Enhanced photoresponse and photocatalytic activities of graphene quantum dots sensitized Ag/TiO2 thin film

TiO₂ thin films were fabricated through hydrothermal method. Silver nanoparticles were loaded on TiO₂ thin films via photoreduction technique. Subsequently, the graphene quantum dots (GQDs) were spin‐coated on the Ag/TiO₂ nanocomposites thin films. The crystal structure, surface morphology and UV‐vis absorbance were tested by XRD, SEM and ultraviolet‐visible spectrophotometer. These results indicated that Ag nanoparticles and GQDs are anchored on the TiO₂ nanorods. Absorbance of Ag/TiO₂ and GQDs/Ag/TiO₂ nanocomposite thin films have been extended into the visible region. Visible‐light response of the samples were investigated by electrochemical workstation. The photoresponse of the sample can be enhanced by sensitization of the Ag nanoparticles and GQDs. The enhanced visible‐light response may be due to the surface plasmon resonance of silver nanoparticles and visible absorbance of GQDs. The highest photocatalytic activity has been observed in the 9‐GQDs/Ag/TiO₂ composite thin film. The efficient charge separation and transportation can be achieved by introducing the Ag nanoparticles and GQDs in the TiO₂ thin film.     

Rutile TiO2(101) based plasmonic nanostructures

TiO₂/Ag and TiO₂/Au nanocrystalline multilayer thin films were deposited using pulsed laser deposition technique. Investigations have been made to understand the influence of different phases of TiO₂ on the surface plasmon characteristics of the thin films. Rutile phase of TiO₂ is found to be a good host matrix for both Ag and Au nanoparticles. Compared to silver, gold nanoparticles are found to enhance the photocatalytic activity of the films by exhibiting a broad and intense absorption with a significant shift to longer wavelength region.     

Influence of Metal (Au, Ag) Micro-Grid on the Photocatalytic Activity of TiO2 Film

In this paper, we prepared TiO₂ thin film with the surface modified by a connected Au micro-grid via a microsphere lithography strategy, and the modified films show higher photocatalytic activity than the pure TiO₂ film. The photocatalytic activity improved as Au loading increased, obtaining the best performance at a certain loading amount, and then decreased at higher loading amount. This behavior, not observed in TiO₂ films modified with Ag micro-grid, can be attributed to the relationship between the energetic positions and the metal clusters size.     

AUGMENTATION OF PHOTOCATALYTIC ACTIVITY OF TiO2 THIN FILMS PREPARED BY A SOL-GEL TECHNIQUE

In order to increase the photocatalytic activity on TiO₂ thin film per its external surface area, the structure of flat thin film was modified by adding a small amount of polyethylene glycol (PEG) to TiO₂ sol solution. By firing PEG contained in a TiO₂ gel film, a porous structure was developed. The photocatalytic activities of the thin films prepared thus were evaluated by the degradation of 2-propanol in the aqueous solutions under black light illumination. The photocatalytic activity of TiO₂ thin film prepared with added PEG 400 by 2.6 wt% or PEG 2000 by 9.5 wt% was increased by about 30% as compared to that prepared without added PEG.     

Photoluminescence decay rate of silicon nanoparticles modified with gold nanoislands

We investigated plasmon-assisted enhancement of emission from silicon nanoparticles (ncs-Si) embedded into porous SiO _x matrix in the 500- to 820-nm wavelength range. In the presence in the near-surface region of gold nanoisland film, ncs-Si exhibited up to twofold luminescence enhancement at emission frequencies that correspond to the plasmon resonance frequency of Au nanoparticles. Enhancement of the photoluminescence (PL) intensity was attributed to coupling with the localized surface plasmons (LSPs) excited in Au nanoparticles and to increase in the radiative decay rate of ncs-Si. It has been shown that spontaneous emission decay rate of ncs-Si modified by thin Au film over the wide emission spectral range was accelerated. The emission decay rate distribution was determined by fitting the experimental decay curves to the stretched exponential model. The observed increase of the PL decay rate distribution width for the Au-coated nc-Si-SiO _x sample in comparison with the uncoated one was explained by fluctuations in the surface-plasmon excitation rate.

