Investigation of transport properties of chitosan-based electrolytes utilizing impedance spectroscopy

A method based on impedance spectroscopy has been utilized to obtain values of transport parameters such as number density, mobility and diffusion coefficient of mobile ions of solid polymer electrolytes (SPEs). SPE membranes consisting of chitosan and various amounts of oxalic acid (C₂O₄H₂) from 10 to 50 wt% have been prepared by the solution casting method. The Nyquist plots of all electrolytes have been fitted using the impedance equations based on equivalent circuits, and the parameters involved have been evaluated by trial and error. Number density, mobility and diffusion coefficient of mobile ions were calculated based on the parameters obtained. The values obtained from the proposed electrical impedance spectroscopy method are in reasonable agreement with those calculated using the percentage of mobile ions obtained from Fourier transform infrared (FTIR) measurements. The results were further compared with the results obtained using broadband dielectric response or Bandara-Mellander approach. The findings were confirmed by repeating the measurements and calculations on a glycerol-chitosan-oxalic acid-based electrolyte.     

Thermoactivation and dielectric spectroscopy of chitosan films

Physics of the Solid State - The polymer films based on chitosan have been studied using dielectric and thermoactivation spectroscopy. Two relaxation processes have been found in the temperature...     

Surface exchange reactions and diffusion in composite materials: A finite element approach

A two-dimensional square grain model has been applied to model oxygen exchange processes between a gas phase and a ceramic composite consisting of two randomly distributed phases of equal grain size (side length of squares). Both average diffusion profiles for thin films and the time dependence of the total amount of exchanged oxygen (relaxation curves) have been calculated numerically by means of the finite element method. The boundary conditions refer to an instantaneous change of the oxygen partial pressure in the surrounding gas phase, which gives rise to surface exchange reactions as well as to diffusion in the composite. Both local equilibrium at the interface between different phases (host phase and inclusions) and blocking heterophase boundaries have been taken into account. The numerical results are compared with the analytical solution for diffusion in a homogeneous medium introducing effective diffusion and surface exchange coefficients. When the relaxation time for effective medium diffusion is considerably shorter than that for the transport process from the host phase into the inclusions, relaxation curves with two separate time constants are predicted. Based on analytical approximations, relaxation times for various limiting cases are given.     

Thermal and conductivity studies of chitosan acetate-based polymer electrolytes

Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC) have been employed to study the thermal stability of the chitosan acetate-based polymer electrolyte films. The glass transition temperature, T_g measurements confirm the conductivity enhancement effect by adding the plasticizer and salt in the chitosan acetate films Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.     

Mechanical and corrosion resistance of hydrophilic sphene/titania composite coatings on titanium and deposition and release of cefazolin sodium/chitosan films

The mechanical and corrosion resistance of hydrophilic sphene/titania composite coatings on titanium formed by a hybid technique of microarc oxidation (MAO) and heat-treatment were investigated. The results indicated that the heat-treatment could improve the hardness, elastic modulus, elastic recovery and corrosion resistance of the MAO coatings, and reinforce the interface bonding between MAO coatings and titanium. A cefazolin sodium/chitosan drug film was prepared on the coating surfaces. The drug load procedures such as the addition of chitosan obviously increased the sustained-release ability of drug films. In addition, the increase of cefazolin sodium concentration could increase the accumulative release concentration of cefazolin sodium. The sustaining-release ability of drug films deposited on the MAO and heat-treated MAO coatings is similar. In the interior of drug film, the physical and chemical bonding reactions such as Coulombic interactions, van der Waals force and H-bonding etc. could be produced, through the chemical group interactions such as -OH and -NH₂ groups of chitosan with -CO of cefazolin sodium.     

On the porosity of coldly condensed sers active Ag films: II. Comparison of adsorption and Raman scattering of pyridine

The adsorption of pyridine on coldly deposited Ag films annealed at temperatures ranging from 58 to 330 K, the porous surface topography of which has been investigated in part I of this work, has been studied by means of UPS, work function change and thermal desorption measurements. Pyridine induced work function changes have been employed to follow the surface diffusion of pyridine molecles into the pores of these Ag films. The surface diffusion is very slow below 60 K, but readily takes place at 130 K with an estimated activation energy of surface migration of E_m ≈ 4 kcal/mol. Preadsorption of Xe into the pores of the films causes inhibition of pyridine diffusion into the pores. The onset of pyridine desorption from porous films is detected at ≈ 200 K while from flat films the desorption begins already at 150 K. The careful analysis of our data on the structure of the coldly deposited Ag films and the adsorption behavior of pyridine on these films as well as a survey of published SERS data lead us to conclude that the SERS active sites of coldly deposited Ag films are within the pores. This conclusion is in agreement with recent theoretical calculations.     

