Growth mode and electronic structure of Au nano-clusters on NiO(0 0 1) and TiO2(1 1 0)

The growth mode and electronic structure of Au nano-clusters grown on NiO and TiO₂ were analyzed by reflection high-energy electron diffraction, a field-emission type scanning electron microscope, medium energy ion scattering and photoelectron spectroscopy. Au was deposited on clean NiO(0 0 1)-1 × 1 and TiO₂(1 1 0)-1 × 1 surfaces at room temperature with a Knudsen cell at a rate of 0.25-0.35 ML/min (1 ML = 1.39 × 10¹⁵ atoms/cm²:Au(1 1 1)). Initially two-dimensional (2D) islands with thickness of one Au-atom layer grow epitaxially on NiO(0 0 1) and then neighboring 2D-islands link each other to form three-dimensional (3D)-islands with the c-axis oriented to the [1 1 1] direction. The critical size to form 3D-islands is estimated to be about 5 nm². The shape of the 3D-islands is well approximated by a partial sphere with a diameter d and height h ranging from 2.0 to 11.8 nm and from 0.95 to 4.2 nm, respectively for Au coverage from 0.13 to 4.6 ML. The valence band spectra show that the Au/NiO and Au/TiO₂ surfaces have metallic characters for Au coverage above 0.9 ML. We observed Au 4f spectra and found no binding energy shift for Au/NiO but significant higher binding energy shifts for Au/TiO₂ due to an electron charge transfer from Au to TiO₂. The work function of Au/NiO(0 0 1) gradually increases with increase in Au coverage from 4.4 eV (NiO(0 0 1)) to 5.36 eV (Au(1 1 1)). In contrast, a small Au deposition(0.15 to 1.5 ML) on TiO₂(1 1 0) leads to reduction of the work function, which is correlated with an electron charge transfer from Au to TiO₂ substrate.     

Structural, optical, and electrical properties of p-type NiO films and composite TiO2/NiO electrodes for solid-state dye-sensitized solar cells

p-Type nickel oxide thin films were prepared by sol-gel method, and their structural, optical and electrical properties were investigated. The Ni(OH)₂ sol was formed from nickel (II) acetate tetrahydrate, Ni(CH₃COO)₂·4H₂O, in a mixture of alcohol solution and poly(ethylene glycol), and deposited on an ITO substrate by spin coating followed by different heat treatments in air (50-800 °C). The formation and composition of NiO thin film was justified by EDX analysis. It is found that the thickness of the NiO film calcined at 450 °C for 1 h is about 120 nm with average particle size of 22 nm, and high UV transparency (∼75%) in the visible region is also observed. However, the transmittance is negligible for thin films calcined at 800 °C and below 200 °C due to larger particle size and the amorphous characteristics, respectively. Moreover, the composite electrode comprising n-type TiO₂ and p-type NiO is fabricated. The current-voltage (I-V) characteristics of the composite TiO₂/NiO electrode demonstrate significant p-type behavior by the shape of the rectifying curve in dark. The effect of calcination temperature on the rectification behavior is also discussed.     

The surface of TiO2 gate of 2DEG-FET in contact with electrolytes for bio sensing use

In order to apply two-dimensional electron-gas-field-effect-transistors (2DEG-FETs) for cell-viability sensors, we investigated the chemical/electrical properties of TiO₂ thin films (13-17 nm) prepared with the sol-gel technique on the gate surface of AlGaAs/GaAs 2DEG-FETs. Photochemical/electrochemical reactions on GaAs surface in electrolytes, which induce the degradation of 2DEG-FET performance, are effectively suppressed by introducing a TiO₂ thin film on the gate area of 2DEG-FETs. Compared to conventional ion-selective FETs (ISFETs), the TiO₂/2DEG-FETs in this study exhibit a high sensitivity (410 mV/mM) for H₂O₂ detection. TiO₂ surfaces show better biocompatibility than GaAs surfaces as demonstrated by direct cell culture on these surfaces.     

