Fabrication and characterization of novel composite membranes composed of photonic crystals and TiO2 nanotube array films

Novel composite membranes composed of photonic crystals (PCs) and TiO₂ nanotube array (TNA) films have been fabricated by combining the room temperature floating self-assembly (RTFSA) method, recently developed by our research group, and the liquid-phase deposition technique. By applying this combined procedure, polystyrene (PS) opal PC/TNA and TiO₂ inverse opal PC/TNA composite membranes were prepared. Scanning electron microscopy and ultraviolet/visible spectroscopy analyses showed that the membrane samples possessed very high crystalline quality. Notably, the ordered packing of the PS microspheres from the top to the bottom of the opal PC film was not affected by the surface roughness of the porous TNA substrate. This is attributed to the self-assembly mechanism of the colloidal particles, which produces a three-dimensional ordered structure in the RTFSA method. Herein, the crystallization of the colloidal particles occurred at the surface of the colloidal suspension, and the crystal growth proceeded downward from the surface of the suspension to the substrate.     

Directed growth of colloidal crystals on a hydrophobic polymer film by using hydrophilic traps

Deposition of colloidal crystal films onto a hydrophobic surface using capillary force-induced self-assembly is difficult to achieve because of wetting problems of the aqueous colloids with the substrate. We present here a method to overcome this problem. By introducing a hydrophilic trench around the hydrophobic polymer, uniform crystalline colloidal films can be deposited onto the surface of the polymer, provided a sufficient volume of suspension is used. The hydrophilic area around the polymer acts like an artificial trap that can help pin the colloidal suspension on the surface of the hydrophobic polymer surface and direct the self-assembly of colloidal spheres, which is the key to fabricate a uniform colloidal crystal film on the polymer surface.     

Confined palladium colloids in mesoporous frameworks for carbon nanotube growth

Palladium colloidal nanoparticles with an average size of approximately 2.4 nm have been incorporated into mesoporous inorganic thin films following a multistep approach. This involves the deposition of mesoporous titania thin films with a thickness of 200 nm by spin-coating on titanium plates with a superhydrophilic titania outer layer and activation by calcination in a vacuum furnace at 573 K. Nanoparticles have been confined within the porous titania network by dip-coating noble metal suspensions onto these mesoporous thin films. Finally, the resulting nanoconfined systems were used as substrates for the growth of oriented carbon nanotubes (CNTs) using plasma-enhanced chemical vapour deposition at 923 K in order to enhance their surface area. These CNTs were tested in the hydrogenation of phenylacetylene by hydrogen in a batch reactor. The initial reaction rate observed on a CNT/TiO₂ structured catalyst was considerably higher than that on 1 wt% Pd/TiO₂ thin films.     

Transmission electron microscopy studies of nanostructured TiO2 films on various substrates

A chemical vapour deposition (CVD) synthetic route to the production of nanocrystalline titanium dioxide has been carefully investigated on various substrates. CVD was performed at a relatively low temperature of 320 °C on KCl crystal, Al foil, KBr pellet and freshly sliced MICA substrates. The influence of substrate material on film formation was studied in order to find a titanium dioxide film with good intercalation properties for an electrode in a dye-sensitized solar cell. Intercalation properties depend on average grain sizes and porosity in nanophased materials. These films were thoroughly characterized with respect to their surface morphology, crystal structure and the phase composition. Transmission electron microscopy (TEM) accompanied by selected area electron diffraction (SAED) was employed for structural characterization of TiO₂ films. The studies showed that films deposited on KCl crystal, KBr pellet and MICA are solely composed of an anatase phase whereas in the film deposited onto Al foil, the brookite phase of TiO₂ is also present. The structural parameters of anatase were determined using the Rietveld refinement of electron diffraction data. By comparison of anatase lattice parameters with their corresponding bulk values, the significant deviation in values of lattice parameters a and c in anatase phase was observed and attributed to the thin-film features. The average grain size and the grain size distribution obtained by TEM were compared for TiO₂ films deposited on different substrates.     

Structural and optical studies of nanocrystalline V2O5 thin films

We report the structural and optical properties of nanocrystalline thin films of vanadium oxide prepared via evaporation technique on amorphous glass substrates. The crystallinity of the films was studied using X-ray diffraction and surface morphology of the films was studied using scanning electron microscopy and atomic force microscopy. Deposition temperature was found to have a great impact on the optical and structural properties of these films. The films deposited at room temperature show homogeneous, uniform and smooth texture but were amorphous in nature. These films remain amorphous even after postannealing at 300 °C. On the other hand the films deposited at substrate temperature T_S > 200 °C were well textured and c-axis oriented with good crystalline properties. Moreover colour of the films changes from pale yellow to light brown to black corresponding to deposition at room temperature, 300 °C and 500 °C respectively. The investigation revealed that nanocrystalline V₂O₅ films with preferred 001 orientation and with crystalline size of 17.67 nm can be grown with a layered structure onto amorphous glass substrates at temperature as low as 300 °C. The photograph of V₂O₅ films deposited at room temperature taken by scanning electron microscopy shows regular dot like features of nm size.     