Time-resolved luminescence quenching in thin films of perylene-tetracarboxylic-dianhydride

We present luminescence quenching experiments and determine the exciton diffusion length in polycrystalline thin films of PTCDA (perylene-3,4,9,10-tetracarboxylic-dianhydride). From an analysis of time-resolved experiments, we can distinguish between exciton transport during an ultra-fast initial relaxation phase and transport in the long-living emitting states. The temperature dependence of the exciton diffusion constant in the emitting states indicates thermally activated hopping.     

六方InN薄膜的载流子输运特性研究

关键词：     

Thermal noise as a spectroscopic tool to determine transport properties

The utilization of thermal fluctuations or Johnson/Nyquist noise as a spectroscopic method to determine transport properties in conductors or semiconductors is developed. The autocorrelation function is obtained from power spectral density measurements thus enabling electronic transport property calculation through the Green–Kubo formalism. This experimental approach is distinct from traditional numerical methods such as molecular dynamics simulations, which have been used to extract the autocorrelation function and directly related physics only. This work reports multi-transport property measurements consisting of the electronic relaxation time, resistivity, mobility, diffusion coefficient, electronic contribution to thermal conductivity and Lorenz number from experimental data. Double validation of the experiment was accomplished through the use of a standard reference material and a standard measurement method, i.e. four-probe collinear resistivity technique. Thermal noise measurements resulted in a 1.1 and 5% agreement with the reference material and four-probe values, respectively. Additional measurements were also taken on nanoscale Au and Cu thin films. Specifically, the validated spectroscopic methodology was applied to 30 nm Au and Cu thin films to obtain transport property data that was again compared to four-probe resistivity measurements. Comparative analysis of the resistivity data showed agreement within 13.6 and 4.8% for the Au and Cu samples, respectively, thus lending further credibility to the experimental method and theory.     

Initial stages of the growth of barium strontium titanate films on a semi-isolating silicon carbide substrate

The initial stages of the growth of ferroelectric barium strontium titanate films on single-crystal silicon carbide substrates have been studied for the first time. The choice of a substrate with high thermal conductivity has been due to the possibility of applying these structures in powerful microwave devices. The temperature ranges separating the mechanism of the surface diffusion of deposited atoms from the diffusion via a gaseous phase during the growth of multicomponent films have been determined. The studies show that the mass transfer by means of surface diffusion leads to the formation of small-height nuclei that cover a large area of the substrate, whereas the mass transfer via a gaseous phase leads to the formation of a “columnar” islandtype structure with small percentage of covering the substrate and larger island heights.     

Oxidation and thermal annealing effects on native and ion-irradiated PbTe films grown by molecular beam deposition

Investigations are reported into the effect of low-pressure oxygen exposure and thermal annealing on the carrier transport properties of native and 350 eV Ar⁺ bombarded PbTe films. The electrical measurements were madein situ on MBD-grown PbTe films without breaking vacuum. On native surfaces, oxidation was initially sustained by diffusion of a donor species from the film bulk to the surface, where reaction with oxygen occured. This diffusion process was apparently inhibited on ion irradiated films and direct doping of the film surface effected a gradual reduction in the ion-induced electron accumulation resident at the film surface. The native properties and behavioural characteristics of the films could be recovered by thermal annealing of the ion-irradiated and/or oxidized films at 300–350 °C.     

Electron transport in dye-sensitized solar cells based on TiO2 nanowires

Anatase titanium dioxide nanowire arrays were prepared by hydrothermally oxidizing titanium foils in aqueous alkali and transferred onto fluorinated tin oxide(FTO)glass for use as the photoanodes of front side illuminated dye-sensitized solar cells(DSCs).Electrochemical impedance spectroscopy(EIS)measurement was applied to compare the electron transport and recombination properties of DSCs using TiO2nanowire films and TiO2nanoparticle films as photoanodes.It was found that the nanowire array films possess smaller electron transport resistance(Rt)and larger electron diffusion length(Le)in the photoanodes,suggesting that the nanowire arrays can enhance the electron transport rate and have a potential to improve the charge collection efficiency of DSCs.     

Extrinsic electronic transport in La0.7(Sr,Ca)0.3MnO3 films deposited on step edges and bicrystal substrates

In this paper, the electronic transport of La(0.7)(Sr,Ca)(0.3)MnO(3) films grown by pulsed laser deposition on a LaAlO(3)(001) substrate with deep parallel structured steps and a 30° symmetric bicrystal SrTiO(3)(001) substrate have been discussed. The electronic transport properties have been related to the well-known extrinsic transport of bulk manganite compounds. The spin-glass-like behavior with a characteristic peak at 20 K and domain formation at the grain boundary is observed. Further, it has been quantified from the resonant tunneling model that mixed magnetic interactions play a significant role in the manganite films deposited on step edges.     

