Growth of ultrathin films of cadmium telluride and tellurium as studied by electrochemical atomic force microscopy

Time dependent, cathodic electrodeposition of ultrathin CdTe and Te films has been studied in 50 mM H(2)SO(4) + 1 mM CdSO(4) + 0.1 mM TeO(2) solutions at room temperature under potential control using electrochemical atomic force microscopy (EC-AFM). The films were also characterized electrochemically and with X-ray diffraction. The growth mechanism and the composition of the films depends on the applied potentials. Island-like growth mode was observed for CdTe films when the deposition potential was -0.35 V (SHE). At a more positive deposition potential of 0.138 V (SHE), Cd was not co-deposited into the film but affected the dynamic growth mode of the deposit. At this voltage smooth Te films were obtained. Depending on the applied potential, Cd acts either as a co-deposition element for CdTe film growth, or as a mediator for layer-by-layer growth of Te films.     

Mechanism of film growth of tellurium by electrochemical deposition in the presence and absence of cadmium ions

The growth morphology and the kinetics of a thin film of Te on Au during electrochemical deposition at -62 mV (vs Ag/AgCl/3 M NaCl) have been studied. The deposition conditions are similar to those used previously by us to grow nanowires inside Au nanotubes by electrochemical deposition in the presence of Cd ions (Cd(2+)). By using electrochemical deposition on a planar Au electrode, we explored the growth of the Te film for two conditions: in the presence of Cd(2+) (0.1 mM TeO(2) + 1 mM CdSO(4) + 50 mM H(2)SO(4) solution) and in the absence of Cd(2+) (0.1 mM TeO(2) + 50 mM H(2)SO(4) solution). We used several surface investigation techniques to study the growth such as: in situ electrochemical atomic force microscopy (EC-AFM), in situ electrochemical surface plasmon resonance (EC-SPR), electrochemical methods, scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). In the presence of Cd(2+), in situ electrochemical atomic microscopy showed that Cd(2+) acted as a mediator at the early deposition stage and caused smoothing of the Te deposit obtained. In the absence of Cd(2+), Te had an island growth. The electrochemical surface plasmon resonance showed that the deposit was characterized by a slower deposition rate in the presence of Cd(2+) than in the absence of Cd(2+). Additionally, the thickness of the film was evaluated using EC-AFM measurements, electrochemical stripping analysis, and EC-SPR. The results obtained from all three measurements agree well with the Te film obtained in the presence of Cd(2+), where a continuous and uniform film was formed. In the presence of Cd(2+), a Te film with a thickness of 1.04 nm and atomically flat surface was deposited on an ultraflat Au surface. The XPS spectrum showed no significant amount of Cd in the deposit, indicating that the Cd ion acted as a mediator and not as a co-deposition element.     

Bismuth Film Voltammetric Sensor on Pyrolyzed Photoresist/Alumina Support for Determination of Heavy Metals

Voltammetric sensors based on bismuth film electrodes are an attractive alternative to other sensors for application in electroanalysis of heavy metals. Bismuth film electrodes can be formed by a similar method on the same substrates as mercury. These systems were used most frequently for simultaneous determination of heavy metals such as Pb, Cd and Zn by anodic stripping voltammetry. Our voltammetric sensor was fabricated on an alumina substrate. A photoresist film prepared by pyrolysis of positive photoresist S‐1813 SP15 on the alumina substrate was used as an electrode support for bismuth film deposition. The influence of the Nafion membrane on the measurement sensitivity of the sensor and mechanical stability of the bismuth film were investigated. The sensor was successfully applied for determination of Pb, Cd and Zn in an aqueous solution in the concentration range of 0.2 to 10 µg L^?1 by square wave anodic stripping voltammetry on an in‐situ formed bismuth film electrode with Nafion‐coating. Parameters of the sensor such as sensitivity, linearity, detection limit, repeatability and life‐time were evaluated. In the best case, the detection limits were estimated as 0.07, 0.11 and 0.63 µg L^?1 for Pb, Cd and Zn, respectively. Finally, the applicability of the sensor was tested in analysis of Pb, Cd and Zn in real samples of tap and river water using the method of standard additions.     

