In situ spectroelectrochemical surface-enhanced Raman scattering (SERS) investigations on composite Ag/TiO2-nanotubes/Ti substrates

A tubular array of TiO₂-nanotubes on a Ti substrate was used as a support for an Ag sputter-deposited layer intended for surface-enhanced Raman scattering (SERS) investigations. Composite samples of Ag/TiO₂-nanotube/Ti were studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to reveal their characteristic morphological and chemical features. Raman spectra of pyridine (as a probe molecule) were measured at different cathodic potentials ranging from −0.2 down to −1.2 V after the pyridine had been adsorbed on the TiO₂-nanotube/Ti substrates covered with the Ag deposit. In addition, SERS spectra on a bulk electrochemically-roughened Ag reference substrate, were also measured.The SERS activity of the composite samples was strongly dependent on the amount of Ag deposit and, in some cases, was even higher than that for the Ag reference substrate. The SERS intensity vs. electrode potential dependences measured were interpreted in terms of the modified electronic structure of the Ag deposits due to the interaction of the Ag clusters with the TiO₂-nanotube/Ti substrate.     

Raman investigations of TiO2 nanotube substrates covered with thin Ag or Cu deposits

A tubular array of TiO₂ nanotubes on Ti matrix was used as a support for Ag or Cu sputter‐deposited layers intended for surface‐enhanced Raman scattering (SERS) investigations. The composite samples of Ag/TiO₂–nanotube/Ti and Cu/TiO₂–nanotube/Ti were studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) [and scanning Auger microscopy (SAM)] to reveal their characteristic morphological and chemical features. Raman spectra of pyridine (as a probe molecule) were measured after it had been adsorbed on the TiO₂–nanotube/Ti substrates covered with thin Ag or Cu deposit as well as on the bulk electrochemically roughened Ag or Cu reference substrates. It was found that the SERS spectra measured for pyridine adsorbed on the bulk silver substrate were significantly different than the spectra measured on the TiO₂–nanotube/Ti substrates covered the Ag layer. The spectra measured for pyridine adsorbed on the Ag/TiO₂–nanotube/Ti suggest that on the surface of such a composite substrate there are many Lewis acidic sites. Spectra typical for pyridine adsorbed on acidic sites were observed even after deposition of a relatively thick silver layer (e.g. an Ag layer with an average thickness of 80 nm) on the TiO₂–nanotube/Ti support. Our findings suggest that TiO₂–nanotube/Ti support is a promising substrate for the preparation of metallic nano‐clusters on a support containing acidic active sites. Copyright © 2009 John Wiley & Sons, Ltd.     

Surface enhanced Raman scattering (SERS) of chemisorbed species on various kinds of metals and semiconductors

SERS spectra of pyridine adsorbed on various kinds of vacuum evaporated (10^?5 Torr) metals (Ag, Au, Ni, Pd, Pt, Ti and Co) and on single crystals of semiconductors (NiO and TiO₂) were obtained at room temperature. The peak frequencies as shifted from those of free pyridine are assigned to the bands of N-bonded pyridine (chemisorbed pyridine). The λ₀ dependence varied remarkably from metal to metal. The peak frequency and the λ₀ dependence for the pyridine adsorbed on NiO or TiO₂ are in good agreement with those on Ni or Ti, respectively, showing the chemical bonding between the N atom and the Ni or Ti atom. The effects of background and of polarization on the SERS spectra were examined in detail, thus revealing the orientation of the adsorbed molecules. Carbon monoxide chemisorbed on Ag was measured by infrared specular reflection as well as by SERS. The results indicate that chemisorbed species on the same substrate do not always give SERS. The SERS spectra obtained are well interpreted as being due to the mechanism of resonance Raman scattering via charge transfer excitation of the adsorbent-adsorbate interaction.     

