Analysis of electrochemical impedance of polypyrrole|sulfate and polypyrrole|perchlorate films

PPy|SO₄ and PPy|ClO₄ films have been synthesized and investigated in K₂SO₄, ZnSO₄ and NaClO₄ aqueous solutions by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and electron probe microanalysis (EPMA) methods. On the basis of obtained data and calculated impedance parameters as the potential functions, the role of different processes (diffusion of ions, double-layer charging, adsorption and charge transfer) in oxidized, partially reduced and reduced PPy films is estimated. The lowest pseudocapacitance values (from n × 10⁻⁶ to n × 10⁻⁴ μF cm⁻² for 1 μm film), independent of solution concentration, were established for PPy|SO₄ in ZnSO₄. This phenomenon is related with strongly aggravated film reduction process in the solution of double-charged cations. In the case of PPy|ClO₄ in NaClO₄ and PPy|SO₄ in K₂SO₄,where the mono-charged cations participate in redox process, the capacitance values are in the range from: n × 10⁻³ to n × 10⁻² μF cm⁻² and even somewhat higher for PPy|ClO₄ system at oxidized state. The calculated effective diffusion coefficients of ions D remain inside the range from n × 10⁻¹² to n × 10⁻¹⁴ cm² s⁻¹ for PPy|SO₄ in 0.1 M K₂SO₄ and PPy|ClO₄ in 0.1 M NaClO₄ aqueous solution. In the case of PPy|SO₄ film in ZnSO₄ solution the D values are essentially lower.     

The effect of a novel organic compound chiral macrocyclic tetraamide-I interfacial layer on the calculation of electrical characteristics of an Al/tetraamide-I/p-Si contact

The Al/tetraamide-I/p-Si Schottky barrier diode (SBD) has been prepared by adding a solution of a novel nonpolymeric organic compound chiral macrocylic tetraamide-I in chloroform on top of a p-Si substrate and then evaporating the solvent. It has been seen that the forward-bias current–voltage (I–V) characteristics of Al/tetraamide-I/p-Si SBD with a barrier height value of 0.75 eV and an ideality factor value of 1.77 showed rectifying behaviour. The energy distribution of the interface state density determined from I–V characteristics increases exponentially with bias from 5.81 × 10¹² cm⁻² eV⁻¹ at (0.59-E_v) eV to 1.02 × 10¹³ cm⁻² eV⁻¹ at (0.40-E_v) eV. It has showed that space charge limited current (SCLC) and trap charge limited current (TCLC) are the dominant transport mechanisms at large forward-bias voltages.     

The calculation of electronic properties of an Ag/chitosan/n-Si Schottky barrier diode

In this study, the film of chitosan by adding the solution of chitosan being a polymeric compound on the top of an n-Si substrate and then by evaporating solvent was formed. It was seen that the chitosan/n-Si contact demonstrated clearly rectifying behavior and the reverse curves exhibit a weak bias voltage dependence by the current–voltage (I–V) curves studied at room temperature. Average barrier height and ideality factor values for this structure were determined as 0.94 eV and 1.81, respectively. Furthermore, the energy distribution of the interface state density located in the semiconductor band gap at the chitosan/n-Si substrate in the energy range (E_c−0.785) to (E_c−0.522) eV have been determined from the I–V characteristics. The interface state density N_ss ranges from 5.39 × 10¹² cm⁻² eV⁻¹ in (E_c−0.785) eV to 1.52 × 10¹³ cm⁻² eV⁻¹ in (E_c−0.522) eV. The interface state density has an exponential rise with bias from the midgap towards the bottom of the conduction band.     

