In situ FTIR study of oxygen adsorption on nanostructured RuO2 thin-film electrode

In situ Fourier transform spectroscopy (FTIR) was used to study interactions of nanostructured ruthenium oxide (RuO₂) thin-film sensing electrode with O₂ at room temperature. RuO₂ nanostructures were pretreated at 1,000 °C for 1 h in order to obtain good crystallinity of amorphous RuO₂ nanoparticles. Morphology and properties of nanostructured RuO₂ were characterized by X-ray diffraction, thermo-gravimetric/differential thermal analysis, scanning electron microscopy, and FTIR. It was shown that pretreated RuO₂ is quite active for O₂ ⁻, O₂ ²⁻, and O²⁻ adsorption with clear 722 cm⁻¹ band for superoxide ions (O₂ ⁻) adsorption for the different oxygen concentrations. The results of in situ FTIR measurements revealed that the active sites for oxygen adsorption are not limited to the triple boundaries, but extended to surfaces of RuO₂ electrodes. Fundamental vibration frequencies of ruthenium–oxygen bond at a temperature of 23 °C as well as region above fundamental frequencies for the nanostructured RuO₂ were identified.     

Field emission investigations of RuO2-doped SnO2 wires

Field emission studies of a bunch and a single isolated RuO₂:SnO₂ wire have been performed. A current density of 5.73 × 10⁴ A/cm² is drawn from the single wire emitter at an applied field of 8.46 × 10⁴ V/μm. Nonlinearity in the Fowler-Nordheim (F-N) plot has been observed and explained on the basis of electron emission from both the conduction and the valence bands of the semiconductor. The current stability recorded at the preset value of 1.5 μA is observed to be good. Overall the high emission current density, good stability and mechanically robust nature of the RuO₂:SnO₂ wires offer advantages as field emitters for many potential applications.     

Laser-Induced Graphitic Carbon with Ultrasmall Nickel Nanoparticles for Efficient Overall Water Splitting

Metal nanoparticles encapsulated in graphitic carbon can show high catalytic efficiency and stability, yet the production method remains improved. Herein, it is demonstrated that a Ni-based metal–organic framework [EG-MOF-74(Ni)] can be rapidly transformed into ultrasmall Ni-nanoparticles with different sizes (4–11 nm) encapsulated in graphitic carbon via the laser-scribing method. The synthesized sample shows the best electrocatalytic performances with excellent stability in alkaline electrolyte for oxygen/hydrogen evolution reactions with overpotentials of 0.35/0.18 V at a current density of 10 mA cm⁻² when the Ni particle size is ≈6 nm. This is because of its well-developed micro/mesoporous structure, high electronic transport, and large electrochemical active surface area. An electrolyzer with Ni-nanoparticles encapsulated in the graphitic carbon shows a current density of 10 mA cm⁻² at a voltage of 1.6 V, which is comparable to the Pt/C and RuO₂ counterparts. The laser-based synthesis can serve as a powerful tool for the size-controlled synthesis of various catalysts out of MOFs.     

Electron field emission from magnetic nanomaterial encapsulated multi-walled carbon nanotubes

The present work describes the field emission characteristics of nanoscale magnetic nanomaterial encapsulated multi-walled carbon nanotubes (MWNTs) fabricated over flexible graphitized carbon cloth. Ni/MWNTs, NiFe/MWNTs and NiFeCo/MWNTs have been synthesized by catalytic chemical vapor decomposition of methane over Mischmetal (Mm)-based AB₃ (MmNi₃, MmFe_1.5Ni_1.5 and MmFeCoNi) alloy hydride catalysts. Metal-encapsulated MWNTs exhibited superior field emission performance than pure MWNT-based field emitters over the same substrate. The results indicate that a Ni-filled MWNT field emitter is a promising material for practical field emission application with a lowest turn-on field of 0.6 V/μm and a high emission current density of 0.3 mA/cm² at 0.9 V/μm.     

