Optical and microstructural properties of ZnO/TiO2 nanolaminates prepared by atomic layer deposition

ZnO/TiO₂ nanolaminates were grown on Si (100) and quartz substrates by atomic layer deposition at 200°C using diethylzinc, titanium isopropoxide, and deionized water as precursors. All prepared multilayers are nominally 50 nm thick with a varying number of alternating TiO₂ and ZnO layers. Sample thickness and ellipsometric spectra were measured using a spectroscopic ellipsometer, and the parameters determined by computer simulation matched with the experimental results well. The effect of nanolaminate structure on the optical transmittance is investigated using an ultraviolet–visible-near-infrared spectrometer. The data from X-ray diffraction spectra suggest that layer growth appears to be substrate sensitive and film thickness also has an influence on the crystallization of films. High-resolution transmission electron microscopy images show clear lattice spacing of ZnO in nanolaminates, indicating that ZnO layers are polycrystalline with preferred (002) orientation while TiO₂ layers are amorphous.     

Excellent antimicrobial properties of mesoporous anatase TiO2 and Ag/TiO2 composite films

Optically transparent, crack-free, mesoporous anatase TiO₂ thin films were fabricated. The Ag/TiO₂ composite films were prepared by incorporating Ag in the pores of TiO₂ films with an impregnation method via photoreduction. The as-prepared composite films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectronic spectra (XPS) and N₂ adsorption. The release behavior of silver ions in the mesoporous composite film was also studied. Moreover, the antimicrobial behaviors of the mesoporous film were also investigated by confocal laser scanning microscopy. The antibacterial activities of the composite films were studied by a fluorescence label method using Escherichia coli (E. coli) as a model. The as-prepared mesoporous TiO₂ films showed much higher antimicrobial efficiency than that of glass and commercial P25 TiO₂ spinning film. The facts would result from the high surface area, small crystal size and more active sites for the mesoporous catalysis. After the doping of Ag, a significant improvement for the antimicrobial ability was obtained. To elucidate the roles of the membrane photocatalyst and the doped silver in the antimicrobial activity, cells from a silver-resistant E. coli were used. These results indicated that Ag nanoparticles in the mesoporous were not only an antimicrobial but also an intensifier for photocatalysis. The as-prepared mesoporous composite film is promising in application of photocatalysis, antimicrobial and self-clean technologies.     

Fabrication and characterization of WO3/Ag/WO3 multilayer transparent anode with solution-processed WO3 for polymer light-emitting diodes

ABSTRACT: The dielectric/metal/dielectric (DMD) multilayer is suitable for a transparent electrode because of its high optical and high electrical properties; however, it is fabricated by an expensive and inefficient multistep vacuum process. We present a WO3/Ag/WO3 (WAW) multilayer transparent anode with solution-processed WO3 for polymer light-emitting diodes (PLEDs). This WAW multilayer not only has high transmittance and low resistance but also can be easily and rapidly fabricated. We devised a novel method to deposit a thin WO3 layer by a solution process in an air environment. A tungstic acid solution was prepared from an aqueous solution of Na2WO4 and then converted to WO3 nanoparticles (NPs) by a thermal treatment. Thin WO3 NP layers form WAW multilayer with a thermal evaporated Ag layer, and they improve the transmittance of the WAW multilayer because of its high transmittance and refractive index. Moreover, the surface of the WO3 layer is homogeneous and flat with low roughness because of the WO3 NP generation from the tungstic acid solution without aggregation. We performed optical simulation and experiments, and the optimized WAW multilayer had a high transmittance of 85% with a sheet resistance of 4 /sq. Finally, PLEDs based on the WAW multilayer anode achieved a maximum luminance of 35550 cd/m2 at 8 V, and this result implies that the solution-processed WAW multilayer is appropriate for use as a transparent anode in PLEDs.     

