Effect of heterogeneous oxidation on electrochemical properties of tailored Cu0.4Ru3.4O7 + RuO2 sensing electrode of potentiometric DO sensor

Effect of heterogeneous oxidation of the thick-film Cu_0.4Ru_3.4O₇ + RuO₂ sensing electrode (SE) of the planar potentiometric dissolved oxygen (DO) sensor on its electrochemical properties has been investigated by field emission beam scanning electron microscopy (FIB-SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltametry (CV) and electrochemical impedance spectroscopy (EIS) techniques. It was found that the most of heterogeneous oxidation has occurred during the first week of SE exposure to the aqueous environment leading to the partial oxidation Ru^IV to Ru^III occurred mostly on the grain boundaries of SE. The presence of the “inner” active surfaces in the bulk of the developed complex oxide SE has been reaffirmed. It was also found that heterogeneous oxidation caused the increase of the Cu 2p peaks intensity on the surface of SE after the water treatment for one month, which has been confirmed by XPS measurement.     

Investigation of electrochemical properties of RuO2 thin films modified by e-beam irradiation

The influence of electron beam irradiation on the electrochemical properties of electrodeposited RuO₂ thin films was investigated using a 1 MeV electron beam. Crystallinity change before and after electron beam irradiation was investigated by X-ray diffraction, and the oxidation state of ruthenium was determined by X-ray photoelectron spectroscopy. Scanning electron microscopy was utilized to examine the morphology of the films. The results show that electron beam irradiation altered the oxidation state of ruthenium and increased crystallinity.Cyclic voltammetry was employed to evaluate the electrochemical properties of the synthesized RuO₂ films in terms of their application as electrodes of electrochemical capacitors. RuO₂ irradiated with 40 kGy showed 2.7 times higher capacitance (520 Fg⁻¹) than the as-electrodeposited sample (190 Fg⁻¹).     

Room temperature ferromagnetism in Zn0.99La0.01O and pure ZnO nanoparticles

Room temperature ferromagnetism (RTFM) was observed in both La-doped and pure ZnO nanoparticles synthesized by the sol–gel method. RTFM is intrinsic according to the results of X-ray diffraction and X-ray photoelectron spectroscopy. The saturation magnetization (M_S), the remnant magnetization at zero field and coercive field are 5 × 10⁻³, 7 × 10⁻⁴ emu g⁻¹, 100 Oe for Zn_0.99La_0.01O nanoparticles and 1.5 × 10⁻⁴, 1 × 10⁻⁵ emu g⁻¹, 50 Oe for pure ZnO nanoparticles, respectively. The magnetization is enhanced greatly by doping of La. Furthermore, the M_S of Zn_0.99La_0.01O nanoparticles decreases from 0.005 to 0.001 emu g⁻¹ as the annealing temperature increases from 500 to 700 °C. The doping of La introduces more oxygen vacancies into ZnO. The decrease of annealing temperature also produces more oxygen vacancies in La-doped ZnO. These results indicate that the origin of the RTFM is related to oxygen vacancies.     

Chemical diffusion coefficient of lithium ion in Li3V2(PO4)3 cathode material

The kinetic properties of monoclinic lithium vanadium phosphate were investigated by potential step chronoamperometry (PSCA) and electrochemical impedance spectroscopy (EIS) method. The PSCA results show that there exists a linear relationship between the current and the square root of the time. The D?_Li values of lithium ion in Li_3-xV₂(PO₄)₃ under various initial potentials of 3.41, 3.67, 3.91 and 4.07 V (vs Li/Li⁺) obtained from PSCA are 1.26 × 10^− 9, 2.38 × 10^− 9, 2.27 × 10^− 9 and 2.22 × 10^− 9 cm²·s^− 1, respectively. Over the measuring temperature range 15-65 °C, the diffusion coefficient increased from 2.67 × 10^− 8 cm²·s^− 1 (at 15 °C) to 1.80 × 10^− 7 cm²·s^− 1 (at 65 °C) as the measuring temperature increased.     

