Fabrication of poly(3,4‐ethylenedioxythiophene)‐polysaccharide composites

Poly(3,4‐ethylenedioxythiophene) (PEDOT) doped with a series of anionic polysaccharides such as carboxymethyl cellulose, sodium hyaluronate, xanthan gum, pectin, gellan gum were prepared by electropolymerization in aqueous solutions. Some other dopants of potassium nitrate, potassium sulfate, sodium poly(styrenesulfonate), and sodium polyacrylate were used in comparison with the anionic polysaccharides. The electrochemical properties and stability of the obtained PEDOT films were also investigated. It was found that indium tin oxide (ITO) conductive glass could be used as the working electrode of the electropolymerization of EDOT and that the dopant had a great influence on polymerization potential and overoxidation potential. These charged biomolecules of anionic polysaccharides were found to facilitate electropolymerization of EDOT instead of common doping anions as counterion. The electroactive PEDOT films doped with anionic polysaccharides showed stable electrochemical properties, good texture, and adhesion properties to the ITO conductive glass. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

ITO薄膜的研究进展

ITO是锡掺杂氧化铟薄膜的简称,属于透明导电氧化物材料。常规沉积方法制备的ITO薄膜通常为非晶态或体心立方晶系晶体,为n型半导体材料,其载流子为自由电子,主要来源于沉积过程中薄膜化学计量比偏离或阳离子掺杂形成的施主杂质。ITO薄膜是当前研究和使用最为广泛的透明导电氧化物薄膜材料,由于具有低电阻率、高可见光透过率、高红外反射率等独特物理特性而被大量应用于平板显示器、太阳能电池、发光二极管、气体传感器、飞机风挡玻璃除霜器等领域。此外,ITO薄膜对微波还具有高达85%的衰减作用,因而在电磁屏蔽等军用领域显示出巨大的潜在应用价值。过去几十年里,针对ITO薄膜的研究工作主要聚焦于薄膜的光电性能上。当前,伴随着ITO薄膜的应用范围在航空航天和军用武器装备等领域的拓展,ITO薄膜在恶劣力学环境中的使用日渐增多。因此,除光电性能外,ITO薄膜的力学性能也开始受到研究者越来越多的关注,人们对薄膜器件在各类恶劣使用环境中的稳定性及耐久性提出了更高的要求,这一要求使得对ITO薄膜力学性能的深入研究分析有了重要的理论及实际意义。本文综述了近年来ITO薄膜在微结构特性、能带结构、光电性能及力学性能等方面的研究进展,简略探讨了ITO薄膜的研究发展方向。     

Effect of heat treatment on the dispersion and sintering behaviour of tin doped indium oxide powders

Due to the importance of structural uniformity of ITO targets on the properties of ITO films, the untreated and heat treated tin doped indium oxide powders were used to study the effects of four different dispersants on the dispersion behaviour of nanosized ITO powders. The optimum dispersant is NH₄PAA and its optimum amount is 1.00?wt% when the pH value is 9.0. In addition, the effect of the treatment temperature of nanosized ITO powders on the dispersion and sintering behaviour was also studied by SEM, TEM and XRD. The solid loading of ITO slurries and the relative density of the sintered bodies prepared with ITO powders treated at 900?°C could reach 40?vol% (untreated, 25?vol%) and 98.53% (untreated, 95.04%), respectively. The results indicate that the heat treatment of powders at 900?°C allowed obtaining powders from which ITO aqueous suspensions with high solid loading could be prepared and dense bodies after sintering. In another word, the appropriate heat treatment process for tin doped indium oxide powders could reduce the sintering temperature by 50?℃ and refine the grain size.     

