Capacitance humidity sensor with carbon nitride detecting element

The humidity sensitive properties of carbon nitride (CN_x) films deposited by two methods, inductively coupled plasma chemical vapour deposition utilizing transport reactions and pulsed laser deposition combined with an rf discharge, have been investigated. For this purpose capacitance humidity sensors with a CN_x detecting element have been fabricated and tested. Fast and significant responses toward moisture are registered by the changes of the electrical parameters. The CN_x films sensing mechanism has been discussed. The results obtained show unambiguously that CN_x films appear to be a promising candidate as a humidity sensitive element in up-to-date electronic noses. Received: 6 December 1999 / Accepted: 7 January 2000 / Published online: 24 March 2000     

Correlation between photoluminescence, optical and structural properties of amorphous nitrogen-rich carbon nitride films

Amorphous nitrogen-rich carbon nitride (CN_x) films have been prepared by inductively coupled plasma chemical vapour deposition (ICP-CVD) utilizing transport reactions from a solid carbon source. The nitrogen atomic fraction N/(C+N) is about 1 or even higher as detected by various surface and bulk sensitive methods. An investigation of the chemical bonding structure showed that the films are composed of >C=N units with a small fraction of C≡N groups. Based on these findings, several structural units derived from cis- and trans-conjugated carbon–nitrogen chains are proposed. The optical properties of the CN_x films were studied by transmission spectroscopy and spectral ellipsometry; the optical Tauc gap was determined to 2.1±0.05 eV. The photoluminescence characteristics were measured at three different excitation wavelengths (476, 488 and 515 nm) and revealed two individual contributions. These data are interpreted in terms of the different structural units comprising the nitrogen-rich CN_x films. Received: 14 July 2000 / Accepted:17 July 2000 / Published online: 22 November 2000     

高温退火对非晶CNx薄膜场发射特性的影响

采用射频磁控溅射方法在纯N₂气氛中沉积了非晶CN_x薄膜样品，并 在真空中退火至900 ℃.对高温退火引起的CN_x薄膜化学成分、键合结构及其场发射特性方面的变 化进行研究.用傅里叶变换红外光谱和x射线光电子能谱分析样品的内部成分及键合结构的变化，其中sp²键及薄膜中N的含量与薄膜的场发射特性密切相关.退火实验的结果表明 高温退火可以导致CN_x薄膜中N含量大量损失，并在薄膜中形成大量sp^{2< 关键词： x薄膜')" href="#">CN_x薄膜 化学键合 退火温度 场致电子发射}     

Influence of temperature on structure as well as adhesion and friction and wear behavior of hydrogenated carbon nitride films prepared on silicon substrate

Hydrogenated-carbon nitride (CN_x:H) films were synthesized on silicon substrate in a large quantity by the pyrolysis of ethylenediamine in a temperature range of 700-950 °C. The influence of temperature on the morphology, structure, adhesion to substrate, and friction and wear behavior of CN_x:H films was investigated. It has been found that CN_x:H films obtained at 700 °C and 800 °C are amorphous, and those prepared at 900 °C and 950 °C consist of carbon nitride nanocrystal. Besides, CN_x:H film sample obtained at 700 °C has the maximum N content of 9.1 at.% but the poorest adhesion to Si substrate, while the one prepared at 900 °C has the lower N content and the highest adhesion to substrate. As a result, nanocrystalline CN_x:H (nc-CN_x:H) film synthesized at 900 °C possesses the best wear resistance when slides against stainless steel counterpart. N atom is incorporated into the graphitic network in three different bonding forms, and their relative content is closely related to temperature, corresponding to different adhesion as well as friction and wear behavior of the films obtained at different temperatures. Furthermore, the friction coefficient and antiwear life of as-deposited CN_x:H films vary with varying deposition temperature and thickness, and the film with thickness of 1.3 μm, obtained at 900 °C, has the longest antiwear life of over 180,000 s.     

