Preparation of cobalt oxide thin films and its use in supercapacitor application

Present work explored a room temperature, simple and low cost chemical route for the cobalt oxide film onto copper substrate from cobalt chloride (CoCl₂·6H₂O) precursor and characterization for its structural and electrochemical properties for supercapacitor application. The morphology and crystal structure of the film were investigated by scanning electron microscopy and X-ray diffraction techniques, respectively. The electrochemical supercapacitive properties of cobalt oxide film were evaluated using cyclic voltammetry and galvanostatic charge-discharge methods. The film showed maximum specific capacitance of (165 F/g) in 1.0 M aqueous KOH electrolyte at scan rate 10 mV/s.     

Effect of oxygen partial pressure on PLD cobalt oxide films

Thin CoO oxide layers with superior properties in terms of crystallographic ordering, surface roughness and constant and controlled chemical compositions have been prepared by pulsed laser deposition in reactive O₂ atmosphere at 400 °C. Such systems are particularly suitable both for applications and for basic studies, any time high quality and controlled surfaces are required, for example in multilayered systems whose behaviour critically depends on interface properties, such as magnetically exchange-coupled systems. A structural and microstructural study of such films is presented, together with the compositional analysis for different process conditions. The best control on film stoichiometry was obtained by protecting the surface with a thin Pt cap-layer, before air exposure.     

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.     

Valence control of cobalt oxide thin films by annealing atmosphere

The cobalt oxide (CoO and Co₃O₄) thin films were successfully prepared using a spin-coating technique by a chemical solution method with CH₃OCH₂CH₂OH and Co(NO₃)₂·6H₂O as starting materials. The grayish cobalt oxide films had uniform crystalline grains with less than 50 nm in diameter. The phase structure is able to tailor by controlling the annealing atmosphere and temperature, in which Co₃O₄ thin film was obtained by annealing in air at 300-600, and N₂ at 300, and transferred to CoO thin film by raising annealing temperature in N₂. The fitted X-ray photoelectron spectroscopy (XPS) spectra of the Co2p electrons are distinguishable from different valence states of cobalt oxide especially for their satellite structure. The valence control of cobalt oxide thin films by annealing atmosphere contributes to the tailored optical absorption property.     

Graphene oxide with improved electrical conductivity for supercapacitor electrodes

Predominant few-layer graphene (FLG) sheets of high electrical conductivity have been synthesized by a multi-step intercalation and reduction method. The electrical conductivity of the as-synthesized FLG is measured to be ∼3.2 × 10⁴ S m⁻¹, comparable to that of pristine graphite. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Raman analysis reveal that the as-synthesized FLG sheets have large areas with single and double layers. The specific capacitance of 180 F g⁻¹ is obtained for the FLG in a 1 M Na₂SO₄ aqueous electrolyte by integrating the cyclic voltammogram. The good capacitive behavior of the FLG is very promising for the application for next-generation high-performance electrochemical supercapacitors.     

Chemical synthesis of nano-porous ruthenium oxide (RuO2) thin films for supercapacitor application

Ruthenium oxide (RuO₂) thin films have been prepared using single step chemical method containing Ru(III) Cl₃ solution in an aqueous medium at low temperature. The structural, morphological and optical properties have been investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and optical absorption technique. The XRD study revealed the formation of amorphous RuO₂ thin film. The surface examination by SEM showed formation of nano-porous material on the substrate. The TEM study revealed the formation of nanostructured material. The optical absorption studies showed the presence of direct band transition with band gap equal to 2.2 eV. The RuO₂ has proved its applicability in supercapacitor showing 50 F/g specific capacitance in 0.5 M H₂SO₄ at 20 mV/s scan rate.     

Microstructural analysis of hard amorphous carbon films deposited with high-energy ion beams

Hard amorphous carbon films produced using high-energy (ca. 30 keV) ion beam deposition of CH₃⁺ and CH₄⁺ on silicon wafers, have been investigated by Positron Annihilation Spectroscopy (PAS), the results are correlated with Raman Spectroscopy and Electrical Resistivity measurements. The microstructural modifications of the films as a function of the annealing temperature in the 300–600°C range have been studied. The evolution of the fractions of sp² and sp³ bonds is described and related to the changes of the open volume defect distribution and the graphitization process.     

