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.     

Effect of plasticizer on safranine-T-dye-based solid-state photo electrochemical cell

Effect of plasticizers on electrical and photovoltaic properties of safranine-T-dye-based solid-state photo electrochemical cell (PEC) is studied. Ethylene carbonate (EC) and propylene carbonate (PC) are used as plasticizers. Dark current–voltage characteristic and different photovoltaic parameters such as open-circuit voltage, short-circuit current, and power conversion efficiency are measured. To understand the effect of plasticizers on charge transport process, we analyze the dark current–voltage characteristics to estimate the trap energy. From detail analysis of dark I–V, it has been observed that there is a crossover voltage called transition voltage where the conduction mechanism changes. Above this voltage, the dark current is a space charge limited current (SCLC) in the presence of exponentially distributed traps. Below transition voltage, current is ohmic for the cell without plasticizers and dark current is an SCLC in presence of discrete traps for the cell with plasticizers. From our analysis, it is shown that the transition voltage reduces due to the presence of plasticizers but the characteristic trap energy (E_T) is not changed significantly. From photovoltaic measurements, it is observed that in presence of EC and PC power conversion efficiency of the device increase from 7.319 × 10⁻⁴% to 14.64 × 10⁻⁴% under illumination with polychromatic light of 100 mW/cm². It is expected that the power conversion efficiency depend on transition voltage. Due to the presence of plasticizers, the barrier potentials of the devices reduce which results lowering of transition voltage. Lowering of it assists the migration of charge carriers and as a result power conversion efficiency enhances.     

Pulsed laser deposition of Zr–N codoped <Emphasis Type="Italic">p</Emphasis>-type ZnO thin films

Present p-type ZnO films tend to exhibit high resistivity and low carrier concentration, and they revert to their natural n-type state within days after deposition. One approach to grow higher quality p-type ZnO is by codoping the ZnO during growth. This article describes recent results from the growth and characterization of Zr–N codoped p-type ZnO thin films by pulsed laser deposition (PLD) on (0001) sapphire substrates. For this work, both N-doped and Zr–N codoped p-type ZnO films were grown for comparison purposes at substrate temperatures ranging between 400 to 700 °C and N₂O background pressures between 10⁻⁵ to 10⁻² Torr. The carrier type and conduction were found to be very sensitive to substrate temperature and N₂O deposition pressure. P-type conduction was observed for films grown at pressures between 10⁻³ to 10⁻² Torr. The Zr–N codoped ZnO films grown at 550 °C in 1×10⁻³ Torr of N₂O show p-type conduction behavior with a very low resistivity of 0.89 Ω-cm, a carrier concentration of 5.0×10¹⁸ cm⁻³, and a Hall mobility of 1.4 cm² V⁻¹ s⁻¹. The structure, morphology and optical properties were also evaluated for both N-doped and Zr–N codoped ZnO films.     

Photovoltaic activity in a ZnSe/PEO–chitosan blend electrolyte junction

Thin films of ZnSe and PEO–chitosan blend polymer doped with NH₄I and iodine crystals were prepared to form the two sides of a semiconductor electrolyte junction. ZnSe was electrodeposited on indium tin oxide (ITO) conducting glass. The polymer is a blend of 50 wt% chitosan and 50 wt% polyethylene oxide. The polymer blend was complexed with ammonium iodide (NH₄I), and some iodine crystals were added to the polymer–NH₄I solution to provide the I⁻/I³⁻redox couple. The room temperature ionic conductivity of the polymer electrolyte is 4.32 × 10⁻⁶ S/cm. The polymer film was sandwiched between the ZnSe semiconductor and an ITO glass to form a ZnSe/polymer electrolyte/ITO photovoltaic cell. The open circuit voltage (V _oc) of the fabricated cells ranges between 200 to 400 mV and the short circuit current between 7 to 10 μA.     

Effect of illumination on the space charge limited current in organic bulk heterojunction diodes

Current–voltage (J–V) characteristics of organic bulk heterojunction diodes based on an interpenetrating network of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C₆₁-butyric acid methyl esters (PCBM) have been studied in the dark and under halogen lamp illumination. The diodes contained 1:1 and 1:0.6 weight ratios of P3HT and PCBM. For both diodes the currents measured in dark (J _d , commonly known as the dark current) in forward bias are found to agree with the space charge limited current (SCLC). The illuminated current consists of a current due to applied voltage (J _da ) and the light generated current (J _L ). J _da  extracted from the illuminated current agrees well with Shockley’s diffusion and recombination current. This observation shows that illumination changes the SCLC into Shockley’s diffusion and recombination current. The forward current under illumination has been observed to be greater than the dark current, which is contrary to the photo–voltaic (PV) theory. This result is well explained by the change of SCLC into Shockley’s diffusion and recombination current. Former address of S.C. Jain: IMEC, Kapeldreef 75, 3001 Leuven, Belgium.     

