The formation of ZnO-based coatings from solutions containing high-molecular polyvinylpyrrolidone

A method for deposition of transparent nanosize ZnO-based coatings on the glass surface from solutions containing high-molecular polyvinylpyrrolidone is described. The method can be used to form transparent homogeneous coatings based on ZnO with an increased energy gap width. It does not require any intricate technological equipment.     

Substrate temperature dependence of the properties of Ga-doped ZnO films deposited by DC reactive magnetron sputtering

Ga-doped zinc oxide (ZnO:Ga) transparent conductive films were deposited on glass substrates by DC reactive magnetron sputtering. The influence of substrate temperature on the structural, electrical, and optical properties of ZnO:Ga films was investigated. The X-ray diffraction (XRD) studies show that higher temperature helps to promote Ga substitution more easily. The film deposited at 350 °C has the optimal crystal quality. The morphology of the films is strongly related to the substrate temperature. The film deposited is dense and flat with a columnar structure in the cross-section morphology. The transmittance of the ZnO:Ga thin films is over 90%. The lowest resistivity of the ZnO:Ga film is 4.48×10⁻⁴ Ω cm, for a film which was deposited at the substrate temperature of 300 °C.     

溶胶-凝胶法制备ZnO薄膜及其表征

用溶胶-凝胶法在普通玻璃表面制备了ZnO薄膜,并通过XRD、SEM、UV—VIS、DSC—TGA等测试手段对ZnO薄膜进行了表征。研究表明：溶胶-凝胶法制备的ZnO薄膜透明,薄膜表面均匀分布着片状ZnO晶粒;随着退火温度的升高,ZnO晶粒在17～30nm范围内逐渐增大。     

平板玻璃表面涂料的研究及应用

透明装饰性涂料在玻璃上的应用使其表面功能多样化,应用范围更加广泛.本文阐述了平板玻璃涂料制备技术中基料树脂的选取、涂膜耐久性以及涂装工艺,并综述了几类玻璃涂料,如普通装饰性涂料、低辐射涂料、防反射涂料以及新型玻璃建材的应用研究进展.     

Fabrication of high quality zinc-oxide layers through electrohydrodynamic atomization

Zinc oxide (ZnO) is a useful material in the fabrication of many electronic devices because of its wide band-gap, excellent transparency and high electron mobility. Thin films of ZnO have been fabricated where an alcosol solution containing 7 wt.% ZnO nano-particles was synthesized and subjected to controlled flow through a metal capillary exposed to an electric field at the ambient temperature to generate an electrohydrodynamic jet, which subsequently disintegrated into droplets thereby depositing a uniform thin film of zinc oxide on the glass substrates with an average thickness of 115 nm at a constant substrate speed of 0.25 mm/s. Pure and perfectly uniform transparent films with an average transmittance of 88% have been deposited with wurtzite crystal structure and an electrical resistivity of approximately 64 Ω.cm.     

低熔可切削生物活性微晶玻璃的研究

选择一种出SiO₂-MgO-Al₂O₃-K₂O-CaO-P₂O₅-F基础玻璃体系,并添加不同量的ZnO,制备出性能良好的可切削生物微晶玻璃.结果表明,由于ZnO的添加,可使母玻璃的熔化温度由1450℃降至1300℃,可切削生物活性微晶玻璃的母玻璃能够在较低的温度熔化制备.母玻璃晶化后析出相主要为云母相和氟磷灰石相;各种晶相的组合形貌为花瓣形态,其断口呈现穿晶断裂的特征,并有晶体拔出,使材料具备了较高的强度;由于析出了较多的云母相,该微晶玻璃兼具良好的可切削性能.     

Effect of substrate on structural and transport properties of sprayed Fe:ZnO polycrystalline thin films

ZnO thin films doped with iron have been grown by spray pyrolysis technique on glass and fused silica substrates in order to study the effect of substrate material on the structural, optical, and electro-magnetotransport properties of grown layers. The polycrystalline Fe:ZnO films have different growth orientation according to the substrate, though both films are highly transparent in the visible region of wavelength. The sample grown on glass substrate has larger magnetoresistance and lower electron mobility than that on fused silica substrate.     

