Sputter deposited LiPON thin films from powder target as electrolyte for thin film battery applications

Lithium phosphorus oxynitride (LiPON) thin films as solid electrolytes were prepared by reactive radio frequency (rf) magnetron sputtering from Li₃PO₄ powder compact target. High deposition rates and ease of manufacturing powder target compared with conventional ceramic Li₃PO₄ targets offer flexibility in handling and reduce the cost associated. Rf power density varied from 1.7 Wcm^− 2 to 3 Wcm^− 2 and N₂ flow from 10 to 30 sccm for a fixed substrate to target distance of 4 cm for best ionic conductivity. The surface chemical analysis done by X-ray photoelectron spectroscopy showed incorporation of nitrogen into the film as both triply, N_t and doubly, N_d coordinated form. With increased presence of N_t, ionic conductivity of LiPON was found to be increasing. The electrochemical impedance spectroscopy of LiPON films confirmed an ionic conductivity of 1.1 × 10^− 6 Scm^− 1 for optimum rf power and N₂ flow conditions.     

Influence of radio frequency power on structure and ionic conductivity of LiPON thin films

Lithium phosphorus oxynitride (LiPON) thin films as solid electrolytes were prepared by radio frequency magnetron sputtering of a Li₃PO₄ target in ambient nitrogen atmosphere. The influence of radio frequency (rf) power on the structure and the ionic conductivity of LiPON thin films has been investigated. The morphology, composition, structure and ionic conductivity of thin films were characterized by scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and a.c. impedance measurement. It was found that ionic conductivity of LiPON thin films increases with N content in thin films. XPS measurements reveal that ionic conductivity also keeps relativity with the structure of thin films. Higher the N _t/N _d ratio, higher will be the ionic conductivity of LiPON thin films. And both of them can be improved by increasing rf power from 1·5 W/cm² to 5·5 W/cm².     

Influence of sputtering pressure on the structure and ionic conductivity of thin film amorphous electrolyte

Ionic conducting thin film amorphous electrolytes are promising candidates for microelectronics applications. This study presents an investigation into the structure and composition of lithium phosphorus oxynitride (LiPON) thin film electrolyte prepared using radio frequency (RF) sputtering on Li₃PO₄ target. The ionic conductivity of LiPON thin films has been dramatically improved by decreasing N₂ pressure. X-ray photoelectron spectra (XPS) were used to determine the structure and composition of LiPON thin films. It was found that increasing the N₂ pressure during the deposition process resulted in a greatly decreased formation of triply coordinated –N<(N_t) as compared to doubly coordinated –N=(N_d) in LiPON thin films. These results indicate that the N_t structural unit plays an important role in the improvement of ionic conductivity as compared to the N_d structural unit. It also shows that PO₂N₂ tetrahedra with two N_t structural units exist in LiPON thin films at low N₂ pressures. Consequently, the improved ionic conductivity of the LiPON thin film deposited at low pressure results from the existence of PO₂N₂ tetrahedra with two N_t structural units in LiPON thin film. PO₂N₂ tetrahedra with two N_t structural units provides higher cross-linking density of the glass network and lower electrostatic energy than with two N_d structural units.     

Nitrogen doped p-type SnO thin films deposited via sputtering

p-Type SnO thin films were fabricated via reactive RF magnetron sputtering on borosilicate substrates with an Sn target and Ar/O₂/N₂ gas mixture. The undoped SnO thin film consisted of a polycrystalline SnO phase with a preferred (1 0 1) orientation; however, with nitrogen doping, the preferred orientation was suppressed and the grain size decreased. The electrical conductivity of the undoped SnO thin films demonstrated a relatively low p-type conductivity of 0.05 Ω⁻¹ cm⁻¹ and it was lowered slightly with nitrogen doping to 0.039 Ω⁻¹ cm⁻¹. The results of the X-ray photoelectron spectroscopy suggested that the nitrogen doping created donor defects in the SnO thin films causing lower electrical conductivity. Lastly, both the undoped and doped SnO thin films had poor optical transmittance in the visible range.     