Solid Substrate–Room Temperature Phosphorimetry for the Determination of Trace Terbutaline Sulfate Based on Its Inhibition Oxidation of Rhodamine 6G by Sodium Periodate

When 1.00 mol l⁻¹ I⁻ is used as ion perturber, rhodamine 6G (Rh 6G) can emit strong and stable room temperature phosphorescence (RTP) on filter paper substrate in KHC₈H₄O₄–HCl buffer solution (pH = 3.50), heated at 70 °C for 10 min. NaIO₄ can oxidize Rh 6G, which makes the RTP signal quench. Terbutaline sulfate (TBS) can inhibit NaIO₄ from oxidizing Rh 6G, which makes the RTP signal of Rh 6G enhance sharply. The content of TBS is linear correlation to ΔIp of the system. Based on the facts above, a new inhibition solid substrate-room temperature phosphorimetry (SS-RTP) for the determination of trace TBS has been established. The linear range of this method is 0.0104–2.08 pg spot⁻¹ (corresponding concentration: 0.026–5.2 ng ml⁻¹, with a sample volume of 0.4 μl) with a detection limit (L.D.) of 2.6 fg spot⁻¹ (corresponding concentration: 6.5 × 10⁻¹² g ml⁻¹), and the regression equation of working curve is ΔIp = 2.040 + 54.54 m_TBS (pg spot⁻¹), n = 6, correlation coefficient is 0.9994. For the samples containing 0.0104 pg spot⁻¹ and 2.08 pg spot⁻¹ TBS, the relative standard deviation (RSD) are 3.8% and 2.3% (n = 8), respectively, indicating good precision. This method has been applied to determination of trace TBS in the practical samples with satisfactory results. The reaction mechanism of NaIO₄ oxidizing Rh 6G to inhibit SS-RTP for the determination of trace TBS is also discussed.     

Vertical electrical conduction in pentacene polycrystalline thin films mediated by Au-induced gap states at grain boundaries

Vertical electrical conduction in Au/(polycrystal-line pentacene)/Al diode structures and the influence of the kinetic energy of incident Au atoms on the conduction property have been comprehensively studied using current–voltage–temperature (I–V–T) measurements, ultraviolet photoelectron spectroscopy (UPS), atomic-force-microscope (AFM) current imaging, etc. In the I–V characteristics, a symmetrical ohmic current component appeared when a low voltage was applied, and a super-linear one appeared when a high positive voltage was applied to Au. The component in the high-forward-voltage region was concluded to be a thermionic emission of holes from Au with a 0.23-eV injection barrier, which is the normal hole conduction through the highest occupied molecular orbital of pentacene. On the other hand, the ohmic component was concluded to be a metal-like electron transport through high-density gap states at grain boundaries which were induced by the Au penetration into pentacene. UPS and I–V–T measurements clearly indicated the generation of the gap states and the enhancement of their density by the reduction of Au kinetic energy. For vertical-type devices with polycrystalline organic films, the ohmic conduction through the grain boundary will increase the leakage current. On the contrary, it possibly enhances the carrier injection in lateral-type transistors in the case of top-contact configuration.     

Effect of mixed glass formers on the crystallization kinetics in AgI–Ag<Subscript>2</Subscript>O–V<Subscript>2</Subscript>O<Subscript>5</Subscript>–MoO<Subscript>3</Subscript> glassy superionic system

The crystallization and glass transition kinetics using differential scanning calorimetry (DSC) in 50AgI–33.33Ag₂O–16.67[(V₂O₅)_1−x –(MoO₃) _x ] superionic glassy system is discussed. Thermal stability of glass, studied using various criteria, does not vary significantly with glass former variation. However, the activation energies for structural relaxation (E _s) at glass transition temperature and crystallization (E _c) obtained using Moynihan and Kissinger, Matusita-Sakka formulations found to exhibit interesting trends with MoO₃ substitution in the glass matrix. It is noticed that the electrical conductivity (σ)–temperature (T) cycles obtained at a typical heating rate of 1 °C/min do exhibit significant thermal events. The conductivity after first heating cycle at room temperature is found to be increasing with MoO₃ content and maximum for x = 0.3 (~10⁻³ Ω⁻¹ cm⁻¹ at 30 °C) which is comparable to that of the host 50AgI–33.33Ag₂O–16.67V₂O₅ glassy system. The parameters obtained from σ–T plots and DSC scans do complement each other in a particular range of composition.     