The microwave-assisted synthesis and characterization of Zn1 − xCoxO nanopowders

In this paper, we present a simple microwave-assisted synthesis of Zn_1 − xCo_xO nanopowders. With the advantages of the microwave-assisted method, we have successfully synthesized good crystalline quality and good surface morphology Zn_1 − xCo_xO nanopowders. The nanopowders are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-VIS absorption, and micro-Raman spectroscopy. We found, in the synthesis process, the surfactant Triethanolamine (TEA) plays an important role on the morphology of Zn_1 − xCo_xO nanoparticles. The XRD study shows that for Co doping up to 5%, Co²⁺ ions are successfully incorporated into the ZnO host matrix. The absorption spectra of Zn_1 − xCo_xO (x = 1-5%) nanopowders show several peaks at 660, 611 and 565 nm, indicating the presence of Co²⁺ ions in the tetrahedral sites. The Raman study shows that the linewidth of E₂^low mode increases with Co concentration, which further indicates the incorporation of Co²⁺ ions into the ZnO host matrix.     

Crystal structure and ionic conductivity of ruthenium diphosphate ARu2(P2O7)2, A=Li, Na, and Ag, with a tunnel structure

Crystal structure and ionic conductivity of ruthenium diphosphates, ARu₂(P₂O₇)₂ A=Li, Na, and Ag, were investigated. The structure of the Ag compound was determined by single crystal X-ray diffraction techniques. It crystallized in the triclinic space group P−1 with a=4.759(2) Å, b=6.843(2) Å, c=8.063(1) Å, α=90.44(2)°, β=92.80(2)°, γ=104.88(2)°, V=253.4(1) Å³. The host structure of it was composed of RuO₆ and P₂O₇ groups and formed tunnels running along the a-axis, in which Ag⁺ ions were situated. The ionic conductivities have been measured on pellets of the polycrystalline powders. The Li and Ag compounds showed the conductivities of 1.0×10⁻⁴ and 3.5×10⁻⁵ S cm⁻¹ at 150 °C, respectively. Magnetic susceptibility measurement of the Ag compound showed that it did not obey the Curie-Weiss law and the effective magnetic moment decreased as temperature decreased due to the large spin-orbital coupling effect of Ru⁴⁺ ions.     

In-situ analysis of positive and negative energetic ions generated during Sn-doped In2O3 deposition by reactive sputtering

Using a quadrupole mass spectrometer combined with an energy analyser, we have investigated the in-situ energy distribution of highly energetic ions generated during reactive sputtering of In-Sn alloy (IT) targets and non-reactive sputtering of Sn-doped In₂O₃ (ITO) ceramic targets. Ar⁺, In⁺, O⁺, O⁻, O₂⁻, InO⁻ and InO₂⁻ ions with kinetic energies greater than 40 eV were clearly observed. Upon increasing the O₂ flow ratio for reactive sputtering, the surface of the IT target changes from metal (metal mode) to oxide (oxide mode) via a state of mixed metal and oxide (transition region). O⁻ ions with the kinetic energy corresponding to cathode voltage are generated at the oxide layer, which expands upon the target surface with increasing O₂ flow ratio in the metal mode and the transition region. In contrast, the flux of 60-eV Ar⁺ ions decreases with increasing O₂ flow ratio. The presence of 125- and 200-eV In⁺ ions is attributed to the dissociation of InSnO₂⁻ and InO₂⁻ with the kinetic energy corresponding to cathode voltage, respectively, while the presence of 40- and 150-eV O⁺ ions is attributed to the dissociation of InO₂⁻ and O₂⁻ with the kinetic energy corresponding to cathode voltage, respectively.     

All-solid-state cells based on solid electrolyte systems Cu1−xAgxI-Ag2O-Y, where x = 0.05-0.25; Y = MoO3, B2O3, SeO2, V2O5 and CrO3

All-solid-state cells of the configuration (−)Ag + SE//SE//I₂-phenothiazine + C(+) using the best conducting compositions of the solid electrolyte systems, namely, Cu_1−xAg_xI-Ag₂O-Y where x = 0.05, 0.1, 0.15, 0.2 and 0.25, Y = MoO₃, B₂O₃, SeO₂, V₂O₅ and CrO₃, as the electrolytes were fabricated. Discharge, polarization and power characteristics of these cells were also evaluated. The open circuit voltage values of these cells were in the range 620-635 mV. The stability of these cells has been indicated by the constancy of their OCV over a period of 6 months. The polarization and discharge studies on these cells have shown that typical cells based on the electrolytes with Y = B₂O₃, SeO₂ and V₂O₅ would possess discharge capacities of 12.84, 3.76 and 5.05 mA h and specific energy of 6.55, 1.81 and 2.77 W h kg⁻¹, respectively. The solid electrolytes have good electrochemical stability and compatibility with the Ag/Phenothiazine-I₂ electrode couple thus offering their suitability of application in microwatt power sources.     