Transparent and high infrared reflection film having sandwich structure of SiO2/Al:ZnO/SiO2

New transparent and high infrared reflection films having the sandwich structure of SiO₂/Al:ZnO(AZO)/SiO₂ were deposited on the soda-lime silicate glass at room temperature by radio frequency (R.F.) magnetron sputtering. The optical and electrical properties of SiO₂ (110 nm)/AZO (860 nm)/SiO₂ (110 nm) sandwich films were compared with those of single layer AZO (860 nm) films and double layer SiO₂ (110 nm)/AZO (860 nm) films. The results show that these sandwich films exhibit high transmittance of over 85% in the visible light range (380–760 nm), and low reflection rate of below 4.5% in the wavelength range of 350–525 nm, which is not shown in the conventional single layer AZO (860 nm) films and double layer SiO₂ (110 nm)/AZO (860 nm) films. Further these sandwich films display a low sheet resistance of 20 Ω/sq by sheet resistance formula and high infrared reflection rate of above 80% in the wavelength range of 15–25 μm. In addition, the infrared reflection property of these sandwich films is determined mainly by the AZO film. The outer SiO₂ film can diminish the interference coloring and increase transparency; the inner SiO₂ film improves the adhesion of the coating to the glass substrate and prevents Ca²⁺ and Na⁺ in the glass substrate from entering the AZO film.     

Facile synthesis of mesoporous Ag-loaded TiO2 thin film and its photocatalytic properties

Ag nanoparticles highly dispersed into TiO₂ thin films are synthesized via a remarkably simple one-pot route in the presence of a P123 triblock copolymer as template directing and reducing agents, where the reduction of Ag⁺ to Ag⁰ by in situ heat-induced reduction through the oxidation of template at 400 °C and the controlled polymerization of TiO₂ take place simultaneously. The obtained mesoporous Ag/TiO₂ films deposited on soda-lime glass were optically transparent and crack-free. SEM and Kr adsorption clearly prove that Ag/TiO₂ films at different Ag contents are mesoporous with large surface area and regularly ordered mesopores and the thickness of the obtained films is ∼280 ± 20 nm. The pristine TiO₂ film exhibits a specific surface area of 63 cm²/cm² and specific pore volume of 0.013 mm³/cm² that it is decreased to 42 cm²/cm² and 0.010 mm³/cm² respectively as a result of Ag-loaded mesoporous TiO₂. The newly prepared photocatalysts Ag/TiO₂ films were evaluated for their photocatalytic degradation of 2-chlorophenol as a model reaction. It was found that the meso-ordered Ag/TiO₂ films are more photoactive 8 times than nonporous commercial photocatalysts Pilkington Glass Activ™. The recycling tests indicated that Ag/TiO₂ films was quite stable during that liquid-solid heterogeneous photocatalysis since no significant decrease in activity was observed even after being used repetitively for 10 times, showing a good potential in practical application. In general, the cubic mesoporous Ag/TiO₂ nanocomposites are stable and can be recycled without loss of their photochemical activity.     

Essential Macleod Program (EMP) simulated fabrication of high quality Zn:SnO2/Ag/Zn:SnO2 multilayer transparent conducting electrode on flexible substrates

In the quest of promising Indium free amorphous transparent conducting oxide (TCO), Zn-doped SnO₂/Ag/Zn-doped SnO₂ (OMO) multilayer films were prepared on flexible polyethylene terephthalate (PET) substrates by RF sputtering at room temperature (RT). Growth parameters were optimized by varying sputtering power and working pressure, to have high electrical conductivity and optical transmittance. Optimization of the thickness of each layer was done by Essential Macleod Program (EMP) simulation to get the higher transmission through OMO multilayer. The sheet resistance and transmittance of 3 at% Zn-doped SnO₂ thin film (30 nm) were 2.23 kΩ/□, (ρ ~ 8.92×10⁻³ Ω∙cm) and 81.3% (at λ ~ 550 nm), respectively. By using optimized thicknesses of Zn-doped SnO₂ (30 nm) and Ag (12 nm) and optimized growth condition Zn-doped SnO₂/Ag/Zn-doped SnO₂ multilayer thin films were deposited. The low sheet resistance of 7.2 Ω/□ and high optical transmittance of 85.1% in the 550 nm wavelength region was achieved with 72 nm multilayer film.     

