Largely enhanced LED efficiency of carbazole-fluorene-silole copolymers by using TPBI hole blocking layer

A new series of soluble 3,6-carbazole-fluorene-silole copolymers (PCz-F-S) with M_w up to 52.1 kDa were synthesized by Suzuki coupling reactions. Chemical structures and optoelectronic properties of the copolymers were characterized by elemental analysis, NMR, UV absorption, cyclic voltammetry, photoluminescence (PL), and electroluminescence (EL) spectra. The main absorption peaks of solutions and films of the copolymers are at 354 nm and 347 nm, respectively, showing the combined contribution from the 3,6-carbazole and fluorene blocks. The silole absorption is at wavelength range between 400 nm and 500 nm. Compared with the solution absorption, largely decreased relative absorption of the silole to the 3,6-carbazole and fluorene blocks can be found for the films of the copolymers. The copolymers possess HOMO levels of around −5.36 eV, mainly from the contribution of 3,6-carbazole. Under excitation, the films of the copolymers show silole-dominated green emissions because of PL excitation energy transfer, with high absolute PL quantum yields up to 86%. EL devices with a configuration of ITO/PEDOT/PCz-F-S/Ba/Al only display a maximum external quantum efficiency of 0.48% whereas a device configuration of ITO/PEDOT/PCz-F-S/TPBI/Ba/Al with TPBI hole blocking layer greatly boosts the efficiency to 3.03% for a practical brightness of 236 cd/m². The improved EL efficiency suggests that more balanced charge injection and transport can be realized by inserting the TPBI hole blocking layer.     

Electroless versus electrodriven deposition of silver crystals in polyaniline: Role of silver anion complexes

Electrocrystallization of silver is studied at polyaniline-coated electrodes using silver cations and two silver anion complexes (silver thiosulfate and silver–EDTA) as reducing species. Use of the silver thiosulfate complex results in a significant shift of the silver deposition potential window in the negative direction and highly impeded metal crystallization. The silver cation and silver–EDTA plating solutions allow to perform both electrodriven and electroless metal deposition. Number and size of silver crystals obtained by the two deposition methods in the different plating solutions are compared. Electroless precipitation in the silver–EDTA solution results in the highest number (10⁸ cm⁻²) of small-sized crystals. This result is discussed in terms of the special role of the EDTA anions for the redox state of the polyaniline layers. It is demonstrated that factors such as polyaniline redox charge, concentration of reducing ions and dipping time allow effective control over the amount of electroless deposited metal.     

The relationship between squaraine dye surface morphology and sensitization behavior on SnS2 electrodes

Bis(4-dimethylamino-2-dihydroxyphenyl)squaraine (1-1 OHSQ) dyes were deposited on van der Waals surfaces of SnS₂ single crystals by two methods, dipping in a dye solution and evaporation of dye solution. Dye morphologies and photosensitization properties on the same samples were studied with atomic force microscopy (AFM) and photoelectrochemical measurements. AFM experiments in air revealed two distinct morphologies of dye aggregates and photocurrent measurements on the same samples in aqueous electrolytes showed correspondingly different photocurrent spectra. Three-dimensional needle-shaped 1-1 OHSQ aggregates aligned along crystal directions and showed a broad excitation spectrum that extended into the near-IR region with a peak around 800 nm. In contrast, flat aggregates presumably consisting of monolayers of 1-1 OHSQ molecules, had a sensitization maximum around 680 nm. Both peaks were red-shifted from absorption peak of 1-1 OHSQ in bulk dichloromethane solution. Spectral differences between these dye aggregates are discussed in terms of intermolecular interactions.     

Electroless versus electrodriven deposition of silver crystals in polyaniline: Role of silver anion complexes

Electrocrystallization of silver is studied at polyaniline-coated electrodes using silver cations and two silver anion complexes (silver thiosulfate and silver-EDTA) as reducing species. Use of the silver thiosulfate complex results in a significant shift of the silver deposition potential window in the negative direction and highly impeded metal crystallization. The silver cation and silver-EDTA plating solutions allow to perform both electrodriven and electroless metal deposition. Number and size of silver crystals obtained by the two deposition methods in the different plating solutions are compared. Electroless precipitation in the silver-EDTA solution results in the highest number (∼10⁸ cm⁻²) of small-sized crystals. This result is discussed in terms of the special role of the EDTA anions for the redox state of the polyaniline layers. It is demonstrated that factors such as polyaniline redox charge, concentration of reducing ions and dipping time allow effective control over the amount of electroless deposited metal.     