Fabrication of p-type ZnO thin films via magnetron sputtering and phosphorus diffusion

ZnO thin films were deposited on heavily phosphorus-doped (n⁺-Si) substrates by radio frequency magnetron sputtering. The films were changed from n-type to p-type by phosphorus diffusion from the n⁺-Si substrates to the ZnO films and being activated thermally during deposition. n-Type ZnO (n-ZnO) films were also deposited onto the p-type ZnO (p-ZnO) films to form n-ZnO/p-ZnO/n⁺-Si multilayer structures. The cross section of the multilayer structure was examined by scanning electron microscopy. Crystal structures of the p-ZnO films were studied by X-ray diffraction and were confirmed to be highly c-axis oriented primarily perpendicular to the substrate. Photoluminescence spectra of the p-ZnO films showed that band-edge UV emission predominated. The hole concentration of the p-ZnO films was between +1.78×10¹⁸ cm⁻³ and +1.34×10¹⁹ cm⁻³, and the hole mobility was 13.1-6.08 cm²/V s measured by Hall effect experiment. The formation of p-ZnO films was confirmed by the rectifying characteristics of the p-ZnO/n⁺-Si heterojunctions and the n-ZnO/p-ZnO homojunction on the multilayer structure as well as by the experimental results of Hall effect.     

Hydrothermally synthesized RuO2/Carbon nanofibers composites for use in high-rate supercapacitor electrodes

A conventional hydrothermal deposition process is used to graft ruthenium oxide (RuO₂) nanoparticles onto carbon nanofibers (CNFs). The obtained RuO₂ nanoparticles have an average diameter of 2 nm and are homogenously distributed on the CNF surfaces. Supercapacitors are fabricated using the resulting RuO₂ grafted CNFs nanocomposite as the electrodes. The existence of CNFs leads to reduced contact resistance among the RuO₂ nanoparticles and provides a network for fast electron transport, which then contributes to enhanced electrochemical performance. The enhancement is proportional to the RuO₂ content and can be as high as 638% at a high sweep rate of 200 mV s⁻¹, at which a capacitance is 155 F g⁻¹. Stability of the RuO₂-grafted CNF capacitor is also demonstrated by subjecting the capacitor to a potential sweep at 500 mV s⁻¹ for 1000 cycles. Furthermore, the RuO₂ grafted CNF capacitor exhibits a very short relaxation time of 0.17 s, which is desirable for high rate charge and discharge.     

Influence of ZnO additive on the properties of Y-doped BaSnO3 proton conductor

The effects of ZnO additive on the phase formation, microstructure and electrical conduction of Y-doped BaSnO₃ have been investigated. The single-phase and dense BaSn_0.75Y_0.25O_3−δ compound with 4 mol% ZnO additive was successfully prepared after sintering at 1300 °C, which significantly reduces the sintering temperature. The conductivities measured under dry and wet air atmospheres reveal that the bulk conductivity of BaSn_0.71Y_0.25Zn_0.04O_3−δ is much lower than that of BaSn_0.75Y_0.25O_3−δ. However, ZnO as a sintering aid does not affect the bulk conductivity. The total conductivity of BaSn_0.75Y_0.25O_3−δ with ZnO as the sintering aid is slightly higher than that of unmodified BaSn_0.75Y_0.25O_3−δ, and reaches 2.4 × 10⁻³ S cm⁻¹ at 621 °C. Therefore, this material can be used as a proton-conducting electrolyte for intermediate temperature solid oxide fuel cells.     

Influence of doping concentration on the properties of ZnO:Mn thin films by sol-gel method

Thin films of Mn-doped ZnO with different doping concentration (0.8, 1, 3, 5 at%) were prepared on Pt/Ti/SiO₂/Si substrates by using sol-gel method. The effects of the doping concentration on the structural properties, electrical characteristics and element binding energy in films were investigated. X-ray diffraction (XRD) results showed that the c-axis orientation of ZnO films was affected by Mn²⁺ content. Current-voltage (I-V) measurements indicated that resistivities of ZnO films were observably enhanced by dopant of Mn²⁺ and the resistivities value increased with a doping level up to 5 at% Mn. X-ray photoelectron spectroscopy (XPS) patterns suggested that the binding energies of O1s and ZnL₃M₄₅M₄₅ were affected by the content of Mn²⁺.     

