Effects of hydrogen dilution on CNx film properties deposited using rf PECVD from a mixture of ethane,nitrogen and hydrogen

Carbon nitride (CN_x) thin films were deposited using radio frequency plasma enhanced chemical vapor deposition (rf PECVD) from a mixture of ethane (C₂H₆), nitrogen (N₂) and hydrogen (H₂) gases. The C₂H₆ and N₂ flow rates were kept constant, while the H₂ flow rate was varied. The effects of hydrogen dilution on the growth rate and structural properties of the films were studied. It was found that a significant increase in the films growth rate was observed with the introduction of H₂ at as low as 25 standard cubic centimeters per minute (sccm). A set of CN_x films deposited from C₂H₆:N₂ mixture without any inclusions of H₂ were also presented in this work as a reference to compare the differences between those two sets and to understand the roles of H₂ to the films properties. At highest H₂ flow rate, the structure of the films changed from polymeric to graphitic and the quenching of PL was observed. Furthermore, higher N incorporation with lower E_g was obtained for these films compared to those of C₂H₆:N₂ films. The change in the structure of the films corresponds to changes in their chemical bonding. As N incorporation increased, the porosity of the films increases and thus affects the disorder in the film structures.     

Metal-doped (Ti, WC) diamond-like-carbon coatings: Reactions with extreme-pressure oil additives under tribological and static conditions

In contrast to non-doped diamond-like-carbon (DLC) coatings, reliable chemical evidence of the reactions between metal-doped DLC coatings and oil additives under tribological conditions using state-of-the-art surface-sensitive chemical analyses is still scarce. In this study we have investigated the reactivity of metal-doped (Ti, WC) DLC coatings with the extreme-pressure (EP) dialkyl dithiophosphate additive — without the presence of a steel counter body in the contact that befogs the actual coating reactions. Static “reactivity” experiments without any tribological or mechanical effects were also performed to provide a further insight into the lubrication mechanisms. The results confirmed the chemical reactions between the EP additive and all the DLC coatings, as well as their oxidation during the tribological contacts. We measured an about 10-times higher chemical activity (a 25-fold P/S ratio increase) for the Ti-doped DLC compared to the WC-doped or non-doped DLC, which also agrees with it having the lowest amount of wear in this study. We suggest that the Ti-DLC boundary lubrication is achieved via binding sites at the O vacancies present in the Ti-doped DLC coating. The data also clearly show, in contrast to most of literature reports, that even though small, some direct chemical activity between the W-DLC and the dialkyl dithiophosphate EP additive is also possible without any iron catalytic effect. However, the chemical changes were significantly smaller, also allowing coating graphitization, which might be one of the reasons for the 50% higher wear of the WC-doped compared to the Ti-doped DLC.     

过滤阴极真空电弧法制备四面体非晶碳薄膜

利用离面双弯曲过滤阴极其空电弧沉积系统，在Ф200mm单晶硅片上制备四面体非晶碳薄膜。利用Dectek3型表面轮廓仪检验膜厚均匀性(小于5％)，并利用扫描电子显微镜(SEM)、原子力显微镜(AFM)、激光拉曼光谱(Raman)、X射线光电子谱(XPS)以及纳米压痕(Nano—Indenter)仪器测试薄膜的性能和结构。结果表明：试验制备的薄膜是四面体非晶碳薄膜，其中sp^3键含量高达80％以上，薄膜表面纯净，几乎没有大颗粒的污染，表面粗糙度(Rq)小于0．3nm(取样面积1μm^2)，薄膜硬度可达50GPa，杨氏弹性模量高于550GPa。     

Core level and valence band investigation of WO3 thin films with synchrotron radiation

In this work, the electronic properties of the surface of WO₃ films with thickness of 150 nm, thermally evaporated in high vacuum onto Si(100) substrates and pre-treated in air by a 24-h-long annealing at 300 °C and 500 °C (obtaining polycrystalline monoclinic samples) have been studied by surface and bulk sensitive core level (W 4f) and angle integrated valence band photoemission using synchrotron radiation (ELETTRA Synchrotron). The photon energy ranged from 50 eV to 200 eV. The line shape analysis of W 4f core level spectra has shown that the surface presents a sub-stoichiometric WO₃ component assigned to oxygen vacancies ultimately responsible for the gas sensitivity of this material. Correspondingly, valence band spectra show well-defined metallic states W 5d in the gap and near the Fermi level. The variations of surface chemical composition caused by Ultra High Vacuum annealing, and prolonged exposure to UV beam has been monitored by changes in spectral line shape. A general consequence of annealing in vacuum is the segregation of oxygen from the bulk toward the surface as confirmed by independent scanning tunnelling spectroscopy measurements.     

