Fabrication of a nanoparticle TiO<Subscript>2</Subscript> photoelectrochemical cell utilizing a solid polymeric electrolyte of PAN–PC–LiClO<Subscript>4</Subscript>

A nanoparticle TiO₂ solid-state photoelectrochemical cell utilizing as a solid electrolyte of poly(acrylonitrile)–propylene–carbonate–lithium perchlorate (PAN–PC–LiClO₄) has been fabricated. The performance of the device has been tested in the dark and under illumination of 100-mW cm⁻² light. A nanoparticle TiO₂ film was deposited onto indium tin oxide-covered glass substrate by controlled hydrolysis technique assisted with spin-coating technique. The average grain size for the TiO₂ film is 76 nm. LiClO₄ salt was used as a redox couple. The room temperature conductivity of the electrolyte is 4.2 × 10⁻⁴ S cm⁻¹. A graphite electrode was prepared onto a glass slide by electron beam evaporation technique. The device shows the rectification property in the dark and shows the photovoltaic effect under illumination. The best J _sc and V _oc of the device were 2.82 μA cm⁻² and V _oc of 0.58 V, respectively, obtained at the conductivity of 4.2 × 10⁻⁴ S cm⁻¹ and intensity of 100 mW cm⁻². The J _sc was improved by about three times by introducing nanoparticle TiO₂ and by using a solid electrolyte of PAN–PC–LiClO₄ replacing PVC–PC–LiClO₄ in the device. The current transport mechanism of the cell is also presented in this paper.     

Structure and electrical properties of HfO<Subscript>2</Subscript> high-<Emphasis Type="Italic">k</Emphasis> films prepared by pulsed laser deposition on Si (100)

High-k gate dielectric hafnium dioxide films were grown on Si (100) substrate by pulsed laser deposition at room temperature. The as-deposited films were amorphous and that were monoclinic and orthorhombic after annealed at 500°C in air and N₂ atmosphere, respectively. After annealed, the accumulation capacitance values increase rapidly and the flat-band voltage shifts from −1.34 V to 0.449 V due to the generation of negative charges via post-annealing. The dielectric constant is in the range of 8–40 depending on the microstructure. The I–V curve indicates that the films possess of a promising low leakage current density of 4.2×10⁻⁸ A/cm² at the applied voltage of −1.5 V.     

Polaron and ion diffusion in a poly(3-hexylthiophene) thin-film transistor gated with polymer electrolyte dielectric

Electrolytes are finding applications as dielectric materials in low-voltage organic thin-film transistors (OTFT). The presence of mobile ions in these materials (polymer electrolytes or ion gels) gives rise to very high capacitance (>10 μF/cm²) and thus low transistor turn-on voltage. In order to establish fundamental limits in switching speeds of electrolyte gated OFETs, we carry out in situ optical spectroscopy measurement of a poly(3-hexylthiophene) (P3HT) OTFT gated with a LiClO₄:poly(ethyleneoxide) (PEO) dielectric. Based on spectroscopic signatures of molecular vibrations and polaron transitions, we quantitatively determine charge carrier concentration and diffusion constants. We find two distinctively different regions: at V _G≥−1.5 V, drift-diffusion (parallel to the semiconductor/dielectric interface) of hole-polarons in P3HT controls charging of the device; at V _G<−1.5 V, electrochemical doping of the entire P3HT film occurs and charging is controlled by drift/diffusion (perpendicular to the interface) of ClO₄ ⁻ counter ions into the polymer semiconductor.     