Cu-doping effect on structure and magnetic properties of Fe-doped ZnO powders

Fe-doped and Cu, Fe co-doped ZnO diluted magnetic semiconductors powders were synthesized by sol–gel method. The x-ray diffraction (XRD) results showed that Zn_0.97−xFe_0.03Cu_xO (x ≤ 0.02) samples were single phase with the ZnO-like wurtzite structure. X-ray photoelectron spectroscopy (XPS) showed that Fe²⁺ and Fe³⁺ existed in Zn_0.97Fe_0.03O, while Fe²⁺, Fe³⁺and Cu⁺, Cu²⁺ were found in Zn_0.95Fe_0.03Cu_0.02O. Both Zn_0.97Fe_0.03O and Zn_0.95Fe_0.03Cu_0.02O exhibited ferromagnetic performance at room temperature. But the Cu incorporation reduced the saturation magnetization of Fe-doped ZnO diluted magnetic semiconductors.     

The effect of In ion on the optical characteristics of Er in Er/Yb:LiNbO3 crystal

The effect of In³⁺ ion on the optical characteristics of Er³⁺ ion in Er/Yb:LiNbO₃ crystal under 980 nm excitation has been investigated. The Er and Yb contents in the crystals were measured by an inductively coupled plasma atomic emission spectrometer (ICP-AES). A significant enhancement of 1.54 μm emission was observed for Er/Yb:LiNbO₃ crystal doped with 1 mol% In₂O₃. The studies on the UV-vis absorption and the OH⁻ absorption spectra indicate that the threshold concentration of In³⁺ ion decreases with the Er/Yb doping in Er/Yb/In:LiNbO₃ crystal. The 1 mol% In₂O₃ doping results in the reduction of absorption cross section in the UV-vis region, meaning the formation of Er³⁺ cluster sites. The enhancement of 1.54 μm emission is attributed to the larger probabilities of the cross relaxation processes ⁴S_3/2 + ⁴I_15/2 → ⁴I_9/2 + ⁴I_13/2 (Er), ⁴S_3/2 + ⁴I_15/2 → ⁴I_13/2 + ⁴I_9/2 (Er) and ⁴I_9/2 + ⁴I_15/2 → ⁴I_13/2 + ⁴I_13/2 (Er) induced by Er³⁺ cluster sites.     

The effects of divalent and trivalent dopants on the luminescence properties of ZnO fine particle with oxygen vacancies

The engineering, various factors, and mechanism responsible for emission and high intensity of ZnO luminescence are well developed. Only a few researchers investigate the role of oxygen vacancy on the luminescence properties of doped ZnO. The objective of this research is to synthesize the ZnO fine particle with tailored oxygen vacancy by doping with 5 at.% of divalent and trivalent dopants, i.e., magnesium (ZnO:Mg²⁺), calcium (ZnO:Ca²⁺), gadolinium (ZnO:Gd³⁺), and lanthanum (ZnO:La³⁺) using spray pyrolysis method. The samples prepared at 700 °C with 5 l/min carrier gas flow characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) spectroscopy. The oxygen vacancy was successfully tuned by introducing various doping into ZnO fine particles. It is found that the oxygen vacancy responsible for the increase of DLE intensity (I_DLE) on the deconvoluted of PL spectra. When the ZnO fine particle doped with trivalent ions (Gd³⁺, La³⁺), the contribution of NBE intensity (I_NBE) is higher than I_DLE. Important phenomena also observed when the excitation wavelength was tuned. The contribution of I_DLE and I_NBE changes, lead to control the luminescence properties.     

CTAB assisted immobilization of RuO2 nanoparticles on graphene oxide for electrochemical sensing of hydrazine

A novel method has been presented to modify glassy carbon electrode (GCE) with graphene oxide (GO) nanocomposite without introducing any electrode binder such as chitosan and Nafion. First, modify GCE with RuO₂ nanoparticles which have been dispersed in cetyltrimethyl ammonium bromide (CTAB) aqueous solution. Then, highly adhesive RuO₂/CTAB/GO nanocomposite membrane formed on GCE by immersing RuO₂/CTAB modified GCE in GO suspension. CTAB plays significant roles not only in the preparation of the nanocomposite but also in the immobilization of nanocomposite on GCE surface. First, CTAB was used as the dispersant of RuO₂ nanoparticles. Second, CTAB acted as the molecular linker to bind RuO₂ nanoparticles on graphene sheets. Third, CTAB formed CTAB/GO nanocomposite which is highly adhesive on the surface of electrodes such as GCE and ITO (indium tin oxide). The obtained RuO₂/CTAB/GO/GCE shows excellent electrocatalytic ability towards the oxidation of hydrazine. The oxidation of hydrazine on RuO₂/CTAB/GO/GCE is an adsorption-controlled process and the oxidation current is linear with the concentration of hydrazine in the range of 1 × 10^?5～1 × 10^?3 M with a detection limit of 2.3 × 10^?6 M. The application of this sensor in the sensing of hydrazine in real water samples confirmed its reliability and accuracy.     