Suppression of bias stress-induced degradation of pentacene-TFT using MoOx interlayer

The bias stress effect in pentacene thin-film transistors (TFTs) with and without MoO_x interlayer was characterized. The device without MoO_x interlayer showed a large threshold voltage shift of 5.1 V after stressing with a constant gate-source voltage of −40 V for 10000 s, while at the same condition, the device with MoO_x interlayer showed a low threshold voltage shift of 1.9 V. The results can be attributed to the stable interface between MoO_x/pentacene and small contact resistance change for the device with MoO_x/Cu electrode. Pentacene-TFTs with MoO_x interlayer showed a high field-effect mobility of 0.61 cm²/V s and excellent bias stability, which could be a significant step toward the commercialization of OTFT technology.     

Potentiometric DO detection in water by ceramic sensor based on sub-micron RuO2 sensing electrode

An alumina sensor using sub-micron RuO₂ sensing electrode (SE) was fabricated and examined for potentiometric dissolved oxygen (DO) detection in water at a temperature range of 9–35 °C. The electromotive force (emf) response at these temperatures was linear to the logarithm of DO concentration in the range from 0.6 to 8.0 ppm (log[O₂], −4.71 to −3.59). RuO₂-SE displays a Nernstian slope of −41 mV per decade at pH 8.0. It was also found that the response/recovery time to DO changes were sluggish as the water temperature cools down. Response time T ₉₀ to DO changes increased from 8 min at a temperature of 23 °C to about 30 min at a temperature of 9 °C. The proton conductivity of hydrous RuO₂ appears to be due to the dissociative adsorption of water and the formation of acidic OH groups in Ru (III,IV) cluster ions. In strong alkaline solutions, the sensor’s emf exhibited a mixed potential of fast and slow electrochemical reactions involving DO, RuO₄ ²⁻ and OH⁻ ions. The results also revealed that as pH of the solution increases to pH 10.0–13.0, the response/recovery rate becomes faster, stabilizing more or less quickly depending upon the solution alkalinity. Scanning electron microscopy, energy dispersive X-ray-analysis and impedance spectroscopy techniques were used to examine respectively the morphology, crystalline structure and electrochemical behaviour of sub-micron RuO₂ oxides.     

Supercapacitive properties of electrodeposited RuO2 electrode in acrylic gel polymer electrolytes

Hydrous ruthenium oxide (RuO₂) is prepared by electrodeposition on a platinum substrate and its supercapacitive properties are characterized adopting acrylic gel polymer electrolytes, such as poly(acrylic acid) (PAA), potassium polyacrylate (PAAK), and poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS). The electrodeposited hydrous RuO₂ exhibits an amorphous compact stratified morphology with a higher loading (0.15 mg cm^?2) than that of a previous report, and shows broad redox peaks on both cathodic and anodic scans in the cyclic voltammetry. In particular, the RuO₂ electrode for supercapacitor adopting the PAMPS electrolyte shows the highest specific capacitance of 642 F g^?1 at 20 mV s^?1. This is due to the efficient utilization of active RuO₂ species and greater proton accommodation toward the negative oxygen sites of PAMPS's side chain. In addition, it is possible to improve sustainability against high-rate current with the RuO₂ electrode with the PAMPS electrolyte, due to the crosslinks of the gel electrolyte, which support the mechanical strength.     

Free radical reactions at the Ru(0 0 0 1) surface: Atomic oxygen and dissociated NH3

X-ray photoelectron spectroscopy was used to study the effect of atomic oxygen on Ru(0 0 0 1), and the effect of dissociated ammonia on RuO₂/Ru(0 0 0 1), in UHV conditions at ambient temperature. The Ru(0 0 0 1) surface was exposed, at ambient temperature, to a mixed flux of atomic and molecular oxygen generated by dissociation of O₂ in a thermal catalytic cracker, with 45% dissociation efficiency. The detailed study of the XPS spectra shows the formation of a disordered multilayer oxide (RuO₂). No formation of higher oxides of Ru was observed. The formation of RuO₂ proceeded without saturation for total oxygen exposures of up to 10⁵ Langmuir, at which point an average oxide thickness of 68 Å was observed. RuO₂ formed by the reaction with atomic oxygen was exposed to a flux of NH_x (x = 1, 2) + H generated by the cracker. The reduction of RuO₂ to Ru metal was observed by XPS. An exposure of 3.6 × 10² L of NH_x + H, resulted in the observation of adsorbed H₂O and OH, but no evidence of lattice oxide. The chemisorbed species were removed by additional NH_x + H exposure. No nitrogen adsorption was observed.     

