The effects of the thickness of TiO2 films on the performance of dye-sensitized solar cells

Nanocrystalline anatase TiO₂ thin films with different thicknesses (0.5-2.0 μm) have been deposited on ITO-coated glass substrates by a sol-gel method and rapid thermal annealing for application as the work electrode for dye-sensitized solar cells (DSSC). From the results, the increases in thickness of TiO₂ films can increase adsorption of the N3 dye through TiO₂ layers to improve the short-circuit photocurrent (J_sc) and open-circuit voltage (V_oc), respectively. However, the J_sc and V_oc of DSSC with a TiO₂ film thickness of 2.0 μm (8.5 mA/cm² and 0.61 V) are smaller than those of DSSC with a TiO₂ film thickness of 1.5 μm (9.2 mA/cm² and 0.62 V). It could be due to the fact that the increased thickness of TiO₂ thin films also resulted in a decrease in the transmittance of TiO₂ thin films thus reducing the incident light intensity on the N3 dye. An optimum power conversion efficiency (η) of 2.9% was obtained in a DSSC with the TiO₂ film thickness of 1.5 μm.     

Room temperature H2S gas sensing characteristics of platinum (Pt) coated porous alumina (PoAl) thick films

The study reports H₂S gas sensing characteristics of platinum (Pt) coated porous alumina (PoAl) films. The porous alumina (PoAl) thick layers were formed in the dark on aluminum substrates using an electrochemical anodization method. Thin semitransparent platinum (Pt) films were deposited on PoAl samples using chemical bath deposition (CBD) method. The films were characterized using energy dispersive X-ray analysis (EDAX) and scanning electron microscopy (SEM). The thicknesses of coated and bare films were measured using ellipsometry. The sensing properties such as sensitivity factor (S.F.), response time, recovery time and repeatability were measured using a static gas sensing system for H₂S gas. The EDAX studies confirmed the purity of Pt–PoAl film and indicated the formation of pure platinum (Pt) phase. The ellipsometry studies revealed the thickness of PoAl layer of about 15–17 μm on aluminum substrates. The SEM studies demonstrated uniform distribution of spherical pores with a size between 0.250 and 0.500 μm for PoAl film and nearly spherical platinum particles with average particle size ∼100 nm for Pt–PoAl film. The gas-sensing properties of these samples were studied in a home-built static gas characterization system. The H₂S gas sensing properties of Pt–PoAl at 1000 ppm of H₂S gave maximum sensitivity factor (S.F.) = 1200. The response time and recovery time were found to be 2–3 min and ∼1 min respectively. Further, the measurement of H₂S gas sensing properties clearly indicated the repeatability of gas sensing response of Pt–PoAl film. The present study indicated the significant potential of Pt coated PoAl films for H₂S gas sensing applications in diverse areas.     

Effect of TiOx seed layer on the texture and electric properties in La and Ca modified PbTiO3 thin films

Lanthanum-and calcium-modified PbTiO₃ (PLCT) ferroelectric thin films were successfully prepared on Pt(111)/Ti/SiO₂/Si substrates by pulsed laser deposition. Influence of TiO_x seed layer on texture and electric properties of PLCT films was investigated. It is found the PLCT films without seed layer exhibited highly (100)-textured, while using about 9 nm TiO_x as seed layer lead to highly (301)-textured. The PLCT film with TiO_x seed layer possess higher remnant polarization (Pr = 26 µC/cm²), better pyroelectric coefficient and figure of merit at room temperature (p = 370 µC/m²k, F_d = 190 × 10^− 5 Pa^− 1/2) than that of film without seed layer. The mechanism of the enhanced electric properties was also discussed.     

