Thin Films that Consist of CuO Mesocrystal Nanosheets: An Application of Microbial‐Mineralization‐Inspired Approaches to Thin‐Film Formation

Thin films of copper oxides can be synthesized on substrates by using approaches that are inspired by microbial mineralization processes. In nature, precipitates of manganese and iron oxides with controlled oxidation states and crystal phases are produced through biomineralization by microorganisms. We have previously reported microbial‐mineralization‐inspired approaches that are comprised of direct and intermediate routes for the controlled syntheses of transition‐metal oxides. Herein, these approaches are applied to the thin‐film formation and coating of copper oxides and a related compound with controlled crystal phases and morphologies. Thin films of CuO, Cu₂O, and Cu₂(OH)₃Cl were selectively synthesized by using direct or intermediate routes. Notably, CuO mesocrystal nanosheets formed a thin film over the whole of the substrate. The resultant CuO mesocrystal nanosheets showed enhanced properties for the electrochemical detection of dopamine. This study shows the potential applicability of microbial‐mineralization‐inspired approaches to thin‐film coatings.     

Tetrahydroxy‐Perylene Bisimide Embedded in a Zinc Oxide Thin Film as an Electron‐Transporting Layer for High‐Performance Non‐Fullerene Organic Solar Cells

By introduction of four hydroxy (HO) groups into the two perylene bisimide (PBI) bay areas, new HO‐PBI ligands were obtained which upon deprotonation can complex Zn^II ions and photosensitize semiconductive zinc oxide thin films. Such coordination is beneficial for dispersing PBI photosensitizer molecules evenly into metal oxide films to fabricate organic–inorganic hybrid interlayers for organic solar cells. Supported by the photoconductive effect of the ZnO: HO‐PBI hybrid interlayers, improved electron collection and transportation is achieved in fullerene and non‐fullerene polymer solar cell devices, leading to remarkable power conversion efficiencies of up to 15.95 % for a non‐fullerene based organic solar cell.     

Comparative Studies on Degradation of Methyl Orange by Nanostructured Zinc and Zinc Oxide Films

Nanostructured zinc and zinc oxide films were prepared by magnetron sputtering processes and succeeded air annealing treatments. Comparison of reductive degradation rate of methyl orange (MO) by zinc films and photocatalytic degradation rate of MO by zinc oxide films was carried out. Both reductive degradation and photocatalytic degradation process of MO by zinc and zinc oxide films can be described by first order kinetic model. It was found that although MO liquid was most quickly decolorized by metallic zinc films, the mineraliza-tion of MO was not thorough. Observation of extra ultraviolet absorption peaks indicated the formation of aromatic intermediates. On the other hand, although the photocatalytic degradation rate of MO liquid by ZnO films was only as about 1/4 large as the reductive degradation rate by zinc films, no signs of aromatic intermediates were found. Moreover, it was found that partially oxidized zinc oxide film showed higher photocatalytic efficiency than the totally oxidized ZnO films. Synergy effect between zinc and zinc oxide phase in the partially oxidized films was considered to be responsible for the higher photocatalytic efficiency.     

氧化锌薄膜的电化学沉积和表征

以透明导电玻璃(TCO)为衬底，用硝酸锌水溶液作为电解液，研究了阴极还原沉积ZnO薄膜的反应机理和电化学行为. 通过改变工艺条件来控制ZnO的生长速率， 得到了粒径为10～15 nm的纳米ZnO薄膜. XRD分析显示纳米ZnO薄膜纯度高， 呈纤锌矿结构. 光学测试结果表明，在可见光区其透光度高达90%，禁带宽度为3.37 eV.     

Soft solution synthesis of a zinc oxide nano-screw superstructure and its composite with nitrogen-doped titania

Novel zinc oxide thin films with nano-screw superstructure were prepared via a soft solution route without any polymer additives. A ZnO thin film could be produced directly on the substrates. The ZnO thin film with nano-screw superstructure was prepared using visible-light-induced nitrogen-doped titania nano-particles. The ZnO nano-screw/TiO_2−x N _y composite film showed excellent photocatalytic deNO _x ability and quantum efficient.     

