Electrical properties of cerium fluoride thin films

Thin films of ionic conductors have low internal resistance. Hence, it could be used as an electrolyte material in sensors to operate at ambient temperatures. Cerium fluoride, a unipolar fluoride ion conductor, has got a different application in electrochemical sensor. In the present work, cerium fluoride thin films have been prepared by physical vapor deposition method and their electrical properties are studied. X-ray diffraction studies reveal the polycrystalline nature of the prepared thin films and the structure of the material. Scanning electron microscopy (SEM) images show grain-like structures. Conductivity analysis of the thin films has been studied by ac impedance analysis and the maximum conductivity value is found to be 1.04 × 10⁻⁶ S cm⁻¹. The impedance spectra emphasize intergranular conduction in the prepared thin films.     

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.     

Detecting a true quantum pump effect

Reflectance measurements from p-type GaSb:Zn epitaxial films with different hole concentrations (10¹⁷–10¹⁸ cm^-3) have been investigated over the frequency region of 100–1000 cm^-1. A minimum broadening feature corresponding to the hole plasmon was observed in the reflectance spectra. The experimental infrared spectra were well fitted using a Lorentz-Drude dispersion model. The real part ε₁ of the dielectric function decreases with increasing hole concentration. However, the imaginary part ε₂ increases with hole concentration in the far-infrared region. This indicates that the acoustic- and optic-phonons mainly participate in the free carrier absorption processes. The hole mobility obtained from Hall-effect measurements is slightly larger than that derived from optical measurements and the average ratio of mobilities is estimated to be 1.33. Owing to overdamping effects, the upper branch of longitudinal-optical phonon plasmon (LPP) coupled modes was observed. The upper LPP⁺ frequency increases with hole concentration and it shows a transition from phonon-like to plasmon-like behavior. A theoretical analysis with solutions in the complex frequency plane describes these experimental results.     

Low temperature dependence of the penetration depth in YBCO thin films revisited by mm wave transmission and surface impedance measurements

We report results obtained with two different experimental set-ups in state-of-the-art YBCO thin films as similar as possible, prepared by pulsed laser deposition on LaAlO₃ substrates: a surface impedance measurement on 4000 ? thick films using a parallel plate resonator (10 GHz), and a far infrared transmission (100-400 GHz) measurement which requires thinner (1000 ?) samples. The former measurement yields the temperature variation of the penetration depth λ(T) and the real part of the conductivity, provided the absolute value of λ(T) is known. The latter yields the imaginary part of the conductivity, hence the absolute value of the penetration depth, as well as its temperature dependence at the measuring frequency. Combining these two experiments, we establish a quasi-linear temperature variation of λ(T), with a 2 ? K^-1 low temperature slope, and a fairly large zero temperature value λ(T = 0)=(1800±200) ? . The scattering rate of the quasi-particles calculated from a two-fluids model shows that the films compare to good quality single crystals, where twice a larger slope has been found. This surprising behavior is described in detail, including an in-depth structural analysis of the samples in order to evaluate their similarities. We find that the 10 GHz data obtained in the thickest films can be fitted to the dirty d-wave mode in the unitarity limit, with an extrapolated slope of 3 ? K^-1, but yield a scattering rate that is difficult to reconcile with the high T _c (92 K) of the films. Received 7 May 2001 and Received in final form 18 October 2001     

Ionic conductivity studies on Sr stabilized zirconia by impedance spectroscopy

Sr stabilized zirconia has been prepared by the co-precipitation method and electrically characterized by using impedance spectroscopy in the frequency range from 42 Hz to 5 MHz. The charge carrier concentration of the material has been calculated from the conductance spectra and it is found to be of the order of 10²⁵ cm⁻³. The conductance spectra show a dc plateau and a dispersive region suggesting correlated hopping motion of the ions. The impedance analysis shows a depressed semicircle indicating non-Debye nature of the material as well as the broad nature of modulus peaks indicates non-Debye behaviour. The bulk resistance of the material has been extracted from the impedance spectra and it is found to be 3.5×10⁷ Ω·cm⁻¹ at 673 K. The low frequency dispersion of the dielectric constant implies the space charge effects arising from the electrodes. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28 – 30, 2003.     