Investigation of the sorption properties of thin Ge–S–AgI films deposited on cantilever-based gas sensor

Thin amorphous Ge–S–AgI films were thermally evaporated on cantilever sensors and their sorption properties were investigated upon exposure to volatile analytes, such as water, ethanol, acetone, and ammonia vapours. The films were smooth and uniform in thickness as revealed by atomic force and scanning electron microscopies. The exposure to the analytes resulted in a change of the resonance frequency of the cantilever. Initially, the largest dynamic responses (frequency shifts) were observed towards acetone, i.e. the cantilever acted as a resonant microbalance. When the sensor was exposed to ammonia, its molecules were chemisorbed on the surface of the sensitive layer. This surface modification increased the sensor sensitivity towards water molecules by the creation of new interaction sites. PACS 81.05.-t; 85.85.+j; 07.07.Df     

Surface nano/micro functionalization of PMMA thin films by 157 nm irradiation for sensing applications

Laser irradiation at 157 nm of polymethylmethacrylate (PMMA) thin films induces major variations of polymer film thicknesses from sorption (absorption/desorption) of methanol and ethanol analytes in the gas phase as much as 400%, in comparison to the film thickness variation of the non-irradiated areas. The structural changes of irradiated areas involve scission of polymeric chains, cross-linking and formation of new bonds. In addition, 157 nm induces surface and volume morphological changes in the nano/micro domain, with different shapes, depending on the irradiation conditions. The reversibility of the sorption processes suggests that the polymer swelling has its origin at the tendency of the system to increase its volume during sorption. The internal forces from sorption are higher than the weak dipole interactions between the polymer and the analytes and they are amplified following 157 nm irradiation. A simple qualitative model explains adequately the experimental results. 157 nm laser treatment forms the basis to engineer a novel class of polymer sensor arrays with enhanced detection efficiency of liquid/gas analytes.     

Deposition of SiOx barrier films by O2/TMDSO RF-PECVD

This paper reports that the SiOx barrier films are deposited on polyethylene terephthalate substrate by plasmaenhanced chemical vapour deposition （PECVD） for the application of transparent barrier packaging. The variations of 02/Tetramethyldisiloxane （TMDSO） ratio and input power in radio frequency （RF） plasma are carried out to optimize barrier properties of the SiOx coated film. The properties of the coatings are characterized by Fourier transform infrared, water vapour transmission rate （WVTR）, oxygen transmission rate （OTR）, and atomic force microscopy analysers. It is found that the 02/TMDSO ratio exceeding 2：1 and the input power over 200 W yield SiOx films with low carbon contents which can be good to the barrier （WVTR and OTR） properties of the SiOx coatings. Also, the film properties not only depend on oxygen concentration of the inlet gas mixtures and input power, but also relate to the surface morphology of the coating.     

Power-law scaling of proton conductivity in amorphous silicate thin films

Amorphous hafnium silicate, a-Hf_0.1Si_0.9O_x, thin film with thickness of 32, 41, 55, 80, 110, 120, 180 and 320 nm was prepared by multiple spin-cast process and the proton conductivity across the films was measured at intermediate temperatures (100-400 °C) in dry atmosphere. The morphologically- and compositionally-uniform films were prepared on a substrate as confirmed by SEM, RBS and XPS measurements. a-Hf_0.1Si_0.9O_x thin film clearly revealed the H/D isotope effect on ionic conductivity, indicating that protonic conduction is dominant in the measured temperature range. The films did not reveal thickness-dependent proton conductivity in dry air and the σ at given temperatures is almost constant at any thickness. No increment of σ in a-Hf_0.1Si_0.9O_x thin films by reduction of thickness might be related to the absence of the highly-conductive acid network with mesoscopically-sized length because of the relatively low concentration of Brønsted acid sites inside films.     

Optical models for the ellipsometric characterization of carbon nitride layers prepared by inverse pulsed laser deposition

Amorphous carbon nitride (CN_x) films were prepared by KrF excimer laser ablation of a graphite target in a nitrogen atmosphere in the inverse PLD geometry. From the ellipsometric point of view, the challenging properties of these films were their exponentially decaying thickness as a function of distance from the ablation source, accompanied by a laterally varying chemical composition and structure. Optical models were developed to accurately describe the dependence of film properties on distance from the ablation, layer thickness, and nitrogen pressure. Multi-layer models were used to characterize the surface roughness as well as lateral inhomogeneities. Multiple angles of incidence and multiple wavelengths were applied in the ranges of 66-72° and 250-1000 nm, respectively. A microspot capability of the spectroscopic ellipsometer (with a spot size of about 100 μm) was exploited to decrease the error caused by the lateral inhomogeneity within the measurement spot. Material properties were derived using the empirical Cauchy dispersion model as well as the Tauc-Lorentz parametric dielectric function model. These models allowed the quantitative determination of the band gap and the oscillator parameters in addition to the layer thicknesses and dielectric functions.     