Determination of Bioactive Matter by Affinity Adsorption Solid Substrate–Room Temperature Phosphorimetry Based on Lectin Labeled with Self-ordered Ring of Eosin Y

A new phosphorescent labeling reagent named self-ordered ring (ESOR) of eosin Y (E) was developed. And the application of the determination of bioactive matter by affinity adsorption solid substrate–room temperature phosphorimetry (AA-SS-RTP) based on ESOR labeling lectin was studied. Results showed that pink and homogeneous ESOR could be formed by E on polyamide membrane (PAM) in the presence of cetyltrimethylammonium bromide (CTAB) and ammonia water. ESOR could emit strong and stable room temperature phosphorescence (RTP) signal of E in the presence of heavy atom perturber. Specific affinity adsorption (AA) reactions could be carried out between the products of concanavalin agglutinin (Con A), triticum vulgaris lectin (WGA) labeled with ESOR and alpha-fetoprotein variant (AFP-V), alkaline phosphatase (ALP), glucose (G), respectively. Not only did the products of the affinity adsorption reactions preserve good RTP characteristic of E, but also the ΔI _p (ΔI _p = I _p2 − I _p1, I _p1 is the RTP intensity of blank reagent, I _p2 is the RTP intensity of sample) of these products was proportional to the content of AFP-V, ALP and G, respectively. According to the facts above, a new method of AA-SS-RTP for the determination of AFP-V, ALP and G was established, based on ESOR labeling lectin. Detection limits (LD) of this method were 0.040 fg spot⁻¹ for AFP-V, 0.045 fg spot⁻¹ for ALP and 0.090 fg spot⁻¹ for G. And it has been successfully applied to the determination of AFP-V in human serum as well as the survey and forecast of human diseases. This method had high sensitivity, good repeatability, long RTP lifetime and little background interference with at the long wavelength area. Meanwhile, the mechanism for the determination of trace AFP-V by AA-SS-RTP based on Con A labeled with ESOR was also discussed.     

Ionic conductivity studies of chitosan-based polymer electrolytes doped with adipic acid

Chitosan acetate–adipic acid film polymer electrolytes have been prepared by the solution cast technique. The highest conductivity is 1.4 × 10⁻⁹ S cm⁻¹ for 35 wt.% of adipic acid at room temperature. The sample with highest conductivity has the lowest activation energy. Calculations using the Rice and Roth model provide number of mobile ions, η. The conductivity is dependent on the diffusion coefficient and mobility.     

Conduction switching in aluminum nitride thin films containing Al nanocrystals

Conduction switching, i.e., a sharp change in the conduction from a lower-conductance state to a higher-conductance state or vice versa in aluminum nitride thin films embedded with Al nanocrystals (nc–Al) has been observed in the ramped-voltage and ramped-current current–voltage (I–V) measurements and the time-domain current measurement as well. Each state is well defined and its I–V characteristic follows a power law. It is observed that the conductance decreases (or increases) with charging (or discharging) in the nc–Al. It is shown that the conduction switching is due to the charging and discharging in the nc–Al at certain strategic sites. With the connecting (or breaking) of some conductive tunneling paths formed by the uncharged nc–Al due to the discharging (or charging) in the nc–Al at the strategic sites, a conduction switching occurs.     

Preparation and electrochemical properties of nano Al<Subscript>0.2</Subscript>V<Subscript>2</Subscript>O<Subscript>5.3−<Emphasis Type="BoldItalic">δ</Emphasis></Subscript> cathode materials for rechargeable lithium batteries

Nano-sized Al³⁺-doped V₂O₅ cathode materials, Al_0.2V₂O_5.3−δ , were prepared by an oxalic acid assisted sol–gel method at 350 °C (sample A) and 400 °C (sample B). X-ray diffraction confirmed that samples A and B were pure phase Al_0.2V₂O_5.3−δ with an orthorhombic structure close to that of V₂O₅. Scanning electron microscopy showed that sample A was in nanoscale with a mean particle size about 50 nm. Cyclic voltammetry showed the good electrochemical and structural reversibility of the Al_0.2V₂O_5.3−δ nanoparticles during the Li⁺ insertion/extraction process. The Al_0.2V₂O_5.3−δ nanoparticles exhibited excellent charge–discharge cycling performance and rate capability compared to that of bulky V₂O₅ electrodes. For instance, the materials delivered a reversible specific capacity about 180 mAh g⁻¹ (sample A) and 150 mAh g⁻¹ (sample B), in the potential window of 4.0–2.0 V at the current density of 150 mA g⁻¹. The Al_0.2V₂O_5.3−δ nanoparticles in particular showed almost no capacity fading for at least 50 cycles.     