Effect of plasticizer on structural and electrical properties of nanocomposite solid polymer electrolytes

The solid polymer electrolyte films based on polyethylene oxide, NaClO₄ with dodecyl amine modified montmorillonite as filler, and polyethylene glycol as plasticizer were prepared by a tape casting method. The effect of plasticization on structural, microstructural, and electrical properties of the materials has been investigated. A systematic change in the structural and microstructural properties of plasticized polymer nanocomposite electrolytes (PPNCEs) on addition of plasticizer was observed in our X-ray diffraction pattern and scanning electron microscopy micrographs. Complex impedance analysis technique was used to calculate the electrical properties of the nanocomposites. Addition of plasticizer has resulted in the lowering of the glass transition temperature, effective dissociation of the salt, and enhancement in the electrical conductivity. The maximum value of conductivity obtained was ∼4.4 × 10⁻⁶ S cm⁻¹ (on addition of ∼20% plasticizer), which is an order of magnitude higher than that of pure polymer nanocomposite electrolyte films (2.82 × 10⁻⁷ S cm⁻¹). The enhancement in conductivity on plasticization was well correlated with the change in other physical properties.     

Ion conduction and space-charge polarization processes in Li<Subscript>2</Subscript>Ge<Subscript>7</Subscript>O<Subscript>15</Subscript> crystals

The electrical properties of a lithium heptagermanate (Li₂Ge₇O₁₅) crystal have been studied in DC and AC measuring fields at temperatures from 500 to 700 K. In a DC field, a substantial decrease of electrical conductivity σ with time has been detected. On the basis of kinetic dependences σ(t), estimates of the charge carrier diffusion coefficient D have been obtained. In the frequency range 10¹–10⁵ Hz, the spectra of complex impedance ρ*(f) have been measured. The analysis of diagrams in the complex plane (ρ″–ρ′) has been performed within the equivalent circuit approach. It has been shown that, in the considered temperature and frequency intervals, the electrical properties of Li₂Ge₇O₁₅ crystals have been determined by the hopping conduction of interstitial lithium ions A _Li and accumulation of charge carriers near the blocking Pt electrodes.     

Multiphonon absorption in a MgO single crystal in the terahertz range

The reflection and transmission spectra of a MgO single crystal at frequencies of 10–1000 cm⁻¹ in the temperature range 10–300 K have been measured using submillimeter and infrared Fourier spectros-copy. The evolution of anharmonic absorption with variations in temperature has been investigated in the frequency range below the frequency of the transverse optical phonon. The parameters of the dispersion model that adequately describes the lattice absorption of terahertz radiation in single-crystal magnesium oxide have been determined.     

NMR study and electrical properties investigation of Zn<Subscript>2</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

The α-Zn₂P₂O₇ compound was obtained by conventional solid-state reaction. The sample was characterized by X-ray powder diffraction, solid state ³¹P NMR MAS, and electrical impedance spectroscopy. The solid state ³¹P MAS NMR, performed at 121.49 MHz, shows three isotropic resonances at −21.1, −18.8, and −15.8 ppm, confirming the non-equivalency of the three PO₄ groups in the α-Zn₂P₂O₇ form. They are characterized by different chemical shift tensor parameters with the local geometrical features of the tetrahedra. Electrical impedance measurements of β-Zn₂P₂O₇, form stable for temperature greater than 403 K, were performed as a function of both temperature and frequency. The electrical conduction and dielectric relaxation have been studied. The AC conductivity obeys the universal power law. The approximation type correlated barrier hopping model explains the universal behavior of the n exponent. The impedance plane plot shows semicircle arcs at different temperatures, and an electrical equivalent circuit has been proposed to explain the impedance results. The circuits consist of the parallel combination of bulk resistance R _p and constant phase elements CPE. The simulated spectra show a good correlation with the experimental data.     