Structure formation and mechanisms of DC conduction in thermally evaporated nanocrystallite structure ZnIn2Se4 thin films

ZnIn₂Se₄ is of polycrystalline structure in as synthesized condition. It transforms to nanocrystallite structure of ZnIn₂Se₄ film upon thermal evaporation. Annealing temperatures influenced crystallite size, dislocation density and internal strain. The hot probe test showed that ZnIn₂Se₄ thin films are n-type semiconductor. The dark electrical resistivity versus reciprocal temperature for planar structure of Au/ZnIn₂Se₄/Au showed existence of two operating conduction mechanisms depending on temperature. At temperatures >365 K, intrinsic conduction operates with activation energy of 0.837 eV. At temperatures <365 K, extrinsic conduction takes place with activation energy of 0.18 eV. The operating conduction mechanism in extrinsic region is variable range hopping. The parameters such as density of states at Fermi level, hopping distance and average hopping energy have been determined and it was found that they depend on film thickness. The dark current–voltage characteristics of Au/n-ZnIn₂Se₄/p-Si/Al diode at different temperatures ranging from 293–353 K have been investigated. Results showed rectification behavior. At forward bias potential <0.2 V, thermionic emission of electrons from ZnIn₂Se₄ film over a potential barrier of 0.28 V takes place. At forward bias potential >0.2 V, single trap space charge limited current is operating. The trap concentration and trap energy level have been determined as 3.12×10¹⁹ cm⁻³ and 0.24 eV, respectively.     

The effect of Si surface nitridation on the interfacial structure and electrical properties of (La2O3)0.5(SiO2)0.5 high-k gate dielectric films

Thermal stability, interfacial structures and electrical properties of amorphous (La₂O₃)_0.5(SiO₂)_0.5 (LSO) films deposited by using pulsed laser deposition (PLD) on Si (1 0 0) and NH₃ nitrided Si (1 0 0) substrates were comparatively investigated. The LSO films keep the amorphous state up to a high annealing temperature of 900 °C. HRTEM observations and XPS analyses showed that the surface nitridation of silicon wafer using NH₃ can result in the formation of the passivation layer, which effectively suppresses the excessive growth of the interfacial layer between LSO film and silicon wafer after high-temperature annealing process. The Pt/LSO/nitrided Si capacitors annealed at high temperature exhibit smaller CET and EOT, a less flatband voltage shift, a negligible hysteresis loop, a smaller equivalent dielectric charge density, and a much lower gate leakage current density as compared with that of the Pt/LSO/Si capacitors without Si surface nitridation.     

Ni-MH battery based on plasticized alkaline solid polymer electrolytes

Solid-state nickel metal hydride cells were fabricated using plasticized alkaline solid polymer electrolytes (ASPE) prepared from polyvinyl alcohol (PVA), potassium hydroxide (KOH), alumina (α-Al₂O₃), and propylene carbonate (PC). The ASPE film with PVA/KOH/α-Al₂O₃/PC/H₂O weight ratio of 1.00:0.67:0.09:2.64:1.32 and conductivity of (6.6 ± 1.7) × 10⁻⁴ S cm⁻¹ was used in fabrication of the electrochemical cells. To investigate the electrochemical properties of the plasticized ASPE, cells with the configuration Mg₂Ni/plasticized ASPE/Ni(OH)₂ were fabricated. At the eighth cycle with a current drain of 0.1 mA and plateau voltage of ∼1.1 V, the discharge lasted for 14 h before the cell was considered to have failed. The failure mode of the cell was due to the formation of thin Mg(OH)₂ insulating layers.     