Gelatin-based protonic electrolyte for electrochromic windows

Proton-conducting gel polymer electrolytes based on gelatin plasticized with glycerol and containing acetic acid were investigated, characterized, and applied to electrochromic window. For glycerol contents varying from 7% to 48%, the conductivity of the uniform and predominantly amorphous gel electrolyte was found to follow a Vogel–Tamman–Fulcher behavior with the temperature. Typically, for the electrolyte chosen to make 7 × 2 cm² electrochromic smart window with the configuration: glass/fluor-doped tin oxide (FTO)/WO₃/gelatin electrolyte/CeO₂–TiO₂/FTO/glass and containing 28% of glycerol, the conductivities were found to be of the order of 5 × 10⁻⁵ S/cm at room temperature and 3.6 × 10⁻⁴ S/cm at 80 °C. The device was characterized by spectroelectrochemical techniques and was tested up to 10,000 cycles showing a fast coloring/bleaching behavior, where the coloring process was achieved in 10 s and the bleaching in 2 s. The transmission variation at the wavelength of 550 nm was about 15%. The cyclic voltammograms showed a very good reversibility of the cathodic/anodic processes, and the charge density was about 3.5 mC/cm². The memory tests showed that the transmittance in the colored state increased by 8% in 90 min after removing the potential.     

AC Conductivity,XRD and transport properties of melt quenched PbI<Subscript>2</Subscript>–Ag<Subscript>2</Subscript>O–Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Composite materials used for electrode and electrolyte materials have been intensely studied in view of their advantages such as higher conductivity and better operational performance compared to their single-phase counterparts. The present work aims at studying the electrical and structural characteristics of a new composite electrolyte namely, (PbI₂) _x  − (Ag₂O–Cr₂O₃)_100−x where x = 5, 10, 15, 20, and 25 mol%, respectively, prepared by the melt quenching technique. The room temperature X-ray diffraction spectra revealed certain crystalline phases in the samples. AC conductivity analysis for all the prepared samples was carried out over the frequency range 1 MHz–20 Hz and in the temperature window 297–468 K. The room temperature conductivity values were calculated to be in the order of 10⁻⁵–10⁻³ Scm⁻¹. An Arrhenius dependence of temperature with conductivity was observed, and the activation energies calculated were found to be in the range 0.27–0.31 eV. Furthermore, the total ionic transport number (t _i) values obtained for all these indicated the ionic nature of this system. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

Conductivity studies of starch-based polymer electrolytes

A proton-conducting polymer electrolyte based on starch and ammonium nitrate (NH₄NO₃) has been prepared through solution casting method. Ionic conductivity for the system was conducted over a wide range of frequency between 50 Hz and 1 MHz and at temperatures between 303 K and 373 K. Impedance analysis shows that sample with 25 wt.% NH₄NO₃ has a smaller bulk resistance (R _b) compared to that of the pure sample. The amount of NH₄NO₃ was found to influence the proton conduction; the highest obtainable room temperature conductivity was 2.83 × 10⁻⁵ S cm⁻¹, while at 100 °C, the conductivity in found to be 2.09 × 10⁻⁴ S cm⁻¹. The dielectric analysis demonstrates a non-Debye behavior. Transport parameters of the samples were calculated using the Rice and Roth model and thus shows that the increase in conductivity is due to the increase in the number of mobile ions.     

Electrical characterization of the [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>][N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]ZnCl<Subscript>4</Subscript> compound

The [N(CH₃)₄][N(C₂H₅)₄]ZnCl₄ compound has been synthesized by a solution-based chemical method. The X-ray diffraction study at room temperature revealed an orthorhombic system with P2₁2₁2 space group. The complex impedance has been investigated in the temperature and frequency ranges 420–520 K and 200 Hz–5 MHz, respectively. The grain interior and grain boundary contribution to the electrical response in the material have been identified. Dielectric data were analyzed using the complex electrical modulus M ^* for the sample at various temperature. The modulus plots can be characterized by full width at half height or in terms of a non-exponential decay function ϕ(t) = exp[(−t/τ) ^β ]. The detailed conductivity study indicated that the electrical conduction in the material is a thermally activated process. The variation of the AC conductivity with frequency at different temperatures obeys the Almond and West universal law.     