Characteristics of p-type ZnO:As thin films prepared by the ampoule-tube method and ZnO p–n homojunction

A p-type ZnO thin film was prepared using arsenic diffusion via the ampoule-tube method. This was followed by fabrication of a ZnO p–n homojunction using n-type ZnO and characterization of the device properties. The ZnO thin film exhibited p-type characteristics, with a resistivity of 2.19×10⁻³ Ω cm, a carrier concentration of 1.73×10²⁰/cm³, and a mobility of 26.7 cm²/V s. Secondary ion mass spectrometer analysis confirmed that in- and out-diffusion occurred simultaneously from the external As source and the GaAs substrate. The device exhibited the rectification characteristics of a typical p–n junction; the forward voltage at 20 mA was approximately 5.5 V. The reverse-bias leakage current was very low—0.1 mA for −10 V; the breakdown voltage was −11 V. The ampoule-tube method for fabricating p-type ZnO thin films may be useful in producing ultraviolet ZnO LEDs and other ZnO-based devices.     

Electrolytic metal deposition onto chemically modified electrodes

Some general features concerning electrochemical metal deposition onto electrodes modified with self-assembled monolayers (SAMs) of alkanethiols are discussed. Although thiols of various chain length are briefly addressed, special emphasis is placed on copper deposition onto an ethanethiol (C2)-modified Au(111) surface. The short alkanethiol blocks the surface to a great extent but does not completely suppress charge transfer. We have used in situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV) to characterize the structure and the electrochemical behavior of the C2 monolayer in sulfuric acid electrolyte before and after introducing copper ions to the system. The C2 adlayer consists of domains of two different ordered structures. It is shown that the adlayer undergoes a reversible order–disorder transition at potentials slightly negative of 0 V vs. SCE, which testifies to a surprisingly high mobility of the C2 molecules within the SAM. Copper deposition on C2-modified gold electrodes shows significant differences from the same process on the bare electrode. A sharp cathodic peak at -0.18 V vs. SCE is ascribed to the insertion of a Cu monolayer between Au and the organic adlayer. At low overpotentials the Cu deposit exhibits a ramified monatomic high morphology, if the ethanethiol adlayer is dense. Three-dimensional growth starts at large substrate defects. Received: 2 May 1999 / Accepted: 17 August 1999 / Published online: 6 October 1999     

Contribution of electrolyte pH and deposition potentials to the magnetic anisotropy of electrodeposited nickel films

The influence of electrolyte pH and cathode potential on the magnetic properties of single layer Nickel films electrodeposited on polycrystalline titanium substrates was studied. The films were deposited at the electrolyte pH=3.5±0.1, 2.5±0.1 and 2.1±0.1 by varying the deposition potentials (?1.2, ?1.5 and ?1.8 V vs saturated calomel electrode, SCE) applied in continuous waveform. The structural analysis by X-ray diffraction revealed that the films have face-centred cubic structure. Results of the magnetic measurements obtained by vibrating sample magnetometer (VSM) indicated that the magnetic properties were affected by the electrolyte pH and the cathode potentials in terms of magnetic anisotropy. At the highest pH the films deposited at the lowest potential had in-plane magnetic anisotropy. As the electrolyte pH decreased from the high (pH=3.5±0.1) to low (pH=2.5±0.1), which is aided by increasing the potentials, resulted in an almost magnetic isotropy in the films. However, isotropic magnetic behaviour was observed for the film deposited at the low pH combined with the high potential (?1.8 V vs SCE). Magnetic thickness profile of the samples obtained by VSM revealed that the isotropic films have a smoother magnetic variation across the film from one edge than the anisotropic ones. This is also verified with a microscopic observation by an optical microscope and the surface of the isotropic films is observed to be smoother than that of the anisotropic ones. Furthermore, all films were found to have planar magnetic anisotropy irrespective of the pH’s and the potentials.     

Polarized Raman spectroscopy study of NiSi film grown on Si(001) substrate

We report on the growth of NiSi film on Si(001) substrate with an orientation of NiSi[200]//Si[001]. Polarized Raman spectroscopy was used to assign the symmetry of the NiSi Raman peaks. Raman peaks at 213 cm⁻¹, 295 cm⁻¹, and 367 cm⁻¹ are assigned to be A _g symmetry and peaks at 196 cm⁻¹, and 254 cm⁻¹ are B _3g symmetry.     