X-ray photoelectron spectroscopy (XPS) and FTIR studies of vanadium barium phosphate glasses

Barium vanadophosphate glasses, having composition 50BaO–xV₂O₅–(50 − x)P₂O₅, (x = 0–50 mol%), were prepared by conventional melt quench method. Density, molar volume and glass transition temperature (T_g) were measured as a function of V₂O₅ content. Structural investigation was done using XPS and FTIR spectroscopy. First, substitution of the P₂O₅ by the V₂O₅ in the metaphosphate 50BaO–50P₂O₅ glass increases the density and T_g and decreases the molar volume. When the amount of V₂O₅ increases, all these properties show a reverse trend. XPS measurement found in the O1s, P2p, and V2p core level spectra indicate the presence of primarily P–O–P, P–O–V and V–O–V structural bonds, the asymmetry in the P 2p spectra indeed arises from the spin-orbit splitting of P 2p core level, and more than one valence state of V ions being present. IR spectroscopy reveals the depolymerization of the phosphate glass network by systematic conversion of metaphosphate chains into pyrophosphate groups and then orthophosphate groups. Even though metaphosphate to pyrophosphate conversion is taking place due to breaking of P–O–P linkages, formation of P–O–V and P–O–Ba linkages provide cross linking between short P-structural units, which make the glass network more rigid. Above 10–20 mol% V₂O₅ content, network is highly depolymerized due to the formation of orthophosphate units and V–O–V bridge bonds, resulting in poor cross-linking, making the glass network less rigid.     

Polyaniline/Vanadium oxide composites: An effective control in morphology by varying reactant concentrations

A one pot synthesis protocol is presented for the realization of organic/inorganic hybrid nanostructures comprised of polyaniline and vanadium oxide. The polyaniline/vanadium oxide hybrid morphology is tailored by controlling the relative concentration of reactants which resulted in diverse morphologies ranging from nanorods, combined nano/microrods to porous nano/microspheres. Temporal evolution of morphology is investigated to elucidate the formation mechanism in detail. The prepared composites exhibit enhanced thermal stability in comparison to pure polyaniline which may be attributed to the strong chemical combination of vanadium oxide and polyaniline within the composites as prevailed by FTIR and TGA analysis of the products. This simple and controllable approach for synthesizing the organic/inorganic hybrid material should have future applications in energy storage devices, sensors and many more.     

Resonant Energy Transfer can Trigger Multiexciton Recombination in Dense Quantum Dot Ensembles

Core/shell quantum dots/quantum rods are nanocrystals with typical application scenarios as ensembles. Resonance energy transfer is a possible process between adjacent nanocrystals. Highly excited nanocrystals can also relax energy by multiexciton recombination, competing against the energy transfer. The two processes have different dependencies and can be convolved, resulting in collective properties different from the superposition of the individual nanocrystals. A platform to study the interplay of energy transfer and multiexciton recombination is presented. CdSe/CdS quantum dot/quantum rods encapsulated in amphiphilic micelles with an interparticle distance control by spacer ligands are used for time‐resolved photoluminescence and transient absorption experiments. At exciton populations around one, the ensemble starts to be in a state where energy transfer can trigger multiexciton Auger recombination, altering the collective dynamics.     

The formation of a SiOx interfacial layer on low-k SiOCH materials fabricated in ULSI application

The characterizations of SiOCH films using oxygen plasma treatment depends linearly on the O₂/CO flow rate ratio. According to the results of Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses, it was found that the carbon composition decreases with increasing O₂/CO flow rate ratio, because more carbon in the Si–O–C and Si–CH₃ bonds on the film surface would be converted by oxygen radicals. It was believed that the oxygen plasma could oxidize the SiOCH films and form a SiO_x interfacial capping layer without much porosity. Moreover, the result of FTIR analysis revealed that there was no water absorbed on the film. A SiO₂-like capping layer formed at the SiOCH film by the O₂/CO flow rate ratio of 0.75 had nearly the same dielectric properties from the result of capacitance–voltage (C–V) measurement in our research.     