Ac electrical parameters of Al-ZnPc-Al organic semiconducting films

The ac electrical parameters of thermally evaporated zinc phthalocyanine, ZnPc, semiconducting thin films was measured in the temperature range of 180–390 K and frequency between 0.1 and 20 kHz. Aluminum electrode contacts were utilized to sandwich the organic ZnPc semiconducting films. Capacitance and loss tangent decreased rapidly with frequency at high temperatures, but at lower temperatures a weak variation is observed. An equivalent circuit model assuming ohmic contacts could qualitatively and successfully explains capacitance and loss tangent behavior. The ac conductivity showed strong dependence on both temperature and frequency depending on the relevant temperature and frequency range under consideration. Ac conductivity σ (ω) is found to vary with ω, as ω ^s with the index s ≤ 1.35 suggesting a dominant hopping conduction process at low temperatures (< 250 K) and high frequency. The conductivity of some samples did not increase monotonically with temperature. This behavior was attributed to oxygen exhaustion of the sample as its temperature is increased. The ac conductivity behavior at low temperatures of ZnPc films could be described well by Elliott model assuming hopping of charge carriers between localized sites.     

Field electron emission of carbon-based nanocone films

Diamond nanocone, graphitic nanocone, and mixed diamond and graphitic nanocone films have been synthesized through plasma enhanced hot filament chemical vapor deposition (HFCVD). The field emission properties of these films have been experimentally investigated. The studies have revealed that all three kinds of nanocone films have excellent field electron emission (FEE) properties including low turn-on electric field and large emission current at low electric field. Compared with the diamond nanocone films (emission current of 86 μA at 26 V/μm with the turn-on field of 10 V/μm), the graphitic nanocone films exhibit higher FEE current of 1.8×10² μA at 13 V/μm and a lower turn-on filed of 4 V/μm. The mixed diamond and graphitic nanocone films have been found to posses FEE properties similar to graphitic nanocone films (emission current of 1.7×10² μA at 20 V/μm with the turn-on field of 5 V/μm), but have much better FEE stability than the graphitic nanocone films. PACS 81.07.Bc; 81.05.Uw; 79.70.+q     

Impedance and dielectric studies of nanocomposite polymer electrolyte systems using MMT and ferroelectric fillers

Impedance and dielectric properties of nanocomposite polymer electrolyte systems modified with nano size MMT and ferroelectric fillers have been investigated for varying lithium to oxygen ratios. The changes in the structural properties of the electrolyte samples were characterized by X-ray diffraction (XRD) and differential scanning calorimetric (DSC) technique. The ion transport number estimated by DC polarization technique is found to be between 0.86 and 0.95. The bulk conductivities of nanocomposite polymer electrolyte films were studied using impedance spectroscopic technique. The impedance plot shows high frequency semicircle, due to the bulk effect of sample and maximum ionic conductivity of 2.15 × 10⁻⁴ Scm⁻¹ was observed for (PEO)₄LiCBSM at 323 K with lithium to oxygen ratio 1: 4. The complex impedance data was used to evaluate ionic conductivity and dielectric relaxation process, to understand the ion transport mechanism in these systems.

     

Performance evaluation of PVdF gel polymer electrolytes

A series of gel polymer electrolytes containing PVdF as homo polymer, a mixture of 1:1 Ethylene Carbonate (EC) : Propylene Carbonate (PC) as plasticizer and lithium-bistrifluoromethane sulphone imide [imide — LiN (CF₃SO₂)₂] has been developed. Amounts of polymer (PVdF), plasticizer and the imide lithium salt have been varied as a function of their weight ratio composition in this regard. Dimensionally stable films possessing appreciable room temperature conductivity values have been obtained with respect to certain weight ratio compositions. However, conductivity data have been recorded at different possible temperatures, i.e., from 20 °C to 65 °C. XRD and DSC studies were carried out to characterize the polymer films for better amorphicity and reduced glass transition temperature, respectively. The electrochemical interface stability of the PVdF based gel polymer electrolytes over a range of storage period (24 h – 10 days) have been investigated using A.C. impedance studies. Test cells containing Li/gel polymer electrolyte (GPE)/Li have been subjected to undergo 50 charge-discharge cycles in order to understand the electrochemical performance behaviour of the dimensionally stable films of superior conductivity. The observed capacity fade of less than 20% even after 50 cycles is in favour of the electrochemical stability of the gel polymer electrolyte containing 27.5% PVdF −67.5 % EC+PC −5% imide salt. Cyclic voltammetry studies establish the possibility of a reversible intercalation — deintercalation process involving Li⁺ ions through the gel polymer electrolyte.     

