Theory of relative sputtering rates in GDOES

A detailed theory of relative sputtering rates for glow discharge optical emission spectroscopy (GDOES) is presented for the first time. The theory suggests that such sputtering rates should be nearly independent of plasma conditions. This is supported by experimental results for r.f. GDOES under varying applied power or varying pressure. Relative sputtering rates are calculated for a range of cast irons, high‐alloy steels and zinc–aluminium alloys. Within measurement uncertainties, the calculated rates agree with measured relative sputtering rates. Copyright © 2003 John Wiley & Sons, Ltd.     

Heavy phosphate adsorption on amorphous ITO film electrodes: nano-barrier effect for highly selective exclusion of anionic species

We prepared an amorphous indium tin oxide (ITO) film and studied it with respect to its surface characterization and the effect of phosphate adsorption on its electrochemical properties. The film was deposited using RF sputtering under ambient low-oxygen conditions at room temperature. The XPS results revealed that the amount of phosphate adsorbed on the amorphous ITO film was more than 4.6 times greater than that adsorbed on commercially available polycrystalline ITO film in spite of the smaller microscopic surface area of the former. Electrochemical responses for anionic species such as L-ascorbic acid (AA) and 3,4-dihydroxyphenylacetic acid (DOPAC) on the phosphate-adsorbed ITO film electrodes were more effectively suppressed at the amorphous ITO film electrode than at the polycrystalline ITO film electrode when a phosphate-containing electrolyte was used. Such suppression could be attributed to the electrostatic repulsion between the anionic species and more heavily adsorbed phosphate on our amorphous ITO film electrode surface. This effect is made more pronounced by increasing the phosphate concentration to 1 mM. With 1 mM phosphate, the amorphous ITO film electrode showed the highest selectivity for dopamine (DA) against the anionic species, namely, 880 for DA/AA and 330 for DA/DOPAC, respectively. In contrast, the selectivity was 120 for DA/AA and 20 for DA/DOPAC with the polycrystalline ITO film electrode.     

Quantitative depth profiling in glow discharge spectroscopies – A new deconvolution technique to separate effects of an uneven erosion crater shape

An algorithm is presented as a concept for the quantification in direct current and radiofrequency glow discharge (GD) modes for GD optical emission spectroscopy. The algorithm is divided into excitation and sputtering part and thus it is possible to distinguish between the different excitation processes and to consider equivalent sputtering crater formations in both modes. Intensity-time profiles are affected corresponding to the method by several effects. One important effect is that sputtering occurs at a single time in different depths because of curved crater bottoms, this is usually called crater effect. The main purpose is to introduce an iterative deconvolution technique which for the quantification numerically takes into account the curved sputtering crater bottom. Input data for the deconvolution technique are the calibrated mass-time profile, the partial densities of the sample constituents and the measured final shape of the sputtering crater. Using a relatively simple model for ion sputtering the deconvolution technique improves iteratively the calculated layer structure by means of information on crater formation. The mathematical handling is illustrated for the quantification of a depth profile of a multilayer sample of ten 100 nm layers. The resulting concentration-depth profile reflects excellently the real elemental distribution of the multilayer system.     

A new reversed-phase liquid chromatographic/tandem mass spectrometric method for analysis of underivatised amino acids: evaluation for the diagnosis and the management of inherited disorders of amino acid metabolism

Seventy-six compounds of biological interest for the diagnosis of inherited disorders of amino acids (AA) metabolism have previously been demonstrated to be detectable in positive mode electrospray ionisation tandem mass spectrometry (ESI-MS/MS), after separation by ion-pairing reversed-phase liquid chromatography (RPLC). The separation method used tridecafluoroheptanoic acid as ion-pairing agent, and a gradient of acetonitrile for the elution of the most retained compounds. This method had previously been demonstrated to be suitable for the qualitative diagnosis of many AA disorders, and for the quantitative measurement of 16 AA in biological fluids, using their stable isotope labelled (SIL) AA as internal standard. For quantification of the other AA, an internal standard was chosen among the available SIL-AA, as close as possible to the analyte to be measured, in terms of structural analogy, and of retention time in the chromatographic system. The performances of the quantitative analysis of the other AA to be measured are reported here. They show validated results for several AA, allowing their accurate quantification, with another SIL-AA as internal standard. For some other AA, quantitative results were not accurate, allowing only semi-quantitative or qualitative determination for these parameters.     

