Electrodeposition of nanostructured Pt films from lyotropic liquid crystalline phases on α-Al2O3 supported dense Pd membranes

Using the lyotropic liquid crystalline templating strategy, the nanostructured platinum film was electrochemically deposited on the α-Al₂O₃ supported dense palladium membrane. The XRD and TEM results of the Pt film revealed a hexagonal array of cylindrical pores with a uniform pore diameter of ca. 3.8 nm and a pore-to-pore separation of ca. 7.6 nm. The structure parameters of the Pt film were almost the same as those of the hexagonal liquid crystalline template. Based on SEM observations, the Pt film was featureless, smooth, and tightly adherent to the dense Pd membrane. The specific surface area of the Pt film, measured by using cyclic voltammetry, was ca. 13.8 m² g⁻¹, which was in accord with the theoretical value of 14.5 m² g⁻¹ for a perfect hexagonal nanostructure with the same structure parameters. By combining the dense Pd membrane for selective permeation to hydrogen with the Pt film of high specific surface area for catalysis, the as-synthesized two-layer film will be a promising catalytic membrane to intensify hydrogen-related reaction processes.     

The characteristics of platinum diffusion in n-type GaN

The electrical and optical characteristics of platinum (Pt) diffusion in n-type gallium nitride (GaN) film are investigated. The diffusion extent was characterized by the SIMS technique. The temperature-dependent diffusion coefficients of Pt in n-GaN are 4.158 × 10⁻¹⁴, 1.572 × 10⁻¹³ and 3.216 × 10⁻¹³ cm²/s at a temperature of 650, 750 and 850 °C, respectively. The Pt diffusion constant and activation energy in GaN are 6.627 × 10⁻⁹ cm²/s and 0.914 eV, respectively. These results indicate that the major diffusion mechanism of Pt in GaN is possibly an interstitial diffusion. In addition, it is also observed that the Pt atom may be a donor because the carrier concentration in Pt-diffused GaN is higher than that in un-diffused GaN. The optical property is studied by temperature-dependent photoluminescence (PL) measurement. The thermal quenching of the PL spectra for Pt-diffused GaN samples is also examined.     

Diffusion-limited electrodeposition of ultrathin Au films on Pt(1 1 1)

The electrodeposition of Au on Pt(1 1 1) from electrolytes containing μM concentrations of was studied by in situ scanning tunneling microscopy. Under these conditions the Au flux is limited by diffusion in the electrolyte over a wide potential range, which allows to assess the effect of the electrochemical environment on the growth kinetics. Similar to gas phase metal deposition Au film growth proceeds via nucleation and lateral growth of Au monolayer islands, with the saturation island density strongly depending on the deposition potential and on the anion species in the electrolyte. For deposition in H₂SO₄ solution the saturation island density continuously increases with increasing potential between −0.2 and 0.5 V (SCE), whereas in Cl-containing H₂SO₄ it first decreases and then increases again. Following nucleation and growth theories this behavior can be attributed to potential-induced changes of the Au surface mobility, caused by changes in the density and structure of coadsorbed sulfate/bisulfate and chloride adlayers. Under conditions of high Au surface mobility multilayer growth proceeds via a typical Stranski-Krastanov growth mode, with layer-by-layer growth of a pseudomorphic Au film up to 2 ML and 3D growth of structurally relaxed islands at higher coverage, indicating thermodynamic control under these conditions.     

