Photocatalytic activity of (sulfur,nitrogen)-codoped mesoporous TiO<Subscript>2</Subscript> thin films

Nitrogen and sulfur co-doped mesoporous TiO₂ thin films were fabricated using thiourea as a doping resource by the combination of the sol–gel and evaporation-induced self-assembly (EISA) processes. Scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N₂ adsorption–desorption, and UV–vis spectra were performed to characterize the as-synthesized mesoporous TiO₂ materials. The XPS result shows that O–Ti–N and O–Ti–S bonds in the (S, N)-codoped mesoporous TiO₂ were formed. The resultant mesoporous (S, N)-codoped TiO₂ exhibited anatase framework with a high porosity and a narrow pore distribution. After being illuminated for 3 h, methyl orange (MO) could be degraded completely by the co-doped sample under the ultraviolet irradiation, whereas mesoporous TiO₂ film without doping could only degrade 60% MO. After being illuminated by visible light, the water contact angles of the mesoporous co-doped TiO₂ samples decreased slightly, but the pure TiO₂ mesoporous film exhibited no change in the hydrophilicity.     

Effect of Al doping on the conductivity type inversion and electro-optical properties of SnO2 thin films synthesized by sol-gel technique

Al doped SnO₂ thin films have been synthesized by a sol-gel dip coating technique with different percentages of Al on glass and silicon substrates. X-ray diffraction studies confirmed the proper phase formation in the films and atomic percentage of aluminium doping in the films was obtained by energy dispersive X-ray studies. SEM studies showed the particle sizes lying in the range 100–150 nm for the undoped films and it decreased with increase of Al doping. Optical transmittance spectra of the films showed high transparency (∼80%) in the visible region and the transparency increases with the increase of Al doping in the films. The direct allowed bandgap of the films have been measured for different Al concentration and they lie within the range of 3.87–4.21 eV. FTIR studies depicted the presence of Sn–O, Al–O, bonding within the films. The room temperature electrical conductivities of the films are obtained in the range of 0.21 S cm⁻¹ to 1.36 S cm⁻¹ for variation of Al doping in the films 2.31–18.56%. Room temperature Seebeck coefficients, S_RT of the films were found in the range +56.0 μVK⁻¹ to −23.3 μVK⁻¹ for variation of Al doping in the films 18.56–8.16%. It is observed that the Seebeck coefficient changes its sign at 12.05% of Al in the films indicating that below 12.05% of Al doping, SnO₂:Al behaves as an n-type material and above this percentage it is a p-type material.     

N,B, Si-tridoped mesoporous TiO<Subscript>2</Subscript> with high surface area and excellent visible-light photocatalytic activity

N, B, Si-tridoped mesoporous TiO₂, together with N-doped, N, B-codoped and N, Si-codoped TiO₂, was prepared by a modified sol–gel method. The samples were characterized by wide-angle X-ray diffraction (WAXRD), N₂ adsorption–desorption, transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, UV–visible adsorbance spectra (UV–vis) and X-ray photoelectron spectra (XPS). The N, B, Si-tridoped mesoporous TiO₂ showed small crystallite size, large specific surface area (350 m²/g), uniform pore distribution (3.2 nm) and strong absorption in the visible light region. The photocatalytic activities of the samples were evaluated by the photodegradation of 2,4-dichlorophenol (2,4-DCP) aqueous solution. The N, B, Si-tridoping sample exhibited much higher photocatalytic activity compared with other synthesized photocatalysts. The high activity could be attributed to the strong absorption in the visible light region, large specific surface area, small crystallite size, large amount of surface hydroxyl groups, and mesoporosity.     