Surface‐enhanced Raman scattering investigations on silver nanoparticles deposited on alumina and titania nanotubes: influence of the substrate material on surface‐enhanced Raman scattering activity of Ag nanoparticles

Silver nanoparticles deposited on various ‘inert’ porous materials (mainly Al₂O₃ and TiO₂) are often used as substrates for surface‐enhanced Raman scattering (SERS) measurements. In this study, we used the sputter deposition technique to cover tubular arrays of Al₂O₃ and TiO₂ with Ag nanoparticles. Raman spectra of pyridine (as a probe molecule) and of two selected dyes (5‐(4‐dimethylaminobenzylidene)rhodanine and 5‐(4‐(dimethylamino)benzylidene)‐3‐(3‐methoxypropyl)rhodanine) adsorbed on fabricated Ag/TiO₂‐n/Ti and Ag/Al₂O₃‐n/Al substrates were measured. We found that the SERS spectra of pyridine adsorbed on Ag nanoparticles deposited on an Al₂O₃‐n/Al substrate are distinctly different from those measured for an Ag/TiO₂‐n/Ti composite. Similar effects were observed for dyes adsorbed on the surface of both composites. The spectral differences between two kinds of composites (Ag/TiO₂‐n/Ti and Ag/Al₂O₃‐n/Al) are discussed in terms of (1) the modified electronic structure of the Ag nanoparticles due to their interaction with different substrate materials and (2) the different atomic topology of the metal particles thus deposited on the surfaces of the substrates. Composite samples were also studied with the aid of scanning electron microscopy (SEM) and Auger electron spectroscopy (AES) to reveal their characteristic morphological and chemical features. Copyright © 2012 John Wiley & Sons, Ltd.     

Dependence of intermediated noble metals on the optical and electrical properties of ITO/metal/ITO multilayers

Sn doped In₂O₃ (ITO) single layer and a sandwich structure of ITO/metal/ITO (IMI) multilayer films were deposited on a polycarbonate substrate using radio-frequency and direct-current magnetron sputtering process without substrate heating. The intermediated metal films in the IMI structure were Au and Cu films and the thickness of each layer in the IMI films was kept constant at 50 nm/10 nm/40 nm. In this study, the ITO/Au/ITO films show the lowest resistivity of 5.6 × 10⁻⁵ Ω cm.However the films show the lower optical transmission of 71% at 550 nm than that (81%) of as deposited ITO films. The ITO/Cu/ITO films show an optical transmittance of 54% and electrical resistivity of 1.5 × 10⁻⁴ Ω cm. Only the ITO/Au/ITO films showed the diffraction peaks in the XRD pattern. The figure of merit indicated that the ITO/Au/ITO films performed better in a transparent conducting electrode than in ITO single layer films and ITO/Cu/ITO films.     

Use of TiB2 diffusion barriers for Ni/Au ohmic contacts on p-GaN

The use of a TiB₂ diffusion barrier for Ni/Au contacts on p-GaN is reported. The annealing temperature (25-950 °C) dependence of ohmic contact characteristics using a Ni/Au/TiB₂/Ti/Au metallization scheme deposited by sputtering were investigated by contact resistance measurements and auger electron spectroscopy (AES). The as-deposited contacts are rectifying and transition to ohmic behavior for annealing at ≥500 °C . A minimum specific contact resistivity of ∼3 × 10⁻⁴ Ω cm⁻² was obtained after annealing over a broad range of temperatures (800-950 °C for 60 s). The contact morphology became considerably rougher at the higher end of this temperature range. AES profiling showed significant Ti and Ni outdiffusion through the TiB₂ at 800 °C. By 900 °C the Ti was almost completely removed to the surface, where it became oxidized. Use of the TiB₂ diffusion barrier produces superior thermal stability compared to the more common Ni/Au, whose morphology degrades significantly above 500 °C.     

