Constitution, microstructure, and battery performance of magnetron sputtered Li-Co-O thin film cathodes for lithium-ion batteries as a function of the working gas pressure

Li-Co-O thin film cathodes have been deposited onto Si and stainless steel substrates by RF magnetron sputtering from a ceramic LiCoO₂ target at various working gas pressures from 0.15 to 25 Pa. Composition, crystal structure and thin film morphology were examined and properties such as intrinsic stress, conductivity and film density were determined. As-deposited films at 0.15 Pa as well as in the range between 5 Pa and 10 Pa working gas pressure showed a nanocrystalline metastable rocksalt structure with disordered cation arrangement and were nearly stoichiometric. To induce a cation ordering the films were annealed in a furnace at temperatures between 100 and 600 °C for 3 h in argon/oxygen atmosphere (Ar:O₂ = 4.5:5) of 10 Pa. This cation ordering process was observed by XRD and Raman spectroscopy. For the films deposited at 10 Pa gas pressure an annealing temperature of 600 °C leads to the formation of the high temperature phase HT-LiCoO₂ with a layered structure. The Raman spectrum of the films deposited at 0.15 Pa and annealed at 400 °C indicates the formation of the low temperature phase LT-LiCoO₂ with a cubic spinel-related structure, which is assumed to be stabilized due to high compressive stress in the film. The electrochemical characterisation of annealed thin film cathodes revealed that the discharge capacity strongly depends on the crystal structure. Thin Li-Co-O films with a perfect layered HT-LiCoO₂ structure showed the highest discharge capacities.     

Electrochemical performance of magnetron sputter deposited LiFePO4-Ag composite thin film cathodes

LiFePO₄ thin films have been sputtered from a pure LiFePO₄ target onto Ag/SS, Ag/Si₃N₄/Si and Si₃N₄/Si substrates. All of the deposited films were annealed at 973 K for 1 hr in H₂/Ar (5 %) atmosphere. Substrate induced microstructural and crystallographic evolutions have been observed by a scanning electron microscope and X-ray diffraction. Energy dispersion spectra and X-ray photoelectron spectra revealed that Ag was mixed in the LiFePO₄ films deposited on Ag under layers. Ceramic metal composite thin films were obtained. The film conductivity (1 × 10^− 3 Scm^− 1) is therefore elevated by an order of six, compared with pure LiFePO₄ (10^− 9 Scm^− 1). The electrochemical measurements of the LiFePO₄-Ag films showed a flat plateau at 3.4 V (v.s. Li/Li⁺) and a reversible capacity of 80 mAh/g. Optimization of Ag contents may further improve the discharge capacity.     

Synthesis and characterization of spray deposited PdO-NiO-SDC composite anode material for potential application in IT-SOFC

The synthesis of mixed conducting PdO-NiO-SDC composite films has been reported for the first time by a simple and cost effective spray pyrolysis technique. The films were deposited at low substrate and annealing temperatures of 350 °C and 500 °C, respectively. The structure, morphology and electrical properties of the films were studied by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray analysis (EDAX), atomic force microscopy (AFM) and impedance spectroscopy (IS). The substrate and annealing temperatures were optimized for obtaining nano-crystalline, porous, adherent and composite films with PdO, NiO and SDC phases. Films showed good microstructure with sufficient porosity and good connectivity of the deposited material. Crystallite size of the deposited material was found to be in the range of 7-9 nm. The deposited film showed high oxygen ion conductivity, 3.94 × 10⁻¹ S cm⁻¹ at 350 °C. Due to their nano-crystalline, porous and composite nature the spray deposited PdO-NiO-SDC films may have high three phase boundary area and hence can be considered as an anode for intermediate temperature solid oxide fuel cells.     

Structural and dielectric properties of Bi2Zn2/3Nb4/3O7 thin films prepared by pulsed laser deposition at low temperature for embedded capacitor applications

Bi₂Zn_2/3Nb_4/3O₇ thin films were deposited on Pt/TiO₂/SiO₂/Si(1 0 0) substrates at a room temperature under the oxygen pressure of 1-10 Pa by pulsed laser deposition. Bi₂Zn_2/3Nb_4/3O₇ thin films were then post-annealed below 200 °C in a rapid thermal process furnace in air for 20 min. The dielectric and leakage current properties of Bi₂Zn_2/3Nb_4/3O₇ thin films are strongly influenced by the oxygen pressure during deposition and the post-annealing temperature. Bi₂Zn_2/3Nb_4/3O₇ thin films deposited under 1 Pa oxygen pressure and then post-annealed at a temperature of 150 °C show uniform surface morphologies. Dielectric constant and loss tangent are 57 and 0.005 at 10 kHz, respectively. The high resolution TEM image and the electron diffraction pattern show that nano crystallites exist in the amorphous thin film, which may be the origin of high dielectric constant in the Bi₂Zn_2/3Nb_4/3O₇ thin films deposited at low temperatures. Moreover, Bi₂Zn_2/3Nb_4/3O₇ thin film exhibits the excellent leakage current characteristics with a high breakdown strength and the leakage current density is approximately 1 × 10⁻⁷ A/cm² at an applied bias field of 300 kV/cm. Bi₂Zn_2/3Nb_4/3O₇ thin films are potential materials for embedded capacitor applications.     