Synthesis of Tapered CdS Nanobelts and CdSe Nanowires with Good Optical Property by Hydrogen-Assisted Thermal Evaporation

The tapered CdS nanobelts and CdSe nanowires were prepared by hydrogen-assisted thermal evaporation method. Different supersaturation leads to two different kinds of 1D nanostructures. The PL measurements recorded from the as-prepared tapered CdS nanobelts and CdSe nanowires show only a bandgap emission with relatively narrow full-width half maximum, which means that they possess good optical property. The as-synthesized high-quality tapered CdS nanobelts and CdSe nanowires may be excellent building blocks for photonic devices.     

Methacryloxypropyltrimethoxysilane films on aluminium: Electrochemical characteristics, adhesion and morphology

The electrochemical characteristics, adhesion and morphology of methacryloxypropyltrimethoxysilane (MAPT) films on aluminium were investigated during exposure to 3 wt.% NaCl. The MAPT films were deposited on aluminium surface from 2 to 5 vol.% methacryloxypropyltrimethoxysilane solutions, with the aim to investigate the influence of deposition parameters (silane solution concentration and curing time) on electrochemical characteristics, adhesion and morphology of MAPT films on aluminium.Using electrochemical impedance spectroscopy (EIS), potential–time measurements, adhesion measurements and optical microscopy coupled with image analysis, it was shown that films deposited from 5 vol.% solution exhibited better corrosion stability and adhesion, as well as lower porosity comparing to 2 vol.% solution and improved the corrosion protection of aluminium substrate, while the curing time had no influence on these characteristics.     

Soluble semi-conductive chelate polymers containing Cr(III) in the backbone: Synthesis, characterization, optical, electrochemical, and electrical properties

Soluble kinds of coordination polymers containing Cr(III) ion in the backbone were synthesized. Structures of the polymers were characterized by FT-IR, UV-vis, ¹H and ¹³C NMR, and size exclusion chromatography (SEC). Thermal degradation data were obtained by TG-DTA and DSC techniques. Cyclic voltammetry (CV) measurements were carried out and the HOMO-LUMO energy levels and electrochemical band gaps were calculated. Additionally, the optical band gaps (E_g) were determined by using UV-vis spectra of the materials. Electrical conductivity measurements of doped (with iodine) and undoped polymers related to temperature were carried out by four-point probe technique using a Keithley 2400 electrometer. Measurements were made by using the polymeric films deposited on ITO glass plate by dip-coating method. Also, absorption spectra of doped polymeric films were recorded by a single beam spectrophotometer showing that doping procedure causes shifting in absorption spectra. Their abilities of processing in gas sensors were also discussed. According to obtained results the synthesized chelate polymers are semi-conductors having polyconjugated structures. Also, P-2 is the most electro-conductive polymer among the synthesized, while P-1 is the most thermally stable one.     

Mechanism of potentiostatic deposition of MnO2 and electrochemical characteristics of the deposit in relation to carbohydrate oxidation

Cyclic voltammetric (CV) and chronoamperometric (CA) studies on potentiostatic deposition of MnO₂ on Pt from Mn(II) solution in very weakly alkaline media show the process to be controlled by a one-electron transfer step, which means that the deposition proceeds through the generation of Mn(III). The electrocatalytic activity of the deposited electrode towards carbohydrate oxidation is found to be maximum at an optimum amount of deposition. Chronopotentiometric (CP) and CV measurements show that the oxidation of carbohydrates on the deposited electrodes follows a catalytic EC (electrochemical-chemical) mechanism via electrolytic formation of Mn(V) and its subsequent consumption either by disproportionation or by chemical reaction in the presence of carbohydrates. The rate constants of the reaction of Mn(V) with dextrose and fructose have been obtained from CA results. The relative order of the oxidation currents for dextrose and fructose as well as their dependence on carbohydrate concentration has been discussed. Replacement of Pt by carbon as the electrode support material does not affect the electrocatalytic activity of the MnO₂ deposit. The observed linear variation of the steady state oxidation currents with carbohydrate concentration can be exploited for analytical application.     