Electronic properties of Au nano-particles supported on stoichiometric and reduced TiO2(1 1 0) substrates

Growth modes and electronic properties were analyzed for Au nano-particles grown on stoichiometric and reduced TiO₂(1 1 0) substrates by medium energy ion scattering (MEIS) and photoelectron spectroscopy(PES) using synchrotron-radiation-light. Initially, two-dimensional islands (2D) with a height of one and two atomic layers grow and higher coverage increases the islands height to form three-dimensional (3D) islands for the stoichiometric TiO₂(1 1 0) substrate. In contrast, 3D islands start to grow from initial stage with a small Au coverage (?0.1 ML, 1 ML = 1.39 × 10¹⁵  atoms/cm²: Au(1 1 1)) probably due to O-vacancies acting as a nucleation site. Above 0.7 ML, all the islands become 3D ones taking a shape of a partial sphere and the Au clusters change to metal for both substrates. We observed the Au 4f and Ti 3p core level shifts together with the valence band spectra. The Ti 3p peak for the O-deficient surface shifts to higher binding energy by 0.25 ± 0.05 eV compared to that for the stoichiometric surface, indicating downward band bending by an electron charge transfer from an O-vacancy induced surface state band to n-type TiO₂ substrate. Higher binding energy shifts of Au 4f peaks observed for both substrates reveal an electron charge transfer from Au to TiO₂ substrates. The work functions of Au nano-particles supported on the stoichiometric and reduced TiO₂ substrates were also determined as a function of Au coverage and explained clearly by the above surface and interface dipoles.     

The application of Raman and anti-stokes Raman spectroscopy for in situ monitoring of structural changes in laser irradiated titanium dioxide materials

The use of Raman and anti-stokes Raman spectroscopy to investigate the effect of exposure to high power laser radiation on the crystalline phases of TiO₂ has been investigated. Measurement of the changes, over several time integrals, in the Raman and anti-stokes Raman of TiO₂ spectra with exposure to laser radiation is reported. Raman and anti-stokes Raman provide detail on both the structure and the kinetic process of changes in crystalline phases in the titania material. The effect of laser exposure resulted in the generation of increasing amounts of the rutile crystalline phase from the anatase crystalline phase during exposure. The Raman spectra displayed bands at 144 cm⁻¹ (A1g), 197 cm⁻¹ (Eg), 398 cm⁻¹ (B1g), 515 cm⁻¹ (A1g), and 640 cm⁻¹ (Eg) assigned to anatase which were replaced by bands at 143 cm⁻¹ (B1g), 235 cm⁻¹ (2 phonon process), 448 cm⁻¹ (Eg) and 612 cm⁻¹ (A1g) which were assigned to rutile. This indicated that laser irradiation of TiO₂ changes the crystalline phase from anatase to rutile. Raman and anti-stokes Raman are highly sensitive to the crystalline forms of TiO₂ and allow characterisation of the effect of laser irradiation upon TiO₂. This technique would also be applicable as an in situ method for monitoring changes during the laser irradiation process.     

Influence of Au thickness on the optical and electrical properties of transparent and conducting TiO2/Au/TiO2 multilayer films

Au-intermediate TiO₂/Au/TiO₂ (TAT) multilayer films were deposited by RF magnetron sputtering onto glass substrates. Changes in the optical and electrical properties of the films were investigated with respect to the thickness of the Au interlayer.The observed optical and electrical properties were dependent on the thickness of the Au interlayer. The resistivity decreased to 3.3 × 10⁻⁴ Ω cm for TiO₂ films with a 20 nm-thick Au interlayer and the optical transmittance was also influenced by the Au interlayer. Although optical transmittance deteriorated as Au thickness increased, TiO₂ films with a 5 nm-thick Au interlayer showed a relatively high optical transmittance of 80% at a wavelength of 550 nm. In addition, since a TAT film with a 5 nm-thick Au interlayer showed a relatively high work function value, it is an alternative candidate for use as a transparent anode in OLEDs and flat panel displays.     