Growth and characterization of (Pb,La)TiO3 films with and without a special buffer layer prepared by RF magnetron sputtering

The (Pb, La)TiO₃ (PLT) ferroelectric thin films with and without a special buffer layer of PbO_x have been deposited on Pt/Ti/SiO₂/Si(100) substrates by RF magnetron sputtering technique at room temperature. The microstructure and the surface morphology of the films annealed at 600 °C for 1 h have been investigated by X-ray diffraction (XRD) and atomic force microscope (AFM). The surface roughness of the PLT thin film with a special buffer layer was 4.45 nm (5 μm × 5 μm) in comparison to that of 31.6 nm (5 μm × 5 μm) of the PLT thin film without a special buffer layer. Ferroelectric properties such as polarization hysteresis loop (P–V loop) and capacitance–voltage curve (C–V curve) of the films were investigated. The remanent polarization (P_r) and the coercive field (E_c) are 21 μC/cm² and 130 kV/cm respectively, and the pyroelectric coefficient is 2.75 × 10^− 8 C/cm² K for the PLT film with a special buffer layer. The results indicate that the (Pb, La)TiO₃ ferroelectric thin films with excellent ferroelectric properties can be deposited by RF magnetron sputtering with a special buffer layer.     

Multiferroic properties of BiFeO3/Bi4Ti3O12 double-layered thin films fabricated by chemical solution deposition

Multiferroic BiFeO₃/Bi₄Ti₃O₁₂ (BFO/BTO) double-layered film was fabricated on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. The effect of an interfacial BTO layer on electrical and magnetic properties of BFO was investigated by comparing those of pure BFO and BTO films prepared by the same condition. The X-ray diffraction result showed that no additional phase was formed in the double-layered film, except BFO and BTO phases. The remnant polarization (2P_r) of the double-layered film capacitor was 100 μC/cm² at 250 kV/cm, which is much larger than that of the pure BFO film capacitor. The magnetization-magnetic field hysteresis loop revealed weak ferromagnetic response with remnant magnetization (2M_r) of 0.4 kA/m. The values of dielectric constant and dielectric loss of the double-layered film capacitor were 240 and 0.03 at 100 kHz, respectively. Leakage current density measured from the double-layered film capacitor was 6.1 × 10^− 7 A/cm² at 50 kV/cm, which is lower than the pure BFO and BTO film capacitors.     

Epitaxial growth and properties of cubic Zn0.7Mg0.3O films on TiN-buffered Si(100) substrates by in situ pulsed laser deposition

A novel cubic Zn_0.7Mg_0.3O film on silicon substrate is conducted by KrF excimer pulsed-laser ablation system. By introducing a thin TiN buffer, layer-by-layer growth of cubic Zn_0.7Mg_0.3O film epilayer has been realized. The overall growth process was monitored in situ by reflection high-energy electron diffraction (RHEED) method. It was found that the crystallinity and surface morphology of the Zn_0.7Mg_0.3O films were strongly affected by the TiN buffer layer. The Zn_0.7Mg_0.3O film obtained at an optimal buffer layer exhibited high quality and good surface. For the metal-insulator-metal (MIM) structure of Pt/Zn_0.7Mg_0.3O (200 nm)/TiN (20 nm)/Si (400 μm) prepared at the optimal growth conditions achieved a very low leak current density of ∼10⁻⁶ A cm⁻² at an electric field of 9 × 10⁵ V cm⁻¹ and the permittivity (?_r) of about 8.1, agreed well with that of acquired MgO film and MgO single crystal.     

Callindra haematocephata and Peltophorum pterocarpum flowers as natural sensitizers for TiO2 thin film based dye-sensitized solar cells

We have studied the performance of dye-sensitized solar cells employing natural dye extracted from the flowers Callindra haematocephata and Peltophorum pterocarpum as sensitizers for TiO₂ photoanode. The extracts have shown appreciable absorption in the visible region. FTIR studies indicated the presence of anthocyanins and β-carotene in the flowers of C. haematocephata and P. pterocarpum respectively. The extracts were anchored on TiO₂ film deposited on transparent conductive glass (FTO) which were used as photoanode. The dye coated TiO₂ film electrode, Pt counter electrode and electrolyte (I⁻₃) assembled into a cell module was illuminated by a light source with intensity 100 mW/cm² to measure the photoelectric conversion efficiency of the DSSCs. From the J-V characteristic curves of cells, the parameters related to the solar cell performance were determined. The conversion efficiency of the DSSC employing natural dye extract from the flower C. haematocephata and P. pterocarpumwere was found as 0.06% and 0.04%, with open-circuit voltage (V_OC) of 370 mV & 400 mV, short-circuit current density (J_SC) of 0.25 mA/cm² & 0.15 mA/cm², fill factor (FF) of 0.70 & 0.71 and P_max of 65 & 45 μW cm⁻² respectively. The extract of the flower C. haematocephata exhibited better photosensitization action compared to the flower of P. pterocarpum.     