Process–structure–property relations of micron thick Gd2O3 films deposited by reactive electron-beam physical vapor deposition (EB-PVD)

Thick polycrystalline gadolinium oxide (Gd₂O₃) films up to 11 μm in thickness were deposited via reactive electron beam-physical vapor deposition (EB-PVD) on silicon (111) substrates for use in neutron radiation detection. The effects of coating thickness, substrate temperature, and oxygen flow on film structural, electrical and optical properties were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), transmission electron microscopy (TEM), capacitance–voltage (C–V) measurements, and ultraviolet–visible (UV–Vis) spectroscopy. Films were characterized as either monoclinic or mixed monoclinic and cubic phase depending on deposition parameters. Increasing the deposition temperature resulted in increased film crystallinity and cubic phase volume while decreasing the O₂ flow rate resulted in increased volume of the monoclinic phase. Evidence of a thickness dependent crystallography is also presented. Electrical property measurements showed thin film dielectric constant could be tailored between 12 and 20 at 1 MHz frequency by decreasing the oxygen flow rate at deposition temperatures of 250 °C which is attributed to an increased presence of the monoclinic phase and increased film density. Band gap values were calculated from transmission measurements and ranged between 5.44 and 5.96 eV.     

A facile and environment-friendly method to fabricate thin electrolyte films for solid oxide fuel cells

A facile and environment-friendly method, the so-called vertical deposition (abbreviated as VD) method, is used to prepare thin yttria-stabilized zirconia (YSZ) films (≤5 μm) for solid oxide fuel cells (SOFCs). The YSZ films are self-assembled by VD process based on capillary force. The influence of experimental conditions (e.g. concentration of YSZ dispersion, deposition times, and sintering procedure) on the morphology of the films produced and thereby on the performance of SOFC devices is investigated. The single cell utilizing a 5 μm dense YSZ film as solid electrolyte achieves a high open circuit voltage of 1.05 V which remains stable at 700 °C for 4 h. The peak power density is 0.4 W cm⁻² at 800 °C for the phase inversion anode-supported fuel cell composed of an YSZ electrolyte film of 5 μm thick. The VD method developed herein is promising for preparing ultra-thin electrolyte films for SOFCs.     

Structural, morphological and electrical properties of spray deposited nano-crystalline CeO2 thin films

Nanocrystalline, uniform, dense, and adherent cerium oxide (CeO₂) thin films have been successfully deposited by a simple and cost effective spray pyrolysis technique. CeO₂ films were deposited at low substrate and annealing temperatures of 350 °C and 500 °C, respectively. Films were characterized by differential thermal analysis, X-ray diffraction, scanning electron microscopy, atomic force microscopy; two probe resistivity method and impedance spectroscopy. X-ray diffraction analysis revealed the formation of single phase, well crystalline thin films with cubic fluorite structure. Crystallite size was found to be in the range of 10-15 nm. AFM showed formation of smooth films with morphological grain size 27 nm. Films were found to be highly resistive with room temperature resistivity of the order of 10⁷ Ω cm. Activation energy was calculated and found to be 0.78 eV. The deposited film showed high oxygen ion conductivity of 5.94 × 10⁻³ S cm⁻¹ at 350 °C. Thus, the deposited material shows a potential application in intermediate temperature solid oxide fuel cells (IT-SOFC) and might be useful for μ-SOFC and industrial catalyst applications.     

Preparation and characterization of CoFe2O4 powders and films via the sol-gel method

The CoFe₂O₄ (CFO) starting precursor solutions were prepared by two sol-gel methods. The XRD results show that the second sol-gel method is a better method to obtain CFO materials with high purity. The CFO precursor solutions prepared by the second sol-gel method were spin-coated onto the Pt/Ti/SiO₂/Si substrate to obtain CFO films. With the increase of annealing temperature, the relative amounts of secondary phases in CFO films are decreased. When annealed at 700 °C, CFO films are almost composed of the main phase and the substrate phase without secondary phases. The CFO film is crack-free and has compact structure without any pore. The thickness of CFO film is about 49 nm. The starting precursor solution with the concentration of 0.15 mol L⁻¹ is better for preparing CFO films. The CFO films with nano-scaled film thicknesses have better magnetic properties than the CFO powders.     

