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.     

不同溶剂对溶胶-凝胶法制备La2CuO4晶体的影响

以硝酸镧和硝酸铜为起始原料,柠檬酸为络合剂,分别以蒸馏水、乙醇、乙二醇和乙二醇甲醚为溶剂,采用溶胶-凝胶法制备了La2CuO4纳米晶。通过X射线衍射(XRD)、红外光谱(IR)、扫描电子显微镜(SEM)和紫外-可见-近红外光谱(UV-Vis-NIR)等方法对La2CuO4粉体进行了测试和表征;研究了不同溶剂对La2CuO4相组成、官能团、显微结构以及光学性能的影响。结果表明,以蒸馏水、乙醇和乙二醇为溶剂,600℃煅烧保温2h,均能获得单一La2CuO4物相,而以乙二醇甲醚为溶剂时,产物含有杂质相,所得粉体的形貌依次为网片状、蜂窝状、网状和块状。根据UV-Vis-NIR分析,所得La2CuO4的光学带隙分别为1.37、1.30、1.33和1.32eV。     

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.     

Dip coated 12CaO·7Al2O3 thin films through sol-gel process using metal alkoxide

Transparent nanostructured 12CaO·7Al₂O₃ thin films with cubic structure have been prepared on soda lime glass substrates via the sol-gel dip coating using the precursor sol solution at low temperature. The structural, compositional, morphological and optical properties of the 12CaO·7Al₂O₃ films and powder were studied using X-ray diffractometry (XRD), X-ray photoelectron spectroscopy, scanning electron microscopy (SEM) and atomic force microscopy. Optical properties of 12CaO·7Al₂O₃ films have been investigated using UV-visible spectroscopy. Two different precursor sols were prepared using calcium-2-ethyl hexonate and aluminium isopropoxide as precursor materials in isopropanol and ethylene glycol monomethyl ether solvents. Dip coated gel like films were dried at 120 °C for 15 min and subsequently heat-treated at 450 °C for 1 h in air atmosphere. The influence of films thickness and optical transparency with use of different solvent and sol concentration on microstructure of the films were established. In addition, XRD patterns revealed that 12CaO·7Al₂O₃ films have been composed of cubic phase. SEM observations exhibited that the films structure becomes more homogeneous using isopropanol as compared to ethylene glycol monomethyl ether solvent. The 12CaO·7Al₂O₃ films prepared using 2 (wt.%) sol in isopropanol had high transparency nearly 88% in wide visible range with maximum of 90% at 600 nm wavelength.     

Synthesis of c-axis preferred orientation ZnO:Al transparent conductive thin films using a novel solvent method

Transparent aluminum doped zinc oxide (ZnO:Al, AZO) conducting thin films with a high-preferential c-axis orientation were synthesized using a new sol-gel formula. The films were deposited using a spin-coating route onto borosilicate glass substrates. We used propylene glycol methyl ether (PGME) as the solvent in place of ethylene glycol monomethyl ether (EGME), which is commonly used because it is easier to deposit onto the substrates. PGME is also superior in terms of health and safety. PGME solvent does not need to settle for several days before use and can be spin-coated as soon as the raw material and solvent are mixed. The effects of this novel solvent on the structural, morphological, electrical and optical properties are discussed using XRD, SEM, a four-point probe and UV-VIS spectrophotometry. It was found that the films produced with PGME showed a high-preferential c-axis orientation and compact microstructure in comparison films produced using EGME. The electrical resistivity of AZO thin films produced with PGME solvent was lowered to 3.474 × 10^− 3Ω cm after annealing in 95 N₂/5H₂ atmosphere. In addition, the optical transmittances of AZO thin films on glass plates were higher than 90% in the visible wavelength region.     

Effect of binders on microstructure and photoelectrochemical properties of the TiO2 film photoelectrodes

In order to obtain thick, crack-free TiO₂ film photoelectrodes, the screen-printed method was employed by using ethylene glycol and ethylene glycol monomethylether (EGME) as binder. The surface morphology of TiO₂ film observed by scanning electron microscope (SEM) is porous and coarse. SEM results also show that TiO₂ films with binder are crack-free in the microstructure. Optical absorption spectra show that films with binder have stronger ability to adsorb dye molecules than that without binder. I–V curves show that films with binder have better photoelectrochemical (PEC) property than films without binder. Moreover, EGME improves the PEC property of the sample stronger than ethylene glycol.     