团簇离子枪对CH3NH3PbI3钙钛矿薄膜的影响研究

以氩离子团簇为溅射源,对采用一步旋涂法制备的CH₃NH₃PbI₃钙钛矿薄膜进行溅射实验,通过XPS分析检测样品表面Pb元素的价态变化。结果表明,新制备的钙钛矿薄膜材料表面没有检测出Pb⁰,而经过团簇离子枪溅射的样品中部分Pb²⁺还原成Pb⁰,证明了氩离子团簇刻蚀对钙钛矿材料具有破坏作用。一方面,溅射时间的增加以及团簇离子枪能量的增大均会加大钙钛矿材料的损伤程度;另一方面,离子枪团簇规模大小与溅射损伤程度呈近抛物线关系。因此,在进行此类样品表面清洁时,应尽量减小离子枪能量和溅射时间,选择较小或较大的团簇规模以减少对样品的损伤。该研究对于钙钛矿样品在进行XPS检测和数据分析时具有参考价值。     

Sputtering of aluminium alloys in the grimm glow lamp for emission spectrochemical analysis

The effects of surface roughness, grain size and target thickness on the cathodic sputtering and emission intensities of spectral lines in the Grimm glow lamp have been investigated for samples of aluminium alloys. The intensities of the alloying elements changed with discharge time because the θ phase (Al²Cu) and β phase (Si) are sputtered selectively. The selective sputtering of the θ phase in an Al—8% Cu alloy can be decreased and the intensities can be made constant during discharge by polishing the target surface with coarse sand paper before discharge. When a fine-grained Al—4.9% Cu—7.2% Si alloy sample was used as a target, the intensities remained nearly constant during discharge. The sample preparation for obtaining fine-grained samples involves casting the melt in a metal mould. The thickness of disk samples influences not only the sample temperature but the current, sputtering and intensities. Special attention should be paid to the thickness for the determination of copper in aluminium alloys.     

催化裂解低碳烷烃制备碳纳米管薄膜

碳纳米管性质奇特、用途广泛[1]。目前制备碳纳米管薄膜的方法主要有电弧放电法[2]、催化裂解[3]、及真空过滤碳纳米管悬浮液制备“巴基管纸”(Buckypaper)[4]等。本文采用镀镍基板催化裂解低碳烷烃法制备碳纳米管薄膜,考察了镀膜时间、蚀刻和氨水处理等条件对碳纳米管薄膜产物形貌的影响。1　实验部份1 1　镀膜与后处理采用离子溅射法在硅酸盐基板上镀镍,镀镍电流7 5mA,镀镍时间分别为2min、15min、30min、45min或60min;对镀镍基板再进行蚀刻(蚀刻电流7 5mA,蚀刻时间2min)或用氨水浸泡处理(含NH325%,超声振荡30min),然后烘干备用。1 …     

Synthesis of thin-film electrodes based on LiPON and LiPON-LLTO-LiPON

Thin lithium-conducting amorphous films of lithium phosphorus oxynitride (LiPON) are synthesized by high-frequency (HF) magnetron sputtering. The effect of sputtering conditions (HF power, support temperature, working gas pressure, and deposition time) on the microstructure of LiPON films is studied. The optimal conditions of HF magnetron sputtering that allow dense, uniform, crack-free, air-stable, amorphous thin LIPON films to be formed are studied. The composite solid electrolyte LiPON-LLTO-LiPON is synthesized based on LiPON films and the La_{2/3 ? x} Li_3x TiO₃ (LLTO) ceramics characterized by the high conductivity with respect to lithium ions but unstable in contact with metal lithium. Its microstructure and electrophysical properties are studied. It is found that the LiPON film prevents the chemical reaction of metal lithium with the LLTO solid electrolyte. Due to the high chemical stability and the enhanced conductivity, the composite solid electrolyte based on LiPON-LLTO-LiPON can be used in electrochemical devices.     