EDXRF measurements on gold diffusion-doped Bi1.8Pb0.35Sr1.9Ca2.1Cu3Oy

Gold (Au) diffusion in superconducting Bi_1.8Pb_0.35Sr_1.9Ca_2.1Cu₃O_y was investigated over the temperature range 500-800 °C by the energy dispersive X-ray fluorescence (EDXRF) technique. It is found that the Au diffusion coefficient decreases as the diffusion-annealing temperature decreases. The temperature dependences of Au diffusion coefficient in grains and over grain boundaries are described by the relations D₁=6.7×10⁻⁵exp(−1.19 eV/k_BT) and D₂=9.7×10⁻⁴exp(−1.09 eV/k_BT), respectively. The diffusion doping of Bi-2223 by Au causes a significant increase of the lattice parameter c by about 0.19%. For the Au-diffused samples, dc electrical resistivity and transport critical current density measurements indicated the critical transition temperature increased from 100 to 104 K and the critical current density increased from 40 to 125 A cm⁻², in comparison with those of undoped samples. From scanning electron microscope (SEM) and X-ray diffraction (XRD) measurements it is observed that Au doping of the sample also improved the surface morphology and increased the ratio of the high-T_c phase to the low-T_c phase. The possible reasons for the observed improvement in microstructure and superconducting properties of the samples due to Au diffusion are also discussed.     

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.     

Poly(3-methylthiophene)-based porous silicon substrates as a urea-sensitive electrode

Poly(3-methylthiophene) (P3MT)-based porous silicon (PS) substrates were fabricated and characterized by cyclic voltammetry, scanning electron microscopy, and auger electron spectroscopy. After doping urease (Urs) into the polymeric matrix, sensitivity and physicochemical properties of the P3MT-based PS substrate was investigated compared to planar silicon (PLS) and bulk Pt substrates. PS substrate was formed by electrochemical anodization in an etching solution composed of HF, H₂O, and ethanol. Subsequently, Ti and Pt thin-films were sputtered on the PS substrate. Effective working electrode area (A_eff) of the Pt-deposited PS substrate was determined from a redox reaction of Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ redox couple in which nearly reversible cyclic voltammograms were obtained. The i_p versus v^1/2 plots showed that A_eff of the PS-based Pt thin-film electrode was 1.62 times larger than that of the PLS-based electrode.Electropolymerization of P3MT on both types of electrodes were carried out by the anodic potential scanning under the given potential range. And then, urease molecules were doped to the P3MT film by the chronoamperometry. Direct electrochemistry of a Urs/P3MT/Pt/Ti/PS electrode in an acetonitrile solution containing 0.1 mol/L NaClO₄ was introduced compared to a P3MT/Pt/Ti/PS electrode at scan rates of 10 mV s⁻¹, 50 mV s⁻¹, and 100 mV s⁻¹.Amperometric sensitivity of the Urs/P3MT/Pt/Ti/PS electrode was ca. 1.67 μA mM⁻¹ per projected unit square centimeter, and that of the Urs/P3MT/Pt/Ti/PLS electrode was ca. 1.02 μA mM⁻¹ per projected unit square centimeter in a linear range of 1-100 mM urea concentrations. 1.6 times of sensitivity increase was coincident with the results from cyclic voltammetrc analysis.Surface morphology from scanning electron microscopy (SEM) images of Pt-deposited PS electrodes before and after the coating of Urs-doped P3MT films showed that pore diameter and depth were 2 μm and 10 μm, respectively. Multilayered-film structures composed of metals and organics for both electrodes were also confirmed by auger electron spectroscopy (AES) depth profiles.     

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.     

Electrochemical corrosion behaviors of a-C:H and a-C:NX:H films

The a-C:H and a-C:N_X:H films were deposited onto silicon wafers using radio frequency (rf) plasma enhanced chemical vapor deposition (PECVD) and pulsed-dc glow discharge plasma CVD, respectively. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize chemical nature and bond types of the films. The results demonstrated that the a-C:H film prepared by rf-CVD (rf C:H) has lower I_D/I_G ratio, indicating smaller sp² cluster size in an amorphous carbon matrix. The nitrogen concentrations of 2.9 at.% and 7.9 at.% correspond to carbon nitride films prepared with rf and pulse power, respectively.Electrochemical corrosion performances of the carbon films were investigated by potentiodynamic polarization test. The electrolyte used in this work was a 0.89% NaCl solution. The corrosion test showed that the rf C:H film exhibited excellent anti-corrosion performance with a corrosion rate of 2 nA cm⁻², while the carbon nitride films prepared by rf technique and pulse technique showed a corrosion rate of 6 nA cm⁻² and 235 nA cm⁻², respectively. It is reasonable to conclude that the smaller sp² cluster size of rf C:H film restrained the electron transfer velocity and then avoids detriment from the exchange of electrons.     