PACS

78. 67. Bf; 78.55.-m     

Preparation of SnTe thin films on Au(1 1 1) by electrodeposition route

Tin telluride (SnTe) thin films were deposited onto Au(1 1 1) substrates from an aqueous solution containing SnCl₂, TeO₂, and C₆H₅Na₃ at room temperature (25 °C) for the first time via electrodeposition route. The electrodeposition of the thin films was studied using cyclic voltammetry, compositional, structural, optical measurements and surface morphology. It was found that the stoichiometric SnTe thin films could be obtained at −0.50 V. The as-deposited thin films were crystallized in the preferential orientation along the (2 2 0) plane. SEM investigations indicated that the shape of thin films could be altered from a spherical particle to a dendritic crystal by increasing the deposition potential. The growth of the dendritic films proceeds via formation of nanoparticles and growth of dendritic crystals on these nanoparticles. The optical absorption studies as a function of deposition time indicated that the band gap of the SnTe thin film increases as the deposition time decreases.     

Photocatalytic decomposition of NO on titanium oxide thin film photocatalysts prepared by an ionized cluster beam technique

Transparent TiO₂ thin film photocatalysts were prepared on transparent porous Vycor glass (PVG) by an ionized cluster beam (ICB) method. The UV‐VIS absorption spectra of these films show specific interference fringes, indicating that uniform and transparent TiO₂ thin films are formed. The results of XRD measurements indicate that these TiO₂ thin films consist of both anatase and rutile structures. UV light (λ > 270 nm) irradiation of these TiO₂ thin films in the presence of NO led to the photocatalytic decomposition of NO into N₂, O₂ and N₂O. The reactivity of these TiO₂ thin films for the photocatalytic decomposition of NO is strongly dependent on the film thickness, i.e., the thinner the TiO₂ thin films, the higher the reactivity. This revised version was published online in July 2006 with corrections to the Cover Date.     

Hexagonally ordered arrays of metallic nanodots from thin films of functional block copolymers

We demonstrate a new and simple route to fabricate highly dense arrays of hexagonally close packed inorganic nanodots using functional diblock copolymer (PS-b-P4VP) thin films. The deposition of pre-synthesized inorganic nanoparticles selectively into the P4VP domains of PS-b-P4VP thin films, followed by removal of the polymer, led to highly ordered metallic patterns identical to the order of the starting thin film. Examples of Au, Pt and Pd nanodot arrays are presented. The affinity of the different metal nanoparticles towards P4VP chains is also understood by extending this approach to PS-b-P4VP micellar thin films. The procedure used here is simple, eco-friendly, and compatible with the existing silicon-based technology. Also the method could be applied to various other block copolymer morphologies for generating 1-dimensional (1D) and 2-dimensional (2D) structures.     

Texture effect on the electrochemical properties of LiCoO2 thin films prepared by PLD

LiCoO₂ thin films were prepared by pulsed laser deposition (PLD) on Pt/Ti/SiO₂/Si (Pt) and Au/MgO/Si (Au) substrates, respectively. Crystal structures and surface morphologies of thin films were investigated by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). The LiCoO₂ thin films deposited on the Pt substrates exhibited a preferred (0 0 3) texture with smooth surfaces while the LiCoO₂ thin films deposited on the Au substrates exhibited a preferred (1 0 4) texture with rough surfaces. The electrochemical properties of the LiCoO₂ films with different textures were compared with charge-discharge, dQ/dV, and Li diffusion measurements (PITT). Compared with the (1 0 4)-textured LiCoO₂ thin films, the (0 0 3)-textured thin films exhibited relatively lower electrochemical activity. However, the advantage of the (1 0 4)-textured film only remained for a small number of cycles due to the relatively faster capacity fade. Li diffusion measurements showed that the Li diffusivity in the (0 0 3)-textured film is one order of magnitude lower than that in the (1 0 4)-textured film. As discussed in this paper, we believe that Li diffusion through grain boundaries is comparable to or even faster than Li diffusion through the grains.     