Solution processed Al doped ZnO film fabrication through electrohydrodynamic atomization

In this study, highly transparent, 250 nm thick films of Aluminum doped Zinc-oxide (ZnO:Al) are achieved on glass substrates at ambient conditions through a solution processing technique called electrohydrodynamic atomization. A 10 wt.% monodispersed solution containing 6% ZnO:Al nanoparticles (ZnO/Al₂O₃) in ethanol has been synthesized first and then used in the deposition process as the working solution. Pure and uniform transparent films with an average transmittance of 93% have been deposited with crystal structure exhibiting both zincite and gahnite phases. Surface composition purity has been confirmed using X-ray photoelectron spectroscopy technique and the clear indication of Zn-2p and Al-2p peaks confirms surface integrity. Fourier Transform Infrared analysis further confirms the presence of aluminum in the samples. The electrical properties are studied by recording and analyzing the current-voltage (I-V) measurements and the resistivity has been estimated from the slope of the IV-curve which is approximately 25 mΩ.cm. The layer roughness has been characterized using atomic force microscopy.     

Influence of pH on ZnO nanocrystalline thin films prepared by sol–gel dip coating method

ZnO nanocrystalline thin films have been prepared on glass substrates by sol?Cgel dip coating method. ZnO thin films have been coated at room temperature and at four different pH values of 4, 6, 8 and 10. The X-ray diffraction pattern showed that ZnO nanocrystalline thin films are of hexagonal structure and the grain size was found to be in the range of 25?C45?nm. Scanning electron microscopic images show that the surface morphology improves with increase of pH values. TEM analysis reveals formation of ZnO nanocrystalline with an average grain size of 44?nm. The compositional analysis results show that Zn and O are present in the sample. Optical band studies show that the films are highly transparent and exhibit a direct bandgap. The bandgap has been found to lie in the range of 3 $\boldsymbol\cdot$ 14?C3 $\boldsymbol\cdot$ 32?eV depending on pH suggesting the formation of ZnO nanocrystalline thin films.     

Structural and plasmonic characteristics of sputtered SnO<Subscript>2</Subscript>:Sb and ZnO:Al thin films as a function of their thickness

Heavily doped metal oxide semiconductors are being developed as thin film transparent electrodes for many applications and their deposition at low substrate temperature can extend the use on heat sensitive devices. The structural and electro-optical characteristics of such metal oxide coatings are tightly related and depend on the specific deposition parameters apart from the material composition. In this work, SnO₂:Sb (ATO) and ZnO:Al (AZO) thin films have been prepared by sputtering at room temperature on glass substrates, changing the deposition time to obtain various layer thicknesses from 0.2 to 0.9 μm; and they have been analyzed by X-ray diffraction, spectrophotometry, and Hall-effect measurements. ATO samples crystallize in the tetragonal structure with mean crystallite size increasing from 8 to 20 nm when the film thickness grows. The comparison of Hall mobility and optical mobility values indicates a significant contribution of grain boundary scattering for these ATO layers. Otherwise, AZO films show larger crystallites (21–27 nm) and a strong preferential orientation for analogous thickness increment, resulting in a lower contribution of the grain boundary scattering to the overall Hall mobility. The in-grain mobility for each sample is also related to the respective crystallite size and carrier concentration values.     

Spin coating of transparent zinc oxide films using novel precursor

The coating of transparent ZnO films using zinc 2-ethylhexanoate [Zn(OOCH(C₂H₅)C₄H₉)₂] as a novel metal organic monomer is reported. Zinc 2-ethylhexanoate is liquid at room temperature and can be spin-coated on a flat substrate without precipitation of ZnO under ambient condition. The spin-coated films were heated at different temperatures to remove unwanted organic materials from the surface. It was found that transparent ZnO films could be produced on glass substrates at low heating temperature (~400 °C). The ZnO films produced using the new monomer were free of cracks and defects. Also the ZnO films produced using the new monomer have excellent optical transmittance, mechanical properties and small surface roughness. The surface morphology and degree of crystallinity of the films coated by the new monomer were compared with these properties of ZnO films produced using zinc acetate-based sol–gels. The results clearly indicate that the novel monomer is a potential precursor for coating transparent ZnO films at low temperatures.     