Electrochemical properties of LiPON films made from a mixed powder target of Li3PO4 and Li2O

Lithium phosphorus oxynitride (LiPON) films were prepared by radio frequency magnetron sputtering. In order to control the atomic composition of the films, a mixture of Li₃PO₄ and Li₂O powders was used as the sputtering target. The ionic conductivity of the films showed a maximum (6.4 × 10^− 6 S/cm) when the molar ratio of Li₃PO₄ to Li₂O in the target was 1:2. The films formed from a target not containing Li₂O showed good durability in air at the expense of slightly poorer ionic conductivity. This is probably due to the amount of Li in the film being significantly less which effectively suppressed absorption of CO₂ in air.     

Ion conducting properties of hydrogen-containing Ta2O5 thin films prepared by reactive sputtering

Hydrogen-containing Ta₂O₅ (Ta₂O₅:H) thin films are considered to be a candidate for a proton-conducting solid-oxide electrolyte. In this study, Ta₂O₅:H thin films were prepared by reactively sputtering a Ta metal target in an O₂ + H₂O mixed gas. The effects of sputtering power and post-deposition heat treatment on the ion conducting properties of the Ta₂O₅:H thin films were studied. The ionic conductivity of the films was improved by decreasing the RF power and a maximum conductivity of 2 × 10⁻⁹ S/cm was obtained at an RF power of 20 W. The ionic conductivity decreased by heat-treatment in air, and no ion-conduction was observed after treatment at 300 °C due to the decrease in hydrogen content in the films.     

Lipon thin films grown by plasma-enhanced metalorganic chemical vapor deposition in a N2-H2-Ar gas mixture

Lithium phosphorus oxynitride (Lipon) thin films have been deposited by a plasma-enhanced metalorganic chemical vapor deposition method. Lipon thin films were deposited on approximately 0.2 μm thick Au-coated alumina substrates in a N₂-H₂-Ar plasma at 13.56 MHz, a power of 150 W, and at 180 °C using triethyl phosphate [(CH₂CH₃)₃PO₄] and lithium tert-butoxide [(LiOC(CH₃)₃] precursors. Lipon growth rates ranged from 10 to 42 nm/min and thicknesses varied from 1 to 2.5 μm. X-ray powder diffraction showed that the films were amorphous, and X-ray photoelectron spectroscopy (XPS) revealed approximately 4 at.% N in the films. The ionic conductivity of Lipon was measured by electrochemical impedance spectroscopy to be approximately 1.02 μS/cm, which is consistent with the ionic conductivity of Lipon deposited by radio frequency magnetron sputtering of Li₃PO₄ targets in either mixed Ar-N₂ or pure N₂ atmosphere. Attempts to deposit Lipon in a N₂-O₂-Ar plasma resulted in the growth of Li₃PO₄ thin films. The XPS analysis shows no C and N atom peaks. Due to the high impedance of these films, reliable conductivity measurements could not be obtained for films grown in N₂-O₂-Ar plasma.     

Optimization of thermoelectric properties on Bi2Te3 thin films deposited by thermal co-evaporation

The optimization of the thermal co-evaporation deposition process for n-type bismuth telluride (Bi₂Te₃) thin films deposited onto polyimide substrates and intended for thermoelectric applications is reported. The influence of deposition parameters (evaporation rate and substrate temperature) on film composition and thermoelectric properties was studied for optimal thermoelectric performance. Energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy confirmed the formation of Bi₂Te₃ thin films. Seebeck coefficient (up to 250 μV K^− 1), in-plane electrical resistivity (≈10 μΩ m), carrier concentration (3×10¹⁹-20×10¹⁹ cm^− 3) and Hall mobility (80-170 cm² V⁻¹ s^− 1) were measured at room temperature for selected Bi₂Te₃ samples.     