Gas sensing properties of conducting polymer/Au-loaded ZnO nanoparticle composite materials at room temperature

In this work, a new poly (3-hexylthiophene):1.00 mol% Au-loaded zinc oxide nanoparticles (P3HT:Au/ZnO NPs) hybrid sensor is developed and systematically studied for ammonia sensing applications. The 1.00 mol% Au/ZnO NPs were synthesized by a one-step flame spray pyrolysis (FSP) process and mixed with P3HT at different mixing ratios (1:1, 2:1, 3:1, 4:1, and 1:2) before drop casting on an Al₂O₃ substrate with interdigitated gold electrodes to form thick film sensors. Particle characterizations by X-ray diffraction (XRD), nitrogen adsorption analysis, and high-resolution transmission electron microscopy (HR-TEM) showed highly crystalline ZnO nanoparticles (5 to 15 nm) loaded with ultrafine Au nanoparticles (1 to 2 nm). Film characterizations by XRD, field-emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray (EDX) spectroscopy, and atomic force microscopy (AFM) revealed the presence of P3HT/ZnO mixed phases and porous nanoparticle structures in the composite thick film. The gas sensing properties of P3HT:1.00 mol% Au/ZnO NPs composite sensors were studied for reducing and oxidizing gases (NH₃, C₂H₅OH, CO, H₂S, NO₂, and H₂O) at room temperature. It was found that the composite film with 4:1 of P3HT:1.00 mol% Au/ZnO NPs exhibited the best NH₃ sensing performances with high response (approximately 32 to 1,000 ppm of NH₃), fast response time (4.2 s), and high selectivity at room temperature. Plausible mechanisms explaining the enhanced NH₃ response by composite films were discussed.     

Hollow hybrid titanate/Au@TiO2 hierarchical architecture for highly efficient photocatalytic application

Hollow hybrid titanate/Au@TiO₂ hierarchical architecture consisting of titanate and anatase titanium dioxide (TiO₂) loaded with Au nanoparticles was prepared via a sol-impregnation method combined with a hydrothermal etching process. The titanate/Au@TiO₂ architecture possesses unique hollow spherical configuration with Au nanoparticles loaded in the middle of titanate and TiO₂ shells and allows to be used as a microreactor for photocatalytic application. The hybrid titanate/Au@TiO₂ photocatalyst shows significantly enhanced photocatalytic activity on degradation of methylorange (MO) under UV light irradiation due to the lower electron–hole pairs recombination rate arisen from the synergistic effect of titanate-Au-TiO₂ in hybrid hierarchical architecture.     

Preparation and electrochemical properties of gold nanoparticles containing carbon nanotubes-polyelectrolyte multilayer thin films

Multi-walled carbon nanotubes (MWCNT)/polyelectrolyte (PE) hybrid thin films were fabricated by alternatively depositing negatively charged MWCNT and positively charged (diallyldimethylammonium chloride) (PDDA) via layer-by-layer (LbL) assembly technique. The stepwise growth of the multilayer films of MWCNT and PDDA was characterized by UV–vis spectroscopy. Scanning electron microscopy (SEM) images indicated that the MWCNT were uniformly embedded in the film to form a network and the coverage density of MWCNT increased with layer number. Au nanoparticles (NPs) could be further adsorbed onto the film to form PE/MWCNT/Au NPs composite films. The electron transfer behaviour of multilayer films with different compositions were studied by cyclic voltammetry using [Fe(CN)₆]^3−/4− as an electrochemical probe. The results indicated that the incorporation of MWCNT and Au NPs not only greatly improved the electronic conductivity of pure polyelectrolyte films, but also provided excellent electrocatalytic activity towards the oxidation of nitric oxide (NO).     