Epitaxial 0.65PbMg1/3Nb2/3O3-0.35PbTiO3 (PMN-PT) thin films grown on LaNiO3/CeO2/YSZ buffered Si substrates

Ferroelectric PMN-PT thin films with a thickness of 600 nm were epitaxially grown on buffered Si (0 0 1) substrates at a substrate temperature that ranged from 550 to 700 °C using pulsed laser deposition (PLD). LaNiO₃ (LNO) electrode thin films with a resistivity of ∼1900 μΩ cm were epitaxially grown on CeO₂/YSZ buffered Si (0 0 1) substrates. The PMN-PT thin films grown at 600 °C on LNO/CeO₂/YSZ/Si substrates had a pure perovskite and epitaxial structure. The PMN-PT films exhibited a high dielectric constant of about 1818 and a low dissipation factor of 0.04 at a frequency of 10 kHz. Polarization-electric-field (P-E) hysteresis characteristics, with a remnant polarization of 11.1 μC/cm² and a coercive field of 43 kV/cm, were obtained in the epitaxial PMN-PT films.     

Fabrication and characterization of ITO thin films on heat-resistant transparent flexible clay films

Transparent conductive indium tin oxide (ITO) thin films were deposited on transparent flexible clay films with heat resistant and high gas barrier properties by rf magnetron sputtering. The electrical, structural, and optical properties of these films were examined as a function of deposition temperature. A lowest resistivity of 4.2 × 10^− 4 Ωcm and an average transmittance more than 90% in the visible region were obtained for the ITO thin films fabricated at deposition temperatures more than 300 °C. It was found that ITO thin films with low resistivity and high transparency can be achieved on transparent flexible clay film using conventional rf magnetron sputtering at high temperature, those characteristics are comparable to those of ITO thin films deposited on a glass substrate.     

Preparation and electrochemical performance of copper foam-supported amorphous silicon thin films for rechargeable lithium-ion batteries

Amorphous Si thin films, which have been deposited on copper foam by radio-frequency (rf) magnetron sputtering, are employed as anode materials of rechargeable lithium-ion batteries. The morphologies and structures of the as-prepared Si thin films are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray powder diffraction (XRD). Electrochemical performance of lithium-ion batteries with the as-prepared Si films as the anode materials is investigated by cyclic voltammetry and charge-discharge measurements. The results show that the electrode properties of the prepared amorphous Si films are greatly affected by the deposition temperature. The film electrode deposited at an optimum temperature of 300 °C can deliver a specific capacity of ∼2900 mAh/g and a coulombic efficiency above 95% at charge/discharge current density of 0.2C after 30 cycles. The Li⁺ diffusion coefficiency in copper foam-supported Si thin films is determined to be 2.36 × 10⁻⁹ cm²/s.     

Effect of air annealing on mechanical properties and structure of amorphous B4C films

Amorphous B₄C films were prepared by magnetron sputtering of the hot-pressed B₄C target in different regimes. Hardness, intrinsic stress and film structure were investigated in dependence on the annealing temperature in air.Changes in the film structure and composition were investigated by Raman spectroscopy, confocal microscopy, and electron probe microanalysis. It has been shown that an annealing at 500 °C for 1 h leads to stress reduction, slight thickness decrease and increase of film hardness. However already at 600 °C the film oxidation proceeds very intensively with formation of the phases of boron oxide and amorphous carbon in the surface layer. The thickness of the film decreases quickly.The film oxidation is accompanied by formation of numerous carbon hillocks and redistribution of film material after annealing in furnace at 500 and especially 600 °C. The oxidation of a-B₄C films as well as of the crystalline bulk samples starts in some locations and has clearly pronounced heterogeneous character that indicates heterogeneous structure of amorphous films as well as of bulk crystalline samples.Annealing in air for a long period shifts down the onset of formation of hillocks to 400 °C and changes in film morphology to 300 °C. Thus the upper temperature limit for application of a-B₄C films in air depends also on the exposure time at the operation temperature.     

