EDLC characteristics with high specific capacitance of the CNT electrodes grown on nanoporous alumina templates

Well-ordered nanoporous alumina templates were fabricated by two-step anodization method by applying a constant voltage of 40 V in oxalic acid solution or of 25 V in sulfuric acid solution. The cylindrical pore diameter and pore density of the templates utilized for the carbon nanotube (CNT) growth were 86 ± 5 nm and 1.2 × 10¹⁰ cm⁻² in oxalic acid solution and 53 ± 1 nm and 3.1 × 10¹⁰ cm⁻² in sulfuric acid solution, respectively. The CNTs with uniform diameter of 50 ± 10 nm (oxalic acid) and 44 ± 2 nm (sulfuric acid) were grown on the porous alumina template as electrode materials for the electrochemical double layer capacitor (EDLC). The EDLC characteristics were examined by measuring the capacitances from cyclic voltammograms and the charge–discharge curves. The specific capacitances of the CNT electrodes are 30 ± 1 F/g (Φ = 50 ± 10 nm) and 121 ± 5 F/g (Φ = 44 ± 2 nm). The high specific capacitance of the CNT electrode was achieved by using nanoporous alumina templates with the high pore density and the small and uniform pore diameter.     

SELF-ORGANIZED FORMATION OF HEXAGONAL NANOPORE ARRAYS IN ANODIC ALUMINA

Conditions for a self-organized formation of ordered hexagonal structure in anodic alumina were investigated, using oxalic or sulphuric acid as an electrolyte. Highly-ordered nanopore arrays with pore densities of 9×10⁹-6.5×10¹⁰cm^-2 and high aspect ratios over 3000 were fabricated by a two-step anodization process. The array exhibits characteristics analogous to a two-dimensional polycrystalline structure of a few micrometres in size. The interpore distance can be controlled by changing the electrolyte and/or the applied voltage. The formation mechanism of ordered arrays is consistent with a previously proposed mechanical stress model, i.e., the repulsive forces between neighbouring pores at the metal/oxide interface promote the formation of hexagonally ordered pores during the oxidation process.     

Utilization of saffron (<Emphasis Type="Italic">Crocus sativus L.</Emphasis>) as sensitizer in dye-sensitized solar cells (DSSCs)

Photoelectrodes of dye-sensitized solar cells (DSSCs) have been prepared using nanosized titanium dioxide that have soaked in a solution of different saffron (Crocus sativus L.) spice content in ethanol. The optimized polyacrylonitrile (PAN)-based gel polymer electrolyte with 40.93 wt.% ethylene carbonate, 37.97 wt.% propylene carbonate, 4.37 wt.% tetrapropylammonium iodide, 9.86 wt.% PAN, 1.24 wt.% 1-butyl-3-methylimidazolium iodide, 4.35 wt.% lithium iodide and 1.28 wt.% iodine has been used as the electrolyte for DSSC. The electrolyte has conductivity of 2.91 mS cm^?1 at room temperature (298 K). DSSCs were also sensitized with saffron solution that has been added with 30 wt.% chenodeoxycholic acid (CDCA) co-adsorbent and designated as DSSC P4. The solar cell converts light-to-electricity at an efficiency of 0.31%. This is 29% enhancement in efficiency for the DSSC without addition of CDCA in the saffron-ethanol solution. The DSSC exhibits current density at short-circuit (J _sc ) of 1.26 mA cm^?2, voltage at open circuit (V _oc ) of 0.48 V and 51% fill factor. DSSC P4 also exhibits the highest incident photon-to-current density of more than 40% at 340 nm wavelength.     

Porous PVdF-HFP/P123 electrolyte membrane containing flexible quasi-solid-state dye-sensitized solar cells produced by the compression method

Flexible quasi-solid-state dye-sensitized solar cells (DSSCs) with porous poly(vinylidenefluoride-co-hexafluoropropylene) (PVdF-HFP)/polyethylene oxide-co-polypropylene oxide-co-polyethylene oxide (P123) electrolyte membranes were fabricated and their photocurrent–voltage (I–V) characteristics are studied. Flexible TiO₂ photoelectrodes were prepared using the compression method and porous PVdF-HFP/P123 membranes, by the nonsolvent-induced phase inversion technique. To activate the electrolyte membrane, the membrane was immersed in liquid-state electrolyte. Increased compression pressure improved the interconnection between TiO₂ nanoparticles, enhancing the photovoltaic performances of the flexible liquid-state DSSCs to a maximum of 3.92% efficiency. Meanwhile, the overall pore structure of the PVdF-HFP/P123 membranes was controlled by varying the blend ratio of P123 to PVdF-HFP. Membranes higher in P123 content gave larger pores and pore volume, increasing the electrolyte uptake of the porous membrane, and thus the ionic conductivity of the electrolyte membrane as well. The photovoltaic characteristics of the flexible quasi-solid-state DSSCs containing a porous PVdF-HFP/P123 electrolyte membrane showed a maximum at 50 wt% P123 content, which gave a short-circuit current density (J_sc) value of 7.28 mA/cm², an open-circuit voltage (V_oc) of 0.67 V, a fill factor (FF) of 0.61 and an energy conversion efficiency (η) of 2.98%. Furthermore, the device designed in this study showed good durability compared to those based on liquid-state electrolyte.     