Structural, morphological, and optical properties of TiO2 thin films synthesized by the electro phoretic deposition technique

In this work, we report the structural, morphological, and optical properties of TiO₂ thin films synthesized by the electro phoretic deposition technique. The TiO₂ film was formed on a doped fluorine tin oxide (SnO₂:F, i.e., FTO) layer and used as a photo electrode in a dye solar cell (DSC). Using spectroscopic ellipsometry measurements in the 200 to 800 nm wavelengths domain, we obtain a thickness of the TiO₂ film in the range of 70 to 80 nm. Characterizations by X-ray diffraction and atomic force microscopy (AFM) show a polycrystalline film. In addition, AFM investigation shows no cracks in the formed layer. Using an ultraviolet–visible near-infrared spectrophotometer, we found that the transmittance of the TiO₂ film in the visible domain reaches 75%. From the measured current–voltage or I-V characteristic under AM1.5 illumination of the formed DSC, we obtain an open circuit voltage V_oc = 628 mV and a short circuit current I_sc = 22.6 μA, where the surface of the formed cell is 3.14 cm².     

Dye-sensitized solar cell based on optically transparent TiO2 nanocrystalline electrode prepared by atomized spray pyrolysis technique

Preparation of crack-free thin films of interconnected and non-agglomerated TiO₂ nanoparticles on electronically conducting fluorine doped tin oxide surfaces is instrumental in designing and developing transparent dye-sensitized solar cells (DSCs). A novel technique called “Atomized Spray Pyrolysis” (ASP) has been designed and developed to achieve such perfectly transparent thin films. Optical transmittance of TiO₂ films produced on FTO surface by this ASP method has been compared with those obtained by doctor-blading and by hand spray methods and found that the atomized spray pyrolysis technique give films with high transparency. Dye adsorption per gram of TiO₂ is 2.16 times higher in the sample produced by the ASP method when compared to the film produced by the hand spray method and is 1.60 times higher than that produced by the doctor-blading method using a commercially available TiO₂ nanocrystalline paste. SEM studies show the presence of interconnected discrete particles in the film produced by the ASP method. The fill factor (ff) remains almost constant for the cells with thickness from 6 μm to 13 μm but the highest photovoltage and photocurrent were found in ∼10 μm film based DSC which gave 8.2% conversion efficiency at AM 1.5 irradiation for cells of 0.25 cm² active area.     

Structural colors from TiO2/SiO2 multilayer flakes prepared by sol-gel process

Preparation of TiO₂/SiO₂ multilayer flakes and their application to decorative powders were investigated. In contrast to conventional products prepared through the multicoating of core platelets, the coreless TiO₂/SiO₂ multilayer flakes were prepared by detaching multilayer films from their substrates. These flakes exhibited structural colors, when the optical path length of both the TiO₂ and SiO₂ layers are adjusted to be one fourth of the wavelength of visible light. A multicoating of more than five layers resulted in the propagation of cracks, which prevented the preparation of thick flakes. Paint films fabricated using the multilayer flakes and acrylic resins showed reflectance spectra that were comparable with those obtained for multicoatings on substrates.     

Fabrication and thermo stability of the SnO2/Ag/SnO2 tri-layer transparent conductor deposited by magnetic sputtering

Using the magnetic sputtering technique, the SnO₂/Ag/SnO₂ tri-layer transparent films were fabricated on float glasses successfully. Compared with the commercial FTO (F-doped SnO₂) film, the SnO₂/Ag/SnO₂ tri-layer films have higher visible-light transmittance and better conductivity. The total thickness of the SnO₂/Ag/SnO₂ films is one third of the commercial FTO film leading to the high visible-light transmittance. The high carrier concentration of the SnO₂/Ag/SnO₂ films contributes to the tri-layer films’ low resistivity. In addition, to further improve the performance of the SnO₂/Ag/SnO₂ tri-layer films, samples were annealed under different temperatures. The results illustrate that the lowest sheet resistance (5.92 Ω/sq) and the highest visible-light transmittance (87.0%) were obtained after annealing at 200 °C. Furthermore, the thermal stability of the films could be enhanced by a multi-step annealing process due to the recrystallization effect.     