Growth of ZnO nanorods by air annealing of ZnO films with an applied electric field

A novel method of ZnO nanorods growth is presented based on low temperature (300 °C) air annealing of ZnO film while applying an electric field (∼ 10 V/cm) parallel to the film. The films were deposited on glass substrates using a filtered vacuum arc deposition system equipped with a Zn cathode, at an arc current of 160 A, oxygen pressure of 3.2 mTorr, and deposition time of 30 s. Cu tape electrodes were applied on each end of the coated sample, and used to apply the electric field. The samples were annealed in a quartz furnace at 200, 300, 400 °C for 20 or 60 min. Each sample surface was examined using a Scanning Electron Microscope (SEM) and a High Resolution SEM (HRSEM) to study its micro- and nano-structure. The film crystallographic structure was studied using X-ray diffractometry (XRD). ZnO rods with lengths of ∼ 3 μm were observed on the samples annealed at 300 °C for 20 min with an electric field of ∼ 10³ V/m, while separated conical forms with lengths of ∼ 0.5 μm and base width of ∼ 150 nm were observed after annealing under the same conditions but without any electric field. The rod growth rate and area density were ∼ 2.0-2.5 nm/s, and ∼ 3 × 10⁷ cm^− 2, respectively.     

Perpendicular magnetic anisotropy in 70 nm CoFe2O4 thin films fabricated on SiO2/Si(1 0 0) by the sol-gel method

Cobalt ferrite CoFe₂O₄ films were fabricated on SiO₂/Si(1 0 0) by the sol-gel method. Films crystallized at/above 600 °C are stoichiometric as expected. With increase of the annealing temperature from 600 °C to 750 °C, the columnar grain size of CoFe₂O₄ film increases from 13 nm to 50 nm, resulting in surface roughness increasing from 0.46 nm to 2.55 nm. Magnetic hysteresis loops in both in-plane and out-of-plane directions, at different annealing temperatures, indicate that the films annealed at 750 °C exhibit obvious perpendicular magnetic anisotropy. Simultaneously, with the annealing temperature increasing from 600 °C to 750 °C, the out of plane coercivity increases from 1 kOe to 2.4 kOe and the corresponding saturation magnetization increases from 200 emu/cm³ to 283 emu/cm³. In addition, all crystallized films exhibit cluster-like structured magnetic domains.     

P-type transparent conducting SnO2:Zn film derived from thermal diffusion of Zn/SnO2/Zn multilayer thin films

Highly transparent, p-type conducting SnO₂:Zn thin films are prepared from the thermal diffusion of a sandwich structure of Zn/SnO₂/Zn multilayer thin films deposited on quartz glass substrate by direct current (DC) and radio frequency (RF) magnetron sputtering using Zn and SnO₂ targets. The deposited films were annealed at various temperatures for thermal diffusion. The effect of annealing temperature and time on the structural, electrical and optical performances of SnO₂:Zn films was studied. XRD results show that all p-type conducting films possessed polycrystalline SnO₂ with tetragonal rutile structure. Hall effect results indicate that the treatment at 400 °C for 6 h was the optimum annealing parameters for p-type SnO₂:Zn films which have relatively high hole concentration and low resistivity of 2.389 × 10¹⁷ cm^− 3 and 7.436 Ω cm, respectively. The average transmission of the p-type SnO₂:Zn films was above 80% in the visible light range.     

Effect of annealing temperature on structure and electrochemical properties of LiCoO2 cathode thin films

LiCoO2 thin films, which can be used as a cathode material in microbatteries, were deposited using radio frequency (r.f.) magnetron sputtering system from a LiCoO2 target and in an O2+Ar atmosphere.The films were characterized by various methods such as XRD, SEM and AFM.The LiCoO2 films were annealed in air at 300, 500, 700 and 800 ℃ respectively.The effect of the annealing temperature on the structure, the surface morphology and the electrochemical properties of the films were investigated.The LiCoO2 thin film deposited at room temperature is amorphous and has smaller grain size.With increasing of annealing temperature, the crystallinity of the films is promoted.When the annealing temperature increases to 700 ℃, the films have a perfect crystalline LiCoO2 phase.The LiCoO2 thin film without annealing has no discharge plateau and small discharge capacity (about 27 μAh·cm-2μm).The discharge capacity increases with the increasing of annealing temperature and reaches 47 μAh·cm-2μm for the film annealed with 700 ℃, which also shows the typical discharge plateau of 3.9 V.The cycle performance of LiCoO2 thin films of as grown and annealed at different temperatures were studied.In the case of the film without thermal treatment, the capacity fading is much faster than that of the film annealed at different temperature, showing about 40% capacity loss only after 25 cycles.However, in the case of the film annealed at 700 ℃, the capacity reaches to steady state gradually and maintained constantly with cycling.After 25 times cycling, the discharge capacity of the film annealed at 700 ℃ decreases to about 36.9 μAh·cm-2·μm, only 0.8% capacity loss per cycle.     