How photocatalytic activity of the MAO-grown TiO2 nano/micro-porous films is influenced by growth parameters?

Pure titania porous layers consisted of anatase and rutile phases, chemically and structurally suitable for catalytic applications, were grown via micro-arc oxidation (MAO). The effect of applied voltage, process time, and electrolyte concentration on surface structure, chemical composition, and especially photocatalytic activity of the layers was investigated. SEM and AFM studies revealed that pore size and surface roughness of the layers increased with the applied voltage, and the electrolyte concentration. Moreover, the photocatalytic performance of the layers synthesized at medium applied voltages was significantly higher than that of the layers produced at other voltages. About 90% of methylene blue solution was decomposed after 180 min UV-irradiation on the layers produced in an electrolyte with a concentration of 10 g l⁻¹ at the applied voltage of 450 V.     

Low-resistance and transparent Ni–Co solid solution/Au ohmic contacts to p-type GaN for green GaN-based light-emitting diodes

We report on the formation of low-resistance and transparent p-type ohmic contact for green GaN-based light-emitting diodes (LEDs) using Ni–Co solid solution(5 nm)/Au(5 nm) scheme. The as-deposited Ni–Co solid solution(5 nm)/Au(5 nm) contact shows nonlinear current–voltage (I–V$I\text{–}V$) characteristics. However, annealing the sample at 550 ^°C in air results in the formation of ohmic contacts with specific contact resistance of 6.5×10⁻⁴ Ω cm². The annealed sample shows light transmittance of 71.7% at a wavelength of 530 nm, which is better than that (64.9%) of oxidized Ni/Au contacts. Based on Auger electron spectroscopy and x-ray photoemission spectroscopy results, the annealing-induced improvement of the contacts is described and discussed.     

Fabrication of the uniform CdTe quantum dot array on GaAs substrate utilizing nanoporous alumina masks

Fabrication of quantum dot array (QDA) is attractive for applications in electronic and optoelectronic devices. The CdTe QDAs have potential applications in optoelectronic devices of visible range. One of the major challenges in fabricating QDAs is the uniformity and reproducibility in size and spatial distribution. The uniformity and reproducibility of QDs can be improved by using the nanoporous alumina mask. The geometry of porous alumina is schematically represented as a close-packed array of columnar hexagonal cells, each containing a central pore normal to the substrate. The well-ordered nanoporous alumina masks were able to obtain by two-step anodizing processes from aluminum in oxalic acid solutions at low temperature. The pore size, thickness, and density of nanoporous alumina mask can be controlled with the anodization voltage, time, and electrolyte. The CdTe QDAs on the GaAs substrate was grown by molecular beam epitaxy method using the porous alumina masks. The temperature of substrate and source (Cd, Te) was an important factor for the growth of CdTe QDs on GaAs substrate. The CdTe QDAs of 80 nm dot size was fabricated; using the porous alumina masks (300 nm thickness) of pore diameter (80 nm) and density (10¹⁰ /cm²).     

Low voltage electrodeposition of CNx films and study of the effect of the deposition voltage on bonding configurations

Carbon nitride (CN_x) films were deposited from acetonitrile at low voltage (150-450 V) through electrodeposition. The films were characterized by atomic force microscopy (AFM), Raman spectroscopy and Fourier transform infrared (FT-IR) spectroscopy. AFM investigations revealed that the grain size was ∼200 nm and roughness was ∼10 nm. The films were found to be continuous and close packed. IR spectra revealed existence of strong sp³, sp² type bonding and weak sp type carbon nitrogen bonds and these bonds were found to increase with voltage. The fraction of sp³-bonded species in the sample increased in low voltage range and after reaching maximum at 350 V, decreased for higher voltages. However, the concentration of sp² CN ring structures in the film increased with increasing voltage. Also, the peak width decreased at low voltages reaching a minimum and increased thereafter. It was observed that the voltage dependent increase in the concentration of polymeric type sp² CN (chain) structures was much more pronounced than that of graphitic type sp² CN (ring) structures. Raman spectra showed the presence of both the D and G bands. The shift in the G band indicated the presence of nitrogen in the film. The I_D/I_G ratio was found to increase with the incorporation of nitrogen. Auger electron spectroscopy (AES) showed a clear increase in the nitrogen content with increase in the voltage. The formation of the film could be explained on the basis of dissociation of electrolyte under applied voltage.     