Enhanced photocatalytic activity of TiO2 nano-structured thin film with a silver hierarchical configuration

TiO₂ sol-gels with various Ag/TiO₂ molar ratios from 0 to 0.9% were used to fabricate silver-modified nano-structured TiO₂ thin films using a layer-by-layer dip-coating (LLDC) technique. This technique allows obtaining TiO₂ nano-structured thin films with a silver hierarchical configuration. The coating of pure TiO₂ sol-gel and Ag-modified sol-gel was marked as T and A, respectively. According to the coating order and the nature of the TiO₂ sol-gel, four types of the TiO₂ thin films were constructed, and marked as AT (bottom layer was Ag modified, surface layer was pure TiO₂), TA (bottom layer was pure TiO₂, surface layer was Ag modified), TT (pure TiO₂ thin film) and AA (TiO₂ thin film was uniformly Ag modified). These thin films were characterized by means of linear sweep voltammetry (LSV), X-ray diffraction (XRD), scanning electron microscopy (SEM), electrochemical impedance spectroscopy and transient photocurrent (I_ph). LSV confirmed the existence of Ag⁰ state in the TiO₂ thin film. SEM and XRD experiments indicated that the sizes of the TiO₂ nanoparticles of the resulting films were in the order of TT > AT > TA > AA, suggesting the gradient Ag distribution in the films. The SEM and XRD results also confirmed that Ag had an inhibition effect on the size growth of anatase nanoparticles. Photocatalytic activities of the resulting thin films were also evaluated in the photocatalytic degradation process of methyl orange. The preliminary results demonstrated the sequence of the photocatalytic activity of the resulting films was AT > TA > AA > TT. This suggested that the silver hierarchical configuration can be used to improve the photocatalytic activity of TiO₂ thin film.     

Hierarchically porous nanoflowers from TiO2–B nanosheets with ultrahigh surface area for advanced lithium-ion batteries

In this work, hierarchically porous TiO₂–B nanoflowers have been successfully synthesized via a facile solvothermal method followed by calcination treatment. The TiO₂–B nanoflowers are constructed by thin nanosheets, presenting ultrahigh specific surface area, up to 214.6 m² g⁻¹. As anode materials for Li-ion batteries, the TiO₂–B sample shows high reversible capacity, excellent cycling performance and superior rate capability. The specific capacity of TiO₂–B could remain over 285 mA h g⁻¹ at 1 C and 181 mA h g⁻¹ at 10 C rate after 100 cycles. We believe that the pseudocapacitive mechanism, ultrahigh surface area and scrupulous nanoarchitecture of the TiO₂–B are responsible for the enhancement of electrochemical properties.     

Electrochemical and surface characterisation of carbon-film-coated piezoelectric quartz crystals

The electrochemical properties of carbon films, of thickness between 200 and 500 nm, sputter-coated on gold- and platinum-coated 6 MHz piezoelectric quartz crystal oscillators, as new electrode materials have been investigated. Comparative studies under the same experimental conditions were performed on bulk electrodes. Cyclic voltammetry was carried out in 0.1 M KCl electrolyte solution, and kinetic parameters of the model redox systems Fe(CN)₆^3−/4− and [Ru(NH₃)₆]^3+/2+ as well as the electroactive area of the electrodes were obtained. Atomic force microscopy was used in order to examine the surface morphology of the films, and the properties of the carbon films and the electrode-solution interface were studied by electrochemical impedance spectroscopy. The results obtained demonstrate the feasibility of the preparation and development of nanometer thick carbon film modified quartz crystals. Such modified crystals should open up new opportunities for the investigation of electrode processes at carbon electrodes and for the application of electrochemical sensing associated with the EQCM.     