Nanoparticle ensemble electrodes: fabrication by short-pulse sputtering and characterization by scanning probe microscopy and voltammetry

Nanoparticle ensembles (NPEs) are useful platforms to study the electrocatalytic properties of nano-sized materials. A fabrication method that guarantees a good control over the morphological features, as well as a reliable characterization, are required for a proper analysis of electrochemical data measured on these electrodes. This work describes a simple, fast, and clean procedure for the fabrication of random arrays of Pt nanoparticles (NPs) supported on flat electrodes by sputtering of metal targets for short times. Besides, a strategy for morphological characterization of the ensembles based on a combination of scanning tunneling microscopy (STM) and voltammetric information is reported. The method permits to attain good control on the size and coverage of NPs in the ensemble through the sputtering parameters. Pt NPs sputtered on highly ordered pyrolytic graphite (HOPG) grow bidimensionally with heights in the range 0.8–1.2 nm, while the lateral diameters of NPs and the surface coverage are adjusted in the range 2–15 nm by controlling both the sputtering current and the sputtering time. The stability and electrochemical behavior for proton reduction under mixed control in acid media were evaluated on HOPG-supported Pt ensembles fabricated by the described method.     

Photo- and thermally stimulated relaxation processes in pre-irradiated atomic solids

Atomic and electronic relaxation processes in pre-irradiated atomic solids are considered using preliminary irradiated by an electron beam solid Ar as an example. The results of real-time-correlated study are presented for the first time with an accent on recently found anomalous low-temperature sputtering of Ar atoms from the surface. The experiments were performed using a set of activation spectroscopy methods—thermally stimulated exoelectron emission (TSEE) thermally stimulated luminescence (TSL) in combination with measurements of the sputtering yield. Solid evidence of thermally induced charge recombination mechanism is obtained. Mechanism of energy transfer based on the crowdion model is discussed. Photo-stimulated sputtering from pre-irradiated rare gas solids (RGS) is predicted.     

Microscopic study of ultra-thin gold layers on polyethyleneterephthalate

Continuous and discontinuous gold layers sputtered on polyethyleneterephthalate (PET) were characterized using atomic force microscopy (AFM), scanning electron microscopy (SEM) and by reflection of microwave radiation. The changes in the surface morphology of the continuous and discontinuous gold layers as a function of the sputtering time were clearly observed by AFM technique. SEM imaging of very thin gold layers was adversely affected by specimen charging. For medium sputtering times, when a continuous gold coverage is already formed, the SEM technique still show the presence of regions with very thin gold coverage which gradually disappear at longer sputtering times. Both, the AFM and SEM techniques confirmed that in the course of the gold deposition the initially small gold clusters grow and finally associate in a continuous layer. It was shown that the sub-microne metallic structures could be modeled by artificial, significantly larger structures prepared on PET by lithographic etching.     

Amorphous carbon nitride as an alternative electrode material in electroanalysis: Simultaneous determination of dopamine and ascorbic acid

Boron-doped diamond (BDD) films are excellent electrode materials, whose electrochemical activity for some analytes can be tuned by controlling their surface termination, most commonly either to predominantly hydrogen or oxygen. This tuning can be accomplished by e.g. suitable cathodic or anodic electrochemical pretreatments. Recently, it has been shown that amorphous carbon nitride (a-CN_x) films may present electrochemical characteristics similar to those of BDD, including the influence of surface termination on their electrochemical activity toward some analytes. In this work, we report for the first time a complete electroanalytical method using an a-CN_x electrode. Thus, an a-CN_x film deposited on a stainless steel foil by DC magnetron sputtering is proposed as an alternative electrode for the simultaneous determination of dopamine (DA) and ascorbic acid (AA) in synthetic biological samples by square-wave voltammetry. The obtained results are compared with those attained using a BDD electrode. For both electrodes, a same anodic pretreatment in 0.1 mol L⁻¹ KOH was necessary to attain an adequate and equivalent separation of the DA and AA oxidation potential peaks of about 330 mV. The detection limits obtained for the simultaneous determination of these analytes using the a-CN_x electrode were 0.0656 μmol L⁻¹ for DA and 1.05 μmol L⁻¹ for AA, whereas with the BDD electrode these values were 0.283 μmol L⁻¹ and 0.968 μmol L⁻¹, respectively. Furthermore, the results obtained in the analysis of the analytes in synthetic biological samples were satisfactory, attesting the potential application of the a-CN_x electrode in electroanalysis.     

