Substrate dependent structure and in-plane dielectric properties of Ba(Sn0.15Ti0.85)O3 thin films

The structure, microstructure and in-plane dielectric properties of Barium tin titanate Ba(Sn_0.15Ti_0.85)O₃ (BTS) thin films grown on (100) LaAlO₃ (LAO) and (100) MgO single crystal substrates through sol–gel process were investigated. The films deposited on (100) LAO substrate exhibited a strong (100) preferred orientation while the film deposited on (100) MgO substrate showed polycrystalline structure. The in-plane ɛ–T measurements reveal that the films grown on (100) LAO substrate exhibited an obvious room-temperature ferroelectric state, while the film grown on MgO substrate showed paraelectric state in the temperature range of 10–130 °C. A high tunability of 52.11% was observed for the BTS films deposited on (100) LAO substrate at the frequency of 1 MHz with an applied electric field of 80 kV/cm, which is about two times larger than that of the BTS films deposited on (100) MgO substrate. The obvious differences in the dielectric properties could be attributed to the stress in the films, which come from lattice mismatch and difference in the thermal expansion coefficients between the film and substrates. This work clearly reveals the highly promising potential of BTS films for application in tunable devices.     

Ion–electron transport in strontium ferrites: relationships with structural features and stability

The total electrical conductivity of strontium ferrites, including intergrowth Sr₄Fe₆O_13+δ, Sr₃Fe₂O_6+δ with a Ruddlesden–Popper structure, and SrFeO_2.5+δ where the cubic perovskite lattice transforms into vacancy-ordered brownmillerite at p(O₂)<10 Pa and T<850 °C, was measured at 650–1000 °C in the oxygen partial pressure range 10⁻¹⁵ Pa to 50 kPa. The data were used in order to determine partial ion, p- and n-type electron contributions in the vicinity of electron–hole equilibrium point. The ferrites with brownmillerite and Ruddlesden–Popper structures exhibit substantial ion transport due to thermally-activated disordering of oxygen vacancies and oxygen ions in the perovskite structural slabs, whereas the ion conductivity of Sr₄Fe₆O_13+δ remains below 0.01 S cm⁻¹ in the studied conditions. The bonding energy of oxygen ions, evaluated from the formation enthalpy of n-type charge carriers, increases in the sequence Sr₄Fe₆O_13+δ<SrFeO_3+δ<Sr₃Fe₂O_6+δ. These values correlate with thermodynamic stability of strontium ferrites at low p(O₂). The transition of SrFeO_2.5+δ brownmillerite into disordered cubic phase above 850 °C leads to higher stability in reducing atmospheres. The level of p-type conductivity is mainly governed by the concentration of electron holes, which was calculated from the oxygen content determined by coulometric titration technique. The hole mobility, which is quite similar for all strontium ferrites and has a temperature-activated character, varies in the range 0.005–0.05 cm² V⁻¹ s⁻¹ indicative of small-polaron conduction mechanism.     

Fabrication of highly conductive Ru/a-CNx:H composite films by anode deposit

Ruthenium(0) composite hydrogenated amorphous carbon nitride (Ru/a-CN_x:H) films were deposition on single crystal silicon (1 0 0) substrate by electrochemical deposition technique with acetonitrile as carbon source, and Ru₃(CO)₁₂ as dopant. In the deposited progress, the Si (1 0 0) acted as anode. The relative atomic ratio of Ru/N/C was about 0.28/0.33/1, and Ru nanocrystalline particles about 8 nm were homogeneously dispersed into the amorphous carbon matrix. After doping Ru into a-CN_x:H films, the conductivity of the films were evidently improved and the resistivity drastically decrease from 10⁸ Ω cm to about 100 Ω cm.     

Synthesis and structural mechanisms of the 2201-type ferrites and polytypes: Fe2(Sr2 − xAx)FeO6.5 − δ/2 (A = Ba,La, Tl,Pb and Bi)

The Fe₂(Sr_2 ? xA_x)FeO_6.5 ? δ/2 systems have been investigated, by doping the iron rich 2201-type parent structure with Ba²⁺, La³⁺ and 5d¹⁰ post-transition cations. The syntheses have been carried out up to the limit of the 2201-type solid solutions, in order to test the role of the double iron layer Fe₂O_2.5 ? δ/2. The localisation of the charge carriers in these compounds is consistent with their strong antiferro-magnetism. The investigation was then carried out in the transition part of the diagram up to the formation of stable phases. The study of structural mechanisms was carried using high resolution electron microscopy (transmission and scanning transmission), electron diffraction and energy dispersive spectroscopy. Different non-stoichiometry mechanisms are observed, depending on the electronic structure and chemical properties of the doping elements. The specific behavior of the modulated double iron layer is discussed.     