Performance of palladium electrode for electrochemical hydrogen pump using strontium-zirconate-based proton conductors

An electrode design with no use of three-phase boundary was investigated using palladium electrode. The hydrogen evolution rate of the palladium electrode cell using SrZr_0.9Y_0.1O_3 − α electrolyte followed Faraday’s law up to 180 mA cm⁻², and the anode and cathode overpotentials were significantly lower than those of a platinum electrode cell, suggesting that the palladium electrode is effective to improve the performance of the hydrogen-pumping cell using SrZrO₃-based electrolyte. The rate-determining step (RDS) for electrode reaction was also investigated by changing the electrode morphology and hydrogen partial pressure, and it was suggested that the RDS of the anode is a reaction at electrode/electrolyte interface.     

PARAFAC Analysis of the Quenching of EEM of Fluorescence of Glutathione Capped CdTe Quantum Dots by Pb(II)

Glutathione capped CdTe quantum dots (QD) were synthesised using a simple experimental procedure and two samples were subjected of study (QD₅₅₀ and QD₆₀₀). The maximum of the excitation and emission spectra and the emission full width of half maximum of these two QD were: QD₅₅₀, 307, 550 and 37 nm; QD₆₀₀, 307, 600 and 39 nm. The steady state fluorescence properties of the two QD undergo variation when the pH of the aqueous solution is varied and are characterised by different apparent pKa: QD₅₅₀, 5.2 ± 0.1; QD₆₀₀, 6.3 ± 0.3. The fluorescence intensity of the QD₅₅₀ is markedly quenched by the presence of micromolar quantities of Pb(II) ion (Stern–Volmer constant of about 7 × 10⁵ M⁻¹). PARAFAC analysis of the excitation emission matrices (EEM) of QD₅₅₀ acquired as function of the Pb(II) ion showed that only one linearly independent component describes the quenching of the QD₅₅₀ by the Pb(II) ion allowing robust estimation of the excitation and emission spectra and of the quenching profiles.     

Enhanced field emission from pulsed laser deposited nanocrystalline ZnO thin films on Re and W

Nanocrystalline ZnO thin films have been deposited on rhenium and tungsten pointed and flat substrates by pulsed laser deposition method. An emission current of 1 nA with an onset voltage of 120 V was observed repeatedly and maximum current density ∼1.3 A/cm² and 9.3 mA/cm² has been drawn from ZnO/Re and ZnO/W pointed emitters at an applied voltage of 12.8 and 14 kV, respectively. In case of planar emitters (ZnO deposited on flat substrates), the onset field required to draw 1 nA emission current is observed to be 0.87 and 1.2 V/μm for ZnO/Re and ZnO/W planar emitters, respectively. The Fowler–Nordheim plots of both the emitters show nonlinear behaviour, typical for a semiconducting field emitter. The field enhancement factor β is estimated to be ∼2.15×10⁵ cm⁻¹ and 2.16×10⁵ cm⁻¹ for pointed and 3.2×10⁴ and 1.74×10⁴ for planar ZnO/Re and ZnO/W emitters, respectively. The high value of β factor suggests that the emission is from the nanometric features of the emitter surface. The emission current–time plots exhibit good stability of emission current over a period of more than three hours. The post field emission surface morphology studies show no significant deterioration of the emitter surface indicating that the ZnO thin film has a very strong adherence to both the substrates and exhibits a remarkable structural stability against high-field-induced mechanical stresses and ion bombardment. The results reveal that PLD offers unprecedented advantages in fabricating the ZnO field emitters for practical applications in field-emission-based electron sources.     