The calculation of electronic parameters of an Ag/chitin/n-Si Schottky barrier diode

We have formed polymeric organic compound chitin film on n-Si substrate by adding a solution of polymeric compound chitin in N,N-dimethylacetamide and lithium chloride on top of an n-Si substrate and then evaporating solvent. It has been seen that the chitin/n-Si contact has demonstrated clearly rectifying behavior and the reverse curves exhibit a weak bias voltage dependence by the current–voltage (I–V) curves studied at room temperature. The barrier height and ideality factor values of 0.959 eV and 1.553, respectively, for this structure have been obtained from the forward bias I–V characteristics. Furthermore, the energy distribution of the interface state density located in the semiconductor band gap at the chitin/n-Si substrate in the energy range from (E_c − 0.897) to (E_c − 0.574) eV have been determined from the I–V characteristics. The interface state density, N_ss, ranges from 5.965 × 10¹² cm⁻² eV⁻¹ in (E_c − 0.897) eV to 1.706 × 10¹³ cm⁻² eV⁻¹ in (E_c − 0.574) eV and has an exponential rise with bias this energy range.     

Microwave-assisted synthesis of polythiophenes via the Stille coupling

Microwave radiation has been employed to synthesise soluble polythiophenes 1–4 via the Stille coupling, resulting in the preparation of polythiophene 1 with higher molecular weights (M_n > 15,000) and a lower polydispersity (M_w/M_n ≈ 2) than when synthesised using conventional heating. Field-effect mobilities of greater than 3 × 10⁻² cm²/V s were measured for polymer 1 in an organic field-effect transistors (OFETs) device.     

Electrical and impedance spectral characterisation of ITO/DAG/In device

A Schottky device, with configuration ITO/DAG/In is fabricated using diazopheny diamino glyoxime (DAG) as an n-type organic material. Current–voltage characteristics and impedance spectroscopy measurements were carried out, which reveals that the injection and transport properties are dominated by negative charge carriers. Space charge limited current theory with an exponential distribution of traps is very well followed by observations resulted through current–voltage characteristics at high voltage region. This gives a traps density N_t of about 4.5×10²¹ m⁻³ and mobility of electron is about 3.9×10⁻¹⁰ m² V⁻¹ s⁻¹. It is found that DAG behaves as an n-type materials as it forms Schottky barrier with ITO (high work function electrode) and conduction is governed by majority carriers, i.e. electrons. Using temperature and bias dependence of impedance spectral characteristics in a broad frequency range, i.e. 40 Hz to 100 kHz, it is found that the ac behaviour of In/DAG/ITO device shows several features, described by the simple double RC circuit representing a depleted junction region and an undepleted bulk region. From the large frequency range of impedance spectroscopy two distinct processes were identified, corresponding to bulk DAG layer and junction region. The activation energy of the relaxation times coincides well with the results obtained from the temperature dependent dc conductivity. The temperature dependent capacitance–voltage measurements were analysed at a frequency of 40 Hz. The obtained inherent donor concentration from 1/C²–V plots varies from 1.8×10²³ m⁻³ at room temperature to 5.9×10²³ m⁻³ at 360 K.     

Interstitial and substitutional diffusion of metallic solutes in Ti3Al

Solute diffusion of Ni, Fe and Nb in the intermetallic compound Ti₃Al was studied. The diffusion measurements of Ni and Fe were performed with radiotracers applying the standard precision grinding technique for sectioning, while the concentration profiles of Nb in Ti₃Al were analysed through in-depth profiling by secondary ion mass spectrometry (SIMS). Ni and Fe exhibit fast diffusion behaviour of about 4 and 2 orders of magnitude, respectively, larger than titanium self-diffusion. The temperature dependencies of the diffusion coefficients yield the Arrhenius parameters D₀^Ni=1.76 × 10⁻⁵ m²/s, Q^Ni=195 kJ/mol and D₀^Fe=1.96 × 10⁻³ m²/s, Q^Fe=277.2 kJ/mol, respectively. The high mobility of these solutes with comparatively small atomic radii suggests in the D0₁₉-structure of Ti₃Al some type of interstitial diffusion that is discussed in the context of results of analogous diffusion investigations in α-Ti. Nb-diffusion coefficients in Ti₃Al were found to be lower by about one order of magnitude than self-diffusion. The Arrhenius relation is characterized by D₀^Nb=3.15 × 10⁻⁴ m²/s and Q^Nb=338.7 kJ/mol. It is concluded that Nb-diffusion occurs substitutionally via thermal vacancies in the Ti-sublattice.     