Fe-doped SnO2 transparent semi-conducting thin films deposited by spray pyrolysis technique: Thermoelectric and p-type conductivity properties

In this paper, we report structural, electrical, optical, and especially thermoelectrical characterization of iron (Fe) doped tin oxide films, which have been deposited by spray pyrolysis technique. The doping level has changed from 0 to 10 wt% in solution ([Fe]/[Sn] = 0–40 at% in solution). The thermoelectric response versus temperature difference has exhibited a nonlinear behavior, and the Seebeck coefficient has been calculated from its slope in temperature range of 300–500 K. The Hall effect and thermoelectric measurements have shown p-type conductivity in SnO₂:Fe films with [Fe]/[Sn] ≥ 7.8 at%. In doping levels lower than 7.8 at%, SnO₂:Fe films have been n-type with a negative thermoelectric coefficient. The Seebeck coefficient for SnO₂:Fe films with 7.8 at% doping level has been obtained to be as high as +1850 μV/K. The analysis of as-deposited samples with thicknesses ～350 nm by X-ray diffraction (XRD) and scanning electron microscopy (SEM) has shown polycrystalline structure with clear characteristic peak of SnO₂ cassiterite phase in all films. The optical transparency (T%) of SnO₂:Fe films in visible spectra decreases from 90% to 75% and electrical resistivity (ρ) increases from 1.2 × 10^?2 to 3 × 10³ Ω cm for Fe-doping in the range 0–40 at%.     

Nonstoichiometry,point defects and magnetic properties in Sr2FeMoO6−δ double perovskites

The phase stability, nonstoichiometry and point defect chemistry of polycrystalline Sr₂FeMoO_6?δ (SFMO) was studied by thermogravimety at 1000, 1100, and 1200 °C. Single-phase SFMO exists between ?10.2≤log pO₂≤?13.7 at 1200 °C. At lower oxygen partial pressure a mass loss signals reductive decomposition. At higher pO₂ a mass gain indicates oxidative decomposition into SrMoO₄ and SrFeO_3?x. The nonstoichiometry δ at 1000, 1100, and 1200 °C was determined as function of pO₂. SFMO is almost stoichiometric at the upper phase boundary (e.g. δ=0.006 at 1200 °C and log pO₂=?10.2) and becomes more defective with decreasing oxygen partial pressure (e.g. δ=0.085 at 1200 °C and log pO₂=?13.5). Oxygen vacancies are shown to represent majority defects. From the temperature dependence of the oxygen vacancy concentration the defect formation enthalpy was estimated (ΔH_OV=253±8 kJ/mol). Samples of different nonstoichiometry δ were prepared by quenching from 1200 °C at various pO₂. An increase of the unit cell volume with increasing defect concentration δ was found. The saturation magnetization is reduced with increasing nonstoichiometry δ. This demonstrates that in addition to Fe/Mo site disorder, oxygen nonstoichiometry is another source of reduced magnetization values.     

Solution synthesis and electrical properties of K2NiF4 type LaSrAlO4

K₂NiF₄ type LaSrAlO₄ was synthesised by sol–gel and combustion methods at 1300 °C and characterised by X-ray diffraction (XRD). DC electrical conductivity studies revealed that LaSrAlO₄ is an n-type conductor at low oxygen partial pressures and a p-type conductor at near atmospheric pressures with conductivity of the order of 10⁻⁴ S cm⁻¹. Dilatometric measurements indicated a nonlinear increase in the thermal expansion coefficient, corroborated by a nonlinear expansion along the a axis determined by high temperature XRD. Attempts to synthesise oxygen excess La_1+xSr_1−xAlO_4+δ phases by varying the La:Sr ratio always resulted in a La₂O₃ secondary impurity phase.     

Raman spectra of carriers in ionic-liquid-gated transistors fabricated with poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene)

We observed the Raman spectra of carriers, positive polarons and bipolarons, generated in a poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT-C14) film by FeCl₃ vapor doping. Electrical conductivity and Raman measurements indicate that the dominant carriers in the conducting state were bipolarons. We identified positive polarons and bipolarons generated in an ionic-liquid-gated transistor (ILGT) fabricated with PBTTT-C14 as an active semiconductor and an ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [BMIM][TFSI] as a gate dielectric using Raman spectroscopy. The relationship between the source−drain current (I_D) at a constant source−drain voltage (V_D) and the gate voltage (V_G) was measured. I_D increased above −V_G = 1.1 V and showed a maximum at −V_G = 2.0 V. Positive polarons were formed at the initial stage of electrochemical doping (−V_G = 0.8 V). As I_D increased, positive bipolarons were formed. Above V_G = −2.0 V, bipolarons were dominant. The charge density (n), the doping level (x), and the mobility of the bipolarons were calculated from the electrochemical measurements. The highest mobility (μ) of bipolarons was 0.72 cm² V⁻¹ s⁻¹ at x = 110 mol%/repeating unit (−V_G = 2.0 V), whereas the highest μ of polarons was 4.6 × 10⁻⁴ cm² V⁻¹ s⁻¹ at x = 10 mol%.     

