Chemistry of post-annealing of epitaxial CoFe2O4 thin films

CoFe₂O₄ thin films of different thicknesses were grown on SrTiO₃ substrates. The X-ray diffraction analysis and atomic force microscopy indicated both epitaxy and a granular microstructure. We studied the magnetic properties of these films as a function of oxygen post-annealing and film thickness. All as-deposited films exhibited similar magnetic properties with saturated magnetization (M_s) of approximately 50% of the bulk M_s, (80 Am² kg^− 1). After the post-annealing the M_s changes as a consequence of crystallographic restructuring of the film. Cation ordering in 100 nm thick films reduces M_s, whereas re-oxidation increases M_s for thinner films. 13 nm films, annealed for 1 h, reach the bulk M_s. For even thinner films the quantum-size effect reduces M_s. For a synthesis of ≥ 30 nm films an annealing cycle after deposition of every 15 nm layer is recommended.     

Magnetic field induced ferroelectric and dielectric properties in Pb(Zr0.5Ti0.5)O3 films containing Fe3O4 nanoparticles

About 1.05 µm-thick Pb(Zr_0.5Ti_0.5)O₃ (PZT) films containing Fe₃O₄ nanoparticles were deposited on LaNiO₃-coated silicon substrates through a sol-gel technique. Fe₃O₄ nanoparticles were effectively dispersed into PZT solution under the involvement of polyvinylpyrrolidone. X-ray diffraction confirmed the coexistence of PZT and Fe₃O₄ phases without other impurity phases. Scanning electron microscope revealed that the thick composite films possess well-defined and crack-free microstructure. The composite films exhibit good ferroelectric and ferromagnetic properties at room temperature. An obvious magnetodielectric effect has been demonstrated in the Pb(Zr_0.5Ti_0.5)O₃/Fe₃O₄ composite films. Magnetic field induced change in ferroelectric polarization loop may support the possible magnetoelectric coupling between PZT and Fe₃O₄ phases.     

Synthesis and optical properties of Cu2O/SiO2 composite films via gamma-irradiation route

The Cu₂O particles or clusters dispersed mesoporous SiO₂ composite films were prepared by a new method: First the matrix SiO₂ films were prepared by sol-gel process combined with the dip-coating technique, and then they were soaked in Cu(NO₃)₂ solutions followed by γ-ray irradiation at room temperature and in ambient pressure. Thus prepared Cu₂O/SiO₂ composite films were examined by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and optical absorption spectroscopy. Compared with the pure Cu₂O nanoparticles, an obvious blue shift existed in the obtained Cu₂O/SiO₂ composite films.     

Microstructure and electrical properties of RuO2-CeO2 composite thin films

RuO₂-CeO₂ composite thin films are deposited on various Si substrates by a radiofrequency magnetron sputtering technique. Compacted polycrystalline pellets of the nanostructured CeO₂-RuO₂ composite system are used as standard samples for comparative electrical analyses. All films and composite samples are analyzed by X-ray diffraction and transmission electron microscopy. Electrical measurements of radiofrequency sputtering of thin films are performed as a function of the RuO₂ fraction and of the temperature (between 25 and 400 °C). A nonlinear variation in the electrical conductivity of the RuO₂-CeO₂ composite thin films as a function of the RuO₂ volume fraction (Φ) is observed and discussed. It is interpreted in terms of a power law (in (Φ − Φc)^m ), where m and Φc are parameters characteristic of the distribution of the conducting phase in a composite medium.     

Direct patterning of SnO2 composite films prepared with various contents of Pt nanoparticles by photochemical metal-organic deposition

The optical and electrical characteristics of SnO₂ composite films with various contents (0, 0.05, 0.1, 0.2, and 0.3 at.%) of Pt nanoparticles were evaluated. The Pt nanoparticles were synthesized by a methanol reduction method and their average size was controlled to 3 nm using poly(N-vinyl-2-pyrrolidone) as a protecting agent. The lowest resistivity of 2.031 × 10^− 2 Ω cm was obtained in the SnO₂ film containing 0.2 at.% Pt nanoparticles after annealing at 700 °C while its average transmittance in the visible region was 85.24%. The enhanced electrical properties were attributed to the increase of the carrier concentration and crystallinity of the films due to donation from Pt nanoparticles as well as the increased annealing temperature. Meanwhile, the slight degradation of the transmittance was due to scattering from the introduction of Pt nanoparticles and the increased crystallite size due to the increase of the annealing temperature to 700 °C. Well-defined 20-μm wide direct-patterned composite SnO₂ films containing Pt nanoparticles were formed by a simple photochemical metal-organic deposition process involving a photosensitive starting precursor, UV exposure, and removal of the unpatterned area by rinsing with solvent. Based on the results of this study, we suggest that direct-patternable SnO₂ films with Pt nanoparticles can be easily applied to transparent electrodes in electrical devices without requiring an expensive and toxic process such as dry etching.     