Multivariate calibration of on-line enrichment near-infrared (NIR) spectra and determination of trace lead in water

An on-line enrichment near-infrared spectroscopy (NIRS) technique was developed in order to improve the sensitivity for the determination of trace heavy metal lead. Trace Pb²⁺ was enriched by chelating resin with on-line enrichment equipment and then the enriched lead on the resin was directly determined by near-infrared diffuse reflectance spectroscopy without elution procedure for simplicity of measurements. Partial least squares (PLS) regression was used to build models between the corrected spectra and concentrations of Pb²⁺, and segmental cross-validation was used to search for a reasonable number of PLS factors. The results showed that NIR spectra and concentrations of Pb²⁺ had a good linear relationship with the maximum of correlation coefficient of 0.9228 in the 1006–1383 nm region. The minimum RMSEP was 0.4777 mg L^− 1 when the latent variable number was 5 by using the region of 1006–1383 nm. The limit of detection (LOD) of lead was 0.2384 mg L^− 1 in this case. This study demonstrates that the prediction of trace heavy metal lead concentrations by NIRS is feasible with enrichment technique.     

NIR在导热油定性识别中的应用研究

本文采用近红外光谱技术(NIR)区分识别矿物型和合成型两种类型的导热油,准确率100%。同时以区分识别矿物型导热油为例,对同一类型但属不同品牌的导热油进行区分识别,平均预测准确率95%。研究表明,该方法可用于定性识别不同性能的导热油。     

渐进因子分析法及其在Au/Ni/Si薄膜俄歇深度剖面研究中的应用

将渐进因子分析法应用于俄歇深度剖面的化学态研究。通过对Au／Ni／Si薄膜样品深度剖析过程的渐进因子分析，最终获得了各元素的化学状态和深度分布，并发现Au／Ni／Si样品中Ni／Si界面在室温下已发生反应，生成富Si的NixSi化合物层。样品经真空退火处理后，Ni／Si界面进一步反应生成Ni2Si合金，而原有的NixSi化合物含量相对减少，并向Si基体侧扩展，同时Ni穿透Au膜在样品表面富集。渐进因子分析的结果与XPS分析相一致。     

LY12铝合金表面有机-无机杂化膜特性研究

作为-种有机-无机杂化材料,倍半硅氧烷(SSO)近年来被发现其具有良好的防腐性能,并有望成为传统的防腐材料-铬酸盐转化膜的替代物.本文用乙烯基三甲氧基硅烷(VMS)通过溶胶凝胶法制得了SSO,并涂敷于LY12铝合金表面.用(EIS)对不同水解时间下制得的VMS膜层的结构进行了表征.水解3d所获得的VMS在不同固化时间下的EIS谱图上出现了一个新的时间常数,证实了在VMS膜层与铝合金基体之间产生了一个新的中间层.根据实际的可能性,该层包含Al-O-Si,膜层与基体以化学键合;然而,完全水解的VMS膜层的EIS谱图中没有这个新的时间常数.不同水解时间的VMS膜层的EIS谱图表明为获得致密的膜层且与基体间以化学键合,VMS需在本文反应条件下水解3d.     

Synthesis of carbon nitride powder by selective etching of TiC0.3N0.7 in chlorine-containing atmosphere at moderate temperature

We reported the synthesis of carbon nitride powder by extracting titanium from single inorganic precursor TiC_0.3N_0.7 in chlorine-containing atmosphere at ambient pressure and temperature not exceeding 500 °C. The TiC_0.3N_0.7 crystalline structure acted as a template, supplying active carbon and nitrogen atoms for carbon nitride when it was destroyed in chlorination. X-ray diffraction data showed that the obtained carbon nitride powders were amorphous, which was in good agreement with transmission electron microscope analysis. The composition and structure of carbon nitride powders were analyzed by employing Fourier transform infrared spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. Results indicated that disorder structure was most likely for the carbon nitride powders and the N content depended greatly on the chlorination temperature. Thermal analysis in flowing N₂ indicated that the mass loss started from 300 °C and the complete decomposition occurred at around 650 °C, confirming the low thermal stability of the carbon nitride material.     

Titanium-silicon oxide film structures for polarization-modulated infrared reflection absorption spectroscopy

We present a titanium-silicon oxide film structure that permits polarization modulated infrared reflection absorption spectroscopy on silicon oxide surfaces. The structure consists of a ∼ 6 nm sputtered silicon oxide film on a ∼ 200 nm sputtered titanium film. Characterization using conventional and scanning transmission electron microscopy, electron energy loss spectroscopy, X-ray photoelectron spectroscopy and X-ray reflectometry is presented. We demonstrate the use of this structure to investigate a selectively protein-resistant self-assembled monolayer (SAM) consisting of silane-anchored, biotin-terminated poly(ethylene glycol) (PEG). PEG-associated IR bands were observed. Measurements of protein-characteristic band intensities showed that this SAM adsorbed streptavidin whereas it repelled bovine serum albumin, as had been expected from its structure.     