Decorating reduced graphene oxide with Co3O4 hollow spheres and their application in supercapacitor materials

In this paper, a composite of reduced graphene oxide decorated by Co₃O₄ hollow spheres (Co₃O₄/RGO composite) has been synthesized by a one-pot solvothermal method. The samples are characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FT-IR), Raman spectra and so on. The results demonstrate that the Co₃O₄ hollow spheres with good purity and homogenous size are absorbed onto the reduced graphene oxide sheets as spacers to prevent the aggregation of the graphene oxide sheets. Furthermore, the well electrochemical properties demonstrate that the Co₃O₄/RGO composite might have potential applications as electrode materials for supercapacitors.     

Potentiostatic and galvanostatic electrodeposition of manganese oxide for supercapacitor application: A comparison study

The structural and electrochemical properties of manganese oxide (MnO₂) electrodeposited by potentiostatic and galvanostatic conditions are studied. X‒ray diffraction analyses confirm identical MnO₂ phase (ramsdellite) are deposited under potentiostatic and galvanostatic conditions. Under comparable current density during electrodeposition, MnO₂ deposited by galvanostatic condition shows smaller crystallite size, less compact layered structure, higher surface area and wider band gap, in comparison to the potentiostatic deposition. The MnO₂ morphology difference under different electrodeposition conditions contributes to different capacitive behaviors. The lower compactness of MnO₂ deposited galvanostatically renders facile ions diffusion, leading to higher specific capacitance with low equivalent series resistance. The findings suggest galvanostatic electrodeposition is suitable to produce MnO₂ nanostructure for supercapacitor application.     

Effect of annealing on structural, optical and electrical properties of nanostructured Ge thin films

Ge thin films with a thickness of about 110 nm have been deposited by electron beam evaporation of 99.999% pure Ge powder and annealed in air at 100-500 °C for 2 h. Their optical, electrical and structural properties were studied as a function of annealing temperature. The films are amorphous below an annealing temperature of 400 °C as confirmed by XRD, FESEM and AFM. The films annealed at 400 and 450 °C exhibit X-ray diffraction pattern of Ge with cubic-F structure. The Raman spectrum of the as-deposited film exhibits peak at 298 cm⁻¹, which is left-shifted as compared to that for bulk Ge (i.e. 302 cm⁻¹), indicating nanostructure and quantum confinement in the as-deposited film. The Raman peak shifts further towards lower wavenumbers with annealing temperature. Optical band gap energy of amorphous Ge films changes from 1.1 eV with a substantial increase to ∼1.35 eV on crystallization at 400 and 450 °C and with an abrupt rise to 4.14 eV due to oxidation. The oxidation of Ge has been confirmed by FTIR analysis. The quantum confinement effects cause tailoring of optical band gap energy of Ge thin films making them better absorber of photons for their applications in photo-detectors and solar cells. XRD, FESEM and AFM suggest that the deposited Ge films are composed of nanoparticles in the range of 8-20 nm. The initial surface RMS roughness measured with AFM is 9.56 nm which rises to 12.25 nm with the increase of annealing temperature in the amorphous phase, but reduces to 6.57 nm due to orderedness of the atoms at the surface when crystallization takes place. Electrical resistivity measured as a function of annealing temperature is found to reduce from 460 to 240 Ω-cm in the amorphous phase but drops suddenly to 250 Ω-cm with crystallization at 450 °C. The film shows a steep rise in resistivity to about 22.7 KΩ-cm at 500 °C due to oxidation. RMS roughness and resistivity show almost opposite trends with annealing in the amorphous phase.     