Electrochemical properties of LiCoO2 thin film electrode prepared by ink-jet printing technique

LiCoO₂ thin film electrodes with a thickness of about 1.2 μm were fabricated by an improved ink-jet printing method. LiCoO₂ powder was synthesized via a modified sol-gel method. The LiCoO₂ ink could be easily prepared by an ultrasonic dispersion technique using a commercially available surfactant. The jet printing LiCoO₂ thin films were characterized by X-ray diffraction and Raman spectroscopy, scanning electron microscopy, cyclic voltammetry, charge/discharge cycling and electrochemical impedance spectroscopy. Experimental results showed that the LiCoO₂ thin film electrodes present excellent cycling performance at high discharge rate. At discharge current density of 180 μA/cm² (at this current density, the battery can be fully discharged in 12 min), the initial discharge capacity was 120 mAh/g, and after 100 charge-discharge cycles, the capacity loss was only 5%. It can be even charge-discharged at the current density as high as 384 μA/cm².     

Pt–Au/C cathode with enhanced oxygen-reduction activity in PEFCs

Carbon-supported Pt–Au (Pt–Au/C) catalyst is prepared separately by impregnation, colloidal and micro-emulsion methods, and characterized by physical and electrochemical methods. Highest catalytic activity towards oxygen-reduction reaction (ORR) is exhibited by Pt–Au/C catalyst prepared by colloidal method. The optimum atomic ratio of Pt to Au in Pt–Au/C catalyst prepared by colloidal method is determined using linear-sweep and cyclic voltammetry in conjunction with cell-polarization studies. Among 3:1, 2:1 and 1:1 Pt–Au/C catalysts, (3:1) Pt–Au/C exhibits maximum electrochemical activity towards ORR. Powder X-ray diffraction pattern and transmission electron micrograph suggest Pt–Au alloy nanoparticles to be well dispersed onto the carbon-support. Energy dispersive X-ray analysis and inductively coupled plasma-optical emission spectroscopy data suggest that the atomic ratios of the alloying elements match well with the expected values. A polymer electrolyte fuel cell (PEFC) operating at 0·6 V with (3:1) Pt–Au/C cathode delivers a maximum power-density of 0·65 W/cm ² in relation to 0·53 W/cm ² delivered by the PEFC with pristine carbon-supported Pt cathode.     

Interfacial characteristics and dielectric properties of Ba0.65Sr0.35TiO3 thin films

Ba_0.65Sr_0.35TiO₃ (BST) thin films were deposited on Pt/Ti/SiO₂/Si substrates by radio frequency magnetron sputtering technique. X-ray photoelectron spectroscopy (XPS) depth profiling data show that each element component of the BST film possesses a uniform distribution from the outermost surface to subsurface, but obvious Ti-rich is present to BST/Pt interface because Ti⁴⁺ cations are partially reduced to form amorphous oxides such as TiO_x (x < 2). Based on the measurement of XPS valence band spectrum, an energy band diagram in the vicinity of BST/Pt interface is proposed. Dielectric property measurements at 1 MHz reveal that dielectric constant and loss tangent are 323 and 0.0095 with no bias, while 260 and 0.0284 with direct current bias of 25 V; furthermore, tunability and figure of merit are calculated to be 19.51% and 20.54, respectively. The leakage current density through the BST film is about 8.96 × 10^− 7 A/cm² at 1.23 V and lower than 5.66 × 10^− 6 A/cm² at 2.05 V as well as breakdown strength is above 3.01 × 10⁵ V/cm.     