High thermal stability thick wall mesoporous titania thin films

Mesoporous TiO₂ thin films were prepared by using tetrabutyl titanate as the inorganic precursor and triblock copolymer (Pluronic F127) as the structure directing agent. The obtained mesostructured TiO₂ thin film exhibits a high thermal stability, which can sustain 600 °C thermal treatment. The small angle XRD and wide angle XRD patterns indicate that the samples have mesoporous channel and are composed of anatase. The corresponding TEM images show that the homogeneous mesostructure and very thick pore walls (about 9–13 nm) are formed in the obtained thin films, which could be responsible for the high thermal stability of the framework. In addition, the samples have narrow pore diameter distribution and a mean pore size of 7.4 nm.     

Preparation and characterization of vinyl-functionalized mesoporous SBA-15 silica by a direct synthesis method

Vinyl groups were used to functionalize the pore channels of mesoporous SBA-15 materials by the co-condensation of tetraethyl orthosilicate (TEOS) and triethoxyvinylsilane (TEVS) in the presence of poly(ethylene glycol)-B-poly(propylene glycol)-B-poly(ethylene glycol) (P123) surfactants under acidic conditions. The final materials were investigated in detail by means of FT-IR, XRD, TEM, solid state NMR and N₂ adsorption, in order to study the effect of vinyl concentration on their mesoscopic order and pore structure. The results show that vinyl groups are attached covalently to the pore wall of SBA-15 after modification. The mesoscopic architecture almost remains intact upon functionalization, with only a minor decrease of the intensity of (110) diffractions for the 20 mol% TEVS-functionalized samples, which still preserve a desirable pore structure, with a surface area of 883.7 m²/g, a pore volume of 0.98 cm³/g and a mean pore size of 4.4 nm.     

Fabrication of porous TiO2 film via hydrothermal method and its photocatalytic performances

Porous anatase (TiO₂) films were fabricated onto stainless steel substrates with Ti(OC₄H₉)₄ as a precursor via hydrothermal process. The crystallization and porous structure of TiO₂ film were dependent on the time and temperature of the hydrothermal reaction. A TiO₂ film with orderly porous structure and high crystallization was obtained upon treatment at 150 °C for 2 h. The grain size of TiO₂ is ca. 6 nm, and pore diameter is ca. 10 nm. Diffusion of Fe into the porous TiO₂ film occurred; Fe also diffused onto the surface of the film with the extension of hydrothermal reaction time or increase of the reaction temperature. The diffusion reaction has a large effect on the formation of porous TiO₂ film as well as its interface texture. However, it does not change the crystal phase of the TiO₂. The resultant TiO₂ film showed high photocatalytic activity towards degradation of gaseous formaldehyde.     

Effect of film thickness and agglomerate size on the superwetting and fog-free characteristics of TiO2 films

The effect of TiO₂ film thickness and agglomerate size on the non-UV activated superhydrophilic wetting and antifogging characteristics of TiO₂ films was investigated. Evidence from Atomic Force Microscopy analysis showed that surface roughness is the key parameter requiring control so as to retain the superhydrophilic wetting and antifogging behaviour of the synthesised films. Surface roughness can be tuned by simple manipulation of the multilayer assembly of TiO₂ nanoparticles through varying the film thickness and agglomerate size. A film thickness of ~ 140 nm yielded the optimum roughness (root mean square = 23 nm) to give the best superhydrophilic wetting behaviour. Thicker films reduced the film roughness and were detrimental to their superhydrophilic wetting properties. Smaller agglomerate size was also found to be important in retaining film roughness.     

Fabrication of TiO2 nanotube film by well-aligned ZnO nanorod array film and sol-gel process

High density TiO₂ nanotube film with hexagonal shape and narrow size distribution was fabricated by templating ZnO nanorod array film and sol-gel process. Well-aligned ZnO nanorod array films obtained by aqueous solution method were used as template to synthesize ZnO/TiO₂ core-shell structure through sol-gel process. Subsequently, TiO₂ nanotube array films survived by removing the ZnO nanorod cores using wet-chemical etching. Polycrystalline anatase TiO₂ nanotube films were ∼ 1.5 μm long and ∼ 100 nm in inter diameter with a wall thickness of ∼ 10 nm.     