Microstructures, ferromagnetic, and ferroelectric properties in polyvinylpyrrolidone-assisted CoFe2O4/Pb(Zr0.53Ti0.47)O3 multiferroic composite thick films

CoFe₂O₄/Pb(Zr_0.53Ti_0.47)O₃ (CFO/PZT) multiferroic composite thick films with different CFO mass fractions have been prepared onto Pt/Ti/SiO₂/Si substrate by a hybrid sol–gel process and spin coating technique. Polyvinylpyrrolidone (PVP) was employed to be an assistance to the sol–gel solution for enhancing the film thickness and promising a crack-free film surface. After annealing at 650 °C in air for 1 h, phase structure, microstructure, magnetic and ferroelectric properties as well as leakage current of multiferroic thick films were investigated. X-ray diffraction indicated a deeply buried distribution of CFO particles in the PZT matrix. Scanning electronic microscopes showed crack-free surfaces and a decreasing film thickness from 7.2 μm to 6.2 μm with increasing CFO content. Furthermore, the saturated magnetization and remanent magnetization were also hence increased. In addition, mass fraction of CFO in PZT matrix was also estimated from 0.36% to 4.58% according to the relationship between M _s and magnetic content. Ferroelectric hysteresis loops revealed saturated polarization (P _s) and remanent polarization (P _r) were diluted by CFO till its mass fraction rising to 1.8%. After that, polarization was increased with further increasing CFO content. Enhanced leakage was demonstrated to be partially contributed to them. A critical content of 1.8% was hence confirmed, where ferroelectric and magnetic properties can be balanced, indicating a possible stress-transferred magnetoelectric coupling effect in this composite.     

Reversible transformations of silver oxide and metallic silver nanoparticles inside SiO2 films

Reversible transformation of silver oxide and metallic nanoparticles inside a relatively porous silica film has been established. Annealing of Ag-doped films in oxidizing (air) atmosphere at 450 °C yielded colorless films containing AgO_x. These films were turned yellow when heated in H₂-N₂ (reducing atmosphere) due to the formation of Ag nanoparticles. This yellow coloration (due to nano Ag⁰) and bleaching (conversion of Ag⁰ → Ag⁺) are reversible. Optical and photoluminescence spectra are well consistent with this coloration and bleaching. The soaking test of the air-annealed film in Na₂S₂O₃ solution supports the presence of Ag⁺. Grazing incidence X-ray diffraction and transmission electron microscopy studies reveal the formation of Ag-oxides and Ag nanoparticles in the oxidized and reduced films, respectively.     

The influence of the molar ratio of Al2O3 to Y2O3 on sintering behavior and the mechanical properties of a SiC–Al2O3–Y2O3 ceramic composite

The influence of the molar ratio of Al₂O₃ to Y₂O₃ (i.e. M_Al2O3/M_Y2O3) on sintering densification, microstructure and the mechanical properties of a SiC–Al₂O₃–Y₂O₃ ceramic composite were studied. It was shown that the optimal value of M_Al2O3/M_Y2O3 was 3/2, not 5/3, which is customarily considered the optimal molar ratio for the formation of YAG (Y₃Al₅O₁₂) phase. When M_Al2O3/M_Y2O3 is 5/3, materials existed in two phases of YAG and very little YAM phases. The sintering mechanism of the solid phase occurred at 1850 °C. When M_Al2O3/M_Y2O3 was 3/2, materials existed in the two phases YAG (Y₃Al₅O₁₂) and YAM (Y₄Al₂O₉). The formation of the low melting point eutectic liquid phase (YAG + YAM) increased sintering densification. Flexure strength, hardness and relative density were all higher.     

Magnetization and crystal structure of RF-sputtered nanocrystalline CuFe2O4 thin films

Cu-ferrite films were deposited on glass substrates by RF-magnetron sputtering in pure Ar and mixture of (Ar + O₂) environment. The XRD studies of the as-deposited films indicate nanocrystalline cubic spinel structure. The observed increase in the intensity of (400) line at the expense of (220) line with increase in O₂ content is ascribed to the change in distribution of Cu and Fe-ions among tetrahedral A-site and octahedral B-sites. The highest saturation magnetization (M_S) of 264 emu/cm³ (in-plane) and 188 emu/cm³ (out of-plane) was obtained for the as-deposited films in pure Ar. The high deposition rate in reducing atmosphere leads to the formation of Cu⁺ ions which prefer occupation of the A-site in the spinel structure displacing Fe³⁺ cations to occupy the B-sites giving rise to the change in cation distribution among A and B-sites and consequently leading to high value of M_S. The decrease in M_S value with increase in oxygen content is ascribed to the decrease in film growth rate and Cu⁺ concentration which allow the cations to take up their preferable sites. The observed change in the film properties with environment is due to the presence of multivalent copper and iron ions with differing site preferences.     