Controlling of silicon–insulator–metal junction by organic semiconductor polymer thin film

Electrical and photovoltaic properties of a metal–semiconductor–insulator–polymer–metal diode were investigated. The n-Si/SiO₂/MEH-PPV/Al diode shows a rectifying behavior with the rectification ratio of 2.22 × 10⁵ at ±5 V and exhibits a non-ideal behavior due to the series resistance and oxide-organic layers. The organic semiconductor makes a contribution to the I–V characteristics of the diode and the trap-charge limited space charge and space charge limited current mechanisms were observed for the diode. The current–voltage characteristics of the n-Si/SiO₂/MEH-PPV/Al diode under different illumination intensities give an open circuit voltage (V_oc) along with a short circuit current (I_sc). This suggests that the n-Si/SiO₂/MEH-PPV/Al diode is a photovoltaic device with V_oc = 0.456 V and J_sc = 7.89 × 10^?8 A/cm² values under 100 mW/cm² illumination intensity. The photoconductivity mechanism of the diode is controlled by monomolecular recombination. The interface state density D_it values with time constant τ_it of the diode under dark and illumination conditions were found to be 2.53 × 10¹⁰ eV^?1 cm^?2 with 5.09 × 10^?5 s and 2.50 × 10¹⁰ eV^?1 cm^?2 with 8.27 × 10^?5 s, respectively. The obtained results indicate that the n-Si/SiO₂/MEH-PPV/Al diode is a photo-sensitive diode.     

Synthesis and characterization of triphenylamine derivatives by oxidative polymerization

Hole transport polymers consisting of 4-methoxytriphenylamine (P-MOTPA) and 4-n-butyltriphenylamine (P-BTPA) were synthesized by oxidative coupling reaction using FeCl₃ as an oxidant. These polymers had good solubility and their thin films showed sufficient morphological stability. ¹H NMR and ¹³C NMR revealed that the monomers were exclusively connected at the p-positions of unsubstituted phenyl groups. Polymers had UV absorption maximum around 370 nm. Cyclic voltammograms of polymers showed well-defined pairs of reduction and oxidation peaks at 1.1 V versus Ag/AgCl, indicating that the polymers are electrochemically active. P-MOTPA and P-BTPA had hole drift mobility of being 4.04 × 10⁻⁵ and 2.98 × 10⁻⁵ cm²/V s at the electric field of 50 V/μm, respectively.     

Synthesis,characterization and evaluation of cation-ordered LnBaCo2O5+δ as materials of oxygen permeation membranes and cathodes of SOFCs

LnBaCo₂O_5+δ (Ln = La, Pr, Nd, Sm, Gd, and Y) was synthesized via an EDTA–citrate complexing process. The particular Ln³⁺ dopant had a significant effect on the oxide’s phase structure/stability, oxygen content, electrical conductivity, oxygen permeability, and cathode performance. Stable, cation-ordered oxides with layered lattice structures were obtained with medium-sized Ln³⁺ ions over a wide range of oxygen partial pressures, a property essential for applications as oxygen separation membranes and solid oxide fuel cell (SOFC) cathodes. PrBaCo₂O_5+δ demonstrated the highest oxygen flux (∼5.09 × 10⁻⁷ mol cm⁻² s⁻¹ at 900 °C), but this value was still significantly lower than that of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ perovskite (∼3.1 × 10⁻⁶ mol cm⁻² s⁻¹ at 900 °C). The observed difference was attributed to the much longer diffusion distance through a polycrystalline membrane with a layered lattice structure than through cubic perovskite because bulk diffusion was the rate-limiting step of permeation. An area-specific resistance of ∼0.213 Ω cm² was achieved at 600 °C with a PrBaCo₂O_5+δ cathode, suggesting that the layer-structured oxides were promising alternatives to ceramic membranes for SOFC cathodes.     

