Electrochemical performance of nano-SiO2 modified LiCoO2 thin films fabricated by electrostatic spray deposition (ESD)

With a mixture of a SiO₂ sol and a solution of lithium and cobalt acetates as the precursor, nano-SiO₂ modified LiCoO₂ films were fabricated by the electrostatic spray deposition (ESD) technique. The SiO₂ content of these films was 0, 5, 10, 15 and 20 wt%, respectively. Their structure and electrochemical properties were characterized by means of X-ray diffraction, scanning electron microscopy, galvanostatic cell cycling, AC impedance spectroscopy and cyclic voltammetry. Li₂CoSiO₄ was found formed in the SiO₂-containing films. The film with 15 wt% SiO₂ shows the best cycling stability with the capacity of 130 mAh/g in the voltage range between 2.7 and 4.3 V at the current density of 0.1 mA/cm². Due to its resulted small cell impedance, it has excellent rate capability. A LiCoO₂ (shell)/SiO₂ (core) structure model is proposed to explain the improved properties of these films.     

Tin oxide thin films deposited by ultrasonic spray pyrolysis

This study investigated microstructure of SnO₂ thin films deposited by ultrasonic spray pyrolysis technique using 0.2 M of SnCl₄·5H₂O in absolute ethanol as a precursor. The deposition temperature (350–450 °C) and time (20–90 min) were varied. The influence of film-deposition conditions on grain size and orientation were discussed. The deposited SnO₂ films were textured polycrystalline films. The preferred orientation of SnO₂ films were quantitatively evaluated by texture coefficient (TC). The mean grain size and film thickness determined by SEM could be controlled over a range of 50–325 nm and 80–2690 nm, respectively.     

Electrochromism in spray deposited iridium oxide thin films

Electrochromic iridium oxide thin films were deposited onto fluorine doped tin oxide coated glass substrates from an aqueous iridium chloride solution by pneumatic spray pyrolysis technique. The as-deposited samples were X-ray amorphous. The electrochromic properties of thin films were studied in an aqueous electrolyte (0.5N H₂SO₄) using cyclic voltammetry (CV), chronoamperometry (CA) and spectrophotometry. Iridium oxide films show pronounced anodic electrochromism owing to Ir⁺⁴ ↔ Ir⁺³ intervalency charge transition. The reversibility of cyclic process in Ir oxide films is found to be higher, which increases with increasing number of colour-bleach cycles.     

Preparation and characterization of reticular SSC cathode films by electrostatic spray deposition

Sm_0.5Sr_0.5CoO_3−δ (SSC) cathode films were deposited on CGO (Gd_0.1Ce_0.9O_1.95) electrolyte substrates by electrostatic spray deposition to prepare SSC/CGO/SSC symmetrical cells. Deposition parameters were changed systematically to examine their effects on film microstructure and electrode performance. A set of deposition parameters including a 0.01 M precursor solution containing metal nitrates in a mixture solvent of de-ionized water (0.6 vol%), ethanol (1.5 vol%) and diethyl butyl carbitol (97.9 vol%), a flow rate of 6 ml/h for precursor solution, a deposition temperature of 350 °C and an imposed electric field of 10 kV/3 cm was identified for preparation of films with a highly porous reticular structure. The superior performance of a reticular SSC electrode was evidenced by its low interfacial resistances of 0.275 and 0.018 Ω cm² measured in 500 and 700 °C, respectively. These values were one-half to one order of magnitude smaller than that of the screen-printed or slurry-painted electrodes.     

Seed-mediated electrochemical growth of gold nanostructures on indium tin oxide thin films

Two-dimensional gold nanostructures (Au NSs) were fabricated on amine-terminated indium tin oxide (ITO) thin films using constant potential electrolysis. By controlling the deposition time and by choosing the appropriate ITO surface, Au NSs with different shapes were generated. When Au NSs were formed directly on aminosilane-modified ITO, the surface roughness of the interface was largely enhanced. Modification of such Au NSs with n-tetradecanethiol resulted in a highly hydrophobic interface with a water contact angle of 144°. Aminosilane-modified ITO films further modified with colloidal Au seeds before electrochemical Au NSs formation demonstrated interesting optical properties. Depending on the deposition time, surface colors ranging from pale pink to beatgold-like were observed. The optical properties and the chemical stability of the interfaces were characterized using UV-vis absorption spectroscopy. Well-defined localized surface plasmon resonance signals were recorded on Au-seeded interfaces with λ_max = 675 ± 2 nm (deposition time 180 s). The prepared interfaces exhibited long-term stability in various solvents and responded linearly to changes in the corresponding refractive indices.     