Electrochemical deposition of zinc selenide and cadmium selenide onto porous silicon from aqueous acidic solutions

An electrochemical deposition process of ZnSe and CdSe compound semiconductors from aqueous acidic solutions onto silicon substrates with porous silicon layers formed on their surfaces was studied by the voltammetry method. The experimental data obtained were compared with the deposition data onto metal and silicon substrates, and the optimal conditions for the binary compound deposition onto porous silicon were determined. Semiconductor films deposited were studied by scanning electron microscopy, X-ray diffractometry, and X-ray microanalysis. The films are shown to have the crystalline structure and a nearly stoichiometric composition with a minor Se excess. Further annealing in air for 15 min allowed the Se concentration to be decreased.     

The effect of argon pressure on the structural and photocatalytic characteristics of TiO2 thin films deposited by d.c. magnetron sputtering

TiO₂ thin films of 200-300 nm thickness were deposited by d.c. magnetron sputtering onto glass substrates from a semiconducting TiO_2−x target in pure Ar using pressures between 0.1 and 1.0 Pa. The obtained TiO₂ coatings are transparent and have refractive indices between 2.5 and 1.9. Post deposition heat treatment at different temperatures was performed to achieve crystallization of anatase TiO₂. The as-deposited and heat treated films were examined with UV-VIS (transmission), SEM and XRD to investigate the influence of the argon pressure during deposition on the structural development during heat treatment. Additionally, the photocatalytic activity of the films was tested by measuring the decomposition rate of ethanol in a controlled gas atmosphere simulating air, and was related to their respective microstructures.     

One step room temperature photodeposition of Cu/TiO2 composite films and its conversion to CuO/TiO2

Cu/TiO₂ composite films were prepared at low temperature on glass substrates by a photodeposition method. Films were deposited by irradiating the substrate while in contact with an aqueous TiO₂ suspension containing copper(II) nitrate and ethanol. Cu/TiO₂ composite films of 500 nm in thickness were deposited at room temperature after a short irradiation time (15 min) with a 125 W mercury vapour lamp. According to scanning electron microscopy observations, the obtained films were homogeneous and porous. Energy dispersive X-ray spectroscopy analysis revealed a 3:1 Cu:Ti atomic ratio. Grazing angle X-ray diffraction analysis showed that the films contained Cu and TiO₂ as major components and Cu₂O as a minor component. Heat treatment at 400 °C in air for a period of 3 h transformed the initial material into a CuO/TiO₂ composite, improved the adhesion to the substrate and favoured a more regular distribution of copper oxide according to backscattering micrographs.     

Thermoelectrical properties and optical third harmonic generation of Gd-doped PbTe

Nanocrystalline TiO₂ porous films were prepared by a sol-gel dip coating method from a solution using poly(ethylene glycol) as a template, ethanol as a solvent and terpineol as a highly viscous solvent. The thickness of films increases greatly by increasing the amount of terpineol. However, the overmuch incorporation of terpineol hinders the formation of porous structure and accelerates the crack creation. The crack-free film having a three-dimensionally extended porous structure was obtained at the ethanol/terpineol ratio of 8:1, the film thickness with three depositions being 2.5 μm. Pretreatment of the precursor at an appropriate temperature also plays an important role in pore formation. Single-phase anatase TiO₂ porous films were obtained after calcinations at 550°C for 1 h, and the crystal size increases with an increase in the amount of terpineol. The pore formation mechanism is discussed primarily in relation to the phase separation in the system and self-assembly of PEG.     

Properties of indium tin oxide films prepared by ion-assisted deposition

Conducting transparent films of indium tin oxide were deposited by 100 eV oxygen-ion-assisted deposition. A refractive index of 2.13 at 550 nm was obtained for films deposited onto ambient temperature substrates. The refractive index decreased with increasing substrate temperature to a value of 2.0 at 400°C. The sheet resistance of films 135 nm thick decreased from 800 Ω/□ for layers deposited onto room temperature substrates to around 25 Ω/□ at 400°C. Structural studies revealed that ion-assisted deposition onto ambient temperature substrates produced amorphous films, and that at temperatures above 100°C the films exhibit In₂O₃ crystallinity. In addition, it was found that the number of voids in the ion-bombarded films was reduced relative to that in films produced by conventional reactive evaporation.     