Luminescence of monolayer thin films of the fully conjugated rigid‐rod polymer poly(p‐phenylenebenzobisthiazole)

Poly(p‐phenylenebenzobisthiazole) (PBT) is a heterocyclic, aromatic rigid‐rod polymer with a fully conjugated backbone and excellent dimensional, thermo‐oxidative, and solvent stabilities. A PBT polymer with an intrinsic viscosity of 18.0 dL/g was dissolved in methanesulfonic acid or Lewis acid. The PBT solution was spin‐coated and doctor‐bladed for freestanding films or onto an indium tin oxide (ITO) substrate. The acid was removed via coagulation. Scanning electron microscopy determined that the resultant film thicknesses were about 340 and 60 nm for PBT freestanding films and films on the ITO substrate, respectively. X‐ray scattering demonstrated that the freestanding films were in‐plane isotropic without long‐range order. The freestanding films were excited with a He‐Cd laser at 325 nm for photoluminescence (PL) response. PL spectra showed a distinct intensity maximum at 580 nm, regardless of the film‐forming conditions. After the films cooled to 67 K, the PL maximum shifted to 566 nm with enhanced intensity. Aluminum was evaporated onto the monolayer PBT thin film on the ITO substrate as an electron injector for electroluminescence (EL) response. Diodic electric behavior was observed for all monolayer PBT EL devices for the first time. A threshold voltage as low as 4 V was achieved for the monolayer EL devices. In addition, PBT EL spectra were tunable, with a maximum intensity at 570 nm at a bias voltage of 4.5 V changing to 496 nm at 7.5 V (i.e., a blueshift) with greatly increased intensity. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1760–1767, 2002     

2-(N-十六烷基氨基甲酰基)-8-羟基喹啉镉配合物的电致发光

本文首次报道了采用2-(N-十六烷基氨基甲酰基)-8-羟基喹啉镉配合物作为一种新型发光材料，通过LB膜技术来制备发光层所制得的电致发光器件。在室温下，当直流正向偏压为6.5 V时，可于暗室中用肉眼观察到发光。当电流密度为35 mA/cm²时，可得稳定的发光，其电致发光图谱峰值在490 nm处。     

Efficient immobilization of a cadmium chemosensor in a thin film: generation of a cadmium sensor prototype

[reaction: see text] The development of an ion-selective chemosensor for Cd(2+) allows generation of a "real-time" sensor. Immobilization of the chemosensor on quartz was achieved in a simple monolayer and in a thin film using a polymer intermediary. As intended, the thin film contains much more chemosensor than the monolayer and provides measurable responses to aqueous Cd(2+) concentrations below 1 microM. Alkali and alkaline earth ions do not interfere with Cd(2+) sensing; Zn(2+) and Cu(2+) are potential interferents.     

预镀铋膜阳极溶出伏安法测定废水中微量铅和镉

本文采用预镀铋膜法修饰玻碳电极,并用该电极对废水中微量铅和镉同时进行了阳极溶出伏安法测定,研究了预镀铋膜测定铅和镉的条件。实验结果表明:铅和镉在铋膜电极上可得到灵敏的电位溶出峰,峰高和溶出电位与汞膜电极法相近,使用预镀铋膜电极可避免使用汞电极带来的环境污染。     

烯丙基硫脲和十二烷基硫醇对铜的缓蚀作用

用自组装技术在铜电极表面上制备了纯烯丙基硫服自组装膜，并以十二烷基硫 醇进一步修饰得到混合自组装膜。最后，将混合膜覆盖的铜电极浸入NaCl溶液中， 进行交流电处理，电化学交流阻抗谱和极化曲线测定表明，经过交流电处理后，在 0．5mol·dm^-3 NaCl溶液中，电荷传递电阻增大，腐蚀电流密度下降，膜的最大 覆盖度为98．6％，对金属铜腐蚀的续蚀效率为98．5％。而且，不论交流电处理与 否，混合自组装膜在较宽的电极电位范围内均表现出很强的稳定性。     

镉电极上的衰减全反射表面增强红外光谱

利用两步“湿法镀膜”方法将ATR-SEIRAS的研究进一步拓展到ⅡB族Cd电极上. 选择吡啶(Py)作为模型分子, 初步比较了Py在不同金属电极表面上的吸附构型.     

Resolution of anodic stripping voltammetry with thin-film mercury electrodes

The potentialities of the use of thin-film mercury electrodes (TFME) for the improvement of resolution of stripping voltammetry were discussed from a theoretical viewpoint. A set of current functions was computed numerically on the basis of the de Vries and van Dalen theory. The data obtained permitted the summing of current functions of two neighbouring dissolution processes and the estimation of the influence of the extent of overlap on the enhancement of the peak height and on the separation of peak potentials. The separation is governed mainly by the parameter b_1/2 (peak width at half height) which approaches the value 75.53/n mV at TFME compared to 203/n mV characteristic for HMDE. The variations in film thickness and in voltage scan rate may also improve the separation of two adjacent peaks, but only if different numbers of electrons are involved in both electrode reactions. The maximum separation obtained by changes in film thickness may attain 160 mV for two reactions with a value of n equal to 1 and 3 respectively.The experimental results obtained for the systems: Bi and Sb; Pb and Cd; Pb and Tl; Bi and Cu; Pb, Tl and Cd at TFME with silver or graphite substrate confirmed the theoretical predictions.     