Structural, optical and electrical properties of cubic AlN films deposited by laser molecular beam epitaxy

Cubic AlN films were successfully deposited on TiN buffered Si (100) substrates by a laser molecular beam epitaxy (LMBE) technique, and their crystal structure and optical and electrical properties were studied. The results indicate that cubic AlN films show the NaCl-type structure with a (200) preferred orientation, and the lattice parameter is determined to be 0.4027 nm. The Fourier transform infrared (FTIR) pattern of the cubic AlN film displays sharp absorption peaks at 668 cm⁻¹ and 951 cm⁻¹, corresponding to the transverse and longitudinal optical vibration modes. Ellipsometric measurements evidence a refractive index of 1.66–1.71 and an extinction coefficient of about zero for the cubic AlN film in the visible range. Capacitance–voltage (C–V) traces of the metal–insulator–semiconductor (MIS) device exhibit that the cubic AlN film has a dielectric constant of 8.1, and hysteresis in the C–V traces indicates a significant number of charge traps in the film.     

Line strength and collisional broadening studies of hydrogen sulphide in the 1.58 μm region using diode laser spectroscopy

High resolution diode laser spectroscopy has been applied to the detection of hydrogen sulphide at ppm levels utilizing different transitions within the region of the ν ₁+ν ₂+ν ₃ and 2ν ₁+ν ₂ combination bands around 1.58 μm. Suitable lines in this spectral region have been identified, and absolute absorption cross sections have been determined through single-pass absorption spectroscopy and confirmed in the Doppler linewidth regime using cavity enhanced absorption spectroscopy (CEAS). The desire for a sensitive system potentially applicable to H₂S sensing at atmospheric pressure has led to an investigation on suitable transitions using wavelength modulation spectroscopy (WMS). The set-up sensitivity has been calculated as 1.73×10⁻⁸ cm⁻¹ s^1/2, and probing the strongest line at 1576.29 nm a minimum detectable concentration of 700 ppb under atmospheric conditions has been achieved. Furthermore, pressure broadening coefficients for a variety of buffer gasses have been measured and correlated to the intermolecular potentials governing the collision process; the H₂S–H₂S dimer well depth is estimated to be 7.06±0.09 kJ mol⁻¹.     

Segregation of lead in oxide film of high-purity aluminum containing 100 ppm lead

Surface segregation in high-purity Al–100 ppm Pb foil annealed for 4 h at 540 °C was studied mainly by transmission electron microscopy (TEM) observations. TEM–EDX demonstrated that almost of the lead element segregated not to aluminum surface but predominantly to the oxide amorphous film formed just above aluminum surface. The enrichment of lead in the oxide film was about 30 000 fold.     

Electroluminescence from ZnO nanowire-based p-GaN/n-ZnO heterojunction light-emitting diodes

Vertically aligned ZnO nanowires were successfully grown on the sapphire substrate by nanoparticle-assisted pulsed laser deposition (NAPLD), which were employed in fabricating the ZnO nanowire-based heterojunction structures. p-GaN/n-ZnO heterojunction light-emitting diodes (LEDs) with embedded ZnO nanowires were obtained by fabricating p-GaN:Mg film/ZnO nanowire/n-ZnO film structures. The current–voltage measurements showed a typical diode characteristic with a threshold voltage of about 2.5 V. Electroluminescence (EL) emission having the wavelength of about 380 nm was observed under forward bias in the heterojunction diodes and was intensified by increasing the applied voltage up to 30 V.     

Electrode processes of LaCoO3+La2Zr2O7 cathodes deposited onto GCO

A combination of dc and ac results was used to study the electrode processes of LaCoO₃+La₂Zr₂O₇ cathodes deposited onto a GCO electrolyte, in air and in the range 600–800 °C. Steady state polarisation results showed that the overpotential values are very dependent on the electrode microstructures, which might be optimised by changes in the deposition and/or firing conditions of the electrodes. Tafel plots suggest different mechanisms under low and relatively high cathodic polarisation, with a transition at about −0.2 V at 700 °C. The transition tends to be displaced towards higher cathodic overpotentials with decreasing temperatures. The exchange current density is higher in the high polarisation regime (high values of |η|) than under low polarisation, and the exchange coefficient is lower in the range of high |η| The changes in pseudocapacitance and electrode resistance extracted from ac results also indicate a change in the regime. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Thin TiO2 grown by metal–organic chemical vapor deposition on (NH4)2S x -treated InP

