Oxygen reduction activity of N-doped carbon-based films prepared by pulsed laser deposition

Carbon-based films with nitrogen species on their surface were prepared on a glassy carbon (GC) substrate for application as a non-platinum cathode catalyst for polymer electrolyte fuel cells. Cobalt and carbon were deposited in the presence of N₂ gas using a pulsed laser deposition method and then the metal Co was removed by HCl-washing treatment. Oxygen reduction reaction (ORR) activity was electrochemically determined using a rotating disk electrode system in which the film samples on the GC substrate were replaceable. The ORR activity increased with the temperature of the GC substrate during deposition. A carbon-based film prepared at 600 °C in the presence of N₂ at 66.7 Pa showed the highest ORR activity among the tested samples (0.66 V vs. NHE). This film was composed of amorphous carbons doped with pyridine type nitrogen atoms on its surface.     

Properties of Zn3N2-doped ZnO films deposited by pulsed laser deposition

The optical properties of N-doped ZnO films grown by pulsed laser deposition are examined for which zinc nitride is used as the source of nitrogen. The motivation for this study is to determine if nitrogen-related acceptor state formation can be achieved in ZnO films using Zn₃N₂ doping in the ablation target. The films were deposited in oxygen or nitrogen on c-plane sapphire. Photoluminescence measurements at 20 K reveal a 3.31 eV acceptor-bound exciton emission due to nitrogen substitution on the oxygen site, donor-acceptor pair emission at 3.23 ± 1 eV and free electron-acceptor at 3.27 eV. The binding energy of the N-related acceptor is estimated to be in the range of 170-15 meV. While the as-deposited films were n-type, thermal annealing in oxygen yielded insulating behavior, consistent with compensating acceptor states.     

Effect of oxygen pressure on structure and properties of Bi1.5Zn1.0Nb1.5O7 pyrochlore thin films prepared by pulsed laser deposition

The Bi₂O₃-ZnO-Nb₂O₅ (BZN) cubic pyrochlore thin films were prepared on Pt/TiO₂/SiO₂/Si(1 0 0) substrates by using pulsed laser deposition process. The oxygen pressure was varied in the range of 5-50 Pa to investigate its effect on the structure and dielectric properties of BZN thin films. It is found that oxygen pressure during deposition plays an important role on structure and other properties of BZN films. The BZN films deposited at temperature of 650 °C and at O₂ pressure of 5 Pa have an amorphous BZN and Nb₂O₅ phases but exhibits a cubic pyrochlore structure with a preferential (2 2 2) orientation when the oxygen pressure increases to 10 Pa. Dielectric constant and loss tangent of the films deposited at 10 Pa are 185 and 0.0008 at 10 kHz, respectively. The dielectric tunability is about 10% at a dc bias field of 0.9 MV/cm.     

Structural and optical properties of zinc nitride films prepared by rf magnetron sputtering

Zinc nitride films were prepared on quartz substrates by rf magnetron sputtering using pure zinc target in N₂-Ar plasma. X-ray diffraction (XRD) analysis indicates that the films just after deposition are polycrystalline with a cubic structure and a preferred orientation of (4 0 0). X-ray photoelectron spectroscopy (XPS) analysis also confirms the formation of N-Zn bonds and the substitution incorporation of oxygen for nitrogen on the surface of the films. The optical band gap is calculated from the transmittance spectra of films just after deposition, and a direct band gap of 1.01 ± 0.02 eV is obtained. Room temperature PL measurement is also performed to investigate the effect of defect on the band gap and quality of the zinc nitride films.     

Sputter deposition of high transparent TiO2−xNx/TiO2/ZnO layers on glass for development of photocatalytic self-cleaning application

In this study, TiO_2−xN_x/TiO₂ double layers thin film was deposited on ZnO (80 nm thickness)/soda-lime glass substrate by a dc reactive magnetron sputtering. The TiO₂ film was deposited under different total gas pressures of 1 Pa, 2 Pa, and 4 Pa with constant oxygen flow rate of 0.8 sccm. Then, the deposition was continued with various nitrogen flow rates of 0.4, 0.8, and 1.2 sccm in constant total gas pressure of 4 Pa. Post annealing was performed on as-deposited films at various annealing temperatures of 400, 500, and 600 °C in air atmosphere to achieve films crystallinity. The structure and morphology of deposited films were evaluated by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM). The chemical composition of top layer doped by nitrogen was evaluated by X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of samples was measured by degradation of Methylene Blue (MB) dye. The optical transmittance of the multilayer film was also measured using ultraviolet-visible light (UV-vis) spectrophotometer. The results showed that by nitrogen doping of a fraction (∼1/5) of TiO₂ film thickness, the optical transmittance of TiO_2−xN_x/TiO₂ film was compared with TiO₂ thin film. Deposited films showed also good photocatalytic and hydrophilicity activity at visible light.     