Soluble polyelectrolyte complexes composed of poly(ethylene oxide)-block-poly(sodium methacrylate) and poly(methacryloyloxyethyl trimethylammonium chloride)

Complexation between poly(methacryloyloxyethyl trimethylammonium chloride), PMOTAC, and poly(ethylene oxide)-block-poly(sodium methacrylate), PEO-block-PMANa with MANa blocks with two different molecular weights has been investigated by light scattering, LS, viscosimetry and conductivity measurements. Owing to the PEO blocks the polyelectrolyte complexes are water-soluble particles. Effects of the ratio of the oppositely charged monomer units, the ionic strength of the solution, and solution pH have been studied. With the 1:1 mixing ratio stable polyelectrolyte complexes, PECs, with spherical shape were formed. When either the cationic or anionic component was in excess, charged non-stoichiometric complexes were formed. The complexes were stable also in solutions with comparatively high ionic strength, though stronger secondary aggregation was observed. By changing the solution pH the degree of dissociation of PEO-block-PMANa could be adjusted. In the vicinity of the pK_a,average of PMAA, a minimum in the particle size and a maximum in the solution conductivity were observed. In solutions with lower pH, a typical self-complexation of PEO-block-PMAA was detected. Also, unexpected interactions between PMOTAC and the self-complexes of PEO-block-PMAA were observed.     

Dynamic Analysis of the Removal of Fatty Acid from a Pet Surface Using a Quartz Crystal Microbalance

A quartz crystal microbalance (QCM) was used to study the removal of stearic acid from poly(ethylene terephthalate) (PET) substrate in aqueous alkali and surfactant solutions. The PET substrate was prepared on a QCM gold electrode by spin‐coating; its properties were examined by scanning electron microscopy, X‐ray photoelectron spectroscopy, and water contact angle measurements. As a result, the QCM electrode was found to be completely covered with a smooth PET film. To investigate the effect of soil deposition state on its removal, stearic acid (an oily soil model) was deposited onto the PET substrate with the Langmuir–Blodgett (LB) technique or by spraying. The QCM frequency was recorded during the removal of stearic acid from the PET substrate in aqueous solutions. In NaOH solution, stearic acid deposited by the LB method was more rapidly removed than when deposited by the spraying method. However, the LB films of stearic acid were difficult to be removed in surfactant solutions. With respect to removal behavior of spray‐deposited stearic acid in surfactant solutions, the results determined by the QCM method were compared with those from microscopic image analysis. The removal efficiencies in the sodium dodecyl sulfate solution were in good agreement between the two methods. However, in the alkyl ethoxylate solution, the removal efficiencies obtained by the QCM method were larger than those from microscopic image analysis. These experimental results were explained by the removal mechanism of stearic acid by the alkali and surfactant solutions.     

Surface wettability of human hair. III. Role of surfactants in the surface deposition of cationic polymers

The effects of low molecular weight surfactants of different ionic characteristics on the deposition of a quaternized cellulosic polymer onto the surface of hair from solution have been studied. The uniformity of deposition and the substantivity of the deposited material has been assessed from measurements of the surface wettability of treated hair fibers with water. The results show that anionic surfactants at low-to-moderate concentrations bind with the cationic polymer so that the substantive layer deposited on the fiber surface tends to be hydrophobic due to orientation of lipid chains away from the surface. At high concentration, additional anionic surfactant molecules interact with the cationic polymer molecule by hydrophobic bonding, reducing the polymer–surfactant complex to an anionic polyelectrolyte which has little substantivity to the fiber surface. Cationic surfactants, on the other hand, do not interact with the polymer because of charge repulsion but compete with the polymer for negatively charged sorption sites on the surface, greatly reducing surface coverage by the polymer. The interaction of amphoteric surfactants with the polymer depends on the pH of the solution. Studies on experimental shampoos containing anionic and amphoteric surfactants confirmed these observations, and indicated, in addition, that dilution of the shampoo in the presence of hair plays a significant role in the deposition of the polymer on the hair surface.     