Z-scan measurements of third-order optical non-linearities in poly(phenylacetylenes)

Poly(phenylacetylene) (PPA) and poly(p-methoxyphenylacetylene) (PMOPPA) were synthesized by catalytic polymerization of monosubstituted alkynes and were fully characterized by conventional techniques. Linear and third-order non-linear optical properties of polymers solutions were investigated at λ=780 nm using a Z-scan set-up equipped with a femtosecond laser source at different operating regimes. A high repetition rate (76 MHz) regime was used to measure the linear and non-linear absorption coefficients by means of thermo-optical effects. Values of the linear and non-linear absorption coefficients were α=4.9×10⁻³ cm⁻¹ and β=1.1×10⁻¹¹ cm W⁻¹ for PPA and α=2×10⁻² cm⁻¹ and β=2.1×10⁻¹⁰ cm W⁻¹ for PMOPPA. Very low repetition rate (14 Hz) excitation was used to evidence the purely-optical non-linear refractive indexes, that were γ=6×10⁻¹⁸ cm² W⁻¹ and γ=11×10⁻¹⁸ cm² W⁻¹, respectively, for PPA and PMOPPA.     

Alkyl chain length dependence of the field-effect carrier mobility in regioregular poly(3-alkylthiophene)s

The field-effect mobility of holes in regioregular poly(3-alkylthiophene)s was determined for a series of 5 alkyl chain lengths from C₄ (n-butyl) to C₁₂ (n-dodecyl). Contrary to a previous report, a non-monotonic dependence of field-effect mobility on alkyl chain length was found. The average hole mobility varied from 1.2 × 10⁻³ cm²/Vs in poly(3-butylthiophene) and 1 × 10⁻² cm²/Vs in poly(3-hexylthiophene) to 2.4 × 10⁻⁵ cm²/Vs for poly(3-dodecylthiophene). We believe that the hexyl side chain is optimum for charge transport because of better self-organization in poly(3-hexylthiophene) compared to other polymers in the series. The present results provide an important structure–carrier mobility relationship for the regioregular poly(3-alkylthiophene)s which are of wide interest for thin film transistors and photovoltaic cells.     

Hydrogen diffusion coefficients through Inconel 718 in different metallurgical conditions

We report hydrogen permeation studies through cold rolled, solutionized, and precipitation hardened Inconel 718 foils. The effective hydrogen diffusion coefficient is considerably higher (5.3–6.8 × 10⁻¹¹ cm²/s) for the solutionized Inconel 718 than for either the cold rolled (3.3–4.2 × 10⁻¹¹ cm²/s) or precipitation hardened (2.1–2.9 × 10⁻¹¹ cm²/s) specimens. Microstructural studies indicate that the reduced hydrogen diffusion coefficients in the latter specimens arise from hydrogen trapping at dislocations and precipitates that are present at much lower concentrations in the solutionized specimens. Also, repeated permeation transients provide evidence for irreversible hydrogen trapping in the cold rolled and precipitation hardened specimens, but such effects are insignificant in the solutionized specimens.     

Laser doping of chromium as a double acceptor in silicon carbide with reduced crystalline damage and nearly all dopants in activated state

Chromium, a p-type dopant, has been incorporated into silicon carbide by laser doping. Secondary ion mass spectrometric data revealed enhanced solid solubility (2.29 × 10¹⁹ cm⁻³ in 6H–SiC and 1.42 × 19¹⁹ cm⁻³ in 4H–SiC), exceeding the equilibrium limit (3 × 10¹⁷ cm⁻³ in 6H–SiC above 2500 °C). The roughness, surface chemistry and crystalline integrity of the doped sample were examined by optical interferometry, energy dispersive X-ray spectrometry and transmission electron microscopy, respectively, and showed no crystalline disorder due to laser heating. Deep-level transient spectroscopy confirmed Cr as a deep-level acceptor with activation energies E_v + 0.80 eV in 4H–SiC and E_v + 0.45 eV in 6H–SiC. The Hall effect measurements showed that the hole concentration (1.942 × 10¹⁹ cm⁻³) is almost twice the average Cr concentration (1 × 10¹⁹ cm⁻³), confirming that almost all of the Cr atoms were completely activated to the double acceptor state by the laser-doping process without requiring any additional annealing step.     