Photoacoustic Analysis of Pigments from Archeological Ceramics

Photoacoustic spectroscopy (PAS) is widely used for diverse applications in different areas. These include studies in material, environmental, and life sciences. In the present work the study of pigments from pottery surfaces and volumes of Mexican (Aztec) and Poblana cultures that were developed in central Mexico from 1325 to 1521 and 1521 to 1800, respectively, is reported. The optical absorption spectra from each archeological sample was obtained using PAS. The superficial spectra were also compared with standard color pigments and archeological registers. Complementary energy dispersive spectroscopy (EDS) analysis of these archeological potteries gave us their elemental composition which agreed with other studies about their composition and technology of the pottery manufacturing.     

Microscopic investigations of chemo-mechanical polishing of tungsten

The influence of aqueous solutions of KNO₃, KClO₃, and KIO₃ on tungsten surfaces has been investigated in terms of the degree of surface oxidation, metal dissolution and interfacial friction. The surface properties of tungsten films have been measured ex-situ with X-ray photoelectron spectroscopy and in situ with atomic force microscopy. Measurements of the surface composition reveal a greater degree of oxidation for surfaces treated in solutions of KIO₃ in comparison to the other solutions. This increase in surface oxidation is correlated to a greater rate of localized film dissolution that occurs under the action of the scanning probe tip. In turn, the process of material removal is the predominant origin of the higher interfacial friction measured at tungsten surfaces immersed in KIO₃ solutions, as compared to KClO₃ and KNO₃ solutions. Collectively, these measurements portray a fundamental pathway of material removal at tungsten surfaces in the presence of oxidizing species and highlight complementary roles of chemical and mechanical action.     

激光诱导击穿光谱及其在元素分析中的应用

激光诱导击穿光谱是一种新的元素分析方法,但仍处于不断完善之中。利用它可以分析不同形态样品的成分,因此在成分分析和微量元素检测方面具有重要的应用前景。本文阐述了激光击穿诱导光谱仪的基本原理和激光诱导击穿光谱在多个领域中的应用,研究内容涉及固体样品、液体样品、气体样品、微量杂质分析和成分深度剖析等,并分析了基体效应、自吸收效应、测量时间、环境气体、激光参数等对激光诱导击穿光谱分析结果的影响。     

An IR and XPS spectroscopy assessment of the physico-chemical surface properties of alumina–YAG nanopowders

Well-dispersed nano-crystalline transition alumina suspensions were mixed with yttrium chloride aqueous solutions, with the aim of producing by spray-drying Al₂O₃–Y₃Al₅O₁₂ (YAG) composite powders of increasing YAG vol.%. Two samples were prepared, with different Y content, corresponding to 5 and 20 YAG vol.%, respectively. Both samples were then treated at either 600 or 1150 °C. The obtained powders were characterized by X-Ray Diffraction (XRD), X-ray Photoelectron Spectroscopy (XPS), Fourier Transform Infra Red (FT-IR) spectroscopy and compared to three reference samples: commercial nano-crystalline transition alumina, YAG and Y₂O₃. YAG powders were obtained by co-precipitation route whereas Y₂O₃ powders were yielded by spray-drying of a yttrium chloride aqueous solution. Modification of physico-chemical properties of the surface of alumina nanoparticles were assessed by combining XPS and FT-IR spectroscopies. On the basis of the results obtained, a possible model is proposed for the structure of the obtained composites, in which Y basically reacts with more acidic hydroxyls of alumina, by forming Y-rich surface grains, the extension of which depends on the thermal treatment.     

Spatially resolved positron annihilation spectroscopy on friction stir weld induced defects

A friction stir welded (FSW) Al alloy sample was investigated by Doppler broadening spectroscopy (DBS) of the positron annihilation line. The spatially resolved defect distribution showed that the material in the joint zone becomes completely annealed during the welding process at the shoulder of the FSW tool, whereas at the tip, annealing is prevailed by the deterioration of the material due to the tool movement. This might be responsible for the increased probability of cracking in the heat affected zone of friction stir welds. Examination of a material pairing of steel S235 and the Al alloy Silafont36 by coincident Doppler broadening spectroscopy (CDBS) indicates the formation of annealed steel clusters in the Al alloy component of the sample. The clear visibility of Fe in the CDB spectra is explained by the very efficient trapping at the interface between steel cluster and bulk.