Thermomagnetic hysteresis and electrical transport in amorphous films

We report resistivity and magnetization measurements on an amorphous Ni₇₄Mn₂₄Pt₂ thin film in the temperature range of 3–300 K. Two significant features are apparent in both the magnetic susceptibility and electrical resistivity. A low-temperature (low-T) anomaly is observed at about 40 K, where a cusp appears in the resistivity, while a concomitant step-like increase in zero-field-cooled (ZFC) magnetization (M) appears with increasing temperature. The low-T anomaly is attributed to a crossover from a pure re-entrant spin-glass within individual domains to a mixed ferro-spin-glass regime at lower temperatures. By contrast, the high-temperature (high-T) anomaly, signaled by the appearance of hysteresis below 250 K, corresponds to the freezing of transverse spins in individual domains acting independently. Between the low-T and high-T anomalies a small but discernable magnetic hysteresis is observed for warming vs. cooling in the field-cooled (FC) case. This behavior clearly indicates the presence of domain structure in the sample, while the disappearance of this hysteresis at lower temperatures indicates the complete freezing of the spin orientation of these domains. According to these results, we have divided the magnetic state of this sample into three regions: at temperatures above 250 K, the sample behaves like a soft ferromagnet, exhibiting M vs. H loops with very small hysteresis (less than 5 Oe). As the temperature is lowered into the intermediate region (the range 40–250 K), spins become frozen randomly and progressively within the individual domains. These domains behave independently, rather than as a cooperative behavior of the sample. Weak irreversibility sets in, indicating the onset of transverse spin freezing within the domains. At temperatures below 40 K, the M vs. H loops exhibit larger hysteresis, for both the ZFC and FC cases, as in a pure spin-glass. We have also demonstrated giant noise in the resistivity at temperatures just below 250 K. Such noise can originate from fluctuations of the domains near the film surface because of competing effective bulk and surface anisotropy fields. The large observed amplitude may be explained by means of a large ferromagnetic anisotropy in the resistivity due to the large spin–orbit effect seen in NiMn systems. Finally, the low-T peak in the resistivity has been analyzed using Fisher and Langer's expression based on the Friedel Model proposed for critical transitions in transition metals (s–d systems). The fitted results are in satisfactory agreement with the predictions of this model.     

Electrochemical sensing of H2O2 using cobalt oxide modified TiO2 nanotubes

Cobalt oxide (Co₃O₄) modified anatase titanium dioxide nanotubes (ATNTs) have been investigated for the electrochemical sensing of hydrogen peroxide (H₂O₂). ATNTs have been synthesized by a two-step anodization process. ATNTs were then modified with Co₃O₄ employing chemical bath deposition method. The structure and morphology of ATNTs and their modification with Co₃O₄ has been confirmed by X-ray diffraction by scanning electron microscopy. H₂O₂ sensing has been studied in 0.1 M PBS solution, by cyclic voltammetry and amperometry. Variation in the peak positions and current densities was observed with addition of H₂O₂ for Co₃O₄ modified ATNTs. Sensitivity and limit of detection improved with modification of ATNTs with Co₃O₄ with precursor concentration up to 0.8 M. However, at higher precursor concentrations sensitivity and limit of detection toward H₂O₂ deteriorated. Co₃O₄ Modified ATNTS using 0.8 M precursor concentration are comparatively more suitable for H₂O₂ sensing applications due to the optimum formation of Co₃O₄/ATNTs heterojunctions.     

Bismuth oxide thin films prepared by chemical bath deposition (CBD) method: annealing effect

Bismuth oxide thin films have been deposited by room temperature chemical bath deposition (CBD) method and annealed at 623 K in air. They were characterized for structural, surface morphological, optical and electrical properties. From the X-ray diffraction patterns, it was found that after annealing a non-stoichiometric phase, Bi₂O_2.33, was removed and phase pure monoclinic Bi₂O₃ was obtained. Surface morphology of Bi₂O₃ film at lower magnification SEM showed rod-like structure, however, higher magnification showed a rectangular slice-like structure perpendicular to substrate, giving rise to microrods on the surface. The optical studies showed the decrease in band gap by 0.3 eV after annealing. The electrical resistivity variation showed semiconductor behavior and from thermoemf measurements, the electrical conductivity was found to be of n-type.     

Electrodeposited ruthenium oxide thin films for supercapacitor: Effect of surface treatments

Amorphous and porous ruthenium oxide thin films have been deposited from aqueous Ru(III)Cl₃ solution on stainless steel substrates using electrodeposition method. Cyclic voltammetry study of a film showed a maximum specific capacitance of 650 F g⁻¹ in 0.5 M H₂SO₄ electrolyte. The surface treatments such as air annealing, anodization and ultrasonic weltering affected surface morphology. The supercapacitance of ruthenium oxide electrode is found to be dependent on the surface morphology.     

A novel chemical synthesis and characterization of Mn3O4 thin films for supercapacitor application

Mn₃O₄ thin films have been prepared by novel chemical successive ionic layer adsorption and reaction (SILAR) method. Further these films were characterized for their structural, morphological and optical properties by means of X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), field emission scanning electron microscopy (FESEM), wettability test and optical absorption studies. The XRD pattern showed that the Mn₃O₄ films exhibit tetragonal hausmannite structure. Formation of manganese oxide compound was confirmed from FTIR studies. The optical absorption showed existence of direct optical band gap of energy 2.30 eV. Mn₃O₄ film surface showed hydrophilic nature with water contact angle of 55°. The supercapacitive properties of Mn₃O₄ thin film investigated in 1 M Na₂SO₄ electrolyte showed maximum supercapacitance of 314 F g⁻¹ at scan rate 5 mV s⁻¹.     