Photovoltaic devices based on polythiophenes and substituted polythiophenes

In recent years there has been considerable interest in the fabrication of photovoltaic devices using polymeric and organic materials. This paper presents work carried out using a range of polythiophenes, including some substituted with porphyrin moieties as light harvesters. Homopolymers and copolymers were investigated for their performance in photovoltaic devices, and the use of both solid polymer electrolyte and liquid electrolyte was examined. Both photoelectrochemical cells and Schottky devices were investigated. The best photoelectrochemical cell was fabricated using polyterthiophene which had V_oc=139 mV, I_sc=123.4 μA cm⁻², fill factor=0.38, and energy conversion efficiency=0.02% at a halogen lamp intensity of 317 W m⁻². The Schottky device gave a V_oc=0.5 V and I_sc of 0.98 μA cm⁻² at a halogen lamp intensity of 500 W m⁻².     

Micrometer-scaled OFET channel patterns fabricated by using PEDOT/PSS microfibers

We have easily fabricated channel patterns of organic field-effect transistors (OFETs), in which channel lengths were 5 μm, by using wet-spun poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS) microfibers with diameters of ca. 5 μm. Pentacene-based FETs with a top-contacted configuration, showed a hole mobility of 0.13 cm² V^?1 s^?1 and on/off current ratio of 9.4 × 10⁴. The device also showed large current of ca. 160 μA (V_D = ?50 V; V_G = ?50 V), reflecting shorter channel length of the devices. We have evaluated self-assembled monolayer (SAM) through measurements of water contact angle and by Zisman plot. As a result, critical surface tension of the octadecyltrichlorosilane (OTS)-treated SiO₂ surface is 17 mN m^?1 which is consistent with that of well-known SAM. We also well analyzed the cross-sections of the device by a scanning transmission electron microscopic (STEM) technique. The results indicated that the thicknesses of the pentacene layer in the channel part and Au layer in the source/drain part were ca. 30 and 30 nm, respectively. Furthermore, it is also indicated that the 100-nm grains of the pentacene were well adhered on the surface of the SAM-formed SiO₂ layer.     

Oliogothiophenes end-capped with arylacetylenes for organic thin film transistors

Phenylethynyl, butylphenylethynyl and pentafluorophenylethynyl end-capped terthiophene oligomers (PATTP, BPATTP and FPATTP) have been synthesized and characterized. Their physical, optical and electrochemical properties varied with the end substituents were investigated. DSC results revealed that three compounds were crystalline in the film state and thermally stable by 200 °C under nitrogen atmosphere. The oligothiophenes have exhibited H-aggregation, which was verified by significant blue-shift in UV–vis absorption spectra in the films, indicating a close side-to-side molecular packing. X-ray diffraction measurement on the films has revealed molecular edge-on substrate growth orientation. Top-contact field-effect transistors were demonstrated by spin-coating or ink-jetting the solution of the oligomers. The preliminary results showed that PATTP and BPATTP can serve as p-type carriers with hole-motility as 3 × 10^?4 and 1 × 10^?2 cm²/(V s), respectively, while pentafluorophenylacetylene afforded FPATTP as n-type carriers with electron-motility around 10^?5 cm²/(V s).     