Superior Photostability and Photocatalytic Activity of ZnO Nanoparticles Coated with Ultrathin TiO2 Layers through Atomic‐Layer Deposition

Atomic‐layer deposition (ALD) is a thin‐film growth technology that allows for conformal growth of thin films with atomic‐level control over their thickness. Although ALD is successful in the semiconductor manufacturing industry, its feasibility for nanoparticle coating has been less explored. Herein, the ALD coating of TiO₂ layers on ZnO nanoparticles by employing a specialized rotary reactor is demonstrated. The photocatalytic activity and photostability of ZnO nanoparticles coated with TiO₂ layers by ALD and chemical methods were examined by the photodegradation of Rhodamine B dye under UV irradiation. Even though the photocatalytic activity of the presynthesized ZnO nanoparticles is higher than that of commercial P25 TiO₂ nanoparticles, their activity tends to decline due to severe photocorrosion. The chemically synthesized TiO₂ coating layer on ZnO resulted in severely declined photoactivity despite the improved photostability. However, ultrathin and conformal ALD TiO₂ coatings (≈0.75–1.5 nm) on ZnO improved its photostability without degradation of photocatalytic activity. Surprisingly, the photostability is comparable to that of pure TiO₂, and the photocatalytic activity to that of pure ZnO.     

In situ PM‐IRRAS studies of organothiols and organosilane monolayers–ZnO interfaces at high water activities

In situ photoelastic‐modulated Fourier transform infrared reflection absorption spectroscopy has been applied for the investigation of interfacial stability of organothiol and organosilane monolayer films on nanocrystalline zinc oxide thin films. It has been shown that for octadecyltriethoxysilane films, exposure to high water activities results in physisorption of water in the cross‐linked film. This high water activity at the interface leads to a reversible wet de‐adhesion of the interfacial silanol groups from the ZnO surface. However, the organothiol seems to form a denser monolayer and a stable by S–Zn bond that is resistant to the competition with adsorbed water. The reversible attachment for cross‐linked organosilanol films has been demonstrated for the first time by means of an in situ spectroscopic method on model ZnO surfaces. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation and electro‐optical properties of polymer dispersed liquid crystal films with relatively low liquid crystal content

In this paper, polymer dispersed liquid crystals (PDLC) films with LC content as low as 40 wt% were prepared, and the electro‐optical properties were carefully investigated. To accomplish this, different (meth)acrylate copolymerizaiton monomers have been used. The electro‐optical properties and morphologies of the PDLC films were strongly influenced by the chemical structure of copolymerization monomers (hydroxypropyl methacrylate (HPMA), glycidyl methacrylate, hydroxypropyl acrylate) and their feed ratio. Lower driven voltage and higher contrast ratio were achieved when the PDLC films showed a morphology with suitably LC domain size. At high HPMA content, a thin polymer film was formed on the surface of PDLC samples, which is beneficial to decrease the total LC content in PDLC devices. Copyright © 2013 John Wiley & Sons, Ltd.     

Zinc Oxide/Zinc Hexacyanoferrate Hybrid Film‐Modified Electrodes for Guanine Detection

An electroactive polynuclear hybrid films of zinc oxide and zinc hexacyanoferrate (ZnO/ZnHCF) have been deposited on electrode surfaces from H₂SO₄ solution containing Zn(NO₃)₂ and K₃[Fe(CN)₆] by repetitive potential cycling method. Simultaneous cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM) measurements demonstrate the steady growth of hybrid film. There are two redox couples present in the voltammograms of hybrid film and it is obvious in the case of pH 2. Surface morphology of hybrid film was investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Energy dispersive spectrometer (EDS) data confirm existence of zinc oxide in the hybrid film. The effect of type of monovalent cations on the redox behavior of resulting film was investigated. In pure supporting electrolyte, electrochemical responses of modified electrode resemble with that of a surface immobilized redox couple. The electrocatalytic activity of ZnO/ZnHCF hybrid film was investigated towards guanine using cyclic voltammetry and rotating disc electrode (RDE) techniques. Finally, feasibility of using ZnO/ZnHCF hybrid film‐coated electrodes for guanine estimation in flow injection analysis (FIA) was also investigated.     

Influence of Surface Morphology and Conductivity on Photocatalytic Performance of Solution‐Processed Zinc Oxide Film

Solution‐processed ZnO films with various structures have been fabricated and the influence of surface morphology and conductivity on photocatalytic performance, including improvement of conductivity, hydrogen production, and photodegradation of rhodamine B, has been investigated. Surface morphology was controlled by solution conditions, and as‐fabricated films had rod, dense, and flower‐like structures. Improved conductivity was revealed by the photocatalytic activity of ZnO, the influence of surface morphology on the photodegradation of rhodamine B, and the relationship with conductivity and hydrogen production.     

Does a Photocatalytic Synergy in an Anatase–Rutile TiO2 Composite Thin‐Film Exist?