AC plasma induced modifications in β-In2S3 thin films prepared by spray pyrolysis

β-In₂S₃ thin films, deposited by spray pyrolysis, were treated in N₂ and air plasmas at 240 and 400 Pa. X-ray diffraction, SEM, and EDS analysis, and optical and electrical studies have been used to characterize the as-prepared and plasma treated thin films. The post-deposition plasma treatments affect the morphology and the optoelectronic properties of the In₂S₃ thin films. The In₂S₃ thin films treated with N₂ plasma at 240 Pa showed an optical band gap, E_g, of 2.16 eV and an electrical conductivity of 2 × 10^− 2 (Ω cm)^− 1.     

Thermal co-evaporation of Sb2Te3 thin-films optimized for thermoelectric applications

Antimony telluride (Sb₂Te₃) is a chalcogenide material used in thermoelectric applications. The deposition of thin films of Sb₂Te₃ requires a precisely controlled process to achieve a desirable high thermoelectric figure-of-merit. The optimization of the thermal co-evaporation process for p-type Sb₂Te₃ thin-film onto plastic substrates (Kapton© polyimide) for thermoelectric applications is reported. The influence of deposition parameters and composition on thermoelectric properties was studied, seeking optimal thermoelectric performance. Energy-dispersive X-ray spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Raman spectroscopy all confirmed the formation of Sb₂Te₃ thin films. Seebeck coefficient (up to 190 μVK⁻¹), in-plane electrical resistivity (8-15 μΩm), carrier concentration (1 × 10¹⁹-7 × 10¹⁹ cm⁻³) and Hall mobility (120-180 cm²V⁻¹s⁻¹) were measured at room temperature for the best Sb₂Te₃ thin-films.     

Spray deposition and property analysis of anatase phase titania (TiO2) nanostructures

Anatase phase titanium dioxide thin films have been deposited at various substrate temperatures by chemical spray pyrolysis of an aerosol of titanyl acetylacetonate. Deposited TiO₂ films were nanocrystalline and preferentially oriented along [101] direction, uniform and adherent to the glass substrate. Best films processed at 450 °C were characterized to analyze its phase composition, texture, roughness, optical and electrical properties. X-ray photoelectron spectroscopy revealed that the surface of the film has only the Ti⁴⁺ cations to form perfect TiO₂ stoichiometry with less amount of hydration. Atomic force microscopy image demonstrated the existence of homogeneous and rough surface, suitable for electrocatalytic applications. The film has an optical transmittance more than 90% and the refractive index of 2.07 was recorded at the wavelength 633 nm. Due to nano-sized grains, obtained optical band gap (3.65 eV) of the TiO₂ thin film was larger than that of the bulk TiO₂ (3.2 eV). Calculated porosity of the films 0.44, revealed the porous nature of the films. Hall measurements indicated that these materials are p-type and yield a carrier density of the order 8.8 × 10²⁰ cm⁻³ and a carrier mobility of 0.48 × 10⁻⁶ cm²/Vs. The dc electrical conductivity was therefore very low (8.91 × 10⁻⁶ S/cm) because of lower value of mean free path of the charge carriers (4.36 × 10⁻¹¹ cm). It gives an impression that the process of spray pyrolysis provides an easy way to tailor make thin films possessing superior properties.     

Impact of ethylene carbonate on ion transport characteristics of PVdF-AgCF3SO3 polymer electrolyte system

The ionic transport in thin film plasticized polymer electrolytes based on polyvinylidene fluoride (PVdF) as the polymer host, silver triflate (AgCF₃SO₃) as salt and ethylene carbonate (EC) as plasticizer prepared by solution casting technique has been reported. Addition of silver triflate has resulted in an increase in the room temperature (298 K) electrical conductivity of the polymer from 10⁻⁶ to 10⁻⁵ S cm⁻¹ whereas incorporation of EC as the plasticizer has further enhanced the conductivity value by an order of magnitude to 10⁻⁴ S cm⁻¹ owing to the possible decrease in crystallinity of the polymer matrix as revealed by the detailed temperature-dependent complex impedance, silver ionic transference number, Fourier transform infrared and X-ray diffraction measurements.     