Variable-range hopping in Fe70Pt30 catalyzed multi-walled carbon nanotubes film

Using low-pressure chemical vapour deposition (LPCVD), multi-walled carbon nanotubes (MWNTs) are grown on nanocrystalline Fe₇₀Pt₃₀ film. The Fe₇₀Pt₃₀ nanocrystalline film is deposited by vapour condensation technique. The size of the nanoparticles varies from 5–10 nm, as inferred from SEM micrographs of Fe₇₀Pt₃₀ film. SEM and TEM observations of as-grown CNTs film reveal that these are multi-walled and their diameter varies from 30–80 nm and length is of the order of several micrometers respectively. There is a structural change from ordinary geometry of CNTs to bamboo shaped as suggested by TEM image. Raman spectra shows sharp G and D bands with a higher intensity of G band showing the presence of graphitic nature of the nanotubes. An experimental study of the temperature dependence of electrical conductivity of MWNTs film is done over a wide temperature range from (293–4 K). The measured data gives a good fit to variable-range hopping (VRH) and the results are interpreted using Mott's (VRH) model. The conduction mechanism of the MWNTs film shows a crossover from the exp[ -(T_o/T)^1/4] law in the temperature range (293–110 K) to exp[ -(T_m/T)^1/3] in the low temperature range (110–4 K). This behaviour is attributed to temperature-induced transition from three-dimension (3D) to two-dimension (2D) VRH. Various Mott's parameters like characteristic temperature (T_m), density of states at Fermi level N(E_F), localization length (ξ), hopping distance (R), hopping energy (W) have also been calculated using above-mentioned model.     

Organic acid assisted solid-state synthesis of Li1.2Ni0.16Co0.08Mn0.56O2 nanoparticles as lithium ion battery cathodes

Lithium-rich layered oxide Li_1.2Ni_0.16Co_0.08Mn_0.56O₂ can be referred as a crystalline mixture of Li₂MnO₃ and LiNi_0.4Co_0.2Mn_0.4O₂ at equal molar ratio. In the paper, the solid state reaction of M(AC)₂·4H₂O (M = Mn, Co and Ni) and LiOH·H₂O has been performed to obtain nanocrystalline Li_1.2Ni_0.16Co_0.08Mn_0.56O₂ using a small molecular organic acid (i.e., oxalic acid (OA), citric acid (CA) or tartaric acid (TA)) as additive. The introduction of organic acids can help to improve the layered structure and inhibit the particle growth of Li_1.2Ni_0.16Co_0.08Mn_0.56O₂, and the different organic acids exert distinct influences on the structural and electrochemical properties of Li_1.2Ni_0.16Co_0.08Mn_0.56O₂. In detail, the nanoparticles obtained in the presence of OA have the smallest average size of 50–150 nm, which correspondingly exhibit the highest initial discharge capacity of 267.52 mAh g⁻¹ at 0.1C and the best high-rate capability (e.g., 152.22 mAh g⁻¹, 5C) when applied as a lithium ion battery cathode. Furthermore, the active substance obtained from TA shows the best cycling stability and a discharge capacity of 202.42 mAh g⁻¹ can be retained after 50 cycles at 0.5C.     

Electrochemical characterization on layered lithium ruthenate for electrochemical supercapacitors

Electrochemical characteristics of lithium ruthenate (Li_xRuO_2+0.5x·nH₂O) for electrochemical capacitors' electrode material were first examined in this paper by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge–discharge tests. Results show that Li_xRuO_2+0.5x·nH₂O has electrochemical capacitive characteristic within the potential range of − 0.2–0.9 V (vs. SCE) in 1 M Li₂SO₄ solution. The capacitance mainly arises from pseudo-capacitance caused by lithium ions' insertion/extraction into/out of the Li_xRuO_2+0.5x·nH₂O electrode. The specific capacitance of 391 F g^− 1 can be delivered at 1 mA charge–discharge current for Li_xRuO_2+0.5x·nH₂O electrode with an energy density of 65.7 W h kg^− 1. This material also exhibits an excellent cycling performance and there is no attenuation of capacitance over 600 cycles.     