It has often been suggested that anatase–rutile mixtures/composites synergistically enhance photocatalysis. However, in the case of dense thin‐films containing an intimate mix of both anatase and rutile phases, such an effect has not been observed. In synthesising combinatorial films with graded film thickness and phase, and applying established photocatalytic mapping methods, we were able to assess how dense thin‐films of intimately mixed anatase–rutile mixtures affect photocatalytic performance. We found that no photocatalytic synergy between anatase–rutile composites (29≤rutile %≤83) within such dense thin‐film systems exists. In fact, an increased presence of rutile caused the photocatalytic activity to fall. This was explained by the unfavourable energetics in the multiple electron transfers required between several neighbouring rutile and anatase sites for the photo‐generated electron to reach the material’s surface; encouraging the trapping of electrons within the bulk and increasing the likelihood of charge recombination. The decrease in photocatalytic activity was found to vary linearly with rutile component.     

Controlled Orientation in a Bio‐Inspired Assembly of Ag/AgCl/ZnO Nanostructures Enables Enhancement in Visible‐Light‐Induced Photocatalytic Performance

In a bio‐inspired approach, polyamine‐mediated mineralization of ZnO was explored to develop an environmentally benign methodology for synthesizing Ag/AgCl/ZnO nanostructures. The assembling properties displayed by the polyamines to create composite structures was utilized to have the nanocomponents effectively interact with each other in a way that is desirable for the application envisaged. The polyamines, which act as a mineralizing agent for ZnO nanoparticles, also facilitate the formation of Ag/AgCl within ZnO under ambient conditions. Thus synthesized Ag/AgCl/ZnO nanostructures represent a multi‐heterojunction system in which the nanocomponents lead in a synergistic way to enhancement in the photocatalytic activity under visible‐light irradiation.     

Crystallization and Reduction of Sol-Gel-Derived Zinc Oxide Films by Irradiation with Ultraviolet Lamp

Structural changes in sol-gel films with photo-irradiation were investigated using zinc oxide (ZnO) derived from zinc acetate. The exposure of the films to an ultraviolet lamp induced hexagonal ZnO crystals in a relatively dense amorphous structure. On the other hand, the formation of zinc metal was found in a porous gel film. The photo-induced crystallization and reduction are ascribed to the electronic excitation in the metastable non-crystalline states.     

旋涂水溶液前驱体制备氧化锌薄膜及其性质

通过旋涂法, 采用Zn(OAc)2·2H2O和聚环氧乙烷(PEO)的水溶液为前驱体在不同的热处理温度下制备了ZnO薄膜. PEO的加入增加了溶液的成膜性, 其较低的热分解温度有利于制得纯净的ZnO薄膜. 文中考察了在不同热处理温度下制备的ZnO薄膜的形貌、结晶性、带隙(Eg)以及电导性. 原子力显微镜(AFM)测试表明在热处理温度为400、450和500 ℃制备的ZnO薄膜的粗糙度均方根值分别为3.3、2.7和3.6 nm. 采用透射电子显微镜(TEM)测试发现ZnO薄膜中含有大量纳晶粒子. 通过测试ZnO薄膜的UV-Vis吸收光谱, 根据薄膜位于373 nm处的吸收带边计算得到ZnO的带隙为3.3 eV. 通过对薄膜的电流-电压(I-V)曲线的测试计算得到在热处理温度为400、450和500 ℃制备的ZnO薄膜的电阻率分别为3.3×109、2.7×109和6.6×109 Ω·cm. 450 ℃时制备的ZnO薄膜的电阻率最小, 主要是由于较高的热处理温度有利于提高薄膜的纯度、密度和吸附氧. 而纯度较高、密度较大的薄膜电阻率比较小; 吸附氧含量增加, 晶界势垒增大, 电阻率增大. 因此在纯度和吸附氧的双重作用下450 ℃时制备的ZnO薄膜的电阻率最小, 而500 ℃时制备的ZnO薄膜的电阻率最大.     

Microdomain morphology of lamella‐forming diblock copolymer confined in a thin film

We report the self‐consistent field theory (SCFT) of the morphology of lamella‐forming diblock copolymer thin films confined in two horizontal symmetrical/asymmetrical surfaces. The morphological dependences of thin films on the polymer‐surface interactions and confinement, such as film thickness and confinement spatial structure, have been systematically investigated. Mechanisms of the morphological transitions can be understood mainly through the polymer‐surface interactions and confinement entropy, in which the plat confinement surface provides a surface‐induced effect. The confinement is expressed in the form of the ratio D/L₀, here D is film thickness, and L₀ is the period of bulk lamellar‐structure. Much richer morphologies and multiple surface‐induced morphological transitions for the lamella‐forming diblock copolymer thin films are observed, which have not been reported before. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1–10, 2009     

纳米ZnO薄膜的制备及其可见光催化降解甲基橙

采用溶胶-凝胶方法制备ZnO透明溶胶, 在铝箔上涂膜后经500 ℃处理制得具有可见光响应的纳米ZnO薄膜光催化剂. 以甲基橙模拟有机污染物, 在可见光下研究了薄膜的降解性能, 结果表明, 用一片有效面积为200 cm2的ZnO/Al薄膜作为催化剂, 甲基橙的降解率达到96.3％, 比ZnO负载在玻璃上制得的ZnO/glass薄膜催化剂活性高得多. 采用扫描电镜与原子力显微镜对ZnO/Al薄膜制备条件进行了表征, 结果发现多孔ZnO/Al薄膜比致密ZnO/Al薄膜具有更高的活性, 实验制备的具有高活性的ZnO/Al薄膜颗粒平均直径为52.2 nm. 采用本方法制备的ZnO/Al薄膜是一种具有应用前景的, 能在可见光下降解有机物的有效光催化剂.     