Characterization of indium tin oxide (ITO) thin films prepared by a sol-gel spin coating process

Indium tin oxide (ITO) thin films were prepared by a sol-gel spin coating method, fired, and then annealed in the temperature range of 450-600°. The XRD patterns of the thin films indicated the main peak of the (2 2 2) plane and showed a higher degree of crystallinity with an increase in the annealing temperature. Upon annealing the films at 500 and 600°, two binding energy levels of Sn⁴⁺ ion of 486.9 eV and 486.6 eV, respectively, were measured in the XPS spectra. The ITO film that was annealed at 600° contained two oxidation states of Sn, Sn²⁺ and Sn⁴⁺, and it had a higher sheet resistance based on a rather low doping concentration of Sn⁴⁺. The film that was annealed at 500° and subsequently treated with 0.1 N HCl solution for 40 s showed a sheet resistance of 225 Ω/square. The surface treatment by the acidic solution diminished the RMS (root mean square) roughness value and the residual carbon content (XPS peak intensity of carbon) of the ITO films. It seems that the acid-cleaning of the ITO thin films led to a decrease of the surface roughness and sheet resistance.     

Effect of nickel doping on structural,optical, electrical and ethanol sensing properties of spray deposited nanostructured ZnO thin films

Undoped and nickel (Ni)-doped ZnO thin films were spray deposited on glass substrates at 523 K using 0.1 M of zinc acetate dihydrate and 0.002–0.01 M of nickel acetate tetrahydrate precursor solutions and subsequently annealed at 723 K. The effect of Ni doping in the structural, morphological, optical and electrical properties of nanostructured ZnO thin film was investigated using X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), UV–vis Spectrophotometer and an Electrometer respectively. XRD patterns confirmed the polycrystalline nature of ZnO thin film with hexagonal wurtzite crystal structure and highly oriented along (002) plane. The crystallite size was found to be increased in the range of 15–31 nm as dopant concentration increased. The SEM image revealed the uniformly distributed compact spherical grains and denser in the case of doped ZnO thin films. All the films were highly transparent with average transmittance of 76%. The measured optical band gap was found to be varied from 3.21 to 3.09 eV. The influence of Ni doping in the room temperature ethanol sensing characteristics has also been reported.     

Protective properties of Al2O3 + TiO2 coating produced by the electrostatic spray deposition method

Mechanical resistance of Al₂O₃ + TiO₂ nanocomposite ceramic coating deposited by electrostatic spray deposition method onto X10CrAlSi18 steel to thermal and slurry tests was investigated. The coating was produced from colloidal suspension of TiO₂ nanoparticles dispersed in 3 wt% solution of Al₂(NO₃)₃, as Al₂O₃ precursor, in ethanol. TiO₂ nanoparticles of two sizes, 15 nm and 32 nm, were used in the experiments. After deposition, coatings were annealed at various temperatures, 300, 1000 and 1200 °C, and next exposed to cyclic thermal and slurry tests. Regardless of annealing temperature and the size of TiO₂ nanoparticles, the outer layer of all coatings was porous. The first five thermal cycles caused a rapid increase of aluminum content of the surface layer to 30–37 wt%, but further increase in the number of thermal cycles did not affect the aluminum content. The oxidation rate of coating-substrate system was lower during the thermal tests than during annealing. The oxidation rate was also lower for smaller TiO₂ particles (15 nm) forming the coating than for the larger ones (32 nm). The protective properties of Al₂O₃ + TiO₂ coating against intense oxidation of substrate were lost at 1200 °C. Slurry tests showed that coatings annealed at 1000 °C had the best slurry resistance, but thermal tests had weakened this slurry resistance, mainly due to decreasing adhesion of the coating.     

Nonlinear growth of zinc tin oxide thin films prepared by atomic layer deposition

Zinc tin oxide (ZTO) thin films can be deposited by atomic layer deposition (ALD) with adjustable electrical, optical and structural properties. However, the ternary ALD processes usually suffer from low growth rate and difficulty in controlling film thickness and elemental composition, due to the interaction of ZnO and SnO₂ processes. In this work, ZTO thin films with different Sn levels are prepared by ALD super cycles using diethylzinc, tetrakis(dimethylamido)tin, and water. It is observed that both the film growth rate and atom composition show nonlinear variation versus [Sn]/([Sn]+[Zn]) cycle ratio. The experimental thickness measured by spectroscopic ellipsometry and X-ray reflectivity are much lower than the expected thickness linearly interpolated from pure ZnO and SnO_x films. The [Sn]/([Sn]+[Zn]) atom ratios estimated by X-ray photoelectron spectroscopy have higher values than that expected from the cycle ratios. Hence, to characterize the film growth behavior versus cycle ratio, a numerical method is proposed by simulating the effect of reduced density and reactivity of surface hydroxyls and surface etching reactions. The structure, electrical and optical properties of ZTO with different Sn levels are also examined by X-ray diffraction, atomic force microscope, Hall measurements and ultraviolet–visible–infrared transmittance spectroscopy. The ZTO turns out to be transparent nanocrystalline or amorphous films with smooth surface. With more Sn contents, the film resistivity gets higher (>1 Ω cm) and the optical bandgap rises from 3.47 to 3.83 eV.     