Epitaxial growth of tin ferrite thin films using pulsed laser deposition technique

Epitaxial thin films of tin ferrite (SnFe₂O₄) were deposited on (0 0 2) oriented strontium titanate (SrTiO₃) substrate using pulsed laser deposition method. The quality and epitaxial nature of the films were investigated by X-ray diffraction technique. The phi scan of the film and the substrate shows four folds symmetry indicating cube-on-cube epitaxial growth of the film on the substrate. The optical bandgap of the film was estimated to be 2.6 eV using optical transmittance data. Magnetic measurements indicate that the coercive field and remnant magnetization of the film decrease with increase in temperature. The presence of hysteresis loop in M vs. H plot at room temperature indicates the ferromagnetic nature of the film.     

Thin films of thermoelectric compound Mg2Sn deposited by co-sputtering assisted by multi-dipolar microwave plasma

Magnesium stannide (Mg₂Sn) thin films doped with Ag intended for thermoelectric applications are deposited on both silicon and glass substrates at room temperature by plasma assisted co-sputtering. Characterization by scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction confirms the formation of fine-grained polycrystalline thin films with thickness of 1-3 μm. Stoichiometry, microstructure and crystal structure of thin films are found to vary with target biasing and the distance from targets to substrate. Measurements of electrical resistivity and Seebeck coefficient at room temperature show the maximum power factor of ∼5.0 × 10⁻³ W K⁻² m⁻¹ for stoichiometric Mg₂Sn thin films doped with ∼1 at.% Ag.     

New process for synthesis of ZnO thin films: Microstructural, optical and electrical characterization

Nanocrystalline ZnO thin films were prepared on glass substrates by using spin coating technique. The effect of annealing temperature (400-700 °C) on structural, compositional, microstructural, morphological, electrical and optical properties of ZnO thin films were studied by X-ray diffraction (XRD), Energy dispersive Spectroscopy (EDS), Atomic Force Microscopy (AFM), High Resolution Transmission Microscopy (HRTEM), Scanning Electron Microscopy (SEM), Electrical conductivity and UV-visible Spectroscopy (UV-vis). XRD measurements show that all the films are nanocrystallized in the hexagonal wurtzite structure and present a random orientation. The crystallite size increases with increasing annealing temperature. These modifications influence the optical properties. The AFM analysis revealed that the surface morphology is smooth. The HRTEM analysis of ZnO thin film annealed at 700 °C confirms nanocrystalline nature of film. The SEM results shows that a uniform surface morphology and the nanoparticles are fine with an average grain size of about 40-60 nm. The dc room temperature electrical conductivity of ZnO thin films were increased from 10⁻⁶ to 10⁻⁵ (Ω cm)⁻¹ with increase in annealing temperature. The electron carrier concentration (n) and mobility (μ) of ZnO films annealed at 400-700 °C were estimated to be of the order of 4.75-7.10 × 10¹⁹ cm⁻³ and 2.98-5.20 × 10⁻⁵ cm² V⁻¹ S⁻¹.The optical band gap has been determined from the absorption coefficient. We found that the optical band gap energy decreases from 3.32 eV to 3.18 eV with increasing annealing temperature between 400 and 700 °C. This means that the optical quality of ZnO films is improved by annealing.It is observed that the ZnO thin film annealing at 700 °C has a smooth and flat texture suited for different optoelectronic applications.     

Nano silicon top-layer for composite-induced multiphasic enhancement of thermal stability of hardness of diamond-like carbon nanofilm at 900 °C

The effect of 25-nm silicon top-layer on the hardness and thermal stability of 100-nm diamond-like carbon (DLC) film annealed at 750–900 °C has been investigated. The evolution of surface morphology, microstructure and reaction between C and Si was examined by high resolution scanning/transmission electron microscope, Raman and FTIR spectroscopy. The hardness of films was investigated using nano-indentation. After 750–900 °C annealing, the hardness of single carbon layer greatly decreased at 750 °C and then slightly increased at 900 °C due to the formation of SiC at the interface between the single C film and the Si substrate. In contrast, no significant variation occurred on the hardness of two-layer Si/C film under RTA at 750–900 °C. Although the higher annealing temperature resulted in higher sp²/sp³ bonding ratio as well as more sp² bonding formation in the carbon layer to soften the structure, the added Si top-layer can protect DLC from reaction with environmental oxygen and sustain the hardness of the composite film because of the multiphasic formation with extra SiC on the surface and at the interface between the C layer and Si substrate through great interdiffusion between Si and C for extending DLC high-temperature application.