Applications of vertically oriented TiO2 micro-pillars array on the electrode of dye-sensitized solar cell

In this research, dye-sensitized solar cells based on TiO₂ micro-pillars fabricated by inductive couple plasma etcher were investigated by analyses of X-ray diffraction (XRD), scanning electron microscopy (SEM), contact angle, ultraviolet-visible absorption spectra (UV-vis), and current-voltage characteristics. X-ray diffraction patterns show that the TiO₂ anatase phase forms while sintering at 450 °C for 30 min. The SEM images reveal that the diameter and height of TiO₂ micro-pillars are about 3 and 0.8 μm, respectively. The measurements of contact angle between TiO₂ micro-pillars and deionized water (DI water) reveal that the TiO₂ micro-pillars is super-hydrophilic while annealed at 450 °C for 30 min.The absorption spectrum of TiO₂ micro-pillars is better than TiO₂ thin film and can be widely improved in visible region with N3 dye adsorbed. The results of current-voltage (I-V) characteristics analysis reveal that dye-sensitized solar cell with TiO₂ micro-pillars electrode has better I-V characteristics and efficiency than TiO₂ film electrodes. This result may be due to the annealed TiO₂ micro-pillars applied on the electrode of dye-sensitized solar cell can increase the contact area between TiO₂ and dye, resulting in the enhancement of I-V characteristics and efficiency for dye-sensitized solar cell.     

Synthesis and characterization of polypyrrole/Sn-doped TiO2 nanocomposites (NCs) as a protective pigment

We have chemically polymerized pyrrole in the presence of Sn-doped TiO₂ nanoparticles (NPs) and TiO₂ (NPs) which act as a protective pigment. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) results show a core-shell structure of pigments in which TiO₂ and Sn-doped TiO₂ NPs have a nucleus effect and caused a homogenous PPy core-shell type morphology leading to coverage of the TiO₂ and Sn-doped TiO₂ NPs by PPy deposit. The XRD results indicate that the crystalline size of polypyrrole/TiO₂ NCs and polypyrrole/Sn-doped TiO₂ NCs were approximately 93.46 ± 0.06 and 23.36 ± 0.06 nm respectively. The electrochemical impedance spectroscopy (EIS) results show that the performance of polypyrrole/Sn-doped TiO₂ NCs is better than polypyrrole/TiO₂ NCs. The results indicate that increasing the area of synthesized polypyrrole in the presence of Sn-doped TiO₂ NPs can increase its ability to interact with the ions liberated during the corrosion reaction of steel in the presence of NaCl. The UV-vis results show that the band gap of TiO₂ NPs increases with doped of Sn in lattice of TiO₂. The increase of the band gap of TiO₂ with doping of Sn can decrease the charge transfer through the coating.     

Characterization of TiO2/Au/TiO2 films deposited by magnetron sputtering on polycarbonate substrates

Transparent and conducting TiO₂/Au/TiO₂ (TAuT) films were deposited by reactive magnetron sputtering on polycarbonate substrates to investigate the effect of the Au interlayer on the optical, electrical, and structural properties of the films. In TAuT films, the Au interlayer thickness was kept at 5 nm. Although total thickness was maintained at 100 nm, the stack structure was varied as 50/5/45, 70/5/25, and 90/5/5 nm.In XRD pattern, the intermediate Au films were crystallized, while all TAuT films did not show any diffraction peaks for TiO₂ films with regardless of stack structure. The optical and electrical properties were dependent on the stack structure of the films. The lowest sheet resistance of 23 Ω/□ and highest optical transmittance of 76% at 550 nm were obtained from TiO₂ 90 nm/Au 5 nm/TiO₂ 5 nm films. The work function was dependent on the film stack. The highest work function (4.8 eV) was observed with the TiO₂ 90 nm/Au 5 nm/TiO₂ 5 nm film stack. The TAuT film stack of TiO₂ 90 nm/Au 5 nm/TiO₂ 5 nm films is an optimized stack that may be an alternative candidate for transparent electrodes in flat panel displays.     