Preparation of aluminum doped zinc oxide films and the study of their microstructure, electrical and optical properties

Aluminum doped zinc oxide (AZO) polycrystalline thin films were prepared by sol-gel dip-coating process on optical glass substrates. Zinc acetate solutions of 0.5 M in isopropanol stabilized by diethanolamine and doped with a concentrated solution of aluminum nitrate in ethanol were used. The content of aluminum in the sol was varied from 1 to 3 at.%. Crystalline ZnO thin films were obtained following an annealing process at temperatures between 300 °C and 500 °C for 1 h. The coatings have been characterized by X-ray diffraction, UV-Visible spectrophotometry, scanning electron microscopy, and electrical resistance measurement. The ZnO:Al thin films are transparent (∼ 90%) in near ultraviolet and visible regions. With the annealing temperature increasing from 300 °C to 500 °C, the film was oriented more preferentially along the (0 0 2) direction, the grain size of the film increased, the transmittance also became higher and the electrical resistivity decreased. The X-ray diffraction analysis revealed single-phase ZnO hexagonal wurtzite structure. The best conductors were obtained for the AZO films containing 1 at.% of Al, annealed at 500 °C, 780 nm film thickness.     

Plasma emission monitoring (PEM) controlled DC reactive sputtered ZnO:Al thin films

High deposition rate ZnO:Al films have been produced at room temperature by reactive DC sputtering using a plasma emission monitoring (PEM) control system. We have investigated the relationship between structural, optical and electrical properties of the ZnO:Al films. Crystal structures of the films have been studied by X-ray diffraction. Optimum ZnO:Al films, with 17-40 Ω/□ sheet resistance range and transmittance approaching 88% in the visible region, exhibited a hexagonal ZnO structure with preferential (002) orientation and crystallite sizes of about 27 nm. Resistive transparent films displayed a more random orientation showing peaks at (100) and (102) orientations. Dark “metallic” films were shown to consist of mainly zinc. The optimal ZnO:Al film has been determined from a figure of merit based on power losses due to absorption and series resistance in the ZnO:Al films. It is highly transparent, with low resistance, pronounced (002) peak and large crystallite size.     

溶胶-凝胶法制备ZnO薄膜及其光催化性能

用溶胶-凝胶法在普通玻璃表面制备了薄膜型ZnO光催化剂,通过XRD、Ab2d、UV-VIS等测试技术对ZnO薄膜进行了表征;以偶氮胭脂红为降解物,考察了薄膜退火温度、镀膜层数、溶液初始质量浓度和反应体系初始pH值对ZnO薄膜光催化性能的影响,并进行了相关机理的探讨．研究表明：溶胶-凝胶法制备的ZnO薄膜呈透明状,薄膜表面均匀分布着球形ZnO晶粒;随着退火温度的升高,ZnO晶粒在17～30mm范围内逐渐增大．光催化实验中ZnO薄膜光催化降解偶氮胭脂红的最佳工艺条件是：退火温度为300℃,镀膜层数为5层,溶液初始pH值为8～9．     

Growth of highly oriented ZnO films by the two-step electrodeposition technique

Compact and transparent ZnO films were deposited on the ITO/glass substrates from zinc nitrate aqueous solution by the two-step electrodeposition technique. While the first potentiostatic step was used to produce ZnO seed layer, the ZnO film growth has been done galvanostatically. Effects of the potentiostatic parameters on the crystal structure, morphology and optical properties of ZnO films were investigated. Results show that ZnO films with highly c-axis preferred orientation can been obtained when the potentiostatic deposition at −1.2 V for 15 s has been applied. Such an observation might be attributed to the etching process of ITO substrate in the diluted HCl solution. The film exhibits smooth and compact morphology, high transmittance in the visible band (>80%) and sharp absorption edge (at ∼370 nm). The analysis on the growth mechanism indicates that the short potentiostatic process prior to the film growth can produce ZnO seed layer and substitute the initial nucleation process in the conventional one-step galvanostatic deposition, thus increasing the nucleation density and preventing the formation of loose structures.     