High-temperature transport and stability of SrFe1−xNbxO3 − δ

The conductivity is measured in the series of solid solutions SrFe_1 ? xNb_xO_3 ? δ, where x = 0.05, 0.1, 0.2, 0.3, 0.4, within the oxygen partial pressure limits 10^?18–0.5 atm and temperature range 650–950 °C. The contributions to the total conductivity from oxygen ions, electrons and electron holes are obtained based on their different pressure dependences. The doped derivative with x = 0.1 is found to be a singular composition where ion conductivity attains a maximal value while activation energy for ion transport is minimal. This peculiar behavior is attributed to formation of favorable microstructure in the oxide. The deeper doping results in deterioration of ion transport, which is explained by oxygen vacancy filling. It is shown that replacement of iron for niobium favors enhanced thermodynamic stability towards reduction. The oxygen permeability is evaluated from the conductivity data, and it achieves rather high values in the doped derivatives. These oxides can, therefore, be recommended for further evaluation as oxygen separating membrane materials for partial oxidation of natural gas.     

Effect of Annealing on the Electrical Properties of CuxS Thin Films

Copper sulphide CuS was deposited on three substrates; glass, Indium Tin Oxide (ITO) and Ti by using spray pyrolysis deposition (SPD). After depositing CuS thin films on the substrates at 200 °C, they were annealed at 50, 100, 150, and 200 °C for 1 hour. Structural measurements revealed covellite CuS and chalcocite Cu₂S phases for thin films before and after annealing at 200 °C with changes in intensities, and only covellite CuS phase for thin films after annealing at 50, 100, and 150 °C. Morphological characteristics show hexagonal-cubic crystals for the CuS thin film deposited on glass substrate and plates structures for films deposited on ITO and Ti substrates before annealing, these crystals became bigger in size and there were be oxidation and some agglomerations in some regions with formation of plates for CuS on glass substrate after annealing at 200 °C. For Hall Effect measurements, thin films sheet resistivity and mobility increased after annealing while the carrier concentration decreased. Generally, the thin film deposited on ITO substrate had the lowest resistivity and the highest carrier concentration before and after annealing. The thin film deposited on Ti substrate had the highest mobility before and after annealing, which makes it the best thin film for device performance. The objective of this research is to show the improvement of thin films electrical properties especially the mobility after annealing those thin films.     

Controlling macropore formation in patterned n-type silicon: Existence of a pitch-dependent etching current density lower bound

Experimental results on back-side illumination electrochemical etching of patterned (hole square-lattices with pitch p from 2 to 50 μm) n-type silicon substrates in HF-based electrolytes are reported. Experiments reveal the existence of a threshold current density J_pitch, which is strictly correlated to the pattern pitch, above which pore formation can be finely controlled beyond commonly accepted state-of-the-art rules. For instance, using the same silicon substrate, pore array with density D spanning over two orders of magnitude (from 0.0025 μm^? 2 up to of 0.25 μm^? 2) can be etched above a minimum porosity P_min, and, in turn, a minimum pore diameter d_min, which depends on the pattern pitch. Etching current densities below such a critical value give rise to uncontrolled pore growth. The occurrence of the threshold current density J_pitch is interpreted in terms of current burst model.     

Optoelectronic and nonlinear optical properties of tBu4PcTiO/polymer composite materials

The optoelectronic and nonlinear optical (NLO) properties of a soluble 2,(3)-(tetra-tert-butylphthalocyaninato)titanium(IV) oxide (tBu₄PcTiO) in solutions and in the solid states have been described. The nonlinear response demonstrated that tBu₄PcTiO exhibited strong RSA at 532 nm for both solution and solid-state based experiments. The decrease in the effective intensity dependent nonlinear absorption coefficient with increasing input intensities possibly results from high order triple state transitions of the excited-state population. No evidence of film fatigue or degradation was observed in the PMMA/tBu₄PcTiO film, after numerous scans at varying laser intensity. The doping of tBu₄PcTiO into poly[2-methoxy-5-(2′-ethylhexyloxy)-p-phenylene-vinylene] (MEH-PPV) results in the apparent increases of the open circuit voltage (Voc) and the short circuit photocurrent density under illumination with 40 mW cm⁻² white-light. The light absorption of tBu₄PcTiO incorporated into polymer represents the dominant contribution to the enhancement of the photocurrent. The dependence of the short circuit photocurrent in an ITO/tBu₄PcTiO-doped MEH-PPV/Al cell on the incident light intensity (I_in) between 30 and 200 mW cm⁻² was also investigated.     