Highly active sulfided CoMo catalysts supported on (ZrO2–TiO2)/Al2O3 ternary oxides

(ZrO₂–TiO₂)/Al₂O₃ ternary oxide at 20 mol% Al₂O₃ (80% ZrO₂–TiO₂, in turn at 40–60 mol ratio) prepared by controlled co-precipitation (by urea thermal decomposition) of zirconium (ZrOCl₂·8H₂O) and titanium (TiCl₄) chlorides over a ground alumina substrate constitutes a promising material to be used as carrier of sulfided hydrodesulfurization (HDS) catalysts. After calcining (at 500 °C), the ternary oxide presented textural properties (S_g = 387 m² g⁻¹, V_p = 0.74 ml g⁻¹, mean pore diameter = 7.6 nm) suitable to its utilization as carrier of catalysts applied in the oil-derived middle distillates HDS. As determined by temperature programmed-reduction and Raman and UV–vis spectroscopies ZrO₂–TiO₂ deposition over alumina substrate resulted in decreased proportion of Mo⁶⁺ species in tetrahedral coordination on the oxidic impregnated material. As those species constitute hardly reducible precursors, their diminished concentration could be reflected in enhanced amount of Mo species susceptible of activation by sulfiding (H₂S/H₂ at 400 °C) over our ternary carrier. Limiting the concentration of zirconia-titania (at 40–60 mol ratio) to 20 mol% in the mixed oxides support allowed the preparation of highly active promoted (by cobalt, at Co/(Co + Mo) = 0.3) MoS₂ phase (at 2.8 atoms/nm²), that formulation showing excellent properties in hydrodesulfurization (HDS) of both dibenzothiophene and highly-refractory 4,6-dimethyl-dibenzothiophene. Due to alike yields to various HDS products over CoMo/(ZrO₂–TiO₂)/Al₂O₃ and the corresponding Al₂O₃-supported formulation, presence of similar actives sites over those catalysts was strongly suggested. It seemed that enhanced concentration of octahedral Mo⁶⁺ over the oxidic impregnated precursor with (ZrO₂–TiO₂)/Al₂O₃ ternary carrier resulted, after sulfiding, in increased amount of MoS₂ phase that could be efficiently promoted by cobalt.     

Co-catalysis effect of different morphological facets of as prepared Ag nanostructures for the photocatalytic oxidation reaction by Ag–TiO2 aqueous slurry

This paper highlights the comparative co-catalytic efficiency of different shapes of prepared Ag nanoparticles of size much larger as well as smaller than titania for the Ag–TiO₂ photocatalysis. Quantum sized Ag nanospheres (4^_8 nm), nanorod (length 70–75 nm and width 30–38 nm), polygonal nanosphere (80–120 nm) and truncated triangles (side length 70–140 nm) are prepared by solvothermal process. The co-catalytic activities of these Ag nanostructures were investigated by mixing them with TiO₂ for the photocatalytic degradation of aqueous salicylic (0.5 mM) and benzoic acid (0.5 mM) under UV light (125 W-Hg arc, 10.4 mW cm⁻²) irradiation. The Ag co-catalysis effect imparted to TiO₂ follows as polygonal nanosphere > nanorod > truncated triangle > small nanosphere due to the formation of many Ag–TiO₂ interfaces by a single large-sized Ag nanoparticle than smaller one. As the surface coverage of Ag particles by TiO₂ decreases, the Ag–TiO₂ photoactivity is decreased accordingly. The efficient adsorption of salicylic acid to TiO₂ surface through –COOH and –OH groups render its higher photodegradation rate (1.8–2.7 × 10⁻² μmol min⁻¹) than benzoic acid (1.5–2.5 × 10⁻² μmol min⁻¹) having one chelating –COOH group. Zeta potential and conductance measurement of photoreaction mixture were carried out to investigate the ionic interaction-adsorption of reactant substrates over Ag–TiO₂ surface.     