Oxide film growth on Al-In alloys in a borate buffer solution in conditions of galvanostatic anodising

Anodic oxide films have been formed galvanostatically on Al-In alloys (containing up to 0.074% In) in a borate buffer solution (pH 7.8) at different current densities (20-100 μA cm⁻²). The mechanism, kinetics of growth and properties of formed oxide films have been investigated. The study of charge curves suggests that the growth of oxide films on Al-In alloys occurs by an activation-controlled ionic conduction under the influence of the high electric field through the oxide film according to an exponential law, like on valve metals. The following parameters have been calculated: the constants of the exponential law, ionic conductivity through the film, the effective activation distance for ion movement and the corresponding field strength. The values for the field strength, of the order of magnitude of 10⁶ V cm⁻¹, justify the application of the high field migration mechanism. Properties of anodic oxide films have been determined by means of electrochemical impedance spectroscopy; the resistance and thickness of the oxide film have been found to increase with the increase in the indium content in the alloy and with increased anodic current density. It has been established that the current efficiency in oxide films formation on Al-In alloys is lower than 100%: the increase of the indium content in the alloy, as well as the increase in anodic current density, increases the value of current efficiency.     

Investigations of Electrical Properties in Silica/Indium Tin Oxide Two-Layer Film for Effective Electromagnetic Shielding

The effect of zinc ions added to silica film on the electrical and structural properties of a silica/indium tin oxide two-layer film which had been prepared by solution coating for electromagnetic shielding of displays was studied. The volume resistivity of the undoped silica/indium tin oxide film was more than 3 times as high as that of the zinc-doped silica/indium tin oxide film. The addition of divalent cations, zinc ions, to the overcoated layer led volume resistivity of the two-layer film to decrease significantly and also caused a long-term increase in stability. The decrease in volume resistivity was due to the addition of zinc ions that changed the interface ionization and helped to enhance the electrical conductivity in the two-layer film.     

Enhanced photoelectrochemical performance of Ag–ZnO thin films synthesized by spray pyrolysis technique

Silver doped zinc oxide (Ag–ZnO) thin films were deposited on glass and tin doped indium oxide (ITO) coated glass substrates by using pneumatic spray pyrolysis technique (SPT) at 450 °C from aqueous solutions of zinc acetate and silver nitrate precursors. The effect of silver doping on structural, morphological and optical properties of films was studied. The XRD spectra of the Ag–ZnO films indicate the polycrystalline nature having hexagonal crystal structure. SEM micrographs show the uniform distribution of spherical grains of about 80–90 nm grain size for the pure ZnO thin films. The Ag nanoparticles are clearly visualized in SEM images of Ag–ZnO samples. The optical band gap energy decreases as the percentage of silver doping increases. Surface Plasmon Resonance (SPR) related phenomena are observed and correlated to the optical properties of Ag–ZnO thin films. The overall photoelectrochemical (PEC) performance of the samples was investigated and discussed. Moreover, the samples are more photoactive as compare to the pure ZnO sample and the sample ZnOAg₁₅ shows the highest current. The photocurrent increases upto 249 μA cm⁻² and 303 μA cm⁻² in visible light and in UV illumination, respectively, and then decreases as the Ag doping increases into the film.     

NIR-shielding films based on PEDOT-PSS/polysiloxane and polysilsesquioxane hybrid

Near-infrared (NIR)-shielding films based on polysiloxane or polysilsesquioxanes and poly(3,4-ethylenedioxythiophene)-poly(4-styrene sulfonate) (PEDOT-PSS) were synthesized via a sol–gel reaction. Phase-separated mixtures of tetraethyl orthosilicate (TEOS) or methyltriethoxysilane (MTES) with an aqueous dispersion of PEDOT-PSS formed deep-blue homogeneously dispersed sols after stirring. Thin films were prepared by depositing the resulting homogeneously dispersed sols on a glass substrate by spin coating and heating. PEDOT-PSS/TEOS films maintained uniform flat surfaces after 10 coatings. MTES-based films exhibited mottled patterns with nonuniform surfaces. The 10-layer TEOS-based film has high NIR-shielding properties with moderately visible transmittance. NIR absorption by the PEDOT-PSS/TEOS hybrid suppresses air temperature elevation. The five-layer TEOS-based film showed similar NIR-shielding ability and slightly lower visible light transmittance compared with tin-doped indium oxide glass. The 10-layer TEOS-based film exhibited a 15.6% lower temperature rise than the uncoated glass substrate. Specifically, this is an environmentally friendly NIR-shielding material. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48367.     