Synthesis and tuning of ordering and crystallinity of mesoporous titanium dioxide film

Synthesis of well-organized and highly crystalline mesoporous titania (TiO₂) film is demonstrated using triblock copolymer (Pluronic P123) as a structure directing template, through the evaporation induced self-assembly (EISA) process. The issue of thermal and structural stability of a mesoporous TiO₂ film was addressed via optimization of annealing temperature and time. An anatase phase, high crystallinity TiO₂ film with ordered pores was obtained at 430 °C after annealing for 15 min. The synthesized film was crack free with TiO₂ nanoparticle size of 10–15 nm, quasi-hexagonal pore diameter in the range of 8–10 nm and film thickness of ~ 150 nm.     

Nanocrystalline TiO2 thin films for NH3 monitoring: microstructural and physical characterization

Nanocrystalline titanium oxide thin films have been deposited by spin coating technique and then have been analyzed to test their application in NH₃ gas-sensing technology. In particular, spectrophotometric and conductivity measurements have been performed in order to determine the optical and electrical properties of titanium oxide thin films. The structure and the morphology of such material have been investigated by X ray diffraction, Scanning microscopy, high resolution electron microscopy and selected area electron diffraction. The X-ray diffraction measurements confirmed that the films grown by this technique have good crystalline tetragonal mixed anatase and rutile phase structure. The HRTEM image of TiO₂ thin film showed grains of about 50–60 nm in size with aggregation of 10–15 nm crystallites. Selected area electron diffraction pattern shows that the TiO₂ films exhibited tetragonal structure. The surface morphology (SEM) of the TiO₂ film showed that the nanoparticles are fine with an average grain size of about 50–60 nm. The optical band gap of TiO₂ film is 3.26 eV. Gas sensing properties showed that TiO₂ films were sensitive as well as fast in responding to NH₃. A high sensitivity for ammonia indicates that the TiO₂ films are selective for this gas.     

Influence of calcination ambient and film thickness on the optical and structural properties of sol-gel TiO2 thin films

Influence of both calcination ambient and film thickness on the optical and structural properties of sol-gel derived TiO₂ thin films have been studied. X-ray diffraction results show that prepared films are in an anatase form of TiO₂. Films calcined in argon or in low vacuum (∼2 × 10⁻¹ mbar) are found to be smaller in crystallite size, more transparent at low wavelength region of ∼300-450 nm, denser, have higher refractive index and band gap energy compared to air-calcined films. Scanning electron microscopic study reveals that surfaces of TiO₂ films calcined in argon or in low vacuum are formed by densely packed nano-sized particulates. Presence of voids and signs of agglomeration can be seen clearly in the surface microstructure of air-calcined films. In the thickness range ∼200-300 nm, band gap energy and crystallite size of TiO₂ films remain practically unaffected with film thickness but refractive index of thinner film is found to be marginally higher than that of thicker film. In this work, it has been shown that apart from temperature and soaking time, partial pressure of oxygen of the ambient is also an important parameter by which crystallite size, microstructure and optical properties of the TiO₂ films may be tailored during calcination period.     

Room temperature co-precipitation of nanocrystalline CeO2 and Ce0.8Gd0.2O1.9−δ powder

This paper describes a simple method to co-precipitate CeO₂ and Ce_0.8Gd_0.2O_1.9−δ with ammonium hydroxide from solvents such as: water, ethylene glycol, ethyl alcohol and isopropyl alcohol. Characterization by Raman spectroscopy and XRD evidenced the formation of a solid solution of gadolinium-doped ceria at room temperature. Nanometric particles with crystallite size of 3.1 nm were obtained during synthesis using ethyl alcohol as solvent. This is a promising result compared with those mentioned in the literature, in which the smallest crystallite size reported was 6.5 nm.     

Localized surface plasmon resonance sensing properties of photocatalytically prepared Au/TiO2 films

Photocatalytic deposition of Au nanoparticles from a mixed aqueous solution of HAuCl₄ and ethylene glycol onto TiO₂ films (Au/TiO₂ films) was carried out by using ultraviolet light irradiation at room temperature. In the optical absorption spectra of the Au/TiO₂ film, the localized surface plasmon resonance (LSPR) peak of Au nanoparticles was observed at 534.5 nm. When the film was immersed in various kinds of solutions, such as alcohols, NaCl and d-glucose aqueous solutions, a linear relation was clearly observed between the LSPR peak wavelength and the refractive index of the solutions, in the range of 1.0003–1.4181.     