XPS研究等离子体处理的聚苯乙烯表面结构

采用不同功率(10、20、60、100、150W)、时间(0.5、1、3、6、15和30分),在Ar、N_2、O_2、H_2和空气中,对聚苯乙烯(PS)片基进行了等离子体处理。 通过XPS技术、谱图的拟合、差谱分析和Ar~+小功率剖面处理,研究了PS表面组成与结构变化,指出处理的聚苯乙烯表面有C—O、C—NH_2、C=O、COOH和基团嵌入,因而改变了材料特性。     

Some observations on the mechanisms of atomization in atomic absorption spectrometry with atom-trapping and electrothermal techniques

The mechanisms of collection and release of sixteen elements in atom-trapping atomic absorption spectrometry with a water-cooled silica trap in an air-acetylene flame are examined. Ag, Au, Cd, Co, Cu, Fe, Ni, Pb, Se and Zn appear to accumulate as metals whilst K, Li, Na, Cr, Mg and Mn are trapped as silicates or oxides. Al and V are also trapped as oxides, but were not studied further. No evidence could be found that the surface temperature of the trap exceeds 1700 K during the release cycle. Plots of appearance time of atoms vs. m.p. suggest that while direct evaporation can play a part in atomization, sputtering by energetic species in the scouring flame gases may explain the appearance of gaseous atoms at the relatively low temperatures involved. The atomization phenomena are related to those observed with electrothermal atomizers based on carbon and tantalum. It is suggested that sputtering processes may also be involved in such atomizers.     

真空离子溅射法制备TiO2∶Au复合纳米纤维新型光催化剂及其 降解乙醛性能研究

采用静电纺丝技术与真空离子溅射相结合的方法制备了TiO2∶Au复合纳米纤维, 并采用SEM和X射线电子能谱仪对其进行了表征. 结果表明TiO2∶Au纳米纤维的表面形态能通过Au沉积时间得到很好的控制. 同时在紫外光照射下采用乙醛体系考察了TiO2纳米纤维和TiO2∶Au复合纳米纤维催化剂降解乙醛性能, 结果证明TiO2∶Au复合纳米纤维具有更好的催化效率, 紫外光照射70 min后乙醛被完全降解.     

Selective Detection of Dopamine and Its Metabolite,DOPAC, in the Presence of Ascorbic Acid Using Diamond Electrode Modified by the Polymer Film

The surface of boron‐doped diamond (BDD) electrode is modified by the polymer film for the first time. The cationic polymer film of N,N‐dimethylaniline (DMA) is electrochemically deposited on BDD electrode surface. This polymer (PDMA) film‐coated BDD electrode is used as a sensor which selectively detect dopamine (DA) in the presence of ascorbic acid (AA). This electrode also can detect both DA and its metabolite, 3,4‐dihydroxy phenyl acetic acid (DOPAC) in the presence of AA in the range of the physiological concentrations of these species. Favorable ionic interaction (i.e., electrostatic attraction) between the PDMA film and AA or DOPAC lowers their oxidation potentials and enhances the current response for AA and DOPAC compared to that at the bare electrode. The PDMA film also shows a hydrophobic interaction with DA and DOPAC. In cyclic voltammetric measurements, the PDMA film‐coated electrode can successfully separate the oxidation potentials for AA and DA coexisting in the same solution and the separation is about 200 mV. AA oxidizes at more negative potential than DA. In square‐wave voltammetry, the sensitivity of the PDMA film‐coated BDD electrode for DA in the presence of higher concentration of AA is higher than that of the PDMA film‐coated glassy carbon electrode. The hydrodynamic amperometric experiments confirm that the oxidation of AA is not affected by the oxidized product of DA and vice versa. So, unlike the bare electrode the catalytic oxidation of AA by the oxidized DA is eliminated at the PDMA film‐coated BDD electrode. The sensitivities of the modified electrode for AA, DA and DOPAC, which are present in the same solution with their physiological concentration ratios, are calculated to be 0.070, 0.363 and 0.084 μA μM^?1, respectively. The modified electrode exhibits a stable and sensitive response to DA.     