Immobilization of cholesterol oxidase and potassium ferricyanide on dodecylbenzene sulfonate ion‐doped polypyrrole film

Dodecylbenzene sulfonate (DBS)‐doped polypyrrole (PPY) conducting polymer films were electrochemically deposited onto the indium‐tin‐oxide (ITO)‐coated glass plates in aqueous medium. The enzyme cholesterol oxidase (ChOx) was immobilized on these DBS–PPY films by a physical adsorption technique. These ChOx‐immobilized DBS–PPY films were characterized by ultraviolet–visible and Fourier transform infrared spectroscopy. The enzyme activity studies indicate that ～40% of ChOx leaches out from the ChOx/DBS–PPY film. The ChOx activity in the ChOx/DBS–PPY film was assayed as a function of cholesterol concentration. The results of amperometric measurements conducted on ChOx/DBS–PPY/ITO film show linearity over the range 2–8 mM of cholesterol solution. The ChOx/DBS–PPY/ITO electrodes exhibit a response time of 30 s and are stable for ～3 months at 4 °C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3486–3491, 2001     

聚苯胺-乙烯三叔丁基过氧硅烷复合膜的制备及其电致变色性能的研究

采用恒电位法在氧化铟导电玻璃上电聚合制备了聚苯胺(PAn),利用溶液复合法合成了掺杂态聚苯胺-乙烯三叔丁基过氧硅烷复合电致变色膜,并对其结构和电致变色性能研究。结果表明,复合电致变色膜在稳定态时仅出现第二氧化峰,在外加电压下其颜色在绿色至紫色之间可逆变化,聚合物中加入偶联剂,可提高电致变色膜与导电玻璃基底的粘结性及改善复合膜的耐溶剂性能。     

纳米氧化铟锡透明隔热涂料的制备及性能表征

采用在水中分散好的氧化铟锡(ITO)水浆，以及有机硅树脂成膜剂，通过加入共溶剂并调整体系pH值，制得了性能好的透明隔热涂料。试验结果表明，该涂料具有良好的光谱选择性，在可见光区具有高的透过性，并能有效阻隔红外光区的热辐射。     

有机溶剂热生长技术制备硫族化合物及其光学特性的研究

以有机溶剂热生长技术(solvothermaltechnique)制备了半导体硫族化合物(CdS、ZnS、MoS2)等纳米颗粒,采用XRD、TEM等技术对其结构进行表征.以ITO导电玻璃以及导电聚合物(PANI、PPY)膜为基底,将纳米颗粒涂布其上并以PL法研究其光学特性,实验结果表明:经修饰后,材料的荧光发射位置发生显著的变化.     

Polyaniline electrochromic devices with transparent graphene electrodes

Transparent, conductive and uniform graphene films have been prepared and used as electrodes of the electrochromic devices of polyaniline. Polyaniline films on both graphene and the widely used indium tin oxide (ITO) electrodes showed similar electrochemical and spectroelectrochemical properties. However, graphene electrodes exhibited much higher electrochemical stability than ITO in aqueous acidic electrolytes. The performances of the electrochromic devices with graphene electrodes exhibited slight decrease upon voltage switching while those of the devices with ITO electrodes decreased dramatically. After 300 cycles, the electrochromic devices with graphene electrodes showed much larger optical contrast and shorter switching time than those of the devices with ITO electrodes.     

An electrochromic device combining polypyrrole and WO3-I. Liquid electrolyte

In this work we assembled an electrochromic device using as active materials an organic conductive polymer and a transition metal oxide. We studied the materials used to assemble the device separately, and in complete devices. These materials were: polypyrrole doped with dodecylsulfate and tungsten oxide. The substrates used were glass slides coated with tin doped indium oxide, and the electrolyte was a propylene carbonate solution of lithium perchlorate. We adjusted the charge balance and the chromatic contrast of the devices by controlling the thickness of the polypyrrole films. To illustrate the results obtained, we describe two devices with different polypyrrole film thicknesses. The chromatic contrast in the visible and near-infrared wavelength range is 40% and the electrical and optical properties of the devices remain unchanged after 10⁴ double potential chronoamperometric steps.     