Thin films of lithium manganese oxide spinel as cathode materials for secondary lithium batteries

The miniaturization of rechargeable lithium-ion batteries requires high quality thin-film electrodes. Electrostatic spray deposition (ESD) technique was used to fabricate LiMn₂O₄ thin-film electrodes with three different morphologies: sponge-like porous, fractal-like porous, and dense structures. X-ray diffraction (XRD) and scanning electron microscopy were used to analyze the structures of the electrodes. These electrodes were made into coin cells against metallic lithium for electrochemical characterization. Galvanostatic cycling of the cells revealed different rate capability for the cells with LiMn₂O₄ electrodes of different morphologies. It is found that the cells with LiMn₂O₄ electrodes of porous, especially the sponge-like porous, morphology better rate capability than those with dense LiMn₂O₄ electrodes. Electrochemical impedance spectroscopy (EIS) study indicates that the large surface area of the porous electrodes should be attributed to the smaller interfacial resistance and better rate capability.     

Realization of Eu-doped p-SnO2 thin film by spray pyrolysis deposition

We report the fabrication of p-SnO₂ thin films by spray pyrolysis deposition using europium (Eu) as an acceptor. Structural and chemical investigations verified that Eu³⁺ ions were successfully incorporated into the SnO₂ crystal by substituting the Sn⁴⁺ sites in the lattice. Even though the undoped SnO₂ thin film showed n-type properties with a charge carrier concentration of −2.343 × 10¹⁸ cm⁻³, SnO₂ showed p-type properties as the Eu was incorporated. In addition, the charge carrier concentration of the Eu-doped SnO₂ increased to 9.121 × 10¹⁹ cm⁻³ as the molar content of the Eu source was increased to 0.2 mM. The optical transmittance was not degraded by the Eu doping and was maintained between 70 and 80% in the visible wavelength spectral range, while the optical band gap of the Eu-doped SnO₂ increased due to the Burstein-Moss effect. The thin film field-effect transistor fabricated by using the Eu-doped SnO₂ showed the typical gate-modulated drain current characteristic of a p-channel transistor with depletion mode. These results demonstrated the effectiveness of Eu as a dopant for p-SnO₂.     

Thermal conductivity of plasma-enhanced atomic layer deposited hafnium zirconium oxide dielectric thin films

Hafnium zirconium oxide (HZO) is promising for applications in future memory devices and energy storage and harvesting. While many studies have focused upon the dielectric and structural properties of HZO, much less investigated are their thermal properties, particularly in thin-film form. We present the first report on the thermal conductivity of plasma-enhanced atomic layer deposited (PEALD) HZO thin films. Steady-state thermoreflectance measures the effective thermal conductivity of undoped and yttrium-doped HZO films and their interfaces. The effective thermal conductivity of the undoped film is found to be 0.75 W m^–1 K^–1, which is comparable to those reported previously for thermal ALD HZO films with similar composition. With increasing yttrium doping level, the effective thermal conductivity slightly decreases down to 0.67 W m^–1 K^–1 owing to dopant scattering of phonons. Our PEALD HZO films are nanocrystalline as observed by grazing-incidence X-ray diffraction and transmission electron microscopy.     

Computational simulation of cold spray process assisted by electrostatic force

The integrated model of compressible thermofluid, splat formation and coating formation for the cold spray process has been established. In-flight behavior of nano-micro particles and the interaction between the shock wave and the particles in a supersonic jet flow impinging onto the substrate and further effect of electrostatic force on the particle acceleration are clarified in detail by carrying out a real-time computational simulation. The optimal particle diameters for an impinging particle velocity exceeding critical velocity exist. Particles with the diameter of submicron interact with shock wave and particles are decelerated prior to the impact. However, the particles can be accelerated considerably by utilizing electrostatic forces even in the presence of unavoidable shock waves. Finally, based on the integrated model, the coating thickness in an electrostatic assisted cold spray process is evaluated.     

Preparation of multi-compositional gas sensing films by combinatorial solution deposition

Various compositions of gas sensing films were prepared by the combinatorial deposition of SnO₂, ZnO, and WO₃ sol solutions and their gas sensing behaviors were investigated. The film composition could be manipulated conveniently via the alternate dropping of different oxide sol solutions. From the correlation between film compositions and gas sensitivities, the selective detection of C₂H₅OH and CH₃COCH₃ in the presence of CO, C₃H₈, H₂, and NO₂ could be attained. In addition, the discrimination between C₂H₅OH and CH₃COCH₃, which is a challenging issue due to their similar chemical nature, becomes possible. This research demonstrates the precise design of the sensor-material composition for the selective gas detection via the combinatorial approach.     