TiO2 activation using acid-treated vermiculite as a support: Characteristics and photoreactivity

Vermiculite was treated by sulfuric or nitric acid aqueous solutions with different concentration. These modified materials as the promising supports, were used to immobilize TiO₂. TiO₂ was prepared by the precursor, which was obtained by substituting partly isopropyl alcohol with Cl⁻ in titanium chloride {[Ti(IV)(OR)_nCl_m] (n = 2-3, m = 4 − n)}. The TiO₂/vermiculite composites were characterized by X-ray diffraction, scanning electron microscopy, and the nitrogen absorption. Their photocatalytic activity was evaluated by removal of methylene blue (MB). The pure anatase type crystalline phase was well deposited on the supports. The concentrations of acid for treatment had a significant influence on pore sizes and surface area of vermiculite. The treatment process changed microstructure of vermiculite, modified its characteristics, and farther improved the catalytic activity and absorption capacity of TiO₂/vermiculite composites. The treatment effect of nitric acid was superior to that of sulfuric acid.     

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.     

Porous silicon as efficient surface enhanced Raman scattering (SERS) substrate

Silver nanocrystallites are obtained through immersion of porous silicon samples in AgNO₃ solutions and a successive thermal annealing. The efficiency of nanostructures as surface enhanced Raman scattering (SERS) substrates is checked on cyanine-based dyes and horseradish peroxidase, evidencing detectable concentrations as low as 10⁻⁷ to 10⁻⁸ M. The substrate efficiency is strictly related to the Ag particle morphology, which could yield to either local surface plasmons (LSP) coupled to individual particles or to inter-particle short-range interaction.     

Thermal stability of Ti/Al/Pt/Au and Ti/Au Ohmic contacts on n-type ZnCdO

The specific contact resistivity and chemical intermixing of Ti/Au and Ti/Al/Pt/Au Ohmic contacts on n-type Zn_0.05Cd_0.95O layers grown on ZnO buffer layers on GaN/sapphire templates is reported as a function of annealing temperature in the range 200-600 °C. A minimum contact resistivity of 2.3 × 10⁻⁴ Ω cm² was obtained at 500 °C for Ti/Al/Pt/Au and 1.6 × 10⁻⁴ Ω cm² was obtained at 450 °C for Ti/Al. These values also correspond to the minima in transfer resistance for the contacts. The Ti/Al/Pt/Au contacts show far smoother morphologies after annealing even at 600 °C, whereas the Ti/Au contacts show a reacted appearance after 350 °C anneals. In the former case, Pt and Al outdiffusion is significant at 450 °C, whereas in the latter case the onset of Ti and Zn outdiffusion is evident at the same temperature. The improvement in contact resistance with annealing is suggested to occur through formation of TiO_x phases that induce oxygen vacancies in the ZnCdO.     

The synthesis and kinetic growth of anisotropic silver particles loaded on TiO2 surface by photoelectrochemical reduction method

Silver nanorods with average diameters of 120-230 nm and aspect ratio of 1.7-5.0 were deposited on the surface of TiO₂ films by photoelectrochemical reduction of Ag⁺ to Ag under UV light. The composite films prepared on soda-lime glass substrates were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results show that the TiO₂ film after UV irradiation in AgNO₃ solution is composed of anatase phase TiO₂ and metallic silver with face centered cubic structure. Other compounds cannot be found in the final films. The maximum deposition content of silver particles on the surface of TiO₂ film was obtained with the AgNO₃ concentration of 0.1 M. The kinetic growth rates of silver particles can be controlled by photocatalytic activity of TiO₂ films. The studies suggest that the growth rates of silver particles increase with the enhancement of photocatalytic activity of TiO₂ films. The maximum growth rate of silver particles loaded on TiO₂ films can be up to 0.353 nm min⁻¹ among samples 1#, 2# and 3#, while the corresponding apparent rate constant of TiO₂ is 1.751 × 10⁻³ min⁻¹.     