The electrical characteristics of thin TiO₂ films prepared by metal–organic chemical vapor deposition grown on a p-type InP substrate were studied. For a TiO₂ film of 4.7 nm on InP without and with ammonium sulfide treatment, the leakage currents are 8.8×10⁻² and 1.1×10⁻⁴ A/cm² at +2 V bias and 1.6×10⁻¹ and 8.3×10⁻⁴ A/cm² at −2 V bias. The lower leakage currents of TiO₂ with ammonium sulfide treatment arise from the improvement of interface quality. The dielectric constant and effective oxide charge number density are 33 and 2.5×10¹³ cm², respectively. The lowest mid-gap interface state density is around 7.6×10¹¹ cm⁻² eV⁻¹. The equivalent oxide thickness is 0.52 nm. The breakdown electric field increases with decreasing thickness in the range of 2.5 to 7.6 nm and reaches 9.3 MV/cm at 2.5 nm.     

Polarization of leading Λ hyperons produced by neutrons on target nuclei

The polarization of the leading Λ hyperons produced on carbon and lead target nuclei by 4–10 GeV neutrons in the angle range Θ<8.5° with respect to the beam and with only neutral-particle accompaniment is measured: 〈Π〉=−0.096±0.018 for C and 〈Π〉=− 0.128±0.047 for Pb. The dependence of the polarization on the transverse momentum and the Feynman variable is measured. The normalized invariant cross section as a function of p _⊥ ² is found to be approximated by the function A exp(−Bp _⊥ ² ), where the parameter B is independent of the kind of nucleus (B=8.71±0.09 (GeV/c)⁻² for carbon and B=8.83±0.18 (GeV/c)⁻² for lead). Pis’ma Zh. éksp. Teor. Fiz. 64, No. 4, 237–240 (25 August 1996)     

Microstructure and electrode properties of La0.6Sr0.4Co0.2Fe0.8O3-δ spin-coated on Ce0.8Sm0.2O2?δ electrolyte

Fine and uniform La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ powder was synthesized by a glycine–nitrate combustion process. La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ electrodes were prepared on dense Ce_0.8Sm_0.2O_2−δ electrolyte substrates using a spin-coating technique by sintering at 900–1,000 °C. The electrode properties of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ were investigated by electrochemical impedance spectroscopy and chronopotentiometry techniques with respect to preparation conditions and the resulting microstructures. The results indicate a significant effect of the microstructure on the electrode processes and polarization characteristics. The oxygen adsorption and dissociation process acted as a larger contribution to the overall electrode polarization R _p in magnitude compared with the charge transfer process due to relatively low porosity levels of the electrodes. It was detected that the grain size of the electrodes exhibited a crucial role on the electrocatalytic reactivity. At 800 °C, the electrode sintered at 950 °C attained a polarization resistance of 0.18 Ω cm², an overpotential of 27 mV at a current density of 200 mA cm⁻², and an exchange current density of 308 mA cm⁻².     

Hafnium oxide thin films deposited from a filtered cathodic vacuum arc

The electrical and structural characteristics of hafnium oxide thin films reactively deposited from a filtered cathodic vacuum arc have been investigated. X-ray photoelectron spectroscopy was used to determine the deposition conditions (Ar/O₂ ratio) which produced stoichiometric HfO₂ films. Cross-sectional transmission electron microscopy showed that the micro-structure of the films was highly disordered with electron-diffraction analysis providing evidence for the presence of sub-nano-metre crystallites of the monoclinic HfO₂ (P2₁/c) phase. Further evidence for the presence of this phase was provided by measuring the O k-edge using electron energy loss spectroscopy and comparing it with calculations performed using FEFF8.2, a multiple scattering code. Surface imaging revealed that local film damage occurred in films deposited with substrate bias voltages exceeding −200 V. The current-leakage characteristics of the HfO₂ films deposited with a bias of approximately −100 V suggest that device grade HfO₂ films can be produced from a filtered cathodic vacuum arc.