SnO2 thin films grown by pulsed Nd:YAG laser deposition

SnO₂ thin films have been deposited on glass substrates by pulsed Nd:YAG laser at different oxygen pressures, and the effects of oxygen pressure on the physical properties of SnO₂ films have been investigated. The films were deposited at substrate temperature of 500°C in oxygen partial pressure between 5.0 and 125 mTorr. The thin films deposited between 5.0 to 50 mTorr showed evidence of diffraction peaks, but increasing the oxygen pressure up to 100 mTorr, three diffraction peaks (110), (101) and (211) were observed containing the SnO₂ tetragonal structure. The electrical resistivity was very sensitive to the oxygen pressure. At 100 mTorr the films showed electrical resistivity of 4×10⁻² Ω cm, free carrier density of 1.03×10¹⁹ cm⁻³, mobility of 10.26 cm² V⁻¹ s⁻¹ with average visible transmittance of ∼87%, and optical band gap of 3.6 eV.     

Influence of iodine on the electrical properties of magnesium phthalocyanines thin film devices

The influence of iodine on the electrical properties of sandwich structures of magnesium phthalocyanine (Mg Pc) thin films with gold and aluminium electrodes has been investigated. The various electrical properties and different electrical parameters of the iodine-doped Mg Pc thin film devices have been estimated and compared with the values of normal Mg Pc devices from the analysis of the current-voltage characteristics. Generally samples showed an asymmetric conductivity both under forward and reverse bias. From our study we found that iodine doped Mg Pc films showed an enhanced electrical conductivity of nearly ten times that of typical Mg Pc. At low voltages the films showed an ohmic conduction with a hole concentration of P₀ = 6.34 × 10¹⁸ m⁻³ and hole mobility μ = 9.16 × 10⁻⁵ m ² V⁻¹ s⁻¹, whereas at higher voltage levels the conduction is dominated by space charged limited conduction (SCLC) with a discrete trapping level of 1.33 × 10²² m⁻³ at 0.63 eV above the valance band edge. The ratio of the free charges to trapped charges (trapping factor) for the doped samples was found to be 1.07 × 10⁻⁷. Furthermore the reverse conduction mechanisms have also been investigated. From the current limitations in the reverse condition a strong rectifying behaviour was evident which was attributed to Poole-Frankel emission with a field-lowering coefficient of value 2.24 × 10⁻⁵ eV m^1/2 V^−1/2.     

Dielectric and conductivity relaxations in PVAc based polymer electrolytes

The polymer electrolytes composed of a blend of poly (vinyl acetate) (PVAc) and poly (methylmethacrylate) (PMMA) as a host polymer and LiClO₄ as a salt are prepared by a solution casting technique. The formation of blend polymer- salt complex has been confirmed by FT-IR spectral studies. The conductivity- temperature plots are found to follow an Arrhenius nature. Arrhenius plot shows the decrease in activation energy with the increase in salt concentration. The dielectric behaviour of the sample is analysed using dielectric permittivity (ε′), dielectric loss (ε″) and electric modulus (M″) of the samples. The impedance cole- cole plot shows the high frequency semi- circle is due to the bulk effect of the material and the depression in the semicircle shows the non-Debye nature of the material. The bulk conductivity is found to vary between 2.5×10⁻⁵ Scm⁻¹ to 1.7×10⁻³ Scm⁻¹ with the increase of salt concentration of blend polymer samples. The migration energy derived from the dissipation factor is almost equal to the activation energy calculated from conductivity. The modulus spectrum of the samples shows the non-Debye behaviour of the polymer electrolyte films. The low frequency dispersion of the dielectric constant implies the space charge effects arising from the electrodes. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Relaxation studies of spray deposited Bi2Co0.1V0.9O5.35 solid electrolyte thin films on stainless steel substrate