Thermally stable and transparent F-doped SnO2 (FTO) /Ag/FTO films for transparent thin film heaters used in automobiles

We investigated the characteristics of F-doped SnO₂ (FTO)/Ag/FTO films prepared using thermal evaporation at room temperature for the application of the as-formed films in transparent thin film heaters (TFHs) of automobiles. To optimize the electrical and optical properties of the FTO/Ag/FTO multi-layer, the figure of merit (FoM) values of the FTO/Ag/FTO multi-layers were compared as a function of the thickness of the Ag and FTO layers. The sheet resistance and optical transmittance of the FTO/Ag/FTO multi-layer were primarily affected by the Ag inter-layer and bottom/top FTO thicknesses, respectively. At optimized Ag (10 nm) and FTO (40 nm) thicknesses, we fabricated a FTO/Ag/FTO electrode with a sheet resistance of 8.00 Ohm/square, an optical transmittance of 83.04 % at a visible wavelength (400–800 nm) and a FoM value of 19.49 Ohm^-1. The TFHs comprising the optimal FTO/Ag/FTO electrode exhibited a saturated temperature of 117 °C at a low operating direct current of 6 V, owing to the low sheet resistance. In addition, the FTO/Ag/FTO-based TFHs exhibited thermally stable performances owing to the stability of the bottom and top FTO electrodes. The performance of the FTO/Ag/FTO-based TFHs demonstrated that the thermally evaporated FTO/Ag/FTO multi-layer is a promising, stable, and transparent electrode material for application in the front window TFHs used in automobiles.     

Fe effect on the optical properties of TiO2:Fe2O3 nanostructured composites supported on SiO2 microsphere assemblies

The effect of Fe ion concentration on the morphological, structural, and optical properties of TiO₂ films supported on silica (SiO₂) opals has been studied. TiO₂:Fe₂O₃ films were prepared by the sol-gel method in combination with a vertical dip coating procedure; precursor solutions of Ti and Fe were deposited on a monolayer of SiO₂ opals previously deposited on a glass substrate by the same procedure. After the dip coating process has been carried out, the samples were thermally treated to obtain the TiO₂:Fe₂O₃/SiO₂ composites at the Fe ion concentrations of 1, 3, and 5 wt%. Scanning electron microscopy (SEM) micrographs show the formation of colloidal silica microspheres of about 50 nm diameter autoensembled in a hexagonal close-packed fashion. Although the X-ray diffractograms show no significant effect of Fe ion concentration on the crystal structure of TiO₂, the μ-Raman and reflectance spectra do show that the intensity of a phonon vibration mode and the energy bandgap of TiO₂ decrease as the Fe⁺³ ion concentration increases.     

Effect of rapid thermal annealing on the structural and electrical properties of TiO2 thin films prepared by plasma enhanced CVD

Titanium oxide thin films were deposited on p-type Si(100), SiO₂/Si, and Pt/Si substrates by plasma enhanced chemical vapor deposition using high purity Ti(O-i-C₃H₇)₄ and oxygen. As-deposited amorphous TiO₂ thin films were treated by rapid thermal annealing (RTA) in oxygen ambient, and the effects of RTA conditions on the structural and electrical properties of TiO₂ films were studied in terms of crystallinity, microstructure, current leakage, and dielectric constant. The dominant crystalline structures after 600 and 800 ‡C annealing were an anatase phase for the TiO₂ film on SiO₂/Si and a rutile phase for the film on a Pt/Si substrate. The dielectric constant of the as-grown and annealed TiO₂ thin films increased depending on the substrate in the order of Si, SiO₂/Si, and Pt/ Si. The SiO₂ thin layer was effective in preventing the formation of titanium silicide at the interface and current leakage of the film. TEM photographs showed an additional growth of SiO_x from oxygen supplied from both SiO₂ and TiO₂ films when the films were annealed at 1000 ‡C in an oxygen ambient. Intensity analysis of Raman peaks also indicated that optimizing the oxygen concentration and the annealing time is critical for growing a TiO₂ film having high dielectric and low current leakage characteristics.     