Studying trivalent/bivalent metal ion doped TiO2 as p-TiO2 in bipolar heterojunction devices

Trivalent/bivalent metal ions doped TiO₂ thin films (M_xTi_1−xO₂, M = Cr³⁺, Fe³⁺, Ni²⁺, Co²⁺, Mn²⁺ and x = 0.01, 0.05, 0.1, 0.15, 0.2) were deposited on Indium–tin oxide (ITO) coated glass substrates by spin coating technique. X-ray photoelectron spectroscopy (XPS) showed Ti⁴⁺ oxidation state of the Ti2p band in the doped p-TiO₂. The homogenous M_xTi_1−xO₂ was used to support n-ZnO thin films with thickness ∼40–80 nm and vertically aligned n-ZnO nanorods (NR) with length ∼300 nm and 1.5 μm. Current (I)–voltage (V) characteristics for the Ag/n-ZnO/M_xTi_1−xO₂/ITO/glass assembly showed rectifying behavior with small turn-on voltages (V₀) < 1 V. The ideality factor (η) and the resistances in both forward and reverse bias were calculated. The temperature dependence performance of these bipolar devices was performed and variation of the parameters with temperature was studied.     

Transparent conducting ZnO thin films deposited by vacuum arc plasma evaporation

A high rate deposition of co-doped ZnO:Ga,F and ZnO-In₂O₃ multicomponent oxide thin films on large area substrates has been attained by a vacuum arc plasma evaporation method using oxide fragments as a low-cost source material. Highly transparent and conductive ZnO:Ga,F and ZnO-In₂O₃ thin films were prepared on low temperature substrates at a deposition rate of approximately 375 nm/min with a cathode plasma power of 10 kW. A resistivity of 4.5×10⁻⁴ Ω cm was obtained in ZnO:Ga,F films deposited at 100 °C using ZnO fragments co-doped with 1 wt.% ZnF₂ and 1 wt.% Ga₂O₃ as the source material. In addition, the stability in acid solution of ZnO films was improved by co-doping. It was found that the Zn/(In+Zn) atomic ratio in the deposited ZnO-In₂O₃ thin films was approximately the same as that in the fragments used. The ZnO-In₂O₃ thin films with a Zn/(In+Zn) atomic ratio of approximately 10-30 at.% deposited on substrates at 100 °C exhibited an amorphous and smooth surface as well as a low resistivity of 3-4×10⁻⁴ Ω cm.     

Effect of acetic acid on ZnO:In transparent conductive oxide prepared by ultrasonic spray pyrolysis

Undoped and indium doped zinc oxide (ZnO) transparent conductive oxide were prepared by a low-cost Ultrasonic Spray Pyrolysis. The influence of acetic acid on properties of the ZnO thin films was investigated. The complex formed by [CH₃COO⁻] and [Zn²⁺] in precursor solution was better for the growth of ZnO film. The acetic acid added in precursor solution can supply [CH₃COO⁻] for both [Zn²⁺] and [In³⁺] to form complexes. That made the [Zn²⁺] and [In³⁺] have similar statement, which can promote the indium doping in the ZnO films. The surface morphology, structural and electrical properties of the ZnO thin films were influenced by the acetic acid adding. The total transmittance of the ZnO thin films is above 80% in the wide wavelength region from 400 nm to 2000 nm.     

Effects of growth ambient on electrical properties of Al-N co-doped p-type ZnO films

p-Type zinc oxide thin films with c-axis orientation were prepared in N₂O-O₂ atmosphere by an Al-N co-doping method using reactive magnetron sputtering. Secondary ion mass spectroscopy (SIMS) measurements indicate that as-grown ZnO films were co-doped with Al and N. Hall effect measurements show a dependence of types of conduction, carrier concentration and mobility of as-grown ZnO films on N₂O partial pressure ratios. p-Type ZnO thin films deposited in a N₂O partial ratio of 10% show the highest hole concentration of 1.1×10¹⁷ cm⁻³, the lowest resistivity of about 100 Ω cm, and a low mobility of 0.3 cm² V⁻¹ s⁻¹.