The effect of Sn dopant on crystal structure and photocatalytic behavior of nanostructured titania thin films

In this study, preparation of Sn doped (0–30 mol % Sn) TiO₂ dip-coated thin films on glazed porcelain substrates via sol–gel process have been investigated. The effects of Sn content on the structural, optical, and photo-catalytic properties of applied thin films have been studied by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), field emission SEM (FE-SEM), and high resolution transmission electron microscopy (HR-TEM). Surface topography and surface chemical state of thin films were examined by atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). XRD patterns showed an increase in peak intensities of the rutile crystalline phase by increasing the Sn dopant. The prepared Sn-doped TiO₂ photo-catalyst films showed optical absorption edge in the visible light area and exhibited excellent photo-catalytic ability for degradation of methylene blue solution under UV irradiation. The result shows that doping an appropriate amount of Sn can effectively improve the photo-catalytic activity of TiO₂ thin films, and the optimum dopant amount is found to be 15 mol%. The Sn⁴⁺ dopants substituted Ti⁴⁺ in the lattice of TiO₂ and increased surface oxygen vacancies and the surface hydroxyl groups. TEM results showed small increase in planar spacing (was detected by HR-TEM caused by Sn dopants in titania based crystals).     

Preparation of mesoporous hydroxyapatite films used as biomaterials via sol–gel technology

The mesoporous hydroxyapatite films (MHFs) have been developed on glass slides by sol–gel dip-coating technology using cetyltrimethylammonium bromide (CTAB) as the structure-directing agent and the effects of pH value and calcination temperatures on the surface morphology and the mesostructure have been discussed. The phase composition, surface morphology, mesostructure and surface wettability were characterized by X-ray diffraction, scanning electron microscope, transmission electron microscope, N₂ adsorption–desorption isotherms and water contact angle analyzer, respectively. The continuous thin films consisted of mesoporous hydroxyapatite particles (~50 nm) with mesopores (~2 nm) within the particles have been obtained after being prepared in the condition of concentration of CTAB 0.09 M, pH of sol 3.0, reaction temperature 60 °C and calcination temperature 550 °C. In vitro cell culture, the mesoporous films, which possessed favorable surface wettability resulting from the special pore structure, have exhibited a high degree of MC3T3-E1 cell attachment and spreading, suggesting a better bioactivity. Therefore, the MHFs can be expected to have potential application for decreasing the ion release of implant and improving the bioactivity as a coating on material surface.     

Fe-doped and Mn-doped titanium dioxide thin films

Thin films of TiO₂ doped with Fe and Mn were deposited on F-doped SnO₂-coated glass by spin coating. Dopant concentrations of 3–7 wt% (metal basis) were used. The structural, chemical, and optical characteristics of the films were investigated. Laser Raman microspectroscopy and glancing angle X-ray diffraction data showed that the films consisted of the anatase polymorph of TiO₂. X-ray photoelectron spectroscopy data indicated the presence of Fe³⁺, Mn⁴⁺, and Mn³⁺ in the doped films, as predicted by calculated thermodynamic stability diagrams, and the occurrence of atomic disorder and associated structural distortion. Ultraviolet–visible spectrophotometry data showed that the optical indirect band gap of the films decreased significantly with increasing dopant levels, from 3.36 eV (undoped) to 2.95 eV (7 wt% Fe) and 2.90 eV (7 wt% Mn). These improvements are attributed to single (Fe) or multiple (Mn) shallow electron/hole trapping sites associated with the dopant ions.     

Structure and dielectric properties of 80%Pb(Zn1/3Nb2/3)O3–20%PbTiO3 thin films prepared by modified sol–gel process

80%Pb(Zn_1/3Nb_2/3)O₃–20%PbTiO₃ (PZN–PT) thin films have been prepared on Pt/Ti/SiO₂/Si substrates using a modified sol–gel method. In our method, niobium pentaoxide is used as a substitution instead of niobium ethoxide which is moisture-sensitivity and much more expensive. Microstructure and electrical properties of PZN–PT thin films have been investigated. X-ray diffraction analysis shows that proper annealing temperature of PZN–PT thin films is 600 °C. The PZN–PT thin films annealed at 600 °C are polycrystalline with (111)-preferential orientations. Field-emissiom scanning electron microscope analysis revealed PZN–PT thin films possess well-defined and crack-free microstructure. The thickness of thin films is 290 nm. The Pt/PZN–PT/Pt capacitors have been fabricated and it presents ferroelectric nature. The remanent polarization (Pr), spontaneous polarization (Ps), and the coercive electric field (Ec) are 8.71 μC/cm², 43.06 μC/cm², and 109 kV/cm at 1 MHz, respectively. The dielectric constant (ε_r) and the dissipation factor (tan δ) are about 500.3 and 0.1 at 1 kHz, respectively.     