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.     

Crystallization and surface morphology of Au/SiO2 thin films following furnace and flame annealing

A crystallization and surface evolution study of Au thin film on SiO₂ substrates following annealing at different temperatures above the eutectic point of the Au/Si system are reported. Samples were prepared by conventional evaporation of gold in a high vacuum (10⁻⁷ mbar) environment on substrates at room temperature. Thermal treatments were performed by both furnace and flame annealing techniques. Au thin films can be crystallized on SiO₂ substrates by both furnace and flame annealing. Annealing arranges the Au crystallites in the (1 1 1) plane direction and changes the morphology of the surface. Both, slow and rapid annealing result in a good background in the XRD spectra and hence clean and complete crystallization which depends more on the temperature than on the time of annealing. The epitaxial temperature for the Au/SiO₂ system decreases in the range of 350-400 °C. Furnace and flame annealing also form crystallized gold islands over the Au/SiO₂ surface. Relaxation at high temperatures of the strained Au layer, obtained after deposition, should be responsible for the initial stages of clusters formation. Gold nucleation sites may be formed at disordered points on the surface and they become islands when the temperature and time of annealing are increased. The growth rate of crystallites is highest around 360 °C. Above this temperature, the layer melts and gold diffuses from the substrate to the nucleation sites to increase the distance between islands and modify their shapes. Well above the eutectic temperature, the relaxed islands have hexagonally shaped borders. The mean crystallite diameters grow up to a maximum mean size of around 90 nm. The free activation energy for grain boundary migration above 360 °C is 0.2 eV. Therefore the type of the silicon substrate changes the mechanism of diffusion and growth of crystallites during annealing of the Au/Si system. Epitaxial Au(1 1 1) layers without formation of islands can be prepared by furnace annealing in the range of 300-310 °C and by flame annealing of a few seconds and up to 0.5 min.     

ZrB2/Pt/Au Ohmic contacts on bulk, single-crystal ZnO

There is a strong interest in developing thermally stable metallization schemes for ZnO and boride-based contact stacks are expected to have potential because of their thermodynamic stability. The contact characteristics on bulk single-crystal n-ZnO of a ZrB₂/Pt/Au metallization scheme deposited by sputtering are reported as a function of annealing temperature in the range 300-800°C. The contacts were rectifying for anneal temperatures <500 °C but exhibited Ohmic behavior at higher temperatures and exhibit a minimum specific contact resistivity of 9 × 10⁻³ Ω cm after 700 °C anneals. The contact stack reverts to rectifying behavior after annealing above 800 °C, coincident with a degraded surface morphology and intermixing of the Au, Pt and ZrB₂. The boride-based contacts exhibit higher thermal stability but poorer specific contact resistivity than conventional Ti/Au metal stacks on ZnO.     

Photocatalytic H2 evolution under visible light irradiation on AgIn5S8 photocatalyst

A new visible-light-driven photocatalyst AgIn₅S₈ was prepared by a simple two-step process, which involves the first co-precipitation process at room temperature and subsequently heat-treatment process at 750 °C under pure argon flow protection. The obtained AgIn₅S₈ sample showed high activity for the evolution of hydrogen under visible light irradiation (λ?420 nm) from aqueous solution containing S²⁻ and SO₃²⁻ ions as sacrificial electron donors. It was found that several experimental parameters, such as the concentration of sacrificial reagents and the loading of Pt co-catalyst, play important roles on the evolution rate of H₂ under visible light irradiation.     

An atomic force microscopy study of DNA hairpin probes monolabelled with gold nanoparticle: Grafting and hybridization on oxide thin films