Photocatalytic activities of multilayered ZnO-based thin films prepared by sol–gel route: effect of SnO2 heterojunction layer

In present study, ZnO/SnO₂/ZnO/SnO₂/ZnO multi–layer, ZnO/SnO₂/ZnO triple layer and ZnO single layer films have been deposited on glass substrate by sol–gel dip–coating technique. The structural and optical properties of thin films have been investigated by X-ray diffractometer, UV–visible, photoluminescence spectroscopies and scanning electron microscopy. The structural analysis reveals structural inhomogeneities and different crystallite growth processes as function of number of deposited layers. A comparison between photocatalytic activity of zinc oxide samples toward photodegradation of phenol, 4-aminophenol and 4-nitrophenol has been performed under UV light irradiation. Experiments were conducted to study the effects of operational parameters on the degradation rate. Pseudo-first-order photodegradation kinetics was observed on all films and the reaction constants were determined. The results showed that the photocatalytic activity of ZnO multi–layer film was superior to that of the ZnO single- and triple-layer films. Differences in film efficiencies can be attributed to differences in crystallinity, surface morphology, defect concentration of oxygen vacancy and to presence of SnO₂ sublayer that may act as trap for electrons generated in the ZnO layer thus preventing electron–hole recombination. The results reveal that SnO₂ hetrojunction layers improve crystalline quality, optical and photocatalytic properties of ZnO multilayered films.     

Preparation of nitrogen doped zinc oxide nanoparticles and thin films by colloidal route and low temperature nitridation process

Nitrogen doped zinc oxide (ZnO) nanoparticles have been synthesized using a colloidal route and low temperature nitridation process. Based on these results, 200 nm thick transparent ZnO thin films have been prepared by dip-coating on SiO₂ substrate from a ZnO colloidal solution. Zinc peroxide (ZnO₂) thin film was then obtained after the chemical conversion of a ZnO colloidal thin film by H₂O₂ solution. Finally, a nitrogen doped ZnO nanocrystalline thin film (ZnO:N) was obtained by ammonolysis at 250 °C. All the films have been characterized by scanning electron microscopy, X-ray diffraction, X-Ray photoelectron spectroscopy and UV–Visible transmittance spectroscopy.     

Surface precipitation of highly porous hydrotalcite-like film on Al from a zinc aqueous solution

A hydrotalcite-like film has been successfully deposited on an Al-bearing glass substrate based on an interface reaction between an Al layer and a zinc aqueous solution. The film selectively grew on the Al surface but not on the glass surface. The film on Al was composed of layered nanosheets of a hydrotalcite-like compound containing Al and Zn. Comparably, deposits on the plastic surface and precipitates in solution were wurzite-type ZnO with various morphologies depending upon the preparation conditions. At low supersaturation degrees, single crystals and superstructures of Zn-Al hydrotalcite were also obtained. This porous hydrotalcite film has a potential application as catalyst supports, environmental materials, or matrixes for hydrotalcite-based nanocomposite films. Using Al as a reaction interface makes it easy to coat porous hydrotalcites on a series of matrix materials varying in shapes and properties, which is important for achieving practical applications. In addition, the method developed should be widely applicable to other systems for the preparation of porous or oriented hydrotalcite-like thin films by an appropriate combination of divalent/trivalent solution-substrate systems.     

Liquid‐Crystalline Biomacromolecular Templates for the Formation of Oriented Thin‐Film Hybrids Composed of Ordered Chitin and Alkaline‐Earth Carbonate

Macroscopically ordered inorganic thin films have been formed on unidirectionally oriented, liquid‐crystalline chitin matrices. In the presence of poly(acrylic acid) (PAA), unidirectionally oriented chitin films act as templates for the formation of oriented thin‐film crystals of alkaline‐earth carbonates such as SrCO₃ and BaCO₃. The morphology and orientation of crystals are dependent on the metal ion concentration. For SrCO₃ crystallization, unidirectional thin films and hexagonal‐shaped thin films have been deposited from 200 and 25 mm concentration strontium solutions, respectively.