PVC–PMMA composite electrospun membranes as polymer electrolytes for polymer lithium-ion batteries

Composite nanofibrous membranes based on poly (vinyl chloride) (PVC)?Cpoly (methyl methacrylate) (PMMA) were prepared by electrospinning and then they were soaked in liquid electrolyte to form polymer electrolytes (PEs). The introduction of PMMA into the PVC matrix enhanced the compatibility between the polymer matrix and the liquid electrolyte. The composite nanofibrous membranes prepared by electrospinning involved a fully interconnected pore structure facilitating high electrolyte uptake and easy transport of ions. The ion conductivity of the PEs increased with the increase in PMMA content in the blend and the ion conductivity of the polymer electrolyte based on PVC?CPMMA (5:5, w/w) blend was 1.36?×?10^?3 S cm^?1 at 25?°C. The polymer electrolyte based on PVC?CPMMA (5:5, w/w) blend presented good electrochemical stability up to 5.0?V (vs. Li/Li⁺) and good interfacial stability with the lithium electrode. The promising results showed that nanofibrous PEs based on PVC?CPMMA were of great potential application in polymer lithium-ion batteries.     

Study of EVOH based single ion polymer electrolyte: Composition and microstructure effects on the proton conductivity

A comb-like EVOH based single ion polymer electrolyte (EVOH-g-SPEG) was synthesized by sulfonification of EVOH grafts 2-(2-chloroethoxy) ethanol (C₄H₉O₂Cl)/2-[2-(2-chloroethxy) ethoxy] ethanol (C₆H₁₃O₃Cl) with 1, 3-propane sultone. The main chain of the comb-like polymer is hydrophobic polyethylene segments; the side chain is hydrophilic poly (ethylene glycol) (PEG) segment, which can solubilize large amounts of inorganic salts. The sulfonic acid group was introduced onto the end of the PEG side chain. The acid form of SPE was successfully obtained by being dialyzed from the products with acid solution. The saturation water sorption of EVOH-g-SPEG membrane increased with the side chain length and the immersion time. The XRD results indicate that the water in SPE membrane region can destroy the membrane crystalline structure and the water absorption membranes are nearly amorphous. AFM phase images of the hydration membranes clearly show the hydrophilic domains, with sizes increasing from 10 to 35 nm as a function of the side chain length. A phase inversion could be observed when n ≥ 5, which was consistent with a rapid increase in water absorption. And the ion conductivity is also measured by AC impedance. The conductivity is greatly influenced by ion exchange capacity and water sorption. The comb-like EVOH-g-SPEG polymer electrolyte grafts with 2 PEG side chain provides the highest ionic conductivity (1.65 × 10^− 3 S cm^− 1). The comb-like polymer could be a candidate as new polymeric electrolyte material for fuel cells and other electrochemical devices.     

Improving the mobility of CuPc OFETs by varying the preparation conditions

In this work, three different preparation conditions were used for testing the performance of p-conducting copper phthalocyanine (CuPc) organic field-effect transistors (OFETs). The charge carrier mobility (μ _sat=(1.5±0.6)×10^?3 cm²/V?s) of the CuPc OFETs with the CuPc film deposited while keeping the substrate at room temperature could be improved when the gate dielectric was modified by a self-assembled monolayer of n-octadecyltrichlorosilane (μ _sat=(3.8±0.4)×10^?3 cm²/V?s) or when elevated temperatures were applied to the substrate (T _S,av=127 ^°C) during the deposition of the organic film (μ _sat=(6.5±0.8)×10^?3 cm²/V?s). For the latter case, the dependence of the mobility and threshold voltage with increasing thickness of the organic film was tested—above 13 nm film thickness, no further significant increase of the hole mobility or change in the threshold voltage could be observed. The environmental stability of the OFETs was checked by performing ex situ measurements immediately as the sample was exposed to atmosphere and after 40 days of exposure. The effect of the different preparation conditions on the morphology of the organic films prepared in this work is also discussed in this context.     