Nanoscale coaxial cables produced from vertically aligned carbon nanotube arrays grown via chemical vapor deposition and coated with indium tin oxide via ion assisted deposition

A highly conformal homogeneous indium tin oxide (ITO) thin film coating has been produced on vertically aligned carbon nanotube arrays by ion assisted deposition. The deposition process generates, in effect, a coaxial cable structure of ITO about a carbon nanotube. The deposited ITO films are uniformly 5 nm thick and have high crystallinity and excellent optical absorption properties, indicating they would be good candidates for use in solar cells, flexible electronics and displays. The materials are analyzed by scanning and transmission electron microscopy, X-ray diffraction, and visual light spectrometry.     

Effects of Solution History on Sol‐Gel Processed Tin‐Oxide Thin‐Film Transistors

Antimony‐doped tin‐oxide (SbTO) thin films deposited by solution processing methods represent a promising avenue toward low‐cost transparent and flexible electronics, but reproducibility and performance homogeneity of devices prepared from these thin films have been seldom investigated. In this study, the role of sol‐gel precursor aging is investigated by comparing SbTO thin‐film transistors (TFT) fabricated from two different sol‐gel solutions: the first one was aged for 4 years, whereas the second was prepared freshly. For each of the solutions, a set of TFT was assembled on the same chip, to investigate the distinct roles of aging and sample inhomogeneity on the electronic and transport properties of SbTO. Higher electron mobility, but lower on/off ratios, was found in TFTs assembled from freshly prepared solution, an effect that may be assigned to larger size of SbTO grains. This study demonstrates the critical role of the solution “history” in determining the properties and reproducibility of SbTO TFTs, over other factors, including local film inhomogeneity and local fluctuations of the annealing temperature.     

Effect of heterojunction on photocatalytic properties of multilayered ZnO-based thin films

In the present study, the effects of the heterojunctions on the optical and structural characteristics and the resulting photocatalytic properties of multilayered ZnO-based thin films were investigated. The junctions were composed of semiconducting ZnO nano-porous films coated on the In₂O₃ and SnO₂ counterpart layers. The multilayered ZnO films based on the triple-layered Ag-doped indium oxide (AIO)/tin oxide (TO)/zinc oxide (ZnO), indium oxide (IO)/Ag-doped tin oxide (ATO)/zinc oxide (ZnO), indium oxide (IO)/tin oxide (TO)/zinc oxide (ZnO) and tin oxide (TO)/indium oxide (IO)/zinc oxide (ZnO) have been fabricated by subsequent sol–gel dip coating. Their structural and optical properties combined with photocatalytic characteristics were examined toward degradation of Solantine Brown BRL (C.I. Direct Brown), an azo dye using in Iran textile industries as organic model under UV light irradiation. Effects of operational parameters such as initial concentration of azo dye, irradiation time, solution pH, absence and presence of Ag doping and consequent of sublayers on the photodegradation efficiencies of ZnO nultilayered thin films were also investigated and optimum conditions were established. It was found that the photocatalytic degradation of azo dye on the composite films followed pseudo-first order kinetics. Photocatalytic activity of AIO/TO/ZnO interface composite film was higher compared with other films and the following order was observed for films activities: AIO/TO/ZnO > IO/TO/ZnO > ATO/IO/ZnO > TO/IO/ZnO. Differences in the film efficiencies can be attributed to differences in crystallinity, interfacial lattice mismatch, and surface morphology. Besides, the presence of Ag doping between layers that may act as trap for electrons generated in the ZnO over layer thus preventing electron–hole recombination.     

Effect of donor W and acceptor Ni codoping at Ti site on the structure and electrical properties of Na0.5Bi0.5TiO3 thin film

Pure Na_0.5Bi_0.5TiO₃ (NBT), donor W⁶⁺ doped NBT (NBTW), acceptor Ni²⁺ doped NBT (NBTNi), as well as donor W⁶⁺ and acceptor Ni²⁺ codoped NBT (NBTWNi) polycrystalline films are fabricated on indium tin oxide (ITO)/glass substrates via a chemical solution deposition method. The roles of aliovalent-ion substitution on the crystallinity, ferroelectric and dielectric properties of NBT film are mainly investigated. With the introduction of aliovalent-ion, the surface of the doped film becomes more uniform and the leakage current is reduced. Well saturated polarization-electric field (P-E) loops can be observed in W⁶⁺ and Ni²⁺ codoped NBT film due to its lowest leakage currents compared to those of other films. Also, the effect of voltage and frequency on the capacitance-voltage (C-V) curve and the dielectric tunability for the NBTWNi film is discussed. The ferroelectric and dielectric properties are largely improved in NBTWNi film, which can be ascribed to the synergetic effect of high-valence W⁶⁺ and low-valence Ni²⁺ ions. The cooperation between the acceptor and donor cations can effectively eliminate the mobile oxygen vacancies in NBT films.     