Structural and optical properties of Er, Yb co-doped Y2O3 thin films

Thin Er³⁺, Yb³⁺ co-doped Y₂O₃ films were grown on (1 0 0) YAG substrates by pulsed laser deposition. Ceramic targets having different active ion concentration were used for ablation. The influence of the rare-earth content and oxygen pressure applied during the deposition on the structural, morphological and optical properties of the films were investigated. The films deposited at the lower pressure, 1 Pa, and at 1/10 Er to Yb doping ratio are highly textured along the (1 1 1) direction of the Y₂O₃ cubic phase. In addition to the crystalline structure, these films possess smoother surface compared to those prepared at the higher pressure, 10 Pa. All other films are polycrystalline, consisting of cubic and monoclinic phases of Y₂O₃. The rougher surface of the films produced at the higher-pressure leads to higher scattering losses and different behavior of the reflectivity spectra. Optical anisotropy in the films of less than 0.004 was measured regardless of the monoclinic structure obtained. Waveguide losses of about 1 dB/cm at 633 nm were obtained for the films produced at the lower oxygen pressure.     

Room temperature growth and properties of ZnO films by pulsed laser deposition

ZnO thin films were prepared by pulsed laser deposition at room temperature on glass substrates with oxygen pressures of 10-30 Pa. The structural, electrical, and optical properties of ZnO films were studied in detail. ZnO films had an acceptable crystal quality with high c-axis orientation and smooth surface. The resistivity was in the 10² Ω cm order for ZnO films, with the electron concentration of 10¹⁶-10¹⁷ cm⁻³. All the films showed a high visible transmittance ∼90% and a high UV absorption about 90-100%. The UV emission ∼390 nm was observed in the photoluminescence spectra. The oxygen pressures in the 10-30 Pa range were suitable for room temperature growth of high-quality ZnO films.     

The electrical and magnetic properties of epitaxial orthorhombic YMnO3 thin films grown under various oxygen pressures

Orthorhombic YMnO₃ thin films were epitaxially grown on bare and LaNiO₃ buffered (0 0 1)-SrTiO₃ substrates by pulsed laser deposition under various oxygen pressures from 5 to 30 Pa. The crystal structure and microstructure of these films have been characterized by both X-ray diffractions and transmission electron microscopy. The leakage current, modeled as the space charge limited current (SCLC) mechanism, decreased significantly with the increase of oxygen content. It is further found that the magnetic property of films is greatly enhanced in YMnO₃ films grown under high oxygen pressure, which can be explained decreased oxygen vacancies. In addition, bipolar switching behavior was obtained only in the films grown under 30 Pa oxygen pressure, which is attributed to the decrease of voltage-driven oxygen vacancy migration.     

Study of structural and optical properties of ZnO films grown by pulsed laser deposition

Wurtzite zinc oxides films (ZnO) were deposited on silicon (0 0 1) and corning glass substrates using the pulsed laser deposition technique. The laser fluence, target-substrate distance, substrate temperature of 300 °C were fixed while varying oxygen pressures from 2 to 500 Pa were used. It is observed that the structural properties of ZnO films depend strongly on the oxygen pressure and the substrate nature. The film crystallinity improves with decreasing oxygen pressure. At high oxygen pressure, the films are randomly oriented, whereas, at low oxygen pressures they are well oriented along [0 0 1] axis for Si substrates and along [1 0 3] axis for glass substrates. A honeycomb structure is obtained at low oxygen pressures, whereas microcrystalline structures were obtained at high oxygen pressures. The effect of oxygen pressure on film transparency, band gap E_g and Urbach energies was investigated.     

Crystalline and photoluminescence characteristics of YVO4:Sm thin films grown by pulsed laser deposition under oxygen pressure

YVO₄:Sm³⁺ films were deposited on Al₂O₃ (0 0 0 1) substrates at various oxygen pressures changing from 13.3 to 46.6 Pa by using the pulsed laser deposition method. The crystallinity and surface morphology of these films were investigated by means of X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively. The XRD pattern confirmed that YVO₄:Sm³⁺ film has zircon structure and the AFM study revealed that the films consist of homogeneous grains ranging from 100 to 400 nm. The room temperature photoluminescence (PL) spectra showed that the emitted radiation was dominated by a reddish-orange emission peak at 602 nm radiating from the transition of (⁴G_5/2→⁶H_7/2). The crystallinity, surface morphology, and photoluminescence spectra of thin-film phosphors were highly dependent on the deposition conditions, in particular, the substrate temperature. The surface roughness and photoluminescence intensity of these films showed similar behavior as a function of oxygen pressure.     