Nanocrystalline ruthenium oxide and ruthenium in sensing applications – an experimental and theoretical study

In this project, we have explored RuO₂ and Ru nanoparticles (∼ ∼10 and ∼ ∼5 nm, respectively, estimated from XRD data) to be used as gate material in field effect sensor devices. The particles were synthesized by wet chemical procedure. The capacitance versus voltage characteristics of the studied capacitance shifts to a lower voltage while exposed to reducing gases. The main objectives are to improve the selectivity of the FET sensors by tailoring the dimension and surface chemistry of the nanoparticles and to improve the high temperature stability. The sensors were characterized using capacitance versus voltage measurements, at different frequencies, 500 Hz to 1 MHz, and temperatures at 100–400°C. The sensor response patterns have been found to depend on operating temperature. X-ray photoelectron spectroscopy (XPS) analyses were performed to investigate the oxidation state due to gas exposure. Quantum-chemical computations suggest that heterolytic dissociative adsorption is favored and preliminary computations regarding water formation from adsorbed hydrogen and oxygen was also performed.     

SiOx interlayer to enhance the performance of InGaZnO-TFT with AlOx gate insulator

We have fabricated indium–gallium–zinc (IGZO) thin film transistor (TFT) using SiO_x interlayer modified aluminum oxide (AlO_x) film as the gate insulator and investigated their electrical characteristics and bias voltage stress. Compared with IGZO-TFT with AlO_x insulator, IGZO-TFT with AlO_x/SiO_x insulator shows superior performance and better bias stability. The saturation mobility increases from 5.6 cm²/V s to 7.8 cm²/V s, the threshold voltage downshifts from 9.5 V to 3.3 V, and the contact resistance reduces from 132 Ωcm to 91 Ωcm. The performance improvement is attributed to the following reasons: (1) the introduction of SiO_x interlayer improves the insulator surface properties and leads to the high quality IGZO film and low trap density of IGZO/insulator interface. (2) The better interface between the channel and S/D electrodes is favorable to reduce the contact resistance of IGZO-TFT.     

The growth mechanism and supercapacitor study of anodically deposited amorphous ruthenium oxide films

In the present study, ruthenium oxide (RuO₂) thin films were deposited on the stainless steel (s.s.) substrates by anodic deposition. The nucleation and growth mechanism of electrodeposited RuO₂ film has been studied by cyclic voltammetry (CV) and chronoamperometry (CA). The deposited films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive analysis by X-rays (EDAX) for structural, morphological, and compositional studies. The electrochemical supercapacitor study of ruthenium oxide thin films have been carried out for different film thicknesses in 0.5 M H₂SO₄ electrolyte. The highest specific capacitance was found to be 1190 F/g for 0.376 mg/cm² film thickness.     

ZrO2 coating of LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion batteries

ZrO₂-coated LiNi_1/3Co_1/3Mn_1/3O₂ materials were prepared by hydroxide precipitation. The structure and electrochemical properties of the ZrO₂-coated LiNi_1/3Co_1/3Mn_1/3O₂ were investigated using X-ray diffraction, scanning electron microscope, and charge–discharge tests, indicating that the lattice structure of LiNi_1/3Co_1/3Mn_1/3O₂ were unchanged after the coating but the cycling stability was improved. As the coating amount increased from 0.0 to 0.5 mol.%, the initial capacity of the coated LiNi_1/3Co_1/3Mn_1/3O₂ decreased slightly; however, the cycling stability increased remarkably over the cut-off voltages of 2.5~4.3 V and the capacity retention reached 99.5% after 30 cycles at the coating amount of 0.5 mol.%. ZrO₂ coating also improved the cycling stability of LiNi_1/3Co_1/3Mn_1/3O₂ over wider cut-off voltage of 2.5~4.6 V.     

Growth of multiwalled carbon nanotubes from acetylene over in situ formed Co nanoparticles on MgO support

The performance of Co catalysts supported on MgO at different Co loading (10%-75%) for the formation of carbon nanotubes through acetylene decomposition at 600 ^°C with H₂/C₂H₂ mixture for 1 h is investigated. The yield of MWNTs increases with an increase in Co loading (up to 50%). Starting from 1 g of catalyst precursor, about 8 g of MWNTs was obtained. The XRD patterns of catalyst precursor indicate the presence of cobalt in oxidic phase that eventually transformed into the catalytically active Co nanoparticles (12-18 nm) under the influence of acetylene and was responsible for the growth of coiled-like multi-walled CNTs as revealed by SEM and HRTEM images. It is suggested that bending in coil shaped MWNTs has the potential for functionalization for its biomedical applications.