Fabrication of solid thin film electrolyte and LiCoO2 by aerosol flame pyrolysis deposition

Aerosol flame pyrolysis deposition method was applied to deposit the oxide glass electrolyte film and LiCoO₂ cathode for thin film type Li-ion secondary battery. The thicknesses of as-deposited porous LiCoO₂ and Li₂O–B₂O₃–P₂O₅ electrolyte film were about 6 μm and 15 μm, respectively. The deposited LiCoO₂ was sintered for 2 min at 700 °C to make partially densified cathode layer, and the deposited Li₂O–P₂O₅–B₂O₃ glass film completely densified by the sintering at 700 °C for 1 h. After solid state sintering process the thicknesses were reduced to approximately 4 μm and 6 μm, respectively. The cathode and electrolyte layers were deposited by continuous deposition process and integrated into a layer by co-sintering. It was demonstrated that Aerosol flame deposition is one of the good candidates for the fabrication of thin film battery.     

Study on the effect of Li doping in spinel Li4+xTi5−xO12 (0 ⩽ x ⩽ 0.2) materials for lithium-ion batteries

The effect of Li doping in spinel Li_4+xTi_5−xO₁₂ (0 ⩽ x ⩽ 0.2) materials on the structural and electrochemical properties were investigated. The ratio of the capacity in the voltage plateau (1.5 V) to the overall discharge capacity for Li_4.1Ti_4.9O₁₂ (x = 0.1) and Li_4.2Ti_4.8O₁₂ (x = 0.2) were higher than that of Li₄Ti₅O₁₂ especially at high current rates due to their enhanced lithium-ion and electronic conductivity by the substitution of Ti atoms by Li atoms. With the increasing of Li doping amount, lithium-ion and electronic conductivity of Li_4+xTi_5−xO₁₂ increased, however its cycling stability was depressed when the Li doping was of x = 0.2. The Li doping of x = 0.1, the appropriate Li doping amount, showed improved rate capability and better high rate performance comparing to undoped Li_4+xTi_5−xO₁₂ (x = 0).     

Electronic absorption study on acid–base equilibria for some pyrimidine derivatives containing semi- and thiosemicarbazone moiety

The UV–vis spectra of recently synthesized 5-benzoyl-1-(methylphenylmethyleneamino)-4-phenyl-1H-pyrimidine-2-one, (I), and 5-benzoyl-1-(methylphenylmethyleneamino)-4-phenyl-1H-pyrimidine-2-thione, (II) were studied in aqueous methanol (5%, v/v methanol). The nature of the electronic transitions and the roles of carbonyl oxygen of I and thiocarbonyl sulfur of II on the behavior of UV–vis spectra were discussed.Acid–base equilibria of the compounds against varying pH and pK_a values related equilibria were determined at an ionic strength of 0.10 M by using the Henderson–Haselbalch equation. The mean acidity constants for the protonated forms of the compounds were determined as pK_a1 = 5.121, pK_a2 = 7.929 and pK_a3 = 11.130 for I and pK_a1 = 4.684, pK_a2 = 7.245 and pK_a3 = 10.630 for II. The preferred dissociation mechanisms were discussed based on UV–vis data and a mechanism was proposed for each compound.     

Potentiometric study of acid–base equilibria in the {KCl + LiCl} eutectic melt at temperatures in the range (873 to 1073) K

Some heterogeneous reactions of oxide ion exchange (carbonate ion dissociation and magnesium oxide dissolution) in the molten {KCl + LiCl} eutectic at temperatures of (873, 973 and 1073) K were studied using an electrochemical cell with an oxygen membrane electrode Pt(O₂)|ZrO₂(Y₂O₃). The dissociation constant of the CO₃²⁻ was found to increase with increasing temperature: pK (873 K)=(2.39 ± 0.05); pK (973 K)=(1.81 ± 0.09); pK (1073 K)=(1.53 ± 0.08). Removal of CO₂ from the gas above the melt allows the complete transformation of CO₃²⁻ to O²⁻. pP_MgO values decrease more from (6.99 ± 0.08) to (5.41 ± 0.04). The oxobasicity indices, pI_(KCl+LiCl), were calculated from the solubility data to be 3.2 at 873 K, 3.4 at 973 K, and 3.6 at 1073 K. This trend suggests an increase in acidity with increasing temperature of {KCl + LiCl}.     