Some aspects of removal of copper and cobalt from mixed ion dilute solutions

Some aspects of the electrodeposition of copper and cobalt from aqueous sulphate solutions containing low concentrations of their ions were studied with a view to heavy metal removal via an electrochemical process. Both metals were deposited on a vitreous carbon rotating disc electrode. Deposits formed under different conditions were studied employing linear sweep voltammetry, scanning electron microscopy and EDAX surface analysis. Constant potential electrolysis was used to simulate recovery in a laboratory batch reactor. Copper can be deposited without cobalt interference at potentials as cathodic as –1.0 V despite high Co concentrations. At more negative potentials, both metals are deposited simultaneously, although the copper proportion in the binary mixture is greater than that corresponding to the solution concentration ratio. Voltammetry studies effected under conditions in which codeposition occurs show only minor changes in copper behaviour. On the other hand, cobalt behaviour exhibits significant modifications. Even though formation of an intermetallic compound is possible, ASVL and microscopy tests indicate cobalt deposition in different crystalline forms as the more probable cause. In turn, cobalt deposition depends on the polarization conditions of the electrode and on the cobalt and copper concentrations.     

Methacryloxypropyltrimethoxysilane films on aluminium: Electrochemical characteristics,adhesion and morphology

The electrochemical characteristics, adhesion and morphology of methacryloxypropyltrimethoxysilane (MAPT) films on aluminium were investigated during exposure to 3 wt.% NaCl. The MAPT films were deposited on aluminium surface from 2 to 5 vol.% methacryloxypropyltrimethoxysilane solutions, with the aim to investigate the influence of deposition parameters (silane solution concentration and curing time) on electrochemical characteristics, adhesion and morphology of MAPT films on aluminium.Using electrochemical impedance spectroscopy (EIS), potential–time measurements, adhesion measurements and optical microscopy coupled with image analysis, it was shown that films deposited from 5 vol.% solution exhibited better corrosion stability and adhesion, as well as lower porosity comparing to 2 vol.% solution and improved the corrosion protection of aluminium substrate, while the curing time had no influence on these characteristics.     

Corrosion stability of polyester coatings on steel pretreated with different iron–phosphate coatings

The influence of steel surface pretreatment with different types of iron–phosphate coatings on the corrosion stability and adhesion characteristics of polyester coatings on steel was investigated. The phosphate coating was chemically deposited either from the simple novel plating bath, or with the addition of NaNO₂, as an accelerator in the plating bath. The morphology of phosphate coatings was investigated using atomic force microscopy (AFM). The corrosion stability of polyester coatings on steel pretreated by iron–phosphate coatings was investigated by electrochemical impedance spectroscopy (EIS) in 3% NaCl solution, while “dry” and “wet” adhesion were measured by a direct pull-off standardized procedure. It was shown that greater values of pore resistance, R_p, and smaller values of coating capacitance of polyester coating, C_c, on steel pretreated with iron–phosphate coating were obtained, as compared to polyester coating on steel phosphated with accelerator, and on the bare steel. The surface roughness of phosphate coating deposited on steel from the bath without accelerator is favorable in forming stronger bonds with polyester coating. Namely, the dry and wet adhesion measurements are in accordance with EIS measurements in 3% NaCl solution, i.e. lower adhesion values were obtained for polyester coating on steel phosphated with accelerator and on the bare steel, while the iron–phosphate pretreatment from the novel bath enhanced the adhesion of polyester coating on steel.     

Preparation of supported Pt nanoparticles by supercritical fluid reactive deposition: Influence of precursor,substrate and pressure on product properties

Nanoparticles with high surface area deposited on different substrates are currently used extensively as catalysts for chemical transformations. Numerous experiments demonstrate that metallic nanoparticles can directly be deposited on various solid substrates by supercritical fluid reactive deposition. This technique involves the dissolution of the organometallic precursor in a supercritical fluid and the exposure of a substrate to this solution. In general, different methods such as chemical or thermal reduction under different pressures can be used to convert the precursor to its metal form. Results of these experiments show that uniform metallic nanoparticles in the range of 2 nm can be produced. Average particle size and size distribution can be affected by the precursor reduction method, type and amount of the precursor, the surface properties of the solid substrate such as surface area and chemical nature of the surface. Metal loading depends on the metal content of the precursor and its concentration in CO₂.     