Oxidation states of molybdenum in oxide films formed in sulphuric acid and sodium hydroxide

X-ray photoelectron spectroscopy is used to investigate the oxidation states of molybdenum in thin films formed potentiostatically, over a range of potentials, in either 1 mol dm^− 3 H₂SO₄ or 10 mol dm^− 3 NaOH at 20 °C. Mo 3d spectra suggested that MoO₂ and Mo(OH)₂ were the main components of the films, with smaller amounts of MoO₃ and possibly Mo₂O₅. O 1s spectra indicated the presence of oxygen as oxide and hydroxide species and as bound water. Ion beam analysis revealed the formation of thin films at all potentials, with significant losses of oxidized molybdenum to the electrolyte.     

Optical properties of TiO2 thin films deposited on polycarbonate by ion beam assisted evaporation

TiO₂ thin films were deposited on polycarbonate (PC) substrate by ion beam assisted evaporation. The grain size increased with the ion anode voltage and film thickness. The TiO₂ thin films had an amorphous structure. Moiré deflectometry was used to measure the nonlinear refractive indices of TiO₂ thin films on PC substrates. The nonlinear refractive index was measured to be of the order of 10^− 8 cm² W^− 1 and a change in refractive index was of the order of 10^− 5. Dense TiO₂ films exhibited high linear refractive indices, red-shift of the optical absorbance, and absorbance in the near-IR region.     

Electrical properties of Sm-doped bismuth titanate thin films prepared on Si (100) by metalorganic decomposition

Samarium-doped bismuth titanate [Bi_4−xSm_xTi₃O₁₂ (BSmT)] thin films have been grown on n-type Si (100) substrates using metalorganic decomposition and subsequent annealing at 700 °C for 1 h. X-ray diffraction analysis showed layered perovskite structures with a single phase in the films. The current-voltage characteristics displayed ohmic conductivity in the lower voltage range and space-charge-limited conductivity in the higher voltage range. The capacitance-voltage characteristics of Au/BSmT/Si (100) exhibited hysteresis loops due to the ferroelectricity and did not show large carrier injections. The fixed charge density and the surface state density of BSmT films on Si substrate were calculated to be in the range of 10¹¹ cm⁻² and 10¹² cm⁻² eV⁻¹, respectively.     

Structural and optical properties of amorphous and crystalline antimony sulfide thin-films

Smooth and compact thin films of amorphous and crystalline antimony sulfide (Sb₂S₃) were prepared by radio frequency sputtering of an Sb₂S₃ target. As-deposited films are amorphous. Polycrystalline antimony sulfide films composed of ∼ 500 nm grains are obtained by annealing the as-deposited films at 400 °C in sulfur vapors. Both amorphous and crystalline antimony sulfide have strong absorption coefficients of 1.8 × 10⁵ cm^− 1 at 450 nm and 7.5 × 10⁴ cm^− 1 at 550 nm, and have direct bandgaps with band energies of 2.24 eV and 1.73 eV, respectively. These results suggest the potential use of both amorphous and crystalline antimony sulfide films in various solid state devices.     

Synthesis and characterization of nanocrystalline CdZnO thin films prepared by sol-gel dip-coating process

Nanocrystalline Cd_xZn_1 − xO thin films with different Cd volume ratios in solution (x = 0, 0.25, 0.50, 0.75 and 1) have been deposited on glass substrate by sol-gel dip-coating method. The as-deposited films were subjected to drying and annealing temperatures of 275 °C and 450 °C in air, respectively. The prepared films were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, UV-vis spectroscopy and dc-electrical measurements. The results show that the samples are polycrystalline and the crystallinity of the films enhanced with x. The average grain size is in the range of 20-53 nm. The atomic percent of Cd:Zn was found to be 9.50:1.04, 6.20:3.77 and 4.42:6.61 for x = 0.75, 0.50 and 0.25, respectively. It was observed that the transmittance and the band gap decreased as x increased. All the films exhibit n-type electrical conductivity. The resistivity (ρ) and mobility (μ) are in the range of 3.3 × 10² − 3.4 × 10^− 3 Ω cm, and 1.5 − 45 cm² V^− 1 s^− 1 respectively. The electron density lies between 1.26 × 10¹⁶ and 0.2 × 10²⁰ cm^− 3.     