Support modification to improve the sulphur tolerance of Ag/Al2O3 for SCR of NOx with propene under lean-burn conditions

Ag/Al₂O₃ catalysts with 1 wt% SiO₂ or TiO₂ doping in alumina support have been prepared by wet impregnation method and tested for sulphur tolerance during the selective catalytic reduction (SCR) of NO_x using propene under lean conditions. Ag/Al₂O₃ showed 44% NO_x conversion at 623 K, which was drastically reduced to 21% when exposed to 20 ppm SO₂. When Al₂O₃ support in Ag/Al₂O₃ was doped with 1 wt% SiO₂ or TiO₂ the NO_x conversion remained constant in presence of SO₂ showing the improved sulphur tolerance of these catalysts. Subsequent water addition does not induce significant deactivation. On the contrary, a slight promotional effect on the activity of NO conversion to nitrogen is observed after Si and Ti incorporation. FTIR study showed the sulphation of silver and aluminum sites of Ag/Al₂O₃ catalysts resulting in the decrease in the formation of reactive intermediate species such as –NCO, which in turn decreases NO_x conversion to N₂. In the case of Ag/Al₂O₃ doped with SiO₂ or TiO₂, formation of silver sulphate and aluminum sulphate was drastically reduced, which was evident in FTIR resulting in remarkable improvement in the sulphur tolerance of Ag/Al₂O₃ catalyst. These catalysts before and after the reaction have been characterized with various techniques (XRD, BET surface area, transmittance FTIR and pyridine adsorption) for physico-chemical properties.     

Study of a sandwich structure of transparent conducting oxide films prepared by electron beam evaporation at room temperature

ABSTRACT: Transparent conducting ZnO/Ag/ZnO multilayer electrodes having electrical resistance much lower than that of widely used transparent electrodes were prepared by ion-beam-assisted deposition (IAD) under oxygen atmosphere. The optical parameters were optimized by admittance loci analysis to show that the transparent conducting oxide (TCO) film can achieve an average transmittance of 93%. The optimum thickness for high optical transmittance and good electrical conductivity was found to be 11 nm for Ag thin films and 40 nm for ZnO films, based on the admittance diagram. By designing the optical thickness of each ZnO layer and controlling process parameters such as IAD power when fabricating dielectric-metal-dielectric films at room temperature, we can obtain an average transmittance of 90% in the visible region and a bulk resistivity of 5 x 10^-5 ohm-cm. These values suggest that the transparent ZnO/Ag/ZnO electrodes are suitable for use in dye-sensitized solar cells.     

Effect of TiO2 supporting layer on Fe2O3 photoanode for efficient water splitting

For an electrochemical water splitting system, titanate nanotubular particles with a thickness of ∼700 nm produced by a hydrothermal process were repetitively coated on fluorine-doped tin oxide (FTO) glass via layer-by-layer self-assembly method. The obtained titanate/FTO films were dipped in aqueous Fe solution, followed by heat treatment for crystallization at 500 °C for 10 min in air. The UV–vis absorbance of the Fe-oxide/titanate/FTO film showed a red-shifted spectrum compared with the TiO₂/FTO coated film; this red shift was achieved by the formation of thin hematite-Fe₂O₃ and anatase-TiO₂ phases verified using X-ray diffraction and Raman results. The cyclic voltammetry results of the Fe₂O₃/TiO₂/FTO films showed distinct reversible cycle characteristics with large oxidation–reduction peaks with low onset voltage of I–V characteristics under UV–vis light illumination. The prepared Fe₂O₃/TiO₂/FTO film showed much higher photocurrent densities for more efficient water splitting under UV–vis light illumination than did the Fe₂O₃/FTO film. Its maximum photocurrent was almost 3.5 times higher than that obtained with Fe₂O₃/FTO film because of the easy electron collection in the current collector. The large current collection was due to the existence of a TiO₂ base layer beneath the Fe₂O₃ layer.     