Au/TiO2/Ru(0 0 0 1) model catalysts and their interaction with CO

Au/TiO₂/Ru(0 0 0 1) model catalysts and their interaction with CO were investigated by scanning tunneling microscopy and different surface spectroscopies. Thin titanium oxide films were prepared by Ti deposition on Ru(0 0 0 1) in an O₂ atmosphere and subsequent annealing in O₂. By optimizing the conditions for deposition and post-treatment, smooth films were obtained either as fully oxidized TiO₂ or as partly reduced TiO_x, depending on the preparation conditions. CO adsorbed molecularly on both oxidized and reduced TiO₂, with slightly stronger bonding on the reduced films. Model catalyst surfaces were prepared by depositing submonolayer quantities of Au on the films and characterized by X-ray photoelectron spectroscopy and scanning tunneling microscopy. From X-ray photoelectron spectroscopy, a weak interaction between the Au and the TiO₂ substrate was found. At 100 K CO adsorption occurred on both the TiO₂ film and on the Au nanoparticles. CO desorbed from the Au particles with activation energies between 53 and 65 kJ/mol, depending on the Au coverage. If the Au deposit was annealed to 770 K prior to CO exposure, the CO adsorption energy decreased significantly. STM measurements revealed that the Au particles grow upon annealing, but are not encapsulated by TiO_x suboxides. The higher CO adsorption energy observed for smaller Au coverages and before annealing is attributed to a significantly stronger interaction of CO with mono- and bilayer Au islands, while for higher particles, the adsorption energy becomes more bulk-like. The implications of these effects on the known particle size effects in CO oxidation over supported Au/TiO₂ catalysts are discussed.     

Effects of steps and defects on O2 dissociation on clean and modified Cu(1 0 0)

Dissociative chemisorption of O₂ on Cu(1 0 0), S/Cu(1 0 0) and Ag/Cu(1 0 0) surface alloy has been investigated by Auger electron spectroscopy (AES). A strong reduction in the initial O₂ chemisorption probability (S₀) from 0.05 to 7.4 × 10⁻³ is observed already at an Ag coverage of 0.02 ML. Further Ag deposition results only in a moderate decrease in S₀. Similar inhibition of O₂ dissociation is observed on S/Cu(1 0 0). It is concluded that at very low Ag coverages, the reduced reactivity of Ag/Cu(1 0 0) towards O₂ dissociation is primarily due to the steric blocking of the surface defects and that any electronic effects are only secondary and present only at higher Ag coverages.     

Sunlight photocatalytic activity of CdS modified TiO2 loaded on activated carbon fibers

To improve the photocatalytic application performances of TiO₂, in this work, firstly CdS modified Degussa P25 TiO₂ (CdS/TiO₂) composites were prepared by two methods, sol-gel method and precipitation method. Next they, sol-gel-CdS/TiO₂ (sg-CdS/TiO₂) and precipitation-CdS/TiO₂ (pp-CdS/TiO₂), were loaded on activated carbon fibers (ACFs) by dip-coating method using the sodium carboxymethyl cellulose as adhesives. The composites were characterized by XRD, UV-vis absorbance spectra, SEM, EDS and BET. The photocatalytic activities under sunlight were investigated by the degradation of methylene blue. The results showed that CdS/TiO₂ composites were mainly composed of anatase-TiO₂ and little CdS cubic phases. The absorption wavelengths of sg-CdS/TiO₂ and pp-CdS/TiO₂ composites were extended to 590 nm and 740 nm, respectively. The absorption edge had a pronounced ‘red shift’. From EDS analysis, the elemental contents of CdS/TiO₂ were mainly Ti and O and a small quantity of S and Cd. CdS/TiO₂ loaded on ACFs were in the form of small clusters, but not very uniform; compared with the original ACFs, the surface area and pore volume of CdS/TiO₂/ACFs decreased slightly, respectively, while the average pore diameter was not changed. The photodegradation rate of methylene blue under sunlight with CdS/TiO₂/ACFs composites was markedly higher than that of P25-TiO₂/ACFs, and the effect of pp-CdS/TiO₂/ACFs composites was better than that of sg-CdS/TiO₂/ACFs, when irradiated for 180 min, and the photodegradation rate of methylene blue reached to 90.1%. The photodegradation kinetics of the methylene blue fitted with the Langmuir-Hinshelwood equation. The apparent reaction rate constants of sg-CdS/TiO₂/ACFs and pp-CdS/TiO₂ were 0.0105 min⁻¹ and 0.0146 min⁻¹, respectively, which were about 1.3-1.7 times as large as that of P25-TiO₂/ACFs.     