Preparation of Co–Al and Ni–Al layered double hydroxide thin films by a sol–gel process with hot water treatment

Using hot water treatment of sol–gel derived precursor gel films, Co–Al and Ni–Al layered double hydroxide (LDH) thin films were prepared. The precursor gel films of Al₂O₃–CoO or Al₂O₃–NiO were prepared from cobalt or nickel nitrates and aluminum tri-sec-butoxide using the sol–gel method. Then, the precursor gel films were immersed in a NaOH aqueous solution of 100 °C. Nanocrystallites of Co–Al and Ni–Al LDH were precipitated with the hot water treatment with NaOH solution. The largest amounts of nanocrystals were obtained with a solution of pH = 10 for Co–Al LDH, and with that of pH = 9 for Ni–Al LDH. X-ray diffraction measurements confirmed that this process formed CO₃ ²⁻ intercalated LDHs. Both Co–Al and Ni–Al LDH thin films were confirmed to work as electrodes for electrochemical devices by cyclic voltammogram measurements.     

Formation of cerium titanate,CeTi<Subscript>2</Subscript>O<Subscript>6</Subscript>, in sol–gel films studied by XRD and FAR infrared spectroscopy

The process of formation of cerium titanate films as a function of annealing temperature and composition has been studied by combining X-ray diffraction analysis and far infrared spectroscopy. The films have been prepared by a sol–gel synthesis using metal chlorides as precursors; the synthesis allows obtaining cerium titanate films upon annealing in air. A brannerite type, CeTi₂O₆, phase has been identified by X-ray diffraction and Rietveld analysis on thin films. CeTi₂O₆ is formed upon annealing at 700 °C and in a limited range of ceria-titania mixed compositions. The far infrared spectra are useful to observe the formation of crystalline phases at the beginning of the crystallization process at lower firing temperatures, when the XRD analysis is not enough sensitive.     

Effect of sol temperature on the structure,morphology, optical and photoluminescence properties of nanocrystalline zirconia thin films

Transparent nanocrystalline zirconia thin films were prepared by sol–gel dip coating technique using Zirconium oxychloride octahydrate as source material on quartz substrates, keeping the sol at room temperature (SET I) and 60 °C (SET II). X-ray diffraction (XRD) pattern shows the formation of mixed phase [tetragonal (T) + monoclinic (M)] in SET I and a pure tetragonal phase in SET II ZrO₂ thin films annealed at 400 °C. Phase transformation from tetragonal to monoclinic was achieved in SET II film annealed at 500 °C. Atomic force microscopy analysis reveals lower rms roughness and skewness in SET II film annealed at 500 °C indicating better optical quality. The transmittance spectra gives a higher average transmittance >85% (UV–VIS region) in SET II films. Optical spectra indicate that the ZrO₂ films contain direct—band transitions. The sub- band in the monoclinic ZrO₂ films introduced interstitial O⁻defect states above the top of the valance band. The energy bandgap increased (5.57–5.74 eV) in SET I films and decreased (5.74–5.62 eV) in SET II films, with annealing temperature. This is associated with the variations in grain sizes. Photoluminescence (PL) spectra give intense band at 384 and 396 nm in SET I and SET II films, respectively. A twofold increase in the PL intensity is observed in SET II film. The “Red” shift of SET I films and “Blue” shift of SET II films with annealing temperature, originates from the change of stress of the film due to lattice distortions.     