The synthesis of lead-free ferroelectric Bi0.5Na0.5TiO3-Bi0.5K0.5TiO3 thin films by sol-gel method

(1 − x)Bi_0.5Na_0.5TiO₃-xBi_0.5K_0.5TiO₃ [BNT-BKT-100x] thin films have been successfully deposited on Pt/Ti/SiO₂/Si substrates by a sol-gel process together with rapid thermal annealing. A morphotropic phase boundary (MPB) between Bi_0.5Na_0.5TiO₃ and Bi_0.5K_0.5TiO₃ was determined around x ∼ 0.15. Near the MPB, the film exhibits the largest grain size, the highest ε value (360) and the largest P_r value (13.8 μC/cm²). The BNT-BKT thin film system is expected to be a new and promising candidate for lead-free piezoelectric applications.     

Fabrication of BaTiO3 films on titanium by microarc oxidation method and improvement of bioactivity by electric poling treatment

A microarc oxidation (MAO) method was used to deposit a ferroelectric BaTiO₃ (BTO) film on titanium implant metal. The bioactivity of the sample was enhanced by negatively polarizing the film surface. BTO-1 and BTO-2 sample groups were fabricated by applying a constant AC current of 1.2 A/cm² (900 s) and 2.0 A/cm² (600 s), respectively. The BTO film surface was negatively polarized using a high temperature poling treatment. The bioactivity of the non-polarized BTO and polarized BTO films was compared using an immersion test in Eagle's Minimum Essential Medium (MEM). For both groups, 0.5-2 μm diameter pores were evenly distributed over the BTO film surface fabricated using the MAO method. The crystallinity and film-to-substrate bond strength of the BTO-2 film were higher than those of the BTO-1 film. The in vitro MEM immersion test demonstrated more calcium phosphate deposition on the negatively polarized BTO film than on the non-polarized BTO film.     

Dependence of Zr content on electrical properties of Bi3.15Nd0.85Ti3-xZrxO12 thin films synthesized by chemical solution deposition (CSD)

The Bi_3.15Nd_0.85Ti_3-xZr_xO₁₂ (BNTZ) thin films with Zr content (x = 0, 0.05, 0. 1, 0.15, and 0.2) were prepared on Pt/Ti/SiO₂/Si (100) substrates by chemical solution deposition (CSD) technique. The crystal structures of BNTZ films were analyzed by X-ray diffraction (XRD). The effects of Zr contents on the ferroelectric, dielectric properties, and leakage current of BNTZ films were thoroughly investigated. The XRD results demonstrated that all the films possessed a single phase bismuth-layered structure and exhibited the highly preferred (117) orientation. Among these films, the film with Zr content x = 0.1 held the maximum remanent polarization (2P_r) of 50.21 μC/cm² and a low coercive field (2E_c) of 210 kV/cm.     

Highly a-oriented SrBi2Ta2O9 thin film on (111) Pt/TiO2/SiO2/Si substrate by eclipse pulsed laser deposition

A highly a-oriented SrBi₂Ta₂O₉ thin film with a polycrystalline structure was deposited on a preferentially oriented (111) Pt/TiO₂/SiO₂/Si substrate by eclipse pulsed laser deposition (PLD) method. The SrBi₂Ta₂O₉ thin film exhibited flat and smooth surface with the surface roughness of about 0.5 nm resulting from reducing particulates generated by on-axis PLD. The SrBi₂Ta₂O₉ thin film showed a good ferroelectric property with the high remanent polarization of 12 μC/cm² and the low coercive electric field of 140 kV/cm. For the highly a-oriented SBT thin film, domain switching and reading were performed by Kelvin probe force microscope (KFM). The KFM data indicate a good ferroelectric property of the highly a-oriented SrBi₂Ta₂O₉ thin film with high KFM signals that reflect ferroelectric polarizations.     