Preparation and Characterization of Eu<Superscript>3+</Superscript>-Doped Transparent Oxyfluoride Glasses

A process has been proposed for the preparation of oxyfluoride glasses based on the SiO₂–B₂O₃–Bi₂O₃–ZnO–CaF₂ system at various ratios of batch components, and transparent glasses have been obtained at a temperature below 1000°C. According to X-ray diffraction data, all of the glasses are X-ray amorphous. The surface morphology of the glasses has been examined and their glass transition temperatures have been determined. Their local structure has been studied by IR spectroscopy and it has been shown that, independent of composition, the glasses contain complex polyborate anions formed by [BO₃] and [BO₄] groups. Bismuth is incorporated into the glass network to form Bi–O–Si bonds and [BiO₆] network-formers.     

Superhydrophobic and transparent coatings prepared by self-assembly of dual-sized silica particles

Superhydrophobic and transparent coatings have been prepared by self-assembly of dual-sized silica particles from a mixed dispersion. The desirable micro/nano hierarchical structure for superhydrophobicity is constructed simply by adjusting the size and ratio of the dual-sized particles without organic/inorganic templates. The transparency of the prepared coatings is also researched, and the light scattering can be reduced by lowering the ratio of big sub-micro particles while the superhydrophobicity maintains unchanged. When nano particles with a diameter of 50 nm and sub-micro particles with a diameter of 350 nm are assembled, a superhydrophobic property with a water contact angle of 161° is achieved. Additionally, the coated glass is also very transparent. The highest transmittance of the coated glass can reach 85%. Compared to traditional colloid self-assembly approach, which often involves dozens of steps of layer-by-layer processing and organic/inorganic templates, the present approach is much simpler and has advantages for large-scale coating.     

Ein neues Wärmedämmsystem für Architekturglass

Vacuum coated glass plays an outstanding role for the energy saving of buildings. The basis of such low emissivity coatings is a 10 nm thick silver layer causing an effective reflexion of room temperature radiation. With conventional coatings k‐values of 1,3 W/m²K are realized. In the frame of a research project funded by the BMBF reactive mid frequency sputtering (Leybold TwinMag®) has been introduced for manufacturing of low e glass. The new developed system glass — TiO₂ — ZnO — Ag — NiCrO_x — Si₃N₄ enables a k‐value of 1,1 W/m²K and an improvement of optical properties.     

Effect of substrate temperature and annealing treatment on the electrical and optical properties of silver-based multilayer coating electrodes

Multilayer coatings consisting of thin silver layers sandwiched between layers of transparent conducting metal oxides are investigated from the view point of low-resistance electrodes for use in flat panel displays, solar cells, etc. ZnO/Ag/ZnO multilayer films were prepared on glass substrates by simultaneous RF magnetron sputtering of ZnO and dc magnetron sputtering of Ag. Optimization of the deposition conditions of both ZnO layers and metallic layers were performed for better electrical and optical properties. The structural, electrical and optical properties of the films (deposited at room temperature, different substrate temperature and annealed at different conditions) were characterized with various techniques. We could not produce high-quality transparent conductive electrodes simply by annealing at various temperatures. However, improved electrical properties and a considerable shift in the transmittance curves was observed after heat treatment. The experimental results show that the electrical resistivity of as-grown films can be decreased to 10^− 5 Ω cm level with post-annealing at 400 °C for 2 h in vacuum atmosphere. After heat treatment, the sheet resistance was reduced as much as 20% which was due to the increased grain size of Ag film. The samples heat treated at 200-400 °C under vacuum or nitrogen atmosphere showed the best electrical properties. The key to the superior electrical and optical properties of the multilayer is the optimization of growth conditions of the silver layer by careful control of the oxide properties and the use of appropriate annealing temperature and atmosphere.     

Studies on the seebeck effect in semiconducting ZnO thin films

For ZnO thin films prepared by a pyrolytic technique, the thermoelectric power has been measured from room temperature up to 200 °C with reference to pure lead. The thickness and temperature dependence of its related parameters have been studied. The Fermi levels were determined using a nondegenerate semiconducting model. The carrier scattering index, activation energy and temperature coefficient of activation energy, have all been obtained at different ranges of thickness and temperature. All the samples were polycrystalline in structure and optically transparent.