Sol–gel derived mesoporous Pt and Cr-doped WO<Subscript>3</Subscript> thin films: the role played by mesoporosity and metal doping in enhancing the gas sensing properties

Mesoporous Cr or Pt-doped WO₃ thin films to be employed as ammonia gas sensors were prepared by a fast one-step sol–gel procedure, based on the use of triblock copolymer as templating agent. The obtained films were constituted by aggregates of interconnected WO₃ nanocrystals (20–50 nm) separated by mesopores with dimensions ranging between 2 and 15 nm. The doping metals, Pt and Cr, resulted differently hosted in the WO₃ mesoporous matrix. Chromium is homogeneously dispersed in the oxide matrix, mainly as Cr(III) and Cr(V) centers, as revealed by EPR spectroscopy; instead platinum segregated as Pt (0) nanoparticles (4 nm) mainly included inside the WO₃ nanocrystals. The semiconductor layers containing Pt nanoclusters revealed, upon exposure to NH₃, remarkable electrical responses, much higher than Cr-doped and undoped layers, particularly at low ammonia concentration (6.2 ppm). This behavior was attributed to the presence of Pt nanoparticles segregated inside the semiconductor matrix, which act as catalysts of the N–H bond cleavage, decreasing the activation barrier in the ammonia dissociation. The role of the mesoporous structure in influencing the chemisorption and the gas diffusion in the WO₃ matrix appeared less decisive than the electronic differences between the two examined doping metals. The overall results suggest that a careful combination between mesoporous architecture and metal doping can really promote the electrical response of WO₃ toward ammonia.     

Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript>,Tb<Superscript>3+</Superscript> thin films prepared by sol–gel method: structural and optical studies

Y₂O₃: Eu³⁺,Tb³⁺ transparent, high density and optical quality thin films were prepared by the sol–gel dip-coating technique. Yttrium (III) 2,4-pentadionate was used as a precursor by its hydrolysis in ethanol. The doping agents were incorporated in the form of europium and terbium nitrate. Structural, morphological and optical properties of prepared films were investigated for different annealing temperatures in order to establish the ideal processing route that enhances the luminescent properties. X-ray diffraction (XRD) analysis shows the cubic phase for 10-layer films and annealing temperatures higher than 500°C. At 700°C, highly densified (4.52 g cm⁻³) and very smooth films (1.4 nm at 700°C) are produced, composed of crystallites with a grain size of 11 nm. The film thickness, refractive index and porosity, as well as the luminescent properties, were found to vary with treatment temperature.     

Effects of niobium doping on lead zirconate titanate films deposited by a sol–gel route

Niobium (Nb)-doped lead zirconate titanate (PZT) films have been prepared on platinized silicon substrates using a sol–gel method. The Zr/Ti ratios of the films are 53/47 and 40/60, and the Nb doping level ranges from 0 mol% to 3 mol%. Similar to the cases in bulk ceramics, after the doping with Nb, the remanent polarization P_r, effective transverse piezoelectric coefficients e_31,c and pyroelectric coefficient p of the PZT films increase; but the longitudinal effective piezoelectric coefficient d_33,c remains roughly unchanged. At the optimum Nb doping levels, the observed P_r, −e_31,c and p reach a maximum value of 30 μC/cm², 18 C/m² and 350 μC/m² K, respectively, for the PZT (53/47) films, and 37 μC/cm², 7.9 c/m² and 370 μC/m² K for the PZT (40/60) films. Our results also reveal that there exist linear relations between p, e_31,c/ε_r and P_r.     