Preparation of transparent conductive TiO2:Nb thin films by pulsed laser deposition

This study investigated the optical and electrical properties of Nb-doped TiO₂ thin films prepared by pulsed laser deposition (PLD). The PLD conditions were optimized to fabricate Nb-doped TiO₂ thin films with an improved electrical conductivity and crystalline structure. XRD analyses revealed that the deposition at room temperature in 0.92 Pa O₂ was suitable to produce anatase-type TiO₂. A Nb-doped TiO₂ thin film attained a resistivity as low as 6.7 × 10⁻⁴ Ω cm after annealing at 350 °C in vacuum (<10⁻⁵ Pa), thereby maintaining the transmittance as high as 60% in the UV-vis region.     

AlN:Cr thin films synthesized by pulsed laser deposition: Studies by X-ray diffraction and spectroscopic ellipsometry

The structure and optical properties of AlN thin films doped with Cr atoms were studied by X-ray diffractometry, Fourier transform infrared spectroscopy and spectroscopic ellipsometry analyses. The films were synthesized by pulsed laser deposition from an AlN:Cr (10% Cr) target onto Si(1 0 0) wafers in vacuum at residual pressure of 10⁻³ Pa or in nitrogen at a dynamic pressure of 0.1 Pa. The study of the XRD patterns revealed that both phases co-existed in the synthesized films and that the amorphous one was prevalent. Two different amorphous matrices, i.e. two types of chemical bond arrangements, were found in films deposited at 0.1 Pa N₂. By difference, deposition in vacuum resulted in the coexistence of hexagonal and cubic crystallites embedded into an amorphous matrix. The introduction of Cr atoms into the AlN lattice causes a broadening of the IR spectrum along with the shift toward higher wavenumbers of the characteristic Al-N bands at 2351 cm⁻¹ and 665 cm⁻¹, respectively. This was related to the generation of a compressive stress inside films. In comparison to the optical constants of pure AlN films, the synthesized AlN:Cr films exhibited a smaller refractive index and showed a weak absorption throughout the 300-800 nm spectral region, characteristic to amorphous AlN structure.     

Reactive pulsed laser deposition of gold nitride thin films

We report on the growth and characterization of gold nitride thin films on Si 〈1 0 0〉 substrates at room temperature by reactive pulsed laser ablation. A pure (99.95%) Au target was ablated with KrF excimer laser pulses in nitrogen containing atmosphere (N₂ or NH₃). The gas ambient pressure was varied in the range 0.1-100 Pa. The morphology of the films was studied by using optical, scanning electron and atomic force microscopy, evidencing compact films with RMS roughness in the range 3.6-35.1 nm, depending on the deposition pressure. Rutherford backscattering spectrometry and energy dispersion spectroscopy (EDS) were used to detect the nitrogen concentration into the films. The EDS nitrogen peak does not decrease in intensity after 2 h annealing at 250 °C. Film resistivity was measured using a four-point probe and resulted in the (4-20) × 10⁻⁸ Ω m range, depending on the ambient pressure, to be compared with the value 2.6 × 10⁻⁸ Ω m of a pure gold film. Indentation and scratch measurements gave microhardness values of 2-3 GPa and the Young's modulus close to 100 GPa. X-ray photoemission spectra clearly showed the N 1s peak around 400 eV and displaced with respect to N₂ phase. All these measurements point to the formation of the gold nitride phase.     

Epitaxial growth of delafossite CuFeO2 thin films by pulse laser deposition

CuFeO₂ (CFO) is a delafossite-type compound and is a well known p-type semiconductor. Epitaxial CuFeO₂ thin films were prepared on Al₂O₃ (0 0 0 1) substrates by pulsed laser deposition. The deposition, performed at 500 °C and 10 Pa leads to epitaxial phase with extremely low roughness and high density. The oxygen pressure modulates the band energy properties of Cu 2p, Fe 3p and O1s. The results show that the low deposition oxygen pressure contributes to the chemistry ingredient and magnetization properties. Furthermore, spin-glass behavior is identified and weak-ferromagnetization property is found at a low temperature about ∼5 K.     