ZrB2-based Ohmic contacts to p-GaN

The annealing temperature dependence of contact resistance and layer stability of ZrB₂/Ti/Au and Ni/Au/ZrB₂/Ti/Au Ohmic contacts on p-GaN is reported. The as-deposited contacts are rectifying and transition to Ohmic behavior for annealing at ≥750 °C, a significant improvement in thermal stability compared to the conventional Ni/Au Ohmic contact on p-GaN, which is stable only to <600 °C. A minimum specific contact resistance of ∼2 × 10⁻³ Ω cm⁻² was obtained for the ZrB₂/Ti/Au after annealing at 800 °C while for Ni/Au/ZrB₂/Ti/Au the minimum value was 10⁻⁴ Ω cm⁻² at 900 °C. Auger Electron Spectroscopy profiling showed significant Ti, Ni and Zr out diffusion at 750 °C in the Ni/Au/ZrB₂/Ti/Au while the Ti and Zr intermix at 900 °C in the ZrB₂/Ti/Au. These boride-based contacts show promise for contacts to p-GaN in high temperature applications.     

The enhanced conductivity and stability of AZO thin films with a TiO2 buffer layer

Aluminum doped zinc oxide (AZO) films were substitutes of the SnO₂:F films on soda lime glass substrate in the amorphous thin-film solar cells due to good properties and low cost. In order to improve properties of AZO films, the TiO₂ buffer layer had been introduced. AZO films with and without TiO₂ buffer layer were deposited on soda lime glass substrates by r.f. magnetron sputtering. Subsequently, one group samples were annealed in vacuum (0.1 Pa) at 500 °C for 120 s using the RTA system, and the influence of TiO₂ thickness on the properties of AZO films had been discussed. The XRD measurement results showed that all the films had a preferentially oriented (0 0 2) peak, and the intensity of (0 0 2) peak had been enhanced for the AZO films with TiO₂ buffer layer. The resistivity of TiO₂ (3.0 nm)/AZO double-layer film is 4.76×10⁻⁴ Ω cm with the maximum figure merit of 1.92×10⁻² Ω⁻¹, and the resistivity has a remarkable 28.7% decrease comparing with that of the single AZO film. The carrier scattering mechanism of TiO₂ (3.0 nm)/AZO double-layer film had been described by Hall measurement in different temperatures. The average transmittance of all the films exceeded 92% in the visible spectrum. Another group samples were heat treated in the quartz tube in air atmosphere, and the effect of TiO₂ thickness on thermal stability of AZO films had been discussed.     

First-principles study of electronic structures and optical properties of Cu, Ag, and Au-doped anatase TiO2

We perform first-principles calculations to investigate the band structure, density of states, optical absorption, and the imaginary part of dielectric function of Cu, Ag, and Au-doped anatase TiO₂ in 72 atoms systems. The electronic structure results show that the Cu incorporation can lead to the enhancement of d states near the uppermost of valence band, while the Ag and Au doping cause some new electronic states in band gap of TiO₂. Meanwhile, it is found that the visible optical absorptions of Cu, Ag, and Au-doped TiO₂, are observed by analyzing the results of optical properties, which locate in the region of 400-1000 nm. The absorption band edges of Cu, Ag, and Au-doped TiO₂ shift to the long wavelength region compared with the pure TiO₂. Furthermore, according to the calculated results, we propose the optical transition mechanisms of Cu, Ag, and Au-doped TiO₂. Our results show that the visible light response of TiO₂ can be modulated by substitutional doping of Cu, Ag, and Au.