Rapid microwave-solvothermal synthesis of phospho-olivine nanorods and their coating with a mixed conducting polymer for lithium ion batteries

Olivine LiFePO₄ nanorods have been synthesized, for the first time, by a rapid microwave-solvothermal approach within 5 min at temperatures as low as 300 °C without requiring any inert atmosphere or post annealing at elevated temperatures in reducing gas atmospheres. The resulting LiFePO₄ nanorods have subsequently been encapsulated within a mixed electronically and ionically conducting p-toluene sulfonic acid (p-TSA) doped poly(3,4-ethylenedioxythiophene) (PEDOT) at ambient-temperatures to obtain an organic–inorganic nanohybrid. The LiFePO₄–PEDOT nanohybrid offers discharge capacity (166 mA h/g) close to the theoretical value (170 mA h/g) with excellent capacity retention and rate capability, reducing significantly the manufacturing cost.     

Redox behavior and transport properties of La0.5−2xCexSr0.5+xFeO3−δ and La0.5−2ySr0.5+2yFe1−yNbyO3−δ perovskites

The effects of doping the mixed-conducting (La,Sr)FeO_3−δ system with Ce and Nb have been examined for the solid-solution series, La_0.5−2xCe_xSr_0.5+xFeO_3−δ (x = 0–0.20) and La_0.5−2ySr_0.5+2yFe_1−yNb_yO_3−δ (y = 0.05–0.10). Mössbauer spectroscopy at 4.1 and 297 K showed that Ce⁴⁺ and Nb⁵⁺ incorporation suppresses delocalization of p-type electronic charge carriers, whilst oxygen nonstoichiometry of the Ce-containing materials increases. Similar behavior was observed for La_0.3Sr_0.7Fe_0.90Nb_0.10O_3−δ at 923–1223 K by coulometric titration and thermogravimetry. High-temperature transport properties were studied with Faradaic efficiency (FE), oxygen-permeation, thermopower and total-conductivity measurements in the oxygen partial pressure range 10⁻⁵–0.5 atm. The hole conductivity is lower for the Ce- and Nb-containing perovskites, primarily as a result of the lower Fe⁴⁺ concentration. Both dopants decrease oxide-ion conductivity but the effect of Nb-doping on ionic transport is moderate and ion-transference numbers are higher with respect to the Nb-free parent phase, 2.2 × 10⁻³ for La_0.3Sr_0.7Fe_0.9Nb_0.1O_3−δ cf. 1.3 × 10⁻³ for La_0.5Sr_0.5FeO_3−δ at 1223 K and atmospheric oxygen pressure. The average thermal expansion coefficients calculated from dilatometric data decrease on doping, varying in the range (19.0–21.2) × 10⁻⁶ K⁻¹ at 780–1080 K.     

Stable free-standing aramid resin film containing vanadium pentoxide and new colour electrochromism of the film by electrodeposition of gold

Vanadium pentoxide (V₂O₅) was electrodeposited on a poly(p-phenylene terephtalamide) (PPTA)-film coated electrode. The cyclic voltammogram of the film had a reversible redox current peak. The film was dark green in the reduced state and yellow in the oxidized state. To obtain new colour, gold was further electrodeposited on the film. Not only the redox current peak but also a new redox current shoulder appeared in the cyclic voltammogram of the obtained film, and it exhibited a multicoloured electrochromism: blackish green ↔ dark green ↔ green ↔  bright red. The red colour in the oxidized state was first obtained for the V₂O₅ film. The new redox current shoulder and the colour were probably due to Au_yV₂O₅ partially formed during electrodeposition of the gold. The redox of the Au_yV₂O₅ was accompanied by egress and ingress of Li⁺ ions and the new colour change.     

Effects of Chemical Stirring Time on the Physical Properties for LiNbO3 Photonic Film Using of Optical Waveguide Applications

Lithium niobate (LiNbO₃) structures are deposited on N-type silicon substrate by chemical sol-gel method. The chemical mixture was prepared with different time of stirrer (8 h, 24 h, 48 h) respectively. The nanostructures are deposited by spin coating at 3000 rpm for 30 sec and annealed 400 °C. They are characterized and analyzed by means of x-ray diffraction and Atomic Force Microscopy. The measurement results show that at increasing of mixing time, the photonic film start to crystallize to become a more regular, homogeneous distribution and Improving, which helps to use in the preparing of optical waveguide and the other of the Photonic and optoelectronics applications.