The room temperature-stabilized γ-phase ion conducting Bi₂Co_0.1V_0.9O_5.35 thin film was deposited by spray pyrolysis on stainless steel substrate. The intra-grain and grain interior charge transfer was confirmed in these films with impedance spectroscopic measurements done from 1 Hz to 10 MHz in the temperature range 550 K to 741 K. Impedance data further revealed non-Debye kind of relaxation dispersion in the film. The relaxation frequency ranges from 10 to 100 Hz, which predicts long range jumping of the oxygen ions with chemical diffusivity. The Arrhenius plots for relaxation frequency and grain boundary conductivity were found to have same activation energy revealing grain boundary dominant conduction. The effect of polycrystallinity on relaxation dispersion is investigated for the first time on Bi₂Co_0.1V_0.9O_5.35 thin films using impedance formalism.     

An electrochemical study of copper diffusion in non-stoichiometric copper sulphide

The diffusion of copper in hexagonal chalcocite (Cu₂S) is not very well-known. In this work electrochemical cells with natural polycrystalline chalcocite working electrodes have been studied by electrochemical impedance spectroscopy (EIS) over a large frequency range at equilibrium potential. To study this phenomenon between 120 and 160°C a solid electrolyte RbCu₄Cl₅ has been used. The impedance spectra present two distinct regions. At high frequencies the general shape of the diagram in the Nyquist plane is a depleted are of a circle. Changes in electrolyte resistance, interfacial capacitance and transfer resistance have been studied as a function of temperature. At low frequencies, a diffusion impedance is observed attributed to the mobility of copper vacancies. Diffusion coefficients, with an activation energy of 1.7 eV, have been deduced from the impedance diagrams (4.7·10⁻⁵cm² s⁻¹ at 130°C). These results are compared with those obtained with orthorhombic chalcocite between 30 and 60 °C by EIS and using an electrochemical cell with a cupric liquid electrolyte. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Electrical conductivity studies on PVA/PVP-KOH alkaline solid polymer blend electrolyte

A series of conducting thin-film solid electrolytes based on poly (vinyl alcohol)/ poly (vinyl pyrrolidone) (PVA/PVP) polymer blend was prepared by the solution casting technique. PVA and PVP were mixed in various weight percent ratios and dissolved in 20 ml of distilled water. The samples were analyzed by using impedance spectroscopy in the frequency range between 100 Hz and 1 MHz. The PVA/PVP system with a composition of 80% PVA and 20 wt.% PVP exhibits the highest conductivity of (2.2±1.4) × 10⁻⁷ Scm⁻¹. The highest conducting PVA/PVP blend was then further studied by adding different amounts of potassium hydroxide (KOH) ionic dopant. Water has been used as solvent to prepare PVA/PVP-KOH based alkaline solid polymer blend electrolyte films. The conductivity was enhanced to (1.5 ± 1.1) × 10⁻⁴ Scm⁻¹ when 40 wt.% KOH was added. Paper presented at the International Conference on Functional Materials and Devices 2005, Kuala Lumpur, Malaysia, June 6 – 8, 2005.     

Field-emission characteristics of layered systems in high electric fields

A study has been made of the field-emission characteristics of cerium and BaO films on W within a broad range of field-emission currents and fields. An anomalous broadening of the spectra and a deviation of Fowler-Nordheim characteristics from linearity have been revealed for high (above 10⁹ A/m²) field-emission current densities. The dependence of this anomalous behavior of field-emission characteristics on the work function and topography of the surface has been investigated. Possible reasons for the observed phenomena are discussed. Fiz. Tverd. Tela (St. Petersburg) 41, 732–735 (April 1999)