First and original results are reported regarding the surface evolution of two kinds of oxide film after covalent grafting and hybridization of hairpin oligonucleotide probes. These hairpin probes were monolabelled with a 1.4 nm gold nanoparticle. One kind of oxide film was rough Sb doped SnO₂ oxide film and the other kind was smooth SiO₂ film. Same process of covalent grafting, involving a silanization step, was performed on both oxide surfaces. Atomic force microscopy (AFM) was used to study the evolution of each oxide surface after different steps of the process: functionalization, probe grafting and hybridization. In the case of rough SnO₂ films, a slight decrease of the roughness was observed after each step whereas in the case of smooth SiO₂ films, a maximum of roughness was obtained after probe grafting. Step height measurements of grafted probes could be performed on SiO₂ leading to an apparent thickness of around 3.7 ± 1.0 nm. After hybridization, on the granular surface of SnO₂, by coupling AFM with SEM FEG analyses, dispersed and well-resolved groups of gold nanoparticles linked to DNA duplexes could be observed. Their density varied from 6.6 ± 0.3 × 10¹⁰ to 2.3 ± 0.3 × 10¹¹ dots cm⁻². On the contrary, on smooth SiO₂ surface, the DNA duplexes behave like a dense carpet of globular structures with a density of 2.9 ± 0.5 × 10¹¹ globular structures cm⁻².     

The effect of potential of impedance in the pulsed-laser-deposited SrBi2Ta2O9 thin film

Ferroelectrics SrBi₂Ta₂O₉ (SBTO) thin films were grown on a highly oriented Pt/Ti/SiO₂/Si substrates using the pulsed laser ablation. The ac impedance of SBTO thin films have been measured at room temperature both in the frequency range from 10⁻¹ to 10⁶ Hz and bias voltage range from −6 to 6 V. The ac impedance dispersion was observed at low frequency with increasing bias voltage, which was interpreted based on a blocked charge. We can explain that the blocking interface gives rise to constant phase element (CPE) response, and we give an impedance model function that can fit data along the low frequency range when such a CPE is found. The low frequency dispersion phenomena of SBTO thin film are related to a charge diffusion process at the surface of thin film.     

Current-voltage characteristics of Au/GaN/GaAs structure

Au/GaN/n-GaAs structure has been fabricated by the electrochemically anodic nitridation method for providing an evidence of achievement of stable electronic passivation of n-doped GaAs surface. The change of the electronic properties of the GaAs surface induced by the nitridation process has been studied by means of current-voltage (I-V) characterizations on Schottky barrier diodes (SBDs) shaped on gallium nitride/gallium arsenide structure. Au/GaN/n-GaAs Schottky diode that showed rectifying behavior with an ideality factor value of 2.06 and barrier height value of 0.73 eV obeys a metal-interfacial layer-semiconductor (MIS) configuration rather than an ideal Schottky diode due to the existence of GaN at the Au/GaAs interfacial layer. The formation of the GaN interfacial layer for the stable passivation of gallium arsenide surface is investigated through calculation of the interface state density N_ss with and without taking into account the series resistance R_s. While the interface state density calculated without taking into account R_s has increased exponentially with bias from 2.2×10¹² cm⁻² eV⁻¹ in (E_c−0.48) eV to 3.85×10¹² cm⁻² eV⁻¹ in (E_c−0.32) eV of n-GaAs, the N_ss obtained taking into account the series resistance has remained constant with a value of 2.2×10¹² cm⁻² eV⁻¹ in the same interval. This has been attributed to the passivation of the n-doped GaAs surface with the formation of the GaN interfacial layer.     

Alloy formation of Co/Ni/Pt(1 1 1)

The initial growth and alloy formation of ultrathin Co films deposited on 1 ML Ni/Pt(1 1 1) were investigated by Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and ultraviolet photoelectron spectroscopy (UPS). A sequence of samples of d_Co Co/1 ML Ni/Pt(1 1 1) (d_Co = 1, 2, and 3 ML) were prepared at room temperature, and then heated up to investigate the diffusion process. The Co and Ni atoms intermix at lower annealing temperature, and Co-Ni intermixing layer diffuses into the Pt substrate to form Ni-Co-Pt alloys at higher annealing temperature. The diffusion temperatures are Co coverage dependent. The evolution of UPS with annealing temperatures also shows the formation of surface alloys. Some interesting LEED patterns of 1 ML Co/1 ML Ni/Pt(1 1 1) show the formation of ordered alloys at different annealing temperature ranges. Further studies in the Curie temperature and concentration analysis, show that the ordered alloys corresponding to different LEED patterns are Ni_xCo_1−xPt and Ni_xCo_1−xPt₃. The relationship between the interface structure and magnetic properties was investigated.     