Preparation of nanocrystalline TiO2 porous films from terpineol-ethanol-PEG system

Nanocrystalline TiO₂ porous films were prepared by a sol-gel dip coating method from a solution using poly(ethylene glycol) as a template, ethanol as a solvent and terpineol as a highly viscous solvent. The thickness of films increases greatly by increasing the amount of terpineol. However, the overmuch incorporation of terpineol hinders the formation of porous structure and accelerates the crack creation. The crack-free film having a three-dimensionally extended porous structure was obtained at the ethanol/terpineol ratio of 8:1, the film thickness with three depositions being 2.5 μm. Pretreatment of the precursor at an appropriate temperature also plays an important role in pore formation. Single-phase anatase TiO₂ porous films were obtained after calcinations at 550°C for 1 h, and the crystal size increases with an increase in the amount of terpineol. The pore formation mechanism is discussed primarily in relation to the phase separation in the system and self-assembly of PEG.     

Rapid fabrication of a large-area 3D silica colloidal crystal thin film by a room temperature floating self-assembly method

We demonstrate the room temperature crystallization of colloidal silica particles dispersed in a mixture of ethanol and water at the air–liquid interface of the colloidal suspension spread on a glass substrate. By combining this approach with the dip-drawing technique, a room temperature floating self-assembly method has been developed. Applying this method, a three-dimensional silica colloidal crystal film of several square centimeters in area has been fabricated within 10 min without special facilities or heating of the suspension. SEM images and the normal incidence transmission spectrum of the sample show that the colloidal crystal film fabricated by this method had very high crystalline quality.     

Study of the deposition parameters and Fe-dopant effect in the photocatalytic activity of TiO2 films prepared by dc reactive magnetron sputtering

The reactive magnetron sputtering method was used to prepare pure and Fe-doped titanium dioxide thin films. The films were deposited onto microscope glass slides and polycarbonate plates at different total pressure and Fe-doping concentrations. The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and UV-visible spectroscopy (UV). For glass substrates a polycrystalline TiO₂ structure was verified with X-ray diffraction, which showed typical characteristic anatase reflections. An iron phase appeared in the highly Fe-doped samples. The absorption edges of the Fe-doped TiO₂ films shifted to visible region with increasing concentration of iron. For the polycarbonate substrate an amorphous TiO₂ structure was revealed for all deposition conditions. The effects of different Fe-doping and total pressure levels on the photocatalytic activity were obtained by the degradation rates of Rhodamine-B (RoB) dye under UV light irradiation. For the deposition conditions considered in this study the highest photodegradation rates were achieved for films deposited on the polymer substrates. Of these overall highest rates was achieved for deposition at 0.4 Pa and without doping. However, for both substrates, films prepared at the particular total pressure of 0.5 Pa and a low iron concentration showed better photocatalytic activity than the pure TiO₂ films prepared under the same deposition parameters. On the contrary, the photocatalytic degradation rates of RoB on the highly Fe-doped TiO₂ films decreased strongly.     

Synthesis and characterization of flexible one-dimensional TiO2 nanocrystalline films

The flexible oriented one-dimensional (1-D) TiO₂ nanocrystalline films with large length-diameter ratios were synthesized in 1 M NaOH solution by hydrothermal treatment of the thin titanium layer which was deposited on flexible stainless steel substrates by direct current magnetron sputtering. The films were characterized, respectively by field emission scanning electron microscopy (FESEM), X-Ray diffraction (XRD), and transmission electron microscopy (TEM). Results showed that the TiO₂ films were composed of oriented single-crystalline anatase nanowires, and the morphology of the nanowire film was determined by hydrothermal conditions. The photoelectric property studies revealed that the photoelectric property of TiO₂ films was improved with the increase of the hydrothermal temperature. This approach provides an alternative method to synthesize 1-D TiO₂ nanocrystalline films on non-Ti substrates.     

Photoelectrochemical properties of plasma-deposited TiO2 thin films

Photoanodes were fabricated from TiO₂ films deposited onto titanium substrates by plasma-enhanced chemical vapor deposition. The photocurrent-wavelength and photocurrent-voltage properties of the anodes were determined and compared with those of thermally grown TiO₂ photoanodes. The plasma-deposited photoanodes displayed quantum efficiencies higher than those for the thermally grown films and comparable with those reported for single-crystal rutile. The microstructure of the plasma-deposited films appeared to be primarily responsible for the high quantum efficiencies.     