Study on microarc oxidation of AZ31B magnesium alloy in alkaline metal silicate solution

The effects of pulsating current and voltage sources with different magnitudes on an oxide film formed by microarc oxidation (MAO) of AZ31B magnesium alloy in alkaline metal silicate solution were investigated. The thickness of an oxide film increased with increasing current source but the uniformity of the surface of an oxide film became worse. The unstable oxidation process represented by fluctuating voltage established across an oxide film was discussed and related to the surface roughness and the melting down of magnesium alloy. By comparing the surface of an oxide film a pulsating current source produced more uniform oxide film on magnesium alloy than a pulsating voltage source.     

钙对氮化钼膜电极性能的影响

应用XRD、SEM、循环伏安法 (CV)等测试手段研究了钙对氮化钼膜电极性能的影响 .结果表明 ,采用浸渍_煅烧法制备电极 ,浸渍液中添加剂的量对电极电化学性能的影响显著 ;当添加剂的量为最佳值时 ,电极的比电容约为不加添加剂制备之电极的 2 .1倍 ,工作电势拓宽了 0 .11V .钙对γ_Mo2 N膜电极电化学性能的影响机理可认为是电极新生物质CaxNy、晶粒规整化和电极活性物质吸附能力增强这三种因素的协同作用     

Anion induced adsorption of Cd(II) from acetonitrile solutions

Solutions of Cd(II) in acetonitrile show no adsorption on mercury electrodes with sodium perchlorate as supporting electrolyte but strong adsorption of Cd(II) is produced by the addition of thiocyanate anion. The stoichiometry of the adsorbed species was shown to be Cd(NCS)₂ by means of chronocoulometric measurement of the quantities of both Cd(II) and NCS^? on the surface. The surface appears to reach a saturation coverage corresponding to ca. two monolayers of a tightly packed film. Speculations on the forces driving the adsorption are offered and similarities with previous results obtained in aqueous solutions are pointed out.     

铝阳极化皮膜之显微组织与电化学特性研究

利用超薄切片技术(ultramicrotomy)制作铝阳极化成箔之横截面切片,于穿透式电子显微镜(TEM)下对氧化铝介电皮膜厚度,型态,成份与微结构进行观察与分析,并探讨其与皮膜电化学特性表现之关联性.于85℃己二酸铵水溶液中进行铝阳极化成处理.当电压低于100V时,所成长之介电层为非晶质氧化铝皮膜,其电阻值随化成电压升高而增加,但介电常数不受化成电压之影响.当化成电压超过100V时,结晶状的γ′＿Al2O3开始出现,且其产生的量随电压值的提高而不断增加,结晶化的过程造成皮膜中缺陷与裂缝产生,以致皮膜电阻逐渐降低,但平均介电常数却有明显随皮膜中γ′＿Al2O3增加而升高的趋势.化成电压达到200V时,介电皮膜之结构明显可分为两层,包括内层非晶质氧化铝与外层结晶性γ′＿Al2O3;其电化学交流阻抗行为亦显示界面双电容组件特性,结晶性γ′＿Al2O3层的电阻较低,但比非晶质氧化铝层具较高电容值.     

Simultaneous determination of chromium(III) and cadmium(II) by differential pulse anodic stripping voltammetry on a stannum film electrode

A stannum film electrode has been developed for the simultaneous determination of trace levels of chromium(III) and cadmium(II) by differential pulse anodic stripping voltammetry (DPASV). The stannum film electrode was generated in situ by depositing simultaneously the stannum film and the metals obtained by reduction of Cd(II) and Cr(III) at −1.4 V on a glassy carbon electrode. Then, the reduced products were oxidized by scanning the potential of the electrode from −1.4 to −0.4 V using DPASV. The electrode exhibited well-defined and separated stripping signals for both metals accompanied with a low background contribution. The possible mechanism of this design was proposed. Under the optimized working conditions, the detection limit was 2.0 and 1.1 μg l⁻¹ for Cr(III) and Cd(II) at a deposition time of 3 min. Finally, the stannum film electrode was successfully applied to the determination of Cd(II) in tap water with satisfactory results.     

Effect of thickness and monolayer location on thermostability of metal stearate LB films studied by FT-IR reflection—absorption spectroscopy

LB films of Cd and Ca stearates with 1, 3, 9, and 21 monolayers were fabricated on silver-coated glass slides. 9-Monolayer LB films of Cd and Ca salts of deuterated stearic acid, in which the 1st, 5th, or 9th layer was replaced by 1 monolayer of undeuterated analogues, were also prepared on the above substrates. Temperature dependences of Fourier transform infrared (FT-IR) reflection—absorption (RA) spectra were examined for these LB films in the range 31–140°C. At room temperature, the hydrocarbon chains in these LB films were in a well-ordered state with a high degree of perpendicular orientation to the substrate. However, they became disordered at elevated temperatures. These order-disorder phase transition temperatures were dependent on the film thickness, to a small degree in the Cd stearate LB film (102–108°C), but to a large degree in the Ca stearate LB film (103–129°C). In the latter LB film, the effect of dehydration was inferred. The degree of disorder at high temperatures was dependent on the film thickness and the location of monolayer in the 9-monolayer LB films. This result is discussed in terms of the internal pressure within the LB film.     