Optimization of effective parameters in the synthesis of nanopore anodic aluminum oxide membrane and arsenic removal by prepared magnetic iron oxide nanoparicles in anodic aluminum oxide membrane via ultrasonic-hydrothermal method

In this study, a new anodized aluminum oxide (AAO) nanostructure membrane was synthesized by anodization process under a constant voltage, in oxalic acid solution that was improved with trace amounts of sulfuric acid at room temperature. The effect of various parameters on the morphology of the synthesized nanostructures such as voltage, electrolyte composition, anodization time and type of stripping solution were investigated. According to the results, corrosion of the walls, size regularity, diameter and number of the pores increased in the presence of sulfuric acid (0.018 mol.L⁻¹). Nitrogen adsorption-desorption analysis confirmed significant porosity, array and uniformity of the pore size in the synthesized nanoporous membrane. A new modification method was used based on ultrasonic-hydrothermal method to modify the synthesized AAO with Fe₃O₄/SiO₂ nanoparticles for metals and metalloids removal from aqueous solution. In this method, Fe₃O₄/SiO₂ nanoparticles were placed very regularly and uniformly on the surface and inside the pores. This modification was confirmed by characterization techniques. The modified AAO@Fe₃O₄/SiO₂ membrane showed excellent results for removing arsenic from aqueous media.     

Influence of initial pH on the particle size and fluorescence properties of the nano scale Eu(III) doped yttria

Europium doped ytrrium oxide (Eu:Y₂O₃) was synthesized by a chemical wet method in the presence of tween-80 and ?-caprolactam in pH range 4-10. It has been observed that the variation in surface area, pore size, and pore volume of the final product, was strongly dependent on the initial pH of the solution. The powder with a large surface area (∼230 m²/g) and low pore diameter (∼16 nm) was obtained when the powder was processed at pH ∼4. The crystallite sizes of the powders processed at pH ∼4 and 10, were found to be 35 and 198 nm, respectively. The structural, chemical and thermal studies of the powders were characterized by X-ray diffraction (XRD), Fourier transformed infrared spectrophotometer (FTIR), Carbon analyzer and Thermogravimetry (TGA). High resolution transmission electron microscopic (HRTEM) study of heat treated powders showed a polygonal morphology with particle size of 40 nm when powder was derived at pH ∼4. Observations of fluorescence suggested that the ⁵D₀→⁷F₂ transition within europium was found to be highly dependent on the initial pH.     

Preparation of P(AN-MMA) gel electrolyte for Li-ion batteries

Phase inversion technique was used to prepare poly(acrylonitrile-methyl methacrylate) [P(AN-MMA)]-based microporous gel electrolyte with addition of SiO₂ via in-situ composition for Li-ion batteries. The P(AN-MMA) was synthesized by emulsion polymerization and was dissolved into N,N-dimethylformamide (DMF) to form a uniform solution, while tetraethyl orthosilicate (TEOS) was added into the solution and was hydrolyzed by catalysis of alkali ammonia solution to form SiO₂. Then the solution was cast onto a glass plate using a doctor blade and exposed to humidified atmosphere produced by ultrasonic humidifier, followed by washing, rinsing, and drying, successively. The gel electrolyte was obtained by putting the P(AN-MMA) microporous membrane in a liquid electrolyte. The gelled microporous membrane sucked with 755 wt% of liquid electrolyte vs the dried membrane. It had a porosity of 70%, about 1∼5 μm of pores, and presented an ionic conductivity of 0.94 × 10⁻³ S/cm at room temperature. Electrochemical stability window of the porous gel polymer electrolyte was determined by running a linear sweep voltammetry. The decomposition voltage of the polymer electrolyte exceeds 4.5 V vs Li. The coin test cell with the microporous gel electrolyte showed a good cycling performance. The discharge capacity retention was above 87% at 0.1 C for 45 cycles.     

On the effects of NBTI degradation in p-MOSFET devices

This paper presents the effects of interface trap concentration and threshold voltage shift on NBTI degradation in p-MOSFETs. To explore the degradation mechanisms, transistors having an EOT of 1.1 nm and 5 nm were simulated by applying various stress conditions. The NBTI degradation mechanism was studied by varying the gate voltage, temperature and substrate doping level. The simulations show NBTI degradation in terms of the threshold voltage shift, ΔV_th and number of interface traps, ΔN_it. The simulation results show an improved degradation trend in terms of ΔV_th and ΔN_it when the substrate doping level is increased.     