Preparation of alkaline solid polymer electrolyte based on PVA-TiO2-KOH-H2O and its performance in Zn-Ni battery

A novel composite alkaline polymer electrolyte based on poly(vinyl alcohol) (PVA) polymer matrix, titanium dioxide (TiO₂) ceramic fillers, KOH, and H₂O was prepared by a solution casting method. The properties of PVA-TiO₂-KOH alkaline polymer electrolyte films were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and AC impedance techniques. DSC and XRD results showed that the domain of amorphous region in the PVA polymer matrix augmented when TiO₂ filler was added. The SEM result showed that TiO₂ particles dispersed into the PVA matrix although some TiO₂ aggregates of several micrometers were formed. The alkaline polymer electrolyte showed excellent electrochemical properties. The room temperature (20 °C) ionic conductivity values of typical samples were between 0.102 and 0.171 S cm⁻¹. The Zn-Ni secondary battery with the alkaline polymer electrolyte PVA-TiO₂-KOH had excellent electrochemical property at the low charge-discharge rate.     

Dielectric and leakage current properties of Li doped (Ba,Sr)TiO3 thick film interdigital capacitors on the alumina substrates

Li doped (Ba,Sr)TiO₃ thick films were fabricated by employing the screen printing method on the alumina (Al₂O₃) substrates. Interdigital capacitor patterns with seven fingers of 200 μm gap, 250 μm length were designed and screen printed on the alumina substrates. Ba_0.5Sr_0.5TiO₃ materials, paraelectric state at the room temperature, have been chosen for the microwave devices due to high dielectric permittivity and low loss tangent, however, the sintering temperature of (Ba,Sr)TiO₃ is over 1350 °C. In order to lower the sintering temperature, Li (3 wt%) was added to the (Ba,Sr)TiO₃ materials. Li doped (Ba,Sr)TiO₃ thick films screen printed on the alumina (Al₂O₃) substrates were sintered at 900 °C for 1.5 h. The structural feature was analyzed with X-ray diffraction method. Temperature dependent dielectric properties were characterized from 303 to 403 K at 1 MHz. Within the ±100 V of bias voltage, current-voltage characteristics of Li doped (Ba,Sr)TiO₃ films were investigated from 303 to 403 K. Through the current-voltage characteristics, the resistivity of Li doped (Ba,Sr)TiO₃ films were calculated.In this paper, the significant negative temperature coefficient of resistance (NTCR) of Li doped (Ba,Sr)TiO₃ films will be presented through the activation energy fitting. Measured activation energy is approximately 0.366 eV.     

Ultrathin nickel oxide films grown on Ag(0 0 1): a study by XPS, LEIS and LEED intensity analysis

The structure of a nickel oxide film 2 ML thick has been investigated by LEED intensity analysis. The NiO film was prepared by evaporating Ni in presence of O₂ at a pressure in the 10⁻⁶ mbar range. The growth of the oxide film was followed by XPS, LEIS and LEED. In the early stages of deposition, the film shows a (2 × 1) superstructure in LEED. After deposition of 2 ML of NiO, a sharp (1 × 1) LEED pattern is observed. The intensity versus electron energy curves of the LEED spots were measured for this NiO(1 × 1) film and analysed by means of the tensor LEED method. A good level of agreement of the experimental LEED intensities with those calculated for a pseudomorphic NiO(0 0 1) film was obtained. We found that oxygen atoms at the oxide-substrate interface are on-top silver atoms. The interlayer distance in the oxide does not differ significantly from that in bulk NiO(0 0 1), within the accuracy of the analysis. An outward displacement (0.05 ± 0.05 Å) of oxygen atoms with respect to nickel atoms was found at the oxide film surface. The interlayer distance at the silver-nickel oxide interface is 2.43 ± 0.05 Å.     

The effect of Pt on Ni3Al surface oxidation at low-pressures

The fully-oxidized surface that forms on (1 1 1) oriented Ni₃Al single crystals, with and without Pt addition, at 300-900 K under oxygen pressures of ca. 10⁻⁷ Torr was studied using XPS, AES, and LEIS. Two main types of surfaces form, depending upon oxidation temperature. At low-temperature, the predominant oxide is NiO, capped by a thin layer of aluminum oxide, which we refer to generically as Al_xO_y. At high-temperature (i.e., 700-800 K), NiO is replaced by a thick layer of Al_xO_y. By comparing samples that contain 0, 10 and 20 at.% Pt in the bulk, we find that the effect of Pt is to: (1) reduce the maximum amount of both NiO and Al_xO_y; and (2) shift the establishment of the thick Al_xO_y layer to lower temperatures. Platinum also decreases the adsorption probability of oxygen on the clean surface.     