Atomic layer deposition of GDC cathodic functional thin films for oxide ion incorporation enhancement

In this paper, we report successful fabrication of a gadolinia-doped ceria (GDC) thin film using atomic layer deposition (ALD) for improving the performance of solid oxide fuel cells (SOFCs). By varying the deposition conditions and adjusting the configuration of the ALD supercycle, the doping ratio of ALD GDC was controlled. The morphology, crystallinity, and chemical composition of ALD GDC thin films were analyzed. ALD GDC showed different surface chemistry, including oxidation states, at different doping ratios. The application of ALD GDC in a SOFC led to an output power density enhancement greater than 2.5 times. With an anodic aluminum oxide (AAO) porous support structure, an ALD GDC thin film SOFC (TF-SOFC) showed a high power density of 288.24 mW/cm² at an operating temperature of 450°C.     

Structure deformation of indium oxide from nanoparticles into nanostructured polycrystalline films by in situ thermal radiation treatment

A microstructure deformation of indium oxide (In₂O₃) nanoparticles by an in situ thermal radiation treatment in nitrous oxide plasma was investigated. The In₂O₃ nanoparticles were completely transformed into nanostructured In₂O₃ films upon 10 min of treatment time. The treated In₂O₃ nanoparticle sample showed improvement in crystallinity while maintaining a large surface area of nanostructure morphology. The direct transition optical absorption at higher photon energy and the electrical conductivity of the In₂O₃ nanoparticles were significantly enhanced by the treatment.     

Effect of post annealing treatment on electrochromic properties of spray deposited niobium oxide thin films

Niobium oxide thin films were deposited on the glass and fluorine doped tin oxide (FTO) coated glass substrates using simple and inexpensive spray pyrolysis technique. During deposition of the films various process parameters like nozzle to substrate distance, spray rate, concentration of sprayed solution were optimized to obtain well adherent and transparent films. The films prepared were further annealed and effect of post annealing on the structural, morphological, optical and electrochromic properties was studied. Structural and morphological characterizations of the films were carried out using scanning electron microscopy, atomic force microscopy and X-ray diffraction techniques. Electrochemical properties of the niobium oxide thin films were studied by using cyclic-voltammetry, chronoamperometry and chronocoulometry.     

Effect of doped niobium pentoxide on structure and properties of hafnium oxide films deposited by ion beam assisted deposition

Hafnium oxide is widely used in optical coating materials because of its high refractive index, broad band gap, high laser damage threshold and its high transparency in the wavelength range from ultraviolet to middle infrared (0.20–12 μm). However, hafnium oxide has some defects such as strong crystallinity and poor surface quality, which results in enhanced absorption and reflection of light wave and limits its application in optical field. As a pentoxide with high transparency and excellent optical properties in the wavelength range from ultraviolet to mid-infrared(0.35–9 μm), the doping of niobium pentoxide can effectively improve the surface quality and optical properties of the films. Mixed films with different chemical compositions were prepared by ion beam assisted deposition, and the microstructure, crystallinity, surface quality, optical properties and mechanical properties of the mixed films with different chemical compositions were investigated. The doping of niobium pentoxide inhibits the crystallization of hafnium oxide, optimizes the surface quality of the films, and improves the refractive index and mechanical properties of mixed films, effectively broadens the application of hafnium oxide in the field of optical films.     

Fast switching electrochromism from colloidal indium tin oxide in tungstate-based thin film assemblies

Layer-by-layer assembly was used to alternately deposit tungstate anions with cationic poly(4-vinylpyridine-co-styrene) to generate electrochromic thin films that transit from transparent to dark blue in their oxidized and reduced states, respectively. Tungstate is a good electrochromic material because it is completely colorless in its deposited state, while most other electrochromic materials exhibit some type of color in the absence of an applied voltage. Despite its advantages, tungstates are plagued by long switching time (>30 s), which is common amongst ceramic electrochromics, due to lack of electrical conductivity in at least one of the two states. In an effort to decrease switching time, indium tin oxide (ITO) nanoparticles were incorporated into these tungstate-based assemblies. In the absence of ITO, these films take 30-60 s to completely switch and exhibit reduced contrast with each switch. ITO-containing films, with ITO in every other bilayer, fully switch in 14 s and do not exhibit the same drift in transmittance with repeated switching. ITO allows these films to maintain electrical conductivity in both states, which is the source of this faster, more stable switching. With further optimization, this combination of fast switching and high contrast makes these films promising for use in smart windows and flexible displays.