Charge transport and trapping model for scaled nitride-oxide stacked films

Experimental measurements, including capacitance-voltage and temperature-dependent current-voltage measurements of two nitride/oxide dual-layer films, have been used to characterize the charge transport and trapping mechanisms for scaled nitride-oxide stacked films. For charge transport from the cathode electrode to the adjacent oxide or nitride, electron Fowler-Nordheim tunneling is the dominant mechanism and the tunneling barriers are 3.2 eV for oxide and 2 eV for nitride, respectively. For charge transport from the nitride to the oxide, electron tunneling with limited electron supply from the nitride/oxide injecting interfaces was observed. A new charge transport and trapping model for scaled nitride-oxide stacked films is evolved from the experimental observations. According to the model, nitride-oxide stacked films can be thought of as an oxide film with electron trapping at the nitride/oxide interface. The electron trapping reduces the leakage current and lowers the incidence of early failures for nitride-oxide stacked films.     

Octaethylporphin films. II absorption and emission of amorphous films

Amorphous thin films octaethylporphin have been prepared and are observed to crystallize over time if thicker than about 100 nm. Transmission spectra of amorphous films have a sharper Soret band than transmission spectra of crystalline films and lack the exciton band seen in crystalline films. The exciton band can be resolved in amorphous films by taking a difference spectrum between two amorphous films of different thickness. Fluorescence is observed from one impurity in amorphous films as compared to two impurities in crystalline films. This indicates a smaller exciton diffusion length in amorphous films as compared to crystalline films, consistent with the differences in the transmission spectra of the two kinds of film.     

The influence of UV irradiation on the surface of chitosan films

The surface properties of chitosan films before and after UV-irradiation (λ = 254 nm and 248 nm, respectively) were investigated using the technique of scanning electron microscopy (SEM) and by means of contact angle measurements allowing the calculation of surface free energy. Moreover, in order to determine the film mass changes, quartz crystal microbalance (QCM) measurements were performed. Measurements of the contact angle for diiodomethane (D), formamide (F) and glycerol (G) on the surface of chitosan films were made. The chemical and structural changes during UV irradiation were studied by FTIR-ATR spectroscopy.The contact angle and the surface free energy were altered by UV irradiation of chitosan films. The microscopy images have shown that the KrF excimer laser irradiation caused visible damages on the surface in comparison with the surface exposed to the mercury UV lamp. The surface modification of chitosan films can be achieved using both, the low intensity UV lamp and the excimer laser.     

Analysis of the injection layer of PTCDA in OLEDs using x-ray photoemission spectroscopy and atomic force microscopy

Through the investigation of the sample surface and interface of 3, 4, 9, 10-perylenetetracarboxylic dianhydride (PTCDA)/indium-tin-oxide (ITO) thin films using atomic force microscopy, it has been found that the surface is complanate, the growth is uniform and the defects cover basically the surface of ITO. Furthermore, the number of pinholes is small. The analysis of the sample surface and interface further verifies this result by using x-ray photoemission spectroscopy . At the same time, PTCDA is found to have the ability of restraining the diffusion of chemical constituents from ITO to the hole transport layer, which is beneficial to the improvement of the performance and the useful lifetime of the organic light emitting diodes (OLEDs).     

The transient diffusion of hydrogen in finite metal films and spheres containing trapping sites

Finite difference methods have been used to calculate the transient and steady-state diffusion behavior of H-atoms permeating films of finite thickness and outgassing from uniformly charged spheres. The relationships between the lattice diffusivity obtained from defect-free materials and the diffusivities obtained from samples containing vacancy-related trapping sites and metastable (dislocation-related) traps have been calculated.     

SiOxNy薄膜的微观结构与新的电流传输机理模型

本文研究了SiO_xN_y薄膜的微观结构和电流传输行为,并提出一个新的,用于解释SiO_xN_y薄膜的电流传输,特别对于外加高场直到介质膜发生本征击穿前的电流传输行为的模型。理论与实验符合较好。采用新模型满意地解释了膜的l-V特性中出现的电流增加和陷阱台阶现象,并对外加电场和电子陷阱对电流传输行为的影响进行了讨论。 关键词：     

Kinetic pathways of diffusion and solid-state reactions in nanostructured thin films

Mass transport and solid-state reactions in nanocrystalline thin films are reviewed. It is illustrated that diffusion along different grain boundaries (GBs) can have important effects on the overall intermixing process between two pure films. These processes can be well characterized by a bimodal GB network, with different (fast and slow) diffusivities. First the atoms migrate along fast GBs and accumulate at the film surface. These accumulated atoms form a secondary diffusion source for back diffusion along slow boundaries. Thus the different GBs of the thin films can be gradually filled up with the diffusing atoms and composition depth profiles reflect the result of these processes. Similar processes can be observed in binary systems with intermetallic layers: instead of nucleation and growth of the reaction layer at the initial interface, the reaction takes place in the GBs and the amount of the product phase grows by the motion of its interfaces perpendicular to the GBs. Thus, the entire layer of the pure parent films can be consumed by this GB diffusion-induced solid-state reaction (GBDIREAC), and a fully homogeneous product layer can be obtained.