基于WO3-MoO3和TiO2/CdS复合电极的光电致变色器件

电致变色广泛应用于智能窗领域,但电致变色材料仍需外部电源驱动,将太阳能电池与电致变色材料结合起来的光电致变色器件可实现无需外部供电的智能变色调控。性能优异的变色阴极和光阳极是当下光电致变色器件的研究热点。通过水热法制备WO₃-MoO₃薄膜,研究其电致变色性能;通过水热法结合连续离子层沉积法制备TiO₂/CdS复合薄膜,研究其光电转换性能。最后将WO₃-MoO₃薄膜和TiO₂/CdS复合薄膜分别作为光电致变色器件的变色阴极、光阳极构建WO₃/MoO₃-TiO₂/CdS光电致变色器件。WO₃/MoO₃-TiO₂/CdS光电致变色器件具有较大的光学调制范围(630nm处为41.99%)、更高的着色效率(35.787%),将其作为智能窗应用在现代建筑、通行工具等领域具有重要应用价值。     

Influence of Ag incorporation on the structural,optical and electrical properties of ITO/Ag/ITO multilayers for inorganic all-solid-state electrochromic devices

Indium tin oxide/silver/indium tin oxide (ITO/Ag/ITO, IAI) multilayer structures were prepared by DC magnetron sputtering as a conductive transparent electrode for inorganic all-solid-state electrochromic devices. A thin layer of silver (Ag) with various thicknesses was inserted between two layers of ITO films. The XRD and SEM results revealed that the microscopic morphology of Ag film was closely related to the thickness. Besides, the electrical and optical properties of the IAI multilayers were significantly influenced by the Ag layer thickness. The optimized IAI multilayers demonstrated the best combination of electrical and optical properties with a figure of merit of 54.05 (sheet resistance of 6.14 Ω/cm²and optical transmittance of 90.83%) when the Ag film was 10 nm thick. In order to evaluate the IAI multilayers as a transparent electrode for electrochromic applications, two ECDs with the structures of ITO/NiO_x/LiPON/WO₃/ITO and ITO/NiO_x/LiPON/WO₃/IAI were prepared, and their electro-optical properties were characterized by cyclic voltammetry (CV), chronoamperometry (CA) and spectroscopic measurements. Compared with ECD the pure ITO top electrode (ITO/NiO_x/LiPON/WO₃/ITO), the ECD with the IAI top electrode (ITO/NiO_x/LiPON/WO₃/IAI) presented a slightly smaller optical modulation amplitude, but a faster switching speed. All our findings indicate that the IAI multilayer structure is a promising alternative to the ITO thin film for inorganic all-solid state electrochromic applications.     

Flexible IZO/Ag/IZO/Ag multilayer electrode grown on a polyethylene terephthalate substrate using roll-to-roll sputtering

We investigated the optical, electrical, structural, and surface properties of roll-to-roll [R2R] sputter-grown flexible IZO/Ag/IZO/Ag [IAIA] multilayer films on polyethylene terephthalate substrates as a function of the top indium zinc oxide [IZO] thickness. It was found that the optical transmittance of the IAIA multilayer was significantly influenced by the top IZO layer thickness, which was grown on identical AIA multilayers. However, the sheet resistance of the IAIA multilayer was maintained between the range 5.01 to 5.1 Ω/square regardless of the top IZO thickness because the sheet resistance of the IAIA multilayer was mainly dependent on the thickness of the Ag layers. Notably, the optimized IAIA multilayer had a constant resistance change (ΔR/R ₀) under repeated outer bending tests with a radius of 10 mm. The mechanical integrity of the R2R-sputtered IAIA multilayer indicated that hybridization of an IZO and Ag metal layer is a promising flexible electrode scheme for the next-generation flexible optoelectronics.     

Influence of transition metal doping on the structural,optical, and magnetic properties of TiO2 films deposited on Si substrates by a sol–gel process

Transition metal (TM)-doped TiO₂ films (TM = Co, Ni, and Fe) were deposited on Si(100) substrates by a sol–gel method. With the same dopant content, Co dopants catalyze the anatase-to-rutile transformation (ART) more obviously than Ni and Fe doping. This is attributed to the different strain energy induced by the different dopants. The optical properties of TM-doped TiO₂ films were studied with spectroscopic ellipsometry data. With increasing dopant content, the optical band gap (E_OBG) shifts to lower energy. With the same dopant content, the E_OBG of Co-doped TiO₂ film is the smallest and that of Fe-doped TiO₂ film is the largest. The results are related to electric disorder due to the ART. Ferromagnetic behaviors were clearly observed for TM-doped TiO₂ films except the undoped TiO₂ film which is weakly magnetic. Additionally, it is found that the magnetizations of the TM-doped TiO₂ films decrease with increasing dopant content.