Nanostructure of photocatalytic TiO2 films sputtered at temperatures below 200 °C

The article reports on correlations between the process parameters of reactive pulsed dc magnetron sputtering, physical properties and the photocatalytic activity (PCA) of TiO₂ films sputtered at substrate surface temperature T_surf ≤ 180 °C. Films were deposited using a dual magnetron system equipped with Ti (Ø50 mm) targets in Ar + O₂ atmosphere in oxide mode of sputtering. The TiO₂ films with highly photoactive anatase phase were prepared without a post-deposition thermal annealing. The decomposition rate of the acid orange 7 (AO7) solution during the photoactivation of the TiO₂ film with UV light was used for characterization of the film PCA. It was found that (i) the partial pressure of oxygen pO₂ and the total sputtering gas pressure p_T are the key deposition parameters influencing the TiO₂ film phase composition that directly affects its PCA, (ii) the structure of sputtered TiO₂ films varies along the growth direction from the film/substrate interface to the film surface, (iii) ∼500 nm thick anatase TiO₂ films with high PCA were prepared and (iv) the structure of sputtered TiO₂ films is not affected by the substrate surface temperature T_surf when T_surf < 180 °C. The interruption of the sputtering process and deposition in long (tens of minutes) pulses alternating with cooling pauses has no effect on the structure and the PCA of TiO₂ films and results in a decrease of maximum value of T_surf necessary for the creation of nanocrystalline nc-TiO₂ film. It was demonstrated that crystalline TiO₂ films with high PCA can be sputtered at T_surf ≤ 130 °C. Based on obtained results a phase zone model of TiO₂ films was developed.     

Synthesis and electrochemical properties of Ni doped titanate nanotubes for lithium ion storage

Ni doped titanate nanotubes were synthesized by hydrothermal method using Ni doped rutile TiO₂ nanopowders as a starting material. The electrochemical properties were investigated by cyclic voltammmetric methods. The microstructure and morphology of the synthesized powders were characterized by XRD (X-ray diffraction), and HRTEM (high resolution transmission electron microscopy). Ni doped nanotubes were composed of H₂Ti₂O₅·H₂O with outer and inner diameter of ∼10 nm and 6 nm and showed a initial discharge capacity of 305 mAh/g with poor cycling performance. However, after firing, the Ni doped nanotubes revealed better cycling performance due to lower reaction with hydrate and smaller diameter of the tubes.     

The control of the diameter of the nanorods prepared by dc reactive magnetron sputtering and the applications for DSSC

The TiO₂ nanorod arrays, with about 1.8 μm lengths, have been deposited on ITO substrates by dc reactive magnetron sputtering at different target-substrate distances. The average diameter of these nanorods can be modified from about 45 to 85 nm by adjusting the target-substrate distance from 90 to 50 mm. These nanorods are highly ordered and perpendicular to the substrate. Both XRD and Raman measurements show that the nanorods prepared at different target-substrate distances have only an anatase TiO₂ phase. The nanorods prepared at the target-substrate distance less than 80 mm have a preferred orientation along the (2 2 0) direction. However, this preferred orientation disappears as the target-substrate distance is more than 80 mm. These TiO₂ nanorods have been used as the electrodes for dye-sensitized solar cells (DSSCs). The highest conversion efficiency, about 4.78%, has been achieved for TiO₂ nanorods prepared at 80 mm target-substrate distance.     