Grafting vinyl monomers to starch by ceric ion. I. Acrylonitrile and acrylamide

Studies were carried out on the grafting of acrylonitrile (AN) and acrylamide (AA) to starch by ceric ion. The variables affecting the grafting of AN and AA were investigated with granular wheat starch dispersed in aqueous N,N-dimethylformamide and ceric ammonium nitrate as catalyst. Results showed that the concentrations of monomer and catalyst are the major factors influencing the grafting of AN; thus the monomer content of the grafts can be regulated by these variables. The grafting of AA is also influenced by these variables, but to a much less degree. Increasing concentrations of monomer promote homopolymerization and increasing concentration of catalyst inhibit grafting. The extent of grafting of this monomer can best be controlled by reaction time. Under the most favorable conditions, maximum grafting efficiency (ratio of amount of grafted monomer to total amount of monomer converted to polymer) was 87% for AN and 43.8% for AA. Although the monomer content of the AN grafts was higher than that of AA grafts prepared under identical conditions, the number of branches in the grafts was almost the same; only the length of the branches was different. The AN-starch grafts have branches of higher molecular weight.     

Investigation of glow-discharge-induced morphology modifications on silicon wafers and chromium conversion coatings by AFM and rugosimetry

The effect of radiofrequency glow-discharge sputtering on the sample surface in terms of modifications in the surface morphology were investigated in this work by using atomic force microscopy (AFM) and rugosimetry measurements. The influence of GD operating parameters (e.g. rf power, discharge pressure and sputtering time) on surface roughening was investigated using two different types of samples: mirror-polished and homogeneous silicon wafers and chromate conversion coatings (CCCs). Surface morphology changes produced by GD sputtering into the sample surface were carefully investigated by AFM and rugosimetry, both at the original sample surface and at the bottom of GD craters using different GD experimental conditions, such as the sputtering time (from 1 s to 20 min), rf forward power (20–60 W for the Si wafer and 10–60 W for the CCC), and discharge pressure (400–1,000 Pa for the Si wafer and 500–1000 Pa for the CCC). In the present study, GD-induced morphology modifications were observed after rf-GD-OES analysis, both for the silicon wafers and the CCC. Additionally, the changes observed in surface roughness after GD sputtering were found to be sample-dependent, changing the proportion, shape and roughness of the micro-sized patterns and holes with the sample matrix and the GD conditions.     

Determination of Ascorbic Acid in Blood Plasma or Serum and in Seminal Plasma Using a Simplified Sample Preparation and High-Performance Liquid Chromatography Coupled with Uv Detection

Abstract

A simplified method of sample preparation and high-performance liquid chromatography procedure using UV detection is described for the determination of ascorbic acid (AA) in blood plasma or serum and seminal plasma. Within two hours from collection samples are treated with dithioerythritol (DTE) and then stored under Argon at -80°C. Prior to analysis, protein precipitation is initiated with the addition of cold methanol. AA elution is carried out on a C₁₈ reverse phase column using dodecyltrimethylammonium bromide as an ion-pairing agent. the detection is accomplished by measuring ultraviolet absorption at 265 nm. the analysis time for sample is 10.5 min, the retention time of AA being 9.7 min. Within- and between-day coefficients of variation are 2.9% and 4.9% for blood serum, 1.0 % and 2.3 % for seminal plasma. Mean analytical recovery of 102.5 ± 3.7% was found analyzing a serum pool after addition of a standard amount of AA. AA levels are stable for at least 43 days under the described storage conditions.