Fabrication of dye-sensitized solar cells using TiO2-nanotube arrays on Ti-grid substrates

Self-aligned TiO₂ nanotube arrays (20 μm in length) were fabricated by anodic oxidation of Ti-grid with a thickness of 100 μm in an ethylene glycol electrolyte with an addition of H₂O (1.5 vol.%) and NH₄F (0.2 wt.%). Voltage applied between Ti and Pt cathodes is 60 V at ~ 22 °C. Dye-sensitized solar cell utilizing photoanode structure of TiO₂-nanotube/Ti-grid was fabricated with no transparent conducting oxide (TCO) layer, in which Ti-grid replaces TCO. Overall photoconversion efficiency is very low (< 0.5%) due to the large pore size (100 nm in diameter) of the nanotubes, which may cause insufficient dye molecules to be attached, thus limiting light harvesting.     

Mesoporous TiO2 thin films embedded with Au nanoparticles for the enhancement of the photocatalytic properties

Mesoporous TiO₂ thin films were prepared by hydrothermal-oxidation of titanium metal thin films, which were obtained by DC magnetron sputtering technique. Gold nanoparticles, which were prepared by reduction of HAuCl₄, were embedded into the holes of the mesoporous TiO₂ films by capillary method followed by annealing in air up to 400 °C. The size of pore of TiO₂ films is about 100 nm and that of Au nanoparticles is about 10 nm in average. The morphology of the films was analyzed by field emission scanning electron microscope (FE-SEM) and scanning probe microscopes (SPMs). Subsequently, the photocatalytic performances of the obtained nanosystems in the decomposition of methylene blue solution are discussed. The obtained results show that the dispersion of Au nanoparticles on the mesoporous TiO2 matrix will help enhancing the photocatalytic activity with respect to pure TiO₂ under visible light irradiation.     

Elucidation of the capillarity-promoted sintering of silver nanoparticles produced by a spark ablation vapor source

Through the spark ablation method, high purity, spherical silver nanoparticles (Ag NPs) with a size of 5 ± 3 nm are prepared. A solvent-assisted sintering method is developed to modulate the sintering structure and properties of the as-prepared Ag NPs. The effects of the solvents terpineol, polyethylene glycol-200, 1,2-propanediol, and ethylene glycol are explored. The results show that treatment with ethylene glycol causes the shear strength of the sintered Ag NPs at 180, 220, 260, and 300 °C to significantly improve from 0, 3.7, 22.1, and 64.6 MPa to 37.1, 56.1, 76.6, and 93.1 MPa respectively. Additionally, the size and number of voids in the sintered structure are significantly reduced. From the perspective of the capillary pressure induced by the solvent during sintering, a correlation between low solvent wettability and small agglomerate size of the Ag NPs is revealed, which reasonably explains the structure and properties of the sintered Ag NPs that were treated with different solvents. The spark ablation and solvent-assisted sintering methods provide a new approach for the fabrication and structure–property design of metal NPs for electronic applications.     

Nanoporous TiO2 thin film based conductometric H2 sensor

Nanoporous titanium dioxide (TiO₂) based conductometric sensors have been fabricated and their sensitivity to hydrogen (H₂) gas has been investigated. A filtered cathodic vacuum arc (FCVA) system was used to deposit ultra-smooth Ti thin films on a transducer having patterned inter-digital gold electrodes (IDTs). Nanoporous TiO₂ films were obtained by anodization of the titanium (Ti) thin films using a neutral 0.5% (wt) NH₄F in ethylene glycol solution at 5 V for 1 h. After anodization, the films were annealed at 600 °C for 8 h to convert the remaining Ti into TiO₂. The scanning electron microscopy (SEM) images revealed that the average diameters of the nanopores are in the range of 20 to 25 nm. The sensor was exposed to different concentrations of H₂ in synthetic air at operating temperatures between 100 °C and 300 °C. The sensor responded with a highest sensitivity of 1.24 to 1% of H₂ gas at 225 °C.