Electrochemical, morphological and microstructural characterization of carbon film resistor electrodes for application in electrochemical sensors

The electrochemical and microstructural properties of carbon film electrodes made from carbon film electrical resistors of 1.5, 15, 140 Ω and 2.0 kΩ nominal resistance have been investigated before and after electrochemical pre-treatment at +0.9 V vs SCE, in order to assess the potential use of these carbon film electrodes as electrochemical sensors and as substrates for sensors and biosensors. The results obtained are compared with those at electrodes made from previously investigated 2 Ω carbon film resistors. Cyclic voltammetry was performed in acetate buffer and phosphate buffer saline electrolytes and the kinetic parameters of the model redox system Fe(CN)₆^3−/4− obtained. The 1.5 Ω resistor electrodes show the best properties for sensor development with wide potential windows, similar electrochemical behaviour to those of 2 Ω and close-to-reversible kinetic parameters after electrochemical pre-treatment. The 15 and 140 Ω resistor electrodes show wide potential windows although with slower kinetics, whereas the 2.0 kΩ resistor electrodes show poor cyclic voltammetric profiles even after pre-treatment. Electrochemical impedance spectroscopy related these findings to the interfacial properties of the electrodes. Microstructural and morphological studies were carried out using contact mode Atomic Force Microscopy (AFM), Confocal Raman spectroscopy and X-ray diffraction. AFM showed more homogeneity of the films with lower nominal resistances, related to better electrochemical characteristics. X-ray diffraction and Confocal Raman spectroscopy indicate the existence of a graphitic structure in the carbon films.     

The structure of ordered Au films on TiOx

The growth of Au on an ultra-thin, ordered Mo(1 1 2)-(8 × 2)-TiO_x, was investigated using scanning tunneling microscopy (STM), low energy ion scattering spectroscopy (LEISS), X-ray photoelectron spectroscopy (XPS), and temperature programmed desorption (TPD). Wetting of the TiO_x surface by Au was observed with STM and LEISS, and the ordering of the Au films was atomically resolved with STM. TPD showed that Au binds more strongly to the reduced TiO_x film than to bulk TiO₂, but more weakly than to the Mo substrate. The Au-TiO_x binding energy is greater than Au-Au in bulk Au. The oxidation state of Ti in the TiO_x film was deduced by XPS and from the Ti-O phonon shifts relative to bulk TiO₂. The TiO_x/Mo(1 1 2) film structure and those for the (1 × 1)- and (1 × 3)-Au/TiO_x/Mo(1 1 2) surfaces are discussed.     

Electrochemical capacitance from carbon nanotubes decorated with titanium dioxide nanoparticles in acid electrolyte

The electrochemical activity of an electrode of carbon nanotubes (CNTs) attached with TiO₂ nanoparticles was investigated. A chemical-wet impregnation was used to deposit different TiO₂ particle densities onto the CNT surface, which was chemically oxidized by nitric acid. Transmission electron microscopy showed that each TiO₂ nanoparticle has an average size of 30-50 nm. Nitrogen physisorption measurement indicated that the porosity of CNTs is partially hindered by some titania aggregations at high surface coverage. Cyclic voltammetry measurements in 1 M H₂SO₄ showed that (i) an obvious redox peak can be found after the introduction of TiO₂ and (ii) the specific peak current is proportional to the TiO₂ loading. This enhancement of electrochemical activity was attributed to the fact that TiO₂ particles act as a redox site for the improvement of energy storage. According to our calculation, the electrochemical capacitance of TiO₂ nanocatalysts in acid electrolyte was estimated to be 180 F/g. Charge-discharge cycling demonstrated that the TiO₂-CNT composite electrode maintains stable cycleability of over 200 cycles.     

Application of ultrasonic wave to clean the surface of the TiO2 nanotubes prepared by the electrochemical anodization

In this study, the TiO₂ nanotubes were fabricated by electrochemical anodization in a NH₄F/Na₂SO₄/PEG400/H₂O electrolyte system. Ultrasonic wave (80 W, 40 kHz) was used to clean the surface of TiO₂ nanotube arrays in the medium of water after the completion of the anodization. Surface morphology (FESEM) and X-ray diffraction spectrum of the nanotubes treated by sonication at 0 min, 9 min, 40 min and 60 min were compared. The experimental results showed that the precipitate on the surface of the nanotube arrays could be removed by the ultrasonic wave. The treating time had an influence on the precipitate removal and 9 min (corresponding to 12 Wh) is the suitable time for surface cleaning of the TiO₂ nanotubes on this experimental condition.