Influence of ultrasound irradiation on the adsorption of bovine serum albumin on copper

The effect of irradiation by power ultrasound on the adsorption of proteins on copper has been investigated, using bovine serum albumin (BSA) as a model protein in pH 7 phosphate buffer solution. Open circuit potential measurements, cyclic voltammetry and electrochemical impedance spectroscopy were used to characterise the copper/solution interface. Electrochemical impedance measurements at potentials close to the open circuit potential showed that pulsed ultrasound irradiation removes the naturally formed copper oxide films in phosphate buffer solution, and that their re-formation can lead to an oxide film with different electrical characteristics. Adsorption of BSA blocks the surface, decreasing or increasing the interfacial resistance, depending on the applied potential and the oxide characteristics, as well as changing the interfacial capacitance. This study augurs well for application of the combination of electrochemical impedance plus ultrasound to other systems. Special issue dedicated to Prof. Tony Wragg.     

Metal Propionate Synthesis of Magnetoresistive La1−x(Ca,Sr)xMnO3 Thin Films

A flexible chemical solution deposition (CSD) method for the preparation of magnetoresistive La_1−x (Ca,Sr)x MnO₃thin films based completely on metal propionates is pre-sented.A number of polycrystalline thin films with varying stoichiometries were deposited on different substrate ma-terials at temperatures between 550° and 850°C. The crys-tallization behavior on selected substrates was found to de-pend on the thin film stoichiometry. Magnetoresistivity and magnetization were measured as a function of temperature. For the selected samples, a magnetic Curie temperature TC, a metal–semiconductor transition, and magnetoresistive behavior were observed. These measurements demon-strated that La_1−x(Ca,Sr)x MnO₃ thin films with properties well known from films deposited by PLD or sputtering can be prepared by a simple, propionate-based CSD method.     

在单壁碳纳米管上自动沉积金纳米粒子时所用润湿剂的研究

在用单壁碳纳米管直接自动沉积Au纳米粒子的时候,可以使用不同的溶剂与水混合配制氯金酸溶液,此时这些溶剂所起的作用是润湿碳管表面,从而使Au纳米粒子可以更好地沉积在碳管上。通过将Au沉积在单壁碳纳米管一系列的实验比较,最后发现,润湿碳管的溶剂不仅可用乙醇,还可以使用甲醇、丙酮、异丙醇等,其中沉积效果较好的是：50％的乙醇和30％的丙酮的水溶液。     

Optical, electrochemical and electrogravimetric behavior of poly(1-methoxy-4-(2-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV) films

Poly(1-methoxy-4-(2-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV) films spin-cast from chloroform solution were characterized by cyclic voltammetry, in situ spectroelectrochemistry, and electrochemical quartz crystal microbalance (EQCM) measurements. The MEH-PPV films exhibited two well-defined redox waves during p- and n-electrochemical doping, and a mass gain at the end of each cycle that is characteristic of the movement of ions and solvent into and out the film. The electronic energy gap of MEH-PPV was estimated as 2.35 eV from the anodic and cathodic onset potentials obtained by cyclic voltammetry, in good agreement with the value of optical energy gap determined from the absorption edge, 2.21 eV. The films also showed a reversible and stable electrochromic transition at a positive range of applied potentials from reddish-orange (neutral form) to brownish-green (oxidized form).     

New methods for the study of organic coatings by EIS: New insights into attached and free films

Organic coatings are widely used for the protection of structures against marine corrosion. Based on long-term service experience, their thickness reaches often as high as several hundreds of micrometers. However, for primer coatings, where the barrier effect is believed to play a minor protective purpose, the surface preparation and the nature of the substrate seem to play an important role.Experiments have been performed on free-standing and supported coatings and the comparison showed considerable differences. It is postulated that the adhesion mechanisms provide an important part of the protection afforded by the coating. The insertion of a conducting probe inside the coating allowed separating the impedance of the inner part of the coating in contact with the substrate from that of the outer part in contact with the solution. Information on the influence of the adhesion on the protection was then evidenced. A gold electrode, deposited on the surface of the inner half-layer of the coating, was used as a potential probe to perform electrochemical impedance measurements. The first results presented in this paper show a clear difference between the behaviour of these two parts of the coating.