Kinetics of ammonia oxidation on stepped platinum surfaces. I. Experimental results

The kinetics of ammonia oxidation with oxygen have been investigated in the 10⁻⁵ and 10⁻⁴ mbar range on Pt(5 3 3) and Pt(4 4 3). Only N₂ and NO but no N₂O were detected as reaction products. The dependence of product formation on temperature and on the partial pressures of the reactants has been studied under steady state conditions. The reactive sticking coefficients were determined under reaction conditions with s_reac of ammonia reaching nearly 0.2. The Pt(5 3 3) surface was found to be catalytically more active than Pt(4 4 3) by a factor of 2-4.     

Carbon monoxide adsorption on Co deposited Pt(1 0 0)-hex: IRRAS and LEED investigations

Infrared reflection absorption spectroscopy (IRRAS) was used to investigate carbon monoxide (CO) adsorption on Pt(1 0 0) surfaces deposited with Co layers with different thicknesses. Pt(1 0 0) surfaces cleaned in ultrahigh vacuum showed surface reconstruction, i.e., Pt(1 0 0)-hex: two absorption bands ascribable to adsorbed CO on the 1 × 1 surface and hex domains emerge at 2086 and 2074 cm⁻¹, respectively, after 1.0 L CO exposure. Deposition of a 0.3-nm-thick-Co layer on Pt(1 0 0)-hex at 333 K changes the low-energy electron diffraction (LEED) pattern from hex to p(1 × 1), indicating that the deposited Co lifts the reconstruction. The IRRAS spectrum for 1.0-L-CO-exposed Co_0.3 nm/Pt(1 0 0)-hex fabricated at 333 K yields a single absorption band at 2059 cm⁻¹. For Co_0.3 nm/Pt(1 0 0)-hex fabricated at 693 K, the LEED pattern shows a less-contrasted hex and the pattern remains nearly unchanged even after CO exposure of 11 L, although only 1.0 L CO exposure to Pt(1 0 0)-hex lifts the surface reconstruction. A Co_0.3 nm/Pt(1 0 0)-hex surface fabricated at 753 K exhibits an absorption band at 2077 cm⁻¹, which is considered to originate from CO adsorbed on the Pt-enriched surface alloy. Co_0.3 nm/Pt(1 0 0)-hex surfaces fabricated above 773 K show a clear hex-reconstructed LEED pattern, and the frequencies of the adsorbed CO bands are comparable to those of Pt(1 0 0)-hex, indicating that the deposited Co atoms are diffused near the surface region. The outermost surface of the 3.0-nm-thick-Co-deposited Pt(1 0 0)-hex is composed of Pt-Co alloy domains even at a deposition temperature of 873 K. Based on the LEED and IRRAS results, the outermost surface structures of Co_x/Pt(1 0 0)-hex are discussed.     

Visible photocurrent response of TiO2 anode

The photoelectrochemical response to the electromagnetic radiation over the visible range is particularly sought for from the point of view of the efficiency of hydrogen generation by water photolysis in a photoelectrochemical solar cell, PEC. The PEC used in this work comprises thin film TiO₂ - based photoanode, Pt foil covered with Pt black as a cathode and SCE as a reference electrode, immersed in an electrolyte solution. Titanium dioxide thin films are deposited by means of rf reactive sputtering and modified, when necessary, by Au or Ag ultra-thin overcoatings. Here we show that even unmodified TiO₂ photoanode, shows a photocurrent peak over the visible range of the light spectrum (λ = 500-650 nm). The effect of the surface modification by noble metals and properties of the aqueous electrolyte on the visible photocurrent are studied. The optical spectra indicate an increased absorption due to noble metal deposits at 410 nm for Ag and at 600 nm for Au. In contrast, the photocurrent peak over the visible range (500 nm < λ < 650 nm) changes its symmetry and decreases in intensity with the increasing thickness of noble metals layers. The visible photoresponse is explained in terms of OH formation at the interface between TiO₂ electrode and aqueous electrolyte.     

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.