Fabrication of p-type ZnMgO films via pulsed laser deposition method by using Li as dopant source

p-Type Zn_0.9Mg_0.1O thin films have been realized via monodoping of Li acceptor by using pulsed laser deposition. The Li-doped Zn_0.9Mg_0.1O thin films possessed a good crystallinity with a (0 0 0 2) preferential orientation and a high transmittance in the visible region. Secondary ion mass spectroscopy revealed that Li has been successfully incorporated into the Zn_0.9Mg_0.1O films. The obtained films with the best electrical properties show a hole concentration in the order of 10¹⁷ cm⁻³ and a room-temperature resistivity in the range of 58-72 Ω cm.     

Development of structural and optical properties of WOx films upon increasing oxygen partial pressure during reactive sputtering

WO_x films were prepared by reactive dc magnetron sputtering using tungsten target. Sputtering was carried out at a total pressure of 1.2 Pa using a mixture of argon plus oxygen in an effort to determine the influence of the oxygen partial pressure on structural and optical properties of the films. The deposition rate decreases significantly as the surface of the target is oxidized. X-Ray diffraction revealed the amorphous nature of all the films prepared at oxygen partial pressures higher than 1.71×10⁻³ Pa. For higher oxygen partial pressures, fully transparent films were deposited, which showed a slight increase in optical band gap with increasing oxygen partial pressure, while the refractive index was simultaneously decreased.     

Thin films of semiconducting lithium ferrite produced by pulsed laser deposition

Thin films of lithium ferrite (Li_0.5Fe_2.5O₄) have been deposited on (0 0 1) Al₂O₃ by pulsed laser deposition, with substrate deposition temperatures ranging between 500 and 800 °C, and oxygen pressures between 1 × 10⁻¹ and 4 × 10⁻⁷ mbar. X-ray diffraction shows that films grow with a (1 1 1) orientation. Conversion electron Mössbauer spectra for the high-pressure films show a single sextet with a hyperfine field of 49 T, while the low-pressure films show two sextets with hyperfine fields of 47 and 49 T. The spectra also reveal paramagnetic ferric iron in both types of films. Magnetization measurements of the films show a saturation magnetization of between 1.7 and 3.1μ_B per formula unit and a coercivity of between 10 and 44 mT. The films prepared under the lower oxygen pressures are semiconducting with resistivities of 2 × 10⁻² to 8 × 10⁻² Ω cm. They exhibit an anomalous Hall effect with p-type conduction at 175 K.     

Properties of dc magnetron sputtered Cu2O films prepared at different sputtering pressures

The sputtering pressures maintained during the deposition of Cu₂O films, by dc reactive magnetron sputtering, influence the structural, electrical and optical properties. The crystalline orientation mainly depends on the sputtering pressure. The films deposited at a sputtering pressure of 4 Pa showed single-phase Cu₂O films along (1 1 1) direction. The electrical resistivity of the films increased from 1.1 × 10¹ Ω cm to 3.2 × 10³ Ω cm. The transmittance of the films increased from 69% to 88% with the increase of sputtering pressure from 2.5 Pa to 8 Pa.     

Growth and structure of Bi0.5(Na0.7K0.2Li0.1)0.5TiO3 thin films prepared by pulsed laser deposition technique

Bi_0.5(Na_0.7K_0.2Li_0.1)_0.5TiO₃ (BNKLT) thin films were prepared on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition (PLD) technique. The films prepared were examined by using X-ray diffraction (XRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The effects of the processing parameters, such as oxygen pressure, substrate temperature and laser power, on the crystal structure, surface morphology, roughness and deposition rates of the thin films were investigated. It was found that the substrate temperature of 600 °C and oxygen pressure of 30 Pa are the optimized technical parameters for the growth of textured film, and all the thin films prepared have granular structure, homogeneous grain size and smooth surfaces.     

Optical characterization of PLD grown nitrogen-doped TiO2 thin films

Nitrogen-doped TiO₂ thin films were prepared by pulsed laser deposition (PLD) by ablating metallic Ti target with pulses of 248 nm wavelength in reactive atmospheres of O₂/N₂ gas mixtures. The layers were characterized by UV-VIS spectrophotometry and variable angle spectroscopic ellipsometry with complementary profilometry for measuring the thickness of the films. Band gap and extinction coefficient values are presented for films deposited at different substrate temperatures and for varied N₂ content of the gas mixture. The shown tendencies are correlated to nitrogen incorporation into the TiO_2-xN_x layers. It is shown that layers of significantly increased visible extinction coefficient with band gap energy as low as 2.89 eV can be obtained. A method is also presented how the spectroscopic ellipsometric data should be evaluated in order to result reliable band gap values.