Conductivity studies of plasticized anhydrous PEO-KOH alkaline solid polymer electrolyte

Polyethylene oxide (PEO)–potassium hydroxide (KOH)-based alkaline solid polymer electrolyte films have been prepared by using methanol as solvent. The highest room temperature ionic conductivity of (2.1 ± 0.5) × 10⁻⁸ S cm⁻¹ was achieved for the composition of 70 wt% PEO:30 wt% KOH. The addition of plasticizer, ethylene carbonate, propylene carbonate, or polyethylene glycol to the highest conductivity of PEO–KOH system helps to increase the ambient ionic conductivity to the order of 10⁻⁶–10⁻⁴ S cm⁻¹. The log σ vs 1/T plot of PEO–KOH showed a small conductivity decrease at 50–60 °C range. The small decrease and the hysteresis that occur during the heating–cooling cycle was overcome by the presence of the plasticizer. X-ray diffraction observation supports the conductivity results.     

Non-steady-state photo-EMF in nanostructured GaN and polypyrrole within porous matrices

We report an experimental investigation of the non-steady-state photoelectromotive force in nanostructured GaN within porous glass and polypyrrole within chrysotile asbestos. The samples are illuminated by an oscillating interference pattern created by two coherent light beams and the alternating current is detected as a response of the material. Dependences of the signal amplitude versus temporal and spatial frequencies, light intensity, and temperature are studied for two wavelengths λ=442 and 532 nm. The conductivity of the GaN composite is measured: σ=(1.1–1.6)×10⁻¹⁰ Ω⁻¹ cm⁻¹ (λ=442 nm, I ₀=0.045–0.19 W/cm², T=293 K) and σ=(3.5–4.6)×10⁻¹⁰ Ω⁻¹ cm⁻¹ (λ=532 nm, I ₀=2.3 W/cm², T=249–388 K). The diffusion length of photocarriers in polypyrrole nanowires is also estimated: L _D=0.18 μm.     

Fabrication and characterization of Cu–CdSe–Cu nanowire heterojunctions

The Cu–CdSe–Cu nanowire heterojunctions were fabricated by sequential electrochemical deposition of layers of Cu metal and CdSe semiconductor within the nano-pores of anodic alumina membrane templates. X-ray diffraction reveals the cubic phase for Cu and hexagonal phase for CdSe in the electrodeposited Cu–CdSe–Cu nanowire heterojunctions. The composition of the nanowire heterojunction segments is characterized by energy dispersive X-ray spectroscopy. The morphological study of nanowire heterojunctions has been made using scanning electron microscope and high resolution transmission microscopy. The nanowire heterojunctions grown in 100 and 300 nm nano-pore size templates have been found to have optical band gaps of 1.92 and 1.75 eV, respectively. The absorption spectra of 100 nm nanowire heterojunctions show a blue shift of 0.18 eV. The collective nonlinear current–voltage (I–V) characteristics of the 300 and 100 nm nanowire heterojunctions show their rectifying and asymmetric behaviour, respectively.     

Performance of lithium-ion cells using 1 M LiPF<Subscript>6</Subscript> in EC/DEC (<Emphasis Type="Italic">v</Emphasis>/<Emphasis Type="Italic">v</Emphasis> = 1/2) electrolyte with ethyl propionate additive

In this work, 1 M LiPF₆:EC:DEC (v/v = 1/2) was used as a baseline electrolyte where EC is ethylene carbonate and DEC is diethyl carbonate. Ethyl propionate (EP) was used as an additive. The conductivity of the liquid electrolyte was obtained at ambient and elevated temperatures. The highest room temperature conductivity was observed at (8.05 ± 0.16) mS cm⁻¹ for the electrolyte containing 28.6 vol.% EP. Viscosity of the baseline and EP added baseline electrolytes have been measured at room and elevated temperatures. The electrolyte was also characterized by linear sweep voltammetry. The highest conducting electrolyte with 28.6 vol.% EP and the baseline electrolyte were used to fabricate several batteries. The batteries were charged and discharged at room temperature and at −20°C.