Band gap tuning in nanocomposite ZrO2–SnO2 thin film achieved through sol–gel co-deposition method

Transparent SnO₂, nanocomposite ZrO₂–SnO₂ and ZrO₂ thin films were prepared by sol–gel dip-coating technique. X-ray diffraction (XRD) spectra showed a mixture of three phases: tetragonal ZrO₂ and SnO₂ and orthorhombic ZrSnO₄. X-ray photoelectron spectroscopy (XPS) gave Zr 3d, Sn 3d and O 1s spectra of the nanocomposite ZrO₂–SnO₂ thin film which revealed the presence of oxygen vacancies in the nanocomposite ZrO₂–SnO₂ thin film. Scanning electron microscopy (SEM) observations showed that microstructure of the nanocomposite ZrO₂–SnO₂ thin film consists of uniform dispersion of isolated SnO₂ particles in ZrO₂ matrix. The band gap for the ZrO₂ was estimated to be 5.51 eV and that for the nanocomposite ZrO₂–SnO₂ film was 4.9 eV. These films demonstrated the tailoring of band gap values which can be directly employed in tuning the band gap by simply changing the relative concentration of zirconium and tin elements. Photoluminescence (PL) spectra revealed an intense emission peak at 424 nm in the nanocomposite ZrO₂–SnO₂ film which indicate the presence of oxygen vacancies in ZrSnO₄.     

Preparation of amino-functionalized mesoporous silica thin films with highly ordered large pore structures

Highly ordered amino-functionalized mesoporous silica thin films have been directly synthesized by co-condensation of tetraethoxysilane (TEOS) and 3-aminopropyltriethoxysilane (APTES) in the presence of triblock copolymer Pluronic P123 surfactant species under acidic conditions by sol-gel dip-coating. The effect of the sol aging on thin films organization is systematically studied, and the optimal sol aging time is obtained. The amino-functionalized mesoporous silica thin films exhibit a long-range ordering of 2D hexagonal (p6mm) mesostructure with a large pore size of 8.3 nm, a large Brunauer–Emmett–Teller (BET) specific surface area of 680 m² g⁻¹ and a large pore volume of 1.06 cm³ g⁻¹ following surfactant extraction as demonstrated by X-ray diffraction (XRD), Transmission electron microscope (TEM), and physical adsorption techniques. Based on BET surface area and weight loss, the surface coverage of amino-groups for the amino-functionalized mesoporous silica thin films is calculated to be 3.2 amino-groups per nm². Moreover, the functionalized thin films display improved properties for immobilization of cytochrome c in comparison with pure-silica mesoporous thin films.     

Study of the optimal condition for electroplating of Bi2S3 thin films and their photoelectrochemical characteristics

Bismuth sulfide (Bi₂S₃) thin films were electrodeposited from non-aqueous dimethyl sulfoxide medium containing Bi(NO₃)₃ and thiourea as the precursor salts, triethanol amine as the complexing agent, and TritonX-100 as the surface active agent. The prepared films were subjected to rigorous experimentation in order to validate their potential candidature for solar cells. The films exhibited band gap energy of ∼1.3 eV and resistivity of the order of 2 × 10⁶ Ω cm at room temperature as was obtained from UV–Vis spectroscopy and four-probe measurements, respectively. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and energy dispersive analysis of X-ray were employed to reveal the morphology, structure, and chemical composition of the film matrix. The Bi₂S₃ films were found to be non-decomposable up to the temperature of 1,000 °C with the help of thermogravimetry–differential thermal analysis. The Nyquist and Mott–Schottky plots derived from electrochemical impedance spectroscopy measurements provided important information regarding electrical and semiconducting properties of the films. The n-type film with a donor density of the order of ∼10²³ m⁻³ displayed reasonable photoactivity under illumination and is recommended as a promising candidate for potential photoelectrochemical applications.     

Visible light photocatalytic activity and Photoelectrochemical property of Fe-doped TiO<Subscript>2</Subscript> hollow spheres by sol–gel method

