,conversely,the lattice strain first increases and then decreases.The structural evolution of the film surface from compact and even to sparse and rough is attributed to the enhanced nitrogen doping content in the hydrothermal process.The transmission and photoluminescence properties of the film are closely related to grain size,lattice strain,and nitrogen-related defect arising from the enhanced nitrogen doping content with HMT concentration increasing.     

掺杂对碳纳米管拉曼光谱及场发射性能的影响

采用高温热解法在860℃分别制备出了镓、氮以及硼和氮掺杂的碳纳米管,提纯后利用丝网印刷工艺分别将它们制备成薄膜,并测试了它们的拉曼光谱与场发射性能。测试结果表明,掺杂纳米管的缺陷密集度比纯碳纳米管明显增大,而它们的场致电子发射性能则与掺杂元素的性质密切相关。镓和氮掺杂的纳米管均具有非常优异的场发射性能,而硼和氮共掺杂的纳米管的场发射性能很差。掺杂引起碳纳米管费米能级附近能态密度的变化及功函数的降低是其具有优异场致电子发射性能的主要原因。     

Electrical and electronic properties of nitrogen doped amorphous carbon (a-CNx) thin films

Nitrogen-doped amorphous carbon thin films (a-CN_x) were prepared on silicon substrate by pulsed laser deposition process using methane (CH₄) and nitrogen (N₂) as source gas. The electrical properties of a-CN_x films changes with nitrogen concentration in the film structure. The intensity ratio of the D and G peak (I_D/I_G) increases with higher nitrogen concentration, which means that sp²-clusters were formed in these films and is responsible for the enhancement of conductivity of the a-CN_x films. We observed that the amorphous carbon (a-C) films becoming more graphitic in nature yielding higher conductivity/lower resistivity with increase of nitrogen concentration. Electron field emission result shows that the emission current density enhances with nitrogen doping that indicates the useful in electron field emission devices application.     

Reactivity of ZnO: Impact of polarity and nanostructure

The effects of atomic hydrogen and nitrogen produced by remote r.f. H₂ and N₂ plasmas on the structure, morphology, and optical and electrical properties of Zn- and O-polar ZnO crystals and on ZnO thin films grown by metal–organic chemical vapour deposition (MOCVD) have been studied. It is found that the Zn-polar form is highly reactive with atomic hydrogen, while the O-polar form is almost inert. This difference in reactivity allows one to discern the O-polarity of the (0001) oriented ZnO thin films grown by MOCVD. A decrease of the resistivity of the grain-like MOCVD films is found upon atomic hydrogen treatment. Conversely, atomic nitrogen treatment results in p-type doping of the ZnO film and in an improvement of the surface morphology and microstructure.     

常压MOCVD法生长的p型ZnSe及其光电特性

本文通过常压MOCVD方法,利用NH₃气作为受主掺杂源,在(100)方向的GaAs衬底上生长了ZnSe:N膜。通过测量77K温度下光致发光光谱。观测到了由于掺氮引起的自由到束缚发射(FA)和深中心复合(SA).在低掺杂浓度下FA起主要作用,随着NH₃气浓度增加,FA和SA带的强度随之增强,在重掺杂下SA带成为主要,同时带的半宽度展宽。室温下霍尔测量的结果表明。低掺杂浓度下ZnSe:N膜呈高阻态,而在高掺杂浓度下外延膜呈现P型电导,载流子浓度P～1016cm³.利用p-ZnSe/n-GaAs构成异质pn结,观测到了二极管的整流特性,进一步证实p型ZnSe的实现。     

The field emission of indium-doped ZnO films fabricated by room temperature DC magnetron sputtering

Indium doped ZnO film was fabricated at room temperature by co-sputtering a zinc target and an indium plate under the flow of oxygen and argon. The film was then characterized and the field emission of the film was studied. The indium composition x in the film (Zn_1−xIn_xO) is 5%. The film is hexagonal without any secondary phases or precipitates. The film has two major emission peaks, one related to the band edge emission and another possibly related to the electron acceptor transition. The possible acceptor is nitrogen occupying oxygen site in ZnO. The film is n-type and very resistive. The turn on field of the film at an emission current density of 10 μA/cm² is 17.5 V/μm. The relatively weak field emission property is due to the unintentional incorporation of acceptors such as substitutional nitrogen and oxygen vacancies, which increase the work function of ZnO by reducing the electron density and lowering the Fermi level position of the ZnO:In film.     

First principles calculation of field emission from carbon nanotubes with nitrogen and boron doping

We investigate the field emission properties of nitrogenated and boronated carbon nanotubes using time-dependent density functional theory, where the wave function propagation is performed using the Crank–Nicholson algorithm. We extract the current–voltage characteristics of the emitted electrons from nanotubes with different doping configurations. We found that boron doping alone either impedes, or slightly enhances, field emission. Nitrogen generally enhances the emission current, and the current is sensitive to the location of the nitrogen dopant in the nanotube. Doping with both nitrogen and boron will generally enhance emission, and the closer the nitrogen dopant is to the tip, the higher is the emitted current. The emitted charge cloud from nitrogen-doped carbon nanotubes, however, diffuse more than that from pristine ones, our simulations show the emergence of a branching structure from the charge cloud, which suggests that nitrogenated carbon nanotubes are less convenient for use in precision beam applications.     

Sputter deposition of high transparent TiO2−xNx/TiO2/ZnO layers on glass for development of photocatalytic self-cleaning application

In this study, TiO_2−xN_x/TiO₂ double layers thin film was deposited on ZnO (80 nm thickness)/soda-lime glass substrate by a dc reactive magnetron sputtering. The TiO₂ film was deposited under different total gas pressures of 1 Pa, 2 Pa, and 4 Pa with constant oxygen flow rate of 0.8 sccm. Then, the deposition was continued with various nitrogen flow rates of 0.4, 0.8, and 1.2 sccm in constant total gas pressure of 4 Pa. Post annealing was performed on as-deposited films at various annealing temperatures of 400, 500, and 600 °C in air atmosphere to achieve films crystallinity. The structure and morphology of deposited films were evaluated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM). The chemical composition of top layer doped by nitrogen was evaluated by X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of samples was measured by degradation of Methylene Blue (MB) dye. The optical transmittance of the multilayer film was also measured using ultraviolet-visible light (UV-vis) spectrophotometer. The results showed that by nitrogen doping of a fraction (∼1/5) of TiO₂ film thickness, the optical transmittance of TiO_2−xN_x/TiO₂ film was compared with TiO₂ thin film. Deposited films showed also good photocatalytic and hydrophilicity activity at visible light.