Characterization and enhanced field emission properties of carbon nanotube bundle arrays coated with N-doped nanocrystalline anatase TiO2

Anatase TiO₂ nanocrystals (NCs) were deposited onto patterned carbon nanotube (CNT) bundle arrays to form a TiO₂/CNT composite using metal organic chemical vapor deposition (MOCVD) using titanium-tetraisopropoxide (Ti(OC₃H₇)₄) as a source reagent. The N-doped TiO₂/CNT composite was then fabricated using nitrogen plasma treatment. The structural and spectroscopic properties of TiO₂/CNT composites were characterized by field-emission scanning electron microscopy, micro-Raman spectroscopy and X-ray photoelectron spectroscopy. The combined geometrical structure and low electron affinity effects of N-doped TiO₂ led to a low turn-on field of 1.0 V μm⁻¹ at a current density of 10 μA cm⁻², a low threshold field of 1.9 V μm⁻¹ at a current density of 1 mA cm⁻², a high field enhancement factor of 3.0 × 10³, and long-term stability for the N-doped TiO₂/CNT composite. The results revealed that the N-doped TiO₂/CNT composite can be a potential candidate for field emission devices.     

Low voltage operated,sol–gel derived oxide thin film transistor based on high-k Gd2O3 gate dielectric

Low power-driven oxide thin film transistor (TFT) with a high-k gate dielectric is fabricated by a simple solution process. Sol–gel derived Gd₂O₃ film exhibits the dielectric constant in the range of 9–14 with breakdown field as high as 3.5 MV cm⁻¹. Zn–In–Sn–O based TFTs combined with a corresponding film demonstrate the readiness of solution processed high-k film as gate insulators. The resultant device exhibits the enhanced performance with the field-effect mobility of ∼1.9 cm² V⁻¹ s⁻¹, which is improved by a factor of 4.5 comparing with the conventional TFT based on a SiO₂ insulator, and the exceptionally low operating voltage of 6 V.     

Metal ion-TiO2 nanocomposites for the selective photooxidation of benzene to phenol and cycloalkanol to cycloalkanone

TiO₂ has attracted a great deal of research attention for photochemical redox combined transformation of organic functional groups into useful products. In this context, various transition metal ions impregnated-TiO₂ catalysts are prepared and characterised by SEM surface morphology, TEM size and shape analysis, magnetic susceptibility measurement and tested for benzene and cycloalkanol oxidation. The highest yield (14.8 μmol) and selectivity (80%–86%) of phenol as compared to hydroquinone (yield = 2%–8%) is achieved during 1–2-h irradiation (125 W Hg arc lamp, 10.4 mW/cm²) of aqueous suspension of 5 wt% Fe⁺³-TiO₂ and 20 mM benzene solution. The co-catalytic activity of metal ions imparted to TiO₂ during benzene oxidation was highly enhanced in the order Fe⁺³ > Ag⁺ > Au⁺³ > Cu⁺² as compared to very low reactive elemental metal loading. Metal/metal ion deposition onto TiO₂ highly reduces the cycloketone yield whereas bare TiO₂ exhibits the maximum amount of cyclohexanone (60%) and cycloheptanone (50%) formation from respective cycloalkanol photooxidation up to 4-h irradiation.     

Poly (thienylene methine) grafted nanocrystalline TiO2 based hybrid solar cells

A novel hybrid solar cell fabricated from TiO₂ and in situ polymerized poly (thienylene methane) (PTBBQ) onto the surface of TiO₂ was described. ¹HNMR, FTIR, UV–Vis absorption, thermal and electrochemical properties of PTBBQ were investigated, and the surface morphology of TiO₂/in situ polymerized PTBBQ film was studied via AFM contact mode. Device I/V characterizations with and without in situ polymerized PTBBQ were measured. Efficiency improvements were observed in the in situ polymerized PTBBQ/TiO2 system, and such device showed a short-circuit current density of 1.15 mA/cm², an open-circuit voltage of 0.50 V, a fill factor of 0.50, and a energy conversion efficiency of 0.29% at A.M. 1.5 solar illumination (100 mW/cm²).