Characterization and Tribological Investigation of Sol–Gel Titania and Doped Titania Thin Films

Titania (TiO₂) and doped TiO₂ ceramic thin films were prepared on a glass substrate by a sol–gel and dip-coating process from specially formulated sols, followed by annealing at 460°C. The morphologies of the original and worn surfaces of the films were analyzed with atomic force microscopy (AFM) and scanning electron microscopy. The chemical compositions of the obtained films were characterized by means of X-ray photoelectron spectroscopy (XPS). The tribological properties of TiO₂ and doped TiO₂ thin films sliding against Si₃N₄ ball were evaluated on a one-way reciprocating friction and wear tester. The AFM analysis shows that the morphologies of the resulting films are very different in nanoscale, which partly accounts for their tribological properties. XPS analysis reveals that the doped elements exist in different states, such as oxide and silicate, and diffusion took place between the film and the glass substrate. TiO₂ films show an excellent ability to reduce friction and resist wear. A friction coefficient as low as 0.18 and a wear life of 2280 sliding passes at 3 N were recorded. Unfortunately, all the doped TiO₂ films are inferior to the TiO₂ films in friction reduction and wear resistance, primarily because of their differences in structures and chemical compositions caused by the doped elements. The wear of the glass is characteristic of brittle fracture and severe abrasion. The wear of the TiO₂ thin film is characteristic of plastic deformation with slight abrasive and fatigue wear. The doped TiO₂ thin films show lower plasticity than the TiO₂ thin film, which leads to large cracks. The propagation of the cracks caused serious fracture and failure of the films.     

Electrodeposition and optical properties of highly oriented γ-CuI thin films

A simple electrochemical process has been demonstrated to grow highly oriented γ-CuI thin films on indium doped tin oxide (ITO) glass through reducing Cu(II)-ethylene diamine tetraacetic acid disodium (EDTA) complex in aqueous solutions at or near room temperature. The CuI thin films grow preferential orientation along the 〈1 1 1〉 crystal axis from the X-ray diffraction patterns. The oriented growth of the CuI thin films is not affected by the solution pH and the applied potentials. The possible mechanism of the oriented growth is discussed, and the surface energy of different crystal planes of CuI crystal is believed to play an important role to control the oriented growth of the CuI thin films. The bandgap of the electrodeposited CuI films is 2.98 eV and the photoluminescence spectra of the CuI thin films exhibit relative intense exciton band luminescence at room temperature.     

Characterization and tribological investigation of sol-gel Al2O3 and doped Al2O3 films

Thin films of Al₂O₃ and doped Al₂O₃ were prepared on a glass substrate by dip coating process from specially formulated ethanol sols. The morphologies of the unworn and worn surfaces of the films were observed with atomic force microscope (AFM) and scanning electron microscope (SEM). The chemical compositions of the obtained films were characterized by means of X-ray photoelectron spectroscopy (XPS). The tribological properties of obtained thin films sliding against Si₃N₄ ball were evaluated and compared with glass slide on a one-way reciprocating friction tester. XPS results confirm that the target films were obtained successfully. The doped elements distribute in the film evenly and exist in different kinds of forms, such as oxide and silicate. AFM results show that the addition of the doped elements changes the structure of the Al₂O₃ films, i.e., a rougher and smoother surface is obtained. The wear mechanisms of the films are discussed based on SEM observation of the worn surface morphologies. As the results, the doped films exhibit better tribological properties due to the improved toughness. Sever brittle fracture is avoided in the doped films. The wear of glass is characteristic of brittle fracture and severe abrasion. The wear of Al₂O₃ is characteristic of brittle fracture and delamination. And the wear of doped Al₂O₃ is characteristic of micro-fracture, deformation and slight abrasive wear. The introduction of ZnO is recommended to improve the tribological property of Al₂O₃ film.