Photocatalytic TiO2 films and membranes for the development of efficient wastewater treatment and reuse systems

In order to develop efficient photocatalytic TiO₂ films and membranes for application in water and wastewater treatment and reuse systems, there is a great need to tailor-design the structural properties of TiO₂ material and enhance its photocatalytic activity. Through a simple sol–gel route, employing self-assembled surfactant molecules as pore directing agents along with acetic acid-based sol–gel route, we have fabricated nanostructured crystalline TiO₂ thin films and TiO₂/Al₂O₃ composite membranes with simultaneous photocatalytic, disinfection, separation, and anti-biofouling properties. The highly porous TiO₂ material exhibited high specific surface area and porosity, narrow pore size distribution, homogeneity without cracks and pinholes, active anatase crystal phase, and small crystallite size. These TiO₂ materials were highly efficient in the decomposition of methylene blue dye and creatinine, destruction of biological toxins (microcystin-LR), and inactivation of pathogenic microorganisms (Escherichia coli). Moreover, the photocatalytic TiO₂ membranes exhibited not only high water permeability and sharp polyethylene glycol retention but also less adsorption fouling tendency. Here, we report results on the synthesis, characterization, and environmental application and implication of photocatalytic TiO₂ films and membranes.     

Enhanced photocatalytic activity of Au-buffered TiO2 thin films prepared by radio frequency magnetron sputtering

Au-buffered TiO₂ thin films have been prepared by radio frequency magnetron sputtering method. The structural and morphological properties of the thin films were characterized by X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The photocatalytic activity of the samples was evaluated by the photodecomposition of methylene blue. The Au-buffer thin layer placed between the TiO₂ thin films significantly enhanced photocatalytic activity by 50%. Annealing the Au-buffered TiO₂ thin film at 600 °C decreased the film roughness, but it increased the surface area and anatase crystalline size, enhancing the photocatalytic activity.     

Preparation of PdO-decorated NiO porous film on ceramic substrate for highly selective and sensitive H2S detection

This work is to develop high-performance thin film gas sensors on the alumina ceramic substrate. Here, porous NiO films of about 2 μm were obtained by the simple electrochemical deposition technique. The NiO gas sensing thin films obtained by the in-situ growth overcomes the disadvantages of great thickness, material agglomeration, and uneven size of the conventional device structure. The films exhibit good uniformity, consistency, and reproducibility. The composition of the films and their porous morphological characteristics were demonstrated by SEM, XRD, AFM, and XPS characterization. The doping of PdO significantly enhanced the sensitivity and specificity selection of the NiO films for H₂S gas. 2 wt% PdO/NiO thin film sensor exhibited a high response (515.27) and fast dynamic process at 155 °C for 10 ppm H₂S. The outstanding gas-sensing performance of the thin film sensor is due to the doping of PdO and the porous structure of the film.     

Electrohydrodynamic instabilities of polymer thin films: Filler effect

The influence of various nanoparticles with different dimension, density, dielectric constant, and surface property on electrohydrodynamic (EHD) instabilities of polymer/nanoparticle nanocomposite thin films was examined as a function of nanoparticle concentration. Transmission electron microscopy (TEM) images of polystyrene (PS)/nanoparticles (NPs) thin films demonstrated that all the nanoparticles were uniformly distributed in polymer matrix and the homogeneous dispersions of nanoparticles were not affected by thermal annealing above glass transition temperature. Optical microscopy (OM) observations indicated that thin films of polystyrene containing silica (SiO₂), gold (Au), cadmium selenide (CdSe), and titania (TiO₂) nanoparticles showed electrohydrodynamic instability patterns similar to those seen in pure polystyrene, up to 3 vol% nanoparticles. The presence of nanoparticles changed the dielectric constant of the thin films, which led to systematic variations in the wavelengths of the surface instabilities, which were consistent with calculated values. Cross-sectional transmission electron microscopy (TEM) images showed that migration or aggregation of the nanoparticles occurred only for silica contrary to other nanoparticles. This work points to a simple route to reduce the scale of final well-ordered columnar structures.     