Femtosecond laser interaction with pulsed-laser deposited carbon thin films of nanoscale thickness

The dependence of optical, electronic and thermal penetration zones on the thickness of nanoscale layers grown on silicon wafers is reported. Tetrahedral amorphous carbon (ta-C) and amorphous carbon nitride (a-C_xN_y) films were prepared by inverse pulsed laser deposition (IPLD). Single-pulse modification thresholds for femtosecond laser processing proved to be dependent on the actual film thickness below 60 nm for ta-C and 90 nm for a-C_xN_y. The modification behaviour was governed by multiphoton processes. An effective penetration depth of the laser radiation in a-C_xN_y was of ca. 110 nm in accordance with two-photon absorption. Both the emergence length of ballistic hot electrons and the heat diffusion length are negligible in these thin film materials. The lower bulk value of the threshold fluence of the a-C_xN_y films as compared to ta-C is mainly controlled by optical contributions due to nitrogen-related defects.     

The film thickness dependent thermal stability of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>:Ag thin films as high-temperature solar selective absorbers

The monolayer Al₂O₃:Ag thin films were prepared by magnetron sputtering. The microstructure and optical properties of thin film after annealing at 700 °C in air were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and spectrophotometer. It revealed that the particle shape, size, and distribution across the film were greatly changed before and after annealing. The surface plasmon resonance absorption and thermal stability of the film were found to be strongly dependent on the film thickness, which was believed to be associated with the evolution process of particle diffusion, agglomeration, and evaporation during annealing at high temperature. When the film thickness was smaller than 90 nm, the film SPR absorption can be attenuated until extinct with increasing annealing time due to the evaporation of Ag particles. While the film thickness was larger than 120 nm, the absorption can keep constant even after annealing for 64 h due to the agglomeration of Ag particles. On the base of film thickness results, the multilayer Al₂O₃:Ag solar selective thin films were prepared and the thermal stability test illustrated that the solar selectivity of multilayer films with absorbing layer thickness larger than 120 nm did not degrade after annealing at 500 °C for 70 h in air. It can be concluded that film thickness is an important factor to control the thermal stability of Al₂O₃:Ag thin films as high-temperature solar selective absorbers.     

Characterization of (As.Te)1-xSex thin films

1-x Se_x thin films (where x=0.20, 0.23, 0.27, 0.32 and 0.44) have been studied. Increasing the Se content was found to increase the optical energy gap and the activation energy for conduction of the investigated films. The optical energy gap of the As_0.40Te_0.40Se_0.20 films was increased up to 1.21 eV by increasing the film thickness to ∼120 nm, while thermal annealing at 480 K reduced it down to 0.83 eV. The decrease of the optical gap is discussed on the basis of amorphous–crystalline transformations. Received: 07 July 1997/Accepted: 30 July 1997     

Influence of UV light irradiation on film thickness distribution of tin oxide films by photochemical vapour deposition

Tin oxide (non-doped) films have been prepared by a photochemical vapour deposition (photo-CVD) from Tetramethyltin (TMT) (Sn(CH₃)₄) and O₂ (containing O₃). A low-pressure mercury lamp was used as the light source. The effect of the UV light irradiation on the film thickness distribution along 5 cm×5 cm area was examined. By piling Teflon films on the surface of the suprasil window, the light intensity of 184.9 nm UV wavelength of the low-pressure mercury lamp was controlled, while that of 253.7 nm wavelength through the Teflon hardly changed. As a result, the uniformity of the film thickness distribution was improved as the light intensity (184.9 nm) increased. The UV 184.9 nm light irradiation may have improved the uniformity of the reactive species distribution in the vapour phase, which may result in the formation of the uniform thickness distribution.     

氮掺杂碳纳米管负载铂催化剂的简易制备及催化性能

以氮掺杂碳纳米管为载体,在温和条件下采用简单的浸渍法制备得到铂催化剂,铂的粒径分布在4～7 nm,且氮掺杂碳纳米管无需进行预处理. 采用X射线衍射仪、扫描电子显微镜、透射电镜和能量色散X射线仪等对Pt/CN_x催化剂进行了详细的表征. 结果表明,氮掺杂碳纳米管中高含量的氮原子能够有效俘获Pt(IV) 离子,且表面的含氮官能团及亲水性能的提高都有利于铂纳米粒子的分散. Pt/CN_x催化剂在烯丙醇加氢反应中表现出高的催化性能及循环使用性能,这是由于铂纳米粒子的高分散性及铂与载体间强的连接性阻止了Pt的流失及聚积,从而避免生成Pt黑导致失活等.     