High-temperature thermoelectric properties of Sr2RuYO6 and Sr2RuErO6 double perovskites influenced by structure and microstructure

The high-temperature thermoelectric properties of Sr₂RuYO₆ and Sr₂RuErO₆ double perovskites were evaluated and reported for the first time. These compounds show high Seebeck coefficients not only at room temperature, but also at high temperature (for Sr₂RuYO₆, S_RT ≈ ?475 μV K^?1 and S_1200K ≈ ?250 μV K^?1; Sr₂RuErO₆, S_RT ≈ ?400 μV K^?1 and S_1200K ≈ ?250 μV K^?1). The n-type semiconducting behaviour dominates the resistivity values. Both compounds crystallize in a monoclinic unit cell (space group P2₁/n). The lattice parameters are a = 5.7761(2), b = 5.7804(1), c = 8.1689(1), α = γ = 90° and β = 90.2087(8)° for the Sr₂RuYO₆, and a = 5.7760(1), b = 5.7722(0), c = 8.1544(4), α = γ = 90° and β = 90.2099(7)° for Sr₂RuErO₆. The unit cell can be described approximately as √2a_p × √2a_p × 2a_p, where a_p is the unit cell parameter of the ideal cubic perovskite structure. High-resolution transmission electron microscopy shows an interesting three-dimensional micro-twin-domain texture where the c axis is placed in the three space directions. Structural transitions at high temperatures (T_t(Sr₂RuYO₆) ≈920 K and T_t(Sr₂RuErO₆) ≈890 K) are observed by specific heat measurement in both compounds, which are found to have a strong influence on the Seebeck coefficient and electrical conductivity.     

Electrical properties,sintering and thermal expansion behavior of composite ceramic interconnecting materials,La0.7Ca0.3CrO3−δ/Y0.2Ce0.8O1.9 for SOFCs

This paper presents a high-performance interconnect ceramic for solid oxide fuel cells (SOFCs), based on a modification of La_0.7Ca_0.3CrO_3−δ (LCC). It was found that addition of a small amount of YDC (Y_0.2Ce_0.8O_1.9) into LCC dramatically increased the electrical conductivity. For the best system, LCC + 3 wt.% YDC, the electrical conductivity reached 104.8 S cm⁻¹ at 800 °C in air. The electrical conductivity of the specimen with 2 wt.% YDC in H₂ at 800 °C was 5.9 S cm⁻¹. With the increase of YDC content, the relative density increased, reaching 97.6% when the YDC content was 10 wt.%. The average coefficient of thermal expansion (CTE) at 30–1000 °C in air increased with YDC content, ranging from 11.12 × 10⁻⁶ K⁻¹ to 15.34 × 10⁻⁶ K⁻¹. The oxygen permeation measurement illustrated a negligible oxygen ionic conduction, indicating that it is still an electronically conducting ceramic. Therefore, it is a very promising interconnecting ceramic for SOFCs.     

Kinetic study of the electrochemical degradation of polyaniline

The kinetics of the electrochemical degradation of polyaniline (PANI) layers, deposited by electropolymerization and chemical polymerization onto platinum electrode, was investigated in an acid aqueous solution. The degradation rate was shown to depend greatly on the electrode potential applied. First-order rate constants of degradation, obtained from the kinetic data, were shown to vary between 2.87×10⁻⁵ and 3.11×10⁻³ s⁻¹ for thick PANI films, having the electrochemical charge density of 14 mC/cm², and between 2.0×10⁻⁵ and 3.60×10⁻³ s⁻¹ for thin PANI films, having the charge density of 1.5 mC/cm², within the electrode potential range of 0.3–0.9 V versus Ag/AgCl. Two linear regions were found to present on the dependencies of logarithm of the first-order degradation rate constant on electrode potential, one of them having a slope of 0.44 and 1.34 V⁻¹ within electrode potential limits of 0.3–0.6 V, and another one having a slope of 6.37 and 6.39 V⁻¹ within potential limits of 0.6–0.9 V, for thick and thin polymer films, respectively. The results obtained show that the electrochemical degradation of PANI films proceed at a remarkable rate even at low electrode potential values.