Disposable Nafion-modified micro-fabricated bismuth-film sensors for voltammetric stripping analysis of trace metals in the presence of surfactants

This work is a study of the analytical utility of Nafion-modified microfabricated bismuth film electrodes (BiFEs) for the determination of Pb(II) and Cd(II) by anodic stripping voltammetry (ASV) in the presence of surfactants. Micro-fabricated BiFEs were prepared by depositing a thin film of bismuth on the surface of a silicon substrate by sputtering while the two-dimensional geometry of the final sensors was defined by photolithography. The BiFEs were further drop-coated with a Nafion film. These devices were applied to the determination of Pb(II) and Cd(II) by square wave ASV (SWASV) in the presence of Triton X-100 (a non-ionic surfactant), cetyltrimethylammonium bromide (CTAB) (a cationic surfactant) and sodium dodecyl sulphate (SDS) (an anionic surfactant). It was found that the presence of Nafion afforded an increase in sensitivity and the tolerance against surfactants but these properties were severely influenced by both the thickness of the Nafion film and the nature of the interfering surfactant. Using a Nafion of 0.4 μm thickness and 120 s of preconcentration, the repeatability (expressed as the % relative standard deviation on the same sensor (n = 8)) at the 20 μg l⁻¹ level was 3.8% for Pb(II) and 3.1% for Cd(II) and the limits of detection were 0.5 μg l⁻¹ for Cd(II) and Pb(II). The sensors were applied to Cd(II) and Pb(II) determination in a certified lake-water sample.     

The Monolayer Behavior of Amphiphilic Polymer and Heterostructure of Polymer LB Film/CdS Clusters

In this paper we report the behavior of an amphiphilic polymer monolayer on pure water and Cd2+ subphase. This polymer was composed of hydrophilic ethylene diamine epichlorohydrin slightly crosslinked microgel and hydrophobic stearic chains, noted as ES-1. The introduction of Cd2+ ions in subphase had a marked effect on the process of the organization of the amphiphilic polymer at the air/water interface due to the association of Cd2+ ions with the hydrophilic network, which could be indicated by the pressure-area isotherms and Brewster Angle Microscopy. Ordered ES-1/Cd2+ LB multilayers were fabricated. After the multilayers reacted with H2S gas, CdS clusters were synthesized within the film, which was characterized by X-ray diffraction and UV-visible spectroscopy. Copyright 1999 Academic Press.     

Complexes of cadmium ion with guanine bases detected by electrospray ionization mass spectrometry

The complexations of cadmium ion with guanine bases were detected by electrospray ionization mass spectrometry (ESI-MS). In order to explore the toxicity of cadmium, such as oxidative stress to DNA and carcinogenesis, it is very important to determine the interactions between the cadmium ion and nucleotide. The analysis of mixed cadmium ion-guanosine aqueous solution (molar ratio 1 : 9) using ESI-MS (cone voltage 20 V) showed the presence of various cadmium complex ions, such as [n (guanosine) + Cd](2+) (n = 3-8), [2guanine + Cd](2+), [guanosine + guanine + Cd](2+) and [guanosine + 2guanine + Cd](2+). The observed [2guanine + Cd](2+), [guanosine + guanine + Cd](2+) and [guanosine + guanine + Cd](2+) ions are formed through the dissociation of the N-glycoside bond at the interface of ESI-MS. For deoxyguanosine and ethylguanine, similar cadmium complexes were observed. However, the complexes between the cadmium ion and 8-hydroxydeoxyguanosine were not detected. Furthermore, when a higher molar ratio (Cd : guanosine) or cone voltage were used, more of the monovalent ion peaks, such as [Cd(guanine - H)(2) + H](+) and [Cd(guanosine - H)(2) + H](+), were observed and a decrease in the abundance of the divalent ions, such as [n(guanosine)+Cd](2+), occurred.     

Passivity of titanium,part 1: film growth model diagnostics

Diagnostic criteria for the growth of the anodic oxide film on titanium in H₂SO₄ are reported. The criteria apply to the generalized high field model, which postulates that the electric field within the film is dependent upon the film thickness, and the point defect model, which describes the electric field as being constant during film growth. The diagnostic criteria show that the PDM more realistically models film growth than does the HFM, and we conclude that in this system the electric field strength is invariant with applied voltage and film thickness. The constancy of the electric field in the passive film on titanium, as demonstrated in this work, is attributed to band-to-band Esaki tunneling, which buffers the electric field against changes in the applied voltage and film thickness.