Crystallization of lead zirconate titanate films by laser annealing

The structure of lead zirconate titanate Pb(Zr _x Ti_{1 ? x} )O₃ thin films grown by chemical solution deposition on Si-SiO₂-Ti-Pt substrates has been studied using transmission electron microscopy and energy-dispersive analysis. Films crystallization has been performed using laser annealing. It has been found that, in contrast to isothermal annealing where nucleation on the platinum layer dominates, crystallization and growth of spherical perovskite crystals occur in the film bulk. The perovskite phase crystal size increases from 10 to 120 nm with increasing laser beam energy.     

氮对类金刚石薄膜的微观结构内应力与附着力的影响

采用原子力显微镜(AFM)、俄歇电子能谱(AES)和显微压痕分析等手段对射频等离子体增强化学气相沉积法制备的掺氮类金刚石(DLC：N)薄膜的微观结构和力学性能进行了研究.结果表明,随着含氮量的增加,DLC薄膜的AFM表面形貌中出现了几十纳米的颗粒,原子侧向力显微镜和AES分析表明这种纳米颗粒是x大于0.126的非晶氮化碳CN_x结构.这种非晶DLC/CN_x的纳米复合结构,减小了薄膜的内应力,从而提高了薄膜与衬底的附着力. 关键词： 类金刚石碳膜 微观结构 附着特性     

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.     

Quantitative measurement of local elasticity of SiOx film by atomic force acoustic microscopy

<正>In this paper the elastic properties of SiO_x film are investigated quantitatively for local fixed point and qualitatively for overall area by atomic force acoustic microscopy(AFAM) in which the sample is vibrated at the ultrasonic frequency while the sample surface is touched and scanned with the tip contacting the sample respectively for fixed point and continuous measurements.The SiO_x films on the silicon wafers are prepared by the plasma enhanced chemical vapour deposition(PECVD).The local contact stiffness of the tip-SiO_x film is calculated from the contact resonance spectrum measured with the atomic force acoustic microscopy.Using the reference approach,indentation modulus of SiO_x film for fixed point is obtained.The images of cantilever amplitude are also visualized and analysed when the SiO_x surface is excited at a fixed frequency.The results show that the acoustic amplitude images can reflect the elastic properties of the sample.     

Substrate effects on the microstructure of hydrogenated amorphous carbon films

In this work, plasma enhanced chemical vapour deposition was used to prepare hydrogenated amorphous carbon films (a-C:H) on different substrates over a wide range of thickness. In order to observe clear substrate effect the films were produced under identical growth conditions. Raman and near edge X-ray absorption fine structure (NEXAFS) spectroscopies were employed to probe the chemical bonding of the films. For the films deposited on silicon substrates, the Raman I_D/I_G ratio and G-peak positions were constant for most thickness. For metallic and polymeric substrates, these parameters increased with film thickness, suggesting a change from a sp³-bonded hydrogenated structure to a more sp² network, NEXAFS results also indicate a higher sp² content of a-C:H films grown on metals than silicon. The metals, which are poor carbide precursors, gave carbon films with low adhesion, easily delaminated from the substrate. The delamination can be decreased/eliminated by deposition of a thin (∼10 nm) silicon layer on stainless steel substrates prior to a-C:H coatings. Additionally we noted the electrical resistivity decreased with thickness and higher dielectric breakdown strength for a-C:H on silicon substrate.     

Ablation of silicon suboxide thin layers

We investigate the ablation of SiO _x thin films on fused silica substrates using single-pulse exposures at 193 nm and 248 nm. Two ablation modes are considered: front side (the surface of a film is irradiated from above) and rear side (a film is irradiated through its supporting substrate). Fluence is varied from below 200 mJ/cm² to above 3 J/cm². SiO _x films of thickness 200 nm, 400 nm, and 600 nm are ablated. In the case of rear-side illumination, at moderate fluences (around 0.5 mJ/cm²) the ablation depth corresponds roughly to the film thickness, above 1 J/cm² part of the substrate is ablated as well. In the case of front-side ablation the single-pulse ablation depth is limited for all film thicknesses to less than 200 nm even at fluences up to 4 J/cm². Experimental results are discussed in relation to film thickness, fluence, and ablation mode. Simple numerical calculations are performed to clarify the influence of heat transport on the ablation process.