Use of successive ionic layer adsorption and reaction (SILAR) method for amorphous titanium dioxide thin films growth

Use of successive ionic layer adsorption and reaction (SILAR) method was preferred for the growth of amorphous titanium dioxide (TiO₂) thin films at ambient temperature. Further, these films were annealed at 673 K for 2 h in air for structural improvement and characterized for structural, surface morphological, optical and electrical properties. An amorphous structure of TiO₂ was retained even after annealing as confirmed from XRD studies. The spherical grains of relatively large size were compressed after annealing. A red shift in band gap energy and decrease in electrical resistivity were observed due to annealing treatment.     

Determination of photocatalytic activity in amorphous and crystalline titanium oxide films prepared using plasma-enhanced chemical vapor deposition

Hydro-oxygenated amorphous titanium oxide (a-TiO_x:OH) films were prepared by plasma-enhanced chemical vapor deposition (PECVD) using precursors of titanium tetraisopropoxide (TTIP) and oxygen. The influences of chemical states and crystal quality on the photocatalytic activity were systematically investigated in the as-deposited and post-annealed films. The degree of the photocatalytic activity was deeply correlated with the porosity related to the hydroxyl (OH) groups in the as-deposited amorphous film. The crystallized anatase structures was observed from the 200 °C-deposited a-TiO_x:OH film after a post-annealing treatment at 400 °C. The photocatalytic activity related to the film with anatase structure was markedly superior to that of an amorphous film with porous structures. The larger the crystal size of the anatase structure, the higher the photocatalytic activity obtained. At elevated annealed temperatures, the inferior anatase structure due to the crystalline transformation led to a low photocatalytic activity. It was concluded that the photocatalytic activity of an amorphous TiO_x film prepared using PECVD was determined by the porosity originating from the functional OH groups in the film, whereas the crystalline quality of anatase phase in the annealed poly-TiO_x film was crucial to the photocatalytic activity.     

Silicon rich silicon oxide films deposited by radio frequency plasma enhanced chemical vapor deposition method: Optical and structural properties

Silicon rich silicon oxide films have been deposited by plasma enhanced chemical vapour deposition using a gas mixture of silane, carbon-di-oxide and hydrogen. Silicon nanocrystals formations in the as deposited silicon rich silicon oxide films have been detected by high resolution transmission electron microscopy, scanning electron microscopy, Raman scattering and X-ray diffraction studies. Structural changes under different deposition condition have been studied by Fourier transform infrared spectroscopy. The oxygen and hydrogen bonding configurations have been obtained from Fourier transform infrared spectroscopy. Room temperature photoluminescence spectra have been observed for the as deposited films. The structural properties together with photoluminescence spectra allowed us to gain insight about the Si nanocrystal formation.     

Electrodeposited cobalt coating on Crofer22APU steels for interconnect applications in solid oxide fuel cells

A gas-tight cobalt-based protective coating was successfully applied by electroplating and subsequent oxidation. The coating covered all the surfaces of the machined gas channels of the metallic interconnect and adhered well to this substrate. Such a gas-tight coating offers effective blocking of Cr diffusion or evaporation from the interconnect and hence a reliable protection against Cr poisoning of the SOFC cathode. Chemical interactions were observed between the cobalt coating and the LSM contact layer, resulting in layer spallation during oxidation under pressureless conditions. Applying a pressure to the layers, spallation was effectively prevented. Although the area specific resistance (ASR) of the coated interconnect was higher than the uncoated one, it decreased steadily with time within the measurement period. The ASR was 28 mΩ cm² after an exposure of 1170 h. It seems thus that electroplating followed by oxidation is a promising method for the fabrication of spinel protective coatings for SOFC interconnects or other balance-of-plant components with complicated gas flow paths.     

Investigation of chemical mechanical polishing of zinc oxide thin films

Zinc oxide has become an important material for various applications. Commercially available zinc oxide single crystals and as-grown zinc oxide thin films have high surface roughness which has detrimental effects on the growth of subsequent layers and device performance. A chemical mechanical polishing (CMP) process was developed for the polishing of zinc oxide polycrystalline thin films. Highly smooth surfaces with RMS roughness <6 Å (as compared to the initial roughness of 26 ± 6 Å) were obtained under optimized conditions with removal rates as high as 670 Å/min. Effects of various CMP parameters on removal rate and surface roughness were evaluated. The role of pH on the polishing characteristics was investigated in detail.