Significantly improved energy storage properties of sol-gel derived Mn-modified SrTiO3 thin films

In this paper, x mol% Mn-doped SrTiO₃ (STMx, x?=?0, 0.5, 1, 3 and 5) thin films were synthesized by a sol-gel method. The effect of Mn doping on the microstructure and electrical performance was investigated. STMx (x?≤?1) thin films shows a single cubic perovskite phase while impurity phase appears for STM3 and STM5 thin films confirmed by X-ray diffraction. X-ray photoelectron spectra reveals that STM1 thin film has the lowest concentration of oxygen vacancy. The dielectric constant and loss of STMx (x?≤?1) films display good frequency stability, while decrease with the frequency for STM3 and STM5 thin films. And all samples display excellent bias stability of dielectric constant; this is advantageous for applications in a high electric field. The ferroelectric test demonstrates that the electrical breakdown strength increases and leakage current decreases for Mn doped SrTiO₃ films. A great recoverable energy storage density of 23.8?J/cm³ with an efficiency of 69.8% at 2.286?MV/cm is obtained in STM1 thin film. Furthermore, STM1 thin film shows good frequency stability of energy storage properties. It indicates that Mn doping is a simple and effective method to improve the energy storage properties of dielectric capacitors.     

Preparation of M@BiFeO3 Nanocomposites (M = Ag,Au) Bowl Arrays with Enhanced Visible Light Photocatalytic Activity

High surface area BiFeO₃ (BFO) bowl arrays photocatalyst loaded with different size noble metal nanoparticles were successfully prepared by combining templates method and thermal evaporation followed by heating. The structural and optical properties of the BiFeO₃ bowl arrays and the composite M@BFO bowl arrays (M = Ag, Au) were comparatively characterized. The composite M@BFO bowl arrays showed much higher photocatalytic performance than the pure BFO bowl arrays. The enhanced photocatalytic property of the composite structure could be ascribed to the enhanced near‐field amplitudes of localized surface plasmon of the noble metal nanoparticles which boost the separation of electron–hole pairs and the transfer mechanism of electrons.     

Enhancement of energy storage density in antiferroelectric PbZrO3 films via the incorporation of gold nanoparticles

In this work, antiferroelectric Au–PbZrO₃ (Au–PZO) nanocomposite thin films were prepared by chemical solution deposition (CSD), and the effects of Au concentration on the antiferroelectric properties and the recoverable energy density were investigated. The results showed that the optimal Au concentration in the Au–PZO nanocomposite thin films was about 1 mol% for structural and electric properties. In the Au–PZO nanocomposite thin films with 1 mol% Au, Au nanoparticles (NPs) were distributed uniformly in the perovskite PZO matrix. Moreover, the recoverable energy density was 10.8 J/cm³ at 600 kV/cm, which is 42% higher than that of the pure PZO films. The results demonstrate that adding an appropriate amount of noble metal NPs in antiferroelectric thin films is an effective method to improve the energy storage properties.     

Photocatalytic decomposition of NO under visible light irradiation on the Cr‐ion‐implanted TiO2 thin film photocatalyst

Transparent TiO₂ thin film photocatalysts were prepared on transparent porous Vycor glass (PVG) by the ionized cluster beam (ICB) method. In order to improve the photocatalytic performance of these thin films under visible light irradiation, transition metal ions such as Cr and V were implanted into the deep bulk inside of the films using an advanced metal‐ion‐implantation technique. The UV‐vis absorption spectra of these metal‐ion‐implanted TiO₂ thin films were found to shift smoothly toward visible light regions, its extent depending on the amount and kinds of metal ions implanted. Using these metal‐ion‐implanted TiO₂ thin films as photocatalysts, the photocatalytic decomposition of NO_x into N₂ and O₂ was successfully carried out under visible light (λ 450 nm) irradiation at 275 K. This revised version was published online in July 2006 with corrections to the Cover Date.