High-Sensitivity Acoustic Molecular Sensors Based on Large-Area,Spray-Coated 2D Covalent Organic Frameworks

2D covalent organic frameworks (2D COFs) are a unique materials platform that combines covalent connectivity, structural regularity, and molecularly precise porosity. However, 2D COFs typically form insoluble aggregates, thus limiting their processing via additive manufacturing techniques. In this work, colloidal suspensions of boronate-ester-linked 2D COFs are used as a spray-coating ink to produce large-area 2D COF thin films. This method is synthetically general, with five different 2D COFs prepared as colloidal inks and subsequently spray-coated onto a diverse range of substrates. Moreover, this approach enables the deposition of multiple 2D COF materials simultaneously, which is not possible by polymerizing COFs on substrates directly. When combined with stencil masks, spray-coated 2D COFs are rapidly deposited as thin films larger than 200 cm² with line resolutions below 50 µm. To demonstrate that this deposition scheme preserves the desirable attributes of 2D COFs, spray-coated 2D COF thin films are incorporated as the active material in acoustic sensors. These 2D-COF-based sensors have a 10 ppb limit-of-quantification for trimethylamine, which places them among the most sensitive sensors for meat and seafood spoilage. Overall, this work establishes a scalable additive manufacturing technique that enables the integration of 2D COFs into thin-film device architectures.     

Study on TiO2 thin films grown by advanced pulsed laser deposition on ITO

TiO₂ films were grown by an advanced pulsed laser deposition method (PLD) on ITO substrates to be used as functional electrodes in the manufacturing of solar cells. A pure titanium target (99.99%) was irradiated by a Nd:YAG laser (355 and 532 nm, 5 ns, 35 mJ, 3 J/cm²) in an oxygen atmosphere at different pressures (20-160 mTorr) and at room temperature. After deposition, the films were subjected to an annealing process at 350 °C. The film structure, surface morphology, thickness, roughness, and optical transmission were investigated. Regardless of the wavelength used, the films deposited at room temperature presented only Ti₂O and TiO peaks. After thermal treatment, the TiO₂ films became strongly crystalline, with a tetragonal structure and in the anatase phase; the threshold temperature value was 250 °C. The deposition rate was in the range of 0.035-0.250 nm/pulse, and the roughness was 135-305 nm. Optical transmission of the films in the visible range was between 40% and 60%.     

大面积3D有序介孔二氧化钛薄膜光子晶体制备与性能研究

介绍了大面积有序反蛋白石结构介孔二氧化钛薄膜光子晶体制备与性能研究的进展.为了保证二氧化钛骨架结构的稳定性和有序度,从而使氧化钛介孔薄膜达到大面积结构均匀,在介孔薄膜制备过程中采用了几种新的工艺方法,其中包括二氧化硅晶体模板的应用和用NaOH溶液代替常用的HF溶液作为模板去除剂.制备的介孔二氧化钛薄膜光子晶体的面积达到厘米尺寸,二氧化钛骨架的填充率达到17.4%,薄膜制备过程中的收缩率<3%.薄膜透射光谱研究结果表明,这种大面积3D有序的反蛋白石结构介孔二氧化钛薄膜具有非常优良的光子带隙特性,有望成为一类具有非常好的发展和应用前景的光子晶体材料.     

Apatite formation from simulated body fluid on various phases of TiO2 thin films prepared by filtered cathodic vacuum arc deposition

Hydroxyl (OH⁻)-free TiO₂ thin films with amorphous and crystalline phases were deposited onto (100) silicon substrates using filtered cathodic vacuum arc deposition in order to investigate the in vitro apatite formation in simulated body fluid (SBF). The surface morphology, composition and structure of the TiO₂ thin films were characterized. The X-ray photoelectron spectroscopy results confirmed the presence of calcium and phosphorus on all TiO₂ thin film surfaces after immersion in SBF at 37 °C. Fourier transform infra red results showed the presence of carbonated apatite on the surface of these films. Amorphous structured TiO₂ thin film showed poor ability to form apatite on its surface in SBF. Apatite formation was more pronounced on the surfaces of the anatase films in comparison to those of rutile. The carbonated apatite deposition rate increased significantly when the TiO₂ film was illuminated with UV light prior to immersing in the SBF. In particular, the UV-treated anatase and rutile films showed increased rates of carbonated apatite formation on their surfaces in comparison to samples not treated with radiation. The increase in hydrophilicity due to UV treatment appears beneficial for the apatite growth on these surfaces.     

Reactive sputtering of titanium and properties of titanium suboxide films for photochemical applications

The effect of oxygen partial pressure on the deposition rate, crystalline structure and optical absorption of thin film titanium suboxides prepared by the reactive sputtering of a titanium metal target is given. A wide variety of films ranging from metallic through semiconducting to dielectric specimens were deposited in a reproducible manner simply by controlling the oxygen content in the sputtering plasma atmosphere. In addition, polycrystalline stable semiconducting TiO₂ electrodes were deposited onto heated glass substrates. The spectral response was investigated; a main absorption edge of about 410 nm was obtained. The design of a special substrate table with a unique mask changer that allowed for the fabrication of different geometrical film patterns is also given.