Characterization and optoelectronic properties of sol-gel-derived CuFeO2 thin films

In this study, CuFeO₂ thin films were deposited onto quartz substrates using a sol-gel and a two-step annealing process. The sol-gel-derived films were annealed at 500 °C for 1 h in air and then annealed at 600 to 800 °C for 2 h in N₂. X-ray diffraction patterns showed that the annealed sol-gel-derived films were CuO and CuFe₂O₄ phases in air annealing. When the films were annealed at 600 °C in N₂, an additional CuFeO₂ phase was detected. As the annealing temperature increased above 650 °C in N₂, a single CuFeO₂ phase was obtained. The binding energies of Cu-2p_3/2, Fe-2p_3/2, and O-1s were 932.5 ± 0.1 eV, 710.3 ± 0.2 eV and 530.0 ± 0.1 eV for CuFeO₂ thin films. The chemical composition of CuFeO₂ thin films was close to its stoichiometry, which was determined by X-ray photoelectron spectroscopy. Thermodynamic calculations can explain the formation of the CuFeO₂ phase in this study. The optical bandgap of the CuFeO₂ thin films was 3.05 eV, which is invariant with the annealing temperature in N₂. The p-type characteristics of CuFeO₂ thin films were confirmed by positive Hall coefficients and Seebeck coefficients. The electrical conductivities of CuFeO₂ thin films were 0.28 S cm^− 1 and 0.36 S cm^− 1 during annealing at 650 °C and 700 °C, respectively, in N₂. The corresponding carrier concentrations were 1.2 × 10¹⁸ cm^− 3 (650 °C) and 5.3 × 10¹⁸ cm^− 3 (700 °C). The activation energies for hole conduction were 140 meV (650 °C) and 110 meV (700 °C). These results demonstrate that sol-gel processing is a feasible preparation method for delafossite CuFeO₂ thin films.     

Capacitance-voltage and leakage-current characteristics of sol-gel-derived crystalline and amorphous SrTa2O6 thin films

SrTa₂O₆ (STA) is a promising high-dielectric-constant (ε) material. In this study, STA thin films were fabricated using the sol-gel method. The capacitance-voltage and leakage-current characteristics of crystalline and amorphous STA thin-film capacitors were investigated. STA thin films crystallized at an annealing temperature of 800 °C. Crystalline STA thin films exhibited a high ε of about 110, whereas amorphous STA thin films showed a much lower ε of about 26-41. However, amorphous STA thin films had a much more constant capacitance as a function of voltage. Of the amorphous thin films, the one annealed at 700 °C had the highest ε of about 41, the lowest leakage current of 10^− 8 A/cm², and a very constant capacitance as a function of voltage with a quadratic voltage-capacitance coefficient (α) of 27 ppm/V². The crystalline STA thin film had a negative α that was independent of frequency, which suggests that dipolar relaxation occurs and is responsible for the large change in the capacitance. The amorphous thin films had a positive α that decreased with increasing frequency, which implies that electrode polarization occurs.     

Chemical states of carbon in amorphous boron carbide thin films deposited by radio frequency magnetron sputtering

Boron carbide thin films were deposited by radio frequency (RF) magnetron sputtering and characterized by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and high resolution transmission electron microscopy. The results reveal that the structure of thin films deposited at substrate temperatures lower than 350 °C is amorphous. We found that there are four chemical states for carbon in amorphous boron carbide thin films deposited by RF magnetron sputtering. One is the segregated carbon in form of the graphitic inclusions in the thin film identified by Raman spectroscopy and Raman mapping using two strong peaks at ~ 1360 cm^− 1 and ~ 1590 cm^− 1, but the XPS results show that the graphitic inclusions do not connect to the substrate directly. On the surface the carbon forms C=O bonds characterized by the peak of C1s core level at 285.0 eV besides B-C bonds in the boron carbide with the peak of C1s being at 282.8 eV. The detailed analysis of B-C bonds in the boron carbide shows that there are two states for carbon atoms in B-C bonds: in the C-B-C models with C1s peak at 282.3 eV and in the icosahedra with C1s peak at 283.3 eV.