Thermal and electrical properties of solid polymer electrolyte PEO9 Mg(ClO4)2 incorporating nano-porous Al2O3 filler

Solid polymer electrolyte PEO₉ Mg(ClO₄)₂ incorporating 10 wt.% nano-porous Al₂O₃ filler grains has been prepared by the solvent casting technique using acetonitrile as the common solvent. Al₂O₃ powder (activated acidic, Aldrich) with grain size 104 μm and pore size 5.8 nm were incorporated as an inert filler. Electrolyte films have been characterized by differential scanning calorimetry, complex impedance and dc polarization measurements. The nano-composite electrolyte as well as the filler-free electrolyte appear to be predominantly anionic conductors with ClO₄⁻ ions being the migrating species. The presence of the alumina filler has enhanced the ionic conductivity significantly. The conductivity enhancement has been attributed to Lewis acid–base type interactions between H groups at the filler grain surface and the ClO₄⁻ ions. Transient H-bonding through these interactions is expected to provide additional hopping sites and favourable conducting pathways for migrating ionic species.     

Characterization of high ionic conducting PVAc–PMMA blend-based polymer electrolyte for electrochemical applications

A solid polymer blend electrolyte is prepared using poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) polymers with different molecular weight percentage (wt%) of ammonium thiocyanate (NH₄SCN) by solution casting technique with tetrahydrofuran (THF) as a solvent. The structural, morphological, vibrational, thermal and electrical properties of the prepared polymer blend electrolytes have been studied. The incorporation of NH₄SCN into the polymeric matrix causes decrease in the degree of crystallinity of the samples. The complex formation between the polymer and salt has been confirmed by FTIR technique. The increase in T _g with increase in salt concentration has been investigated. The maximum conductivity of 3.684?×?10^?3 S cm^?1 has been observed for the composition of 70PVAc/30PMMA/30 wt% of NH₄SCN at 303 K. This value of ionic conductivity is five orders of magnitude greater than that of 70PVAc/30PMMA polymer membrane. Dielectric and transport studies have been done. The highest conducting polymer electrolyte is used to fabricate proton battery with the configuration Zn/ZnSO₄·7H₂O (anode) ||polymer electrolyte||PbO₂/V₂O₅ (cathode). The open circuit voltage of the fabricated battery is 1.83 V, and its performance has been studied.     

Transport mechanism of Cu-ion conducting PVA based solid-polymer electrolyte

Copper-ion conducting solid-polymer electrolyte systems based on Polyvinyl alcohol (PVA) has been prepared by solution cast technique. UV-VIS data show a broad peak in the wavelength region 600–800 nm due to complex formation. The 30 wt.% Cu(NO₃)₂ doped system has a maximum conductivity of 1.6×10⁻⁵ Scm⁻¹ at room temperature. The conductance spectrum shows two distinct regions: a dc plateau and a dispersive region. The dielectric spectra show an increase in the dielectric constant with decreasing frequency. The transference number measurements reveal that the transport in these electrolytes is mainly due to ions. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.     

Mechanism of the redox process of conducting polymers

The reversible redox process of electrochemically formed conducting polymers (poly-aniline, poly-3-methylthiophene, poly-carbazole, and poly-bithiophene) was investigated by current transients of potentiostatic steps, impedance spectroscopy, and by mass transients from the electrochemical quartz micro balance. The polymer film thickness (18 nm ≤ d ≤ 6700 nm) and the electrolyte (aqueous H₂SO₄, HClO₄, trichloroacetic acid, and p-toluenesulphonic acid, or non-aqueous acetonitrile/Et₄N ClO₄) was varied. The redox process is a complex sequence of steps. The oxidation starts with a field supported, non-homogeneous formation of conducting pathes. 5 to 10% of the total charge are sufficient to convert the polymer to the conducting state. Up to 50% of the total charge are consumed by a mechanism which involves proton transport. The further redox process requires a transport of anions from the electrolyte. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

Nanospallation induced by an ultrashort laser pulse

A femtosecond laser pulse with power density of 10¹³ to 10¹⁴ W/cm² incident on a metal target causes ablation and ejection of the surface layer. The ejected laser plume has a complicated structure. At the leading front of the plume, there is a spall layer where the material is in a molten state. The spall layer is a remarkable part of the plume in that the liquid-phase density does not decrease with time elapsed. This paper reports theoretical and experimental studies of the formation, structure, and ejection of the laser plume. The results of molecular dynamics simulations and a theoretical survey of plume structure based on these results are presented. It is shown that the plume has no spall layer when the pulse fluence exceeds an evaporation threshold F _ev. As the fluence increases from the ablation threshold F _a to F _ev, the spall-layer thickness for gold decreases from 100 nm to a few lattice constants. Experimental results support theoretical calculations. Microinterferometry combined with a pump-probe technique is used to obtain new quantitative data on spallation dynamics for gold. The ablation threshold is evaluated, the characteristic crater shape and depth are determined, and the evaporation threshold is estimated.