Fe-doped TiO₂ hollow spheres (Fe-THs) were synthesized by sol–gel process using carbon spheres as templates. The prepared samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV–vis diffuse reflectance spectrum (DRS), N₂ adsorption–desorption isotherms, Electron paramagnetic resonance (EPR) spectroscopy and Photoluminescence emission spectroscopy (PL). UV–vis spectra showed that Fe³⁺ doping could extend the absorption edge to the visible region. EPR spectra showed that Fe³⁺ was incorporated into the crystal lattice of TiO₂, which could inhibit the recombination of photo-induced electron–hole pairs and improve the photocatalytic activity. The photocatalytic activities of the prepared samples were evaluated for the degradation of dye Reactive Brilliant Red X-3B (C.I. reactive red 2) under visible light irradiation. The results indicated that Fe³⁺ doping sample showed the highest photocatalytic activity with an optimal doping concentration of 0.50 wt%. The recycle ability of the Fe-THs was also investigated. After 5 cycles, the degradation rate was still higher than 90%, decreased by only 6.36% compared to the first cycle. Moreover, in order to characterize the electron-transferring efficiency in the process of photocatalysis reaction, a photocurrent-time spectrum was examined by anodic photocurrent response.     

Enhanced ferroelectric properties of Ce-substituted BiFeO<Subscript>3</Subscript> thin films prepared by sol–gel process

Ce-substituted BiFeO₃ film (BCFO film) have been prepared by sol–gel process on F doped SnO₂ (FTO)/glass substrates. The effects of Ce substitution on the structural and electrical properties have been reported. X-ray diffraction data confirmed the R3c structure with the elimination of all secondary phases. We observed an increase in the remnant polarization (Pr) with Ce substitution and obtained a maximum value of ∼84 μC/cm² in 5% Ce-substituted film. The dielectric constant of the films was increased from 280 to about 420 for the BiFeO₃ film and 5% Ce-substituted BCFO film, respectively and the films showed excellent dielectric loss behavior. Moreover, the leakage current was substantially reduced by the Ce substitution.     

Structural and optical characterization of sol–gel derived boron doped Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanostructured films

Pure and boron (B) doped iron oxide (Fe₂O₃) nanostructured thin films were prepared by sol–gel spin coating method. The effects of B (0.1, 0.2, 0.5 and 1 %) content on the crystallinity and morphological properties of Fe₂O₃ films were investigated by X-ray diffractometer and atomic force microscopy. X-ray diffraction patterns revealed that the Fe₂O₃ films have a rhombohedral crystalline phase of α-Fe₂O₃ phase (hematite) with nanostructure and their crystallite size (D) is changed from 27 ± 2 to 45 ± 5 nm with B dopant content. The minimum crystallite size value of 27 ± 2 nm was obtained for 0.2 % B doped Fe₂O₃ film. Carrying out UV–VIS absorption study for both doped and undoped films at room temperature, it was realized that allowed optical transitions may be direct or indirect transitions. The direct and indirect energy gap values for pure Fe₂O₃ were obtained to be 2.07 and 1.95 eV, respectively. The optical band gap value of the films was changed with 0.1 % B doping to reach 1.86 eV for direct band gap and 1.66 eV in case of indirect band gap.     

Structural and optical characterization of Zn doped TiO<Subscript>2</Subscript> nanoparticles prepared by sol–gel method

Undoped and zinc-doped TiO₂ nanoparticles (Ti_1−xZn_xO₂ where x = 0.00–0.10) were synthesized by a sol–gel method. The synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and UV–VIS spectrometer. XRD pattern confirmed the tetragonal structure of synthesized samples. Average grain size was determined from X-ray line broadening using the Debye–Scherrer relation. The crystallite size was varied from 10 to 40 nm as the calcination temperature was increased from 350 to 800 °C. The incorporation of 3–5 mol% Zn²⁺ in place of the Ti⁴⁺ provoked a slight decrease in the size of nanocrystals as compared to undoped TiO₂. The SEM and TEM micrographs revealed the agglomerated spherical-like morphology with a diameter of about 10–30 nm and length of several nanometers, which is in agreement with XRD results. Optical absorption measurements indicated a blue shift in the absorption band edge upon 3–5 mol% zinc doping. Direct allowed band gap of undoped and Zn-doped TiO₂ nanoparticles measured by UV–VIS spectrometer were 2.95 and 3.00 eV at 550 °C, respectively.