Preparation and properties of Tl2Ba2CaCu2O8 thin films

Anex situ process has been developed to produce thin superconducting Tl₂Ba₂CaCu₂O₈ films. The properties of films grown on different substrates using different annealing regimes were studied. Critical temperatures of 103–107 K were measured on films prepared in a broad range of annealing temperatures on SrTiO₃, LaAlO₃, and Y-ZrO₂ substrates. A critical current density,J _c, of 2×10⁶ A/cm² at 77 K was measured on LaAlO₃. Film morphology was studied by SEM, AFM, and STM.     

The influence of neutron irradiation on (B0.65C0.35)Ba1.4Sr0.6Ca2Cu3Oz superconducting phase: The role of the grain edge

Using the transport and magnetization measurements, the influence of neutron irradiation at a fluence of 5 × 10¹⁷ n cm⁻² on (B_0.65C_0.35)Ba_1.4Sr_0.6Ca₂Cu₃O _z has been investigated. The neutron irradiation was found to decrease critical temperature and transport critical current density, increase the residual and normal state resistivity, and improve the intragranular critical current density with 1.6 × 10⁵ A/cm² (at 77.3 K and in the applied field up to 160 kA m) and ΔM _irr/ΔM _nonirr ratio (up to factor of 3) at highest field used for investigation. The field dependence of this ratio, which is below the unity at very low field but higher than 1 at high fields, correlated with the shape of the hysteretic loops as well as with the change of the transport parameters after irradiation suggests the role of the irradiation-induced effects on the grain edges. We discuss these effects in the framework of the Bean-Livingstone surface barriers and geometrical barriers.     

Preparation and photoelectrochemical performance of TiO2/HS-CH2-COOH/Cu3Se2 composite film

In this paper, the TiO₂/HS-CH₂-COOH/Cu₃Se₂ composite film photoanodes were fabricated on conducting glass plates. Cu₃Se₂ nanoparticles were used as the sensitizer and the bi-functional modifier HS-CH₂-COOH was used at the interface between Cu₃Se₂ and TiO₂ films to improve the properties of the film photoanode. The characterization results show that the sol-gel prepared anatase TiO₂ film has a compact and uniform surface, while the tetragonal Cu₃Se₂ film has a coarse surface which is made up of uniform elongated particles. The photoelectrochemical experimental results indicate that the TiO₂/HS-CH₂-COOH/Cu₃Se₂ composite film photoanodes have a good photovoltaic property.     

Effects of HNO3 treatment of TiO2 nanoparticles on the photovoltaic properties of dye-sensitized solar cells

The effects of the nitric acid (HNO₃) treatment of TiO₂ nanoparticles on the photovoltaic properties of the dye-sensitized solar cell (DSSC) were investigated. The HNO₃ treatment enhanced the dispersion of TiO₂ particles, increased the surface area and porosity of the sintered TiO₂ films, increased the relative proportion of the Ti³⁺ state in the Ti 2p X-ray photoelectron spectroscopy spectrum, significantly increased the amount of adsorbed dye molecules on the TiO₂ electrode, and reduced the charge-transfer resistance at the TiO₂/dye/electrolyte interface. The short circuit photocurrent density (I_sc) was increased due to the increased amount of adsorbed dye molecules and the reduced charge-transfer resistance. The HNO₃ pre-treatment of TiO₂ particles improved the overall conversion efficiency of the DSSC by about 14%.     

稀土镧掺杂纳米二氧化钛复合保鲜包装薄膜的研究

水果和菌类均为货架期较短的商品,二者皆易因呼吸作用与微生物感染导致失水与腐坏。本工作首次报道了将稀土镧掺杂纳米TiO₂(La³⁺-TiO₂)粒子与PVA共混,采用溶液浇铸法制备了La³⁺-TiO₂复合包装薄膜,并将其用于草莓和姬松茸保鲜的探索研究。XRD、SEM和LPSA表征显示,稀土镧的掺杂引起了纳米TiO₂晶格的畸变,其粒径变小、表面能增大,掺杂后的纳米TiO₂在PVA基体中的分散性得到提高。透湿和透氧率检测结果表明,La³⁺-TiO₂的加入有利于复合薄膜阻隔性能的增加,当La³⁺-TiO₂质量分数为1.6%时,透湿率降低45.9%,透氧率降低38.0%,复合薄膜阻隔性能最佳。抗菌率检测结果显示,稀土镧的掺杂拓宽了TiO₂对光谱的利用范围,复合包装薄膜在自然光下对大肠杆菌和金黄葡萄球菌的杀灭率分别达到84.1%和91.8%。保鲜实验结果表明,复合包装薄膜因其优良的阻隔性和抗菌性,有效抑制了草莓贮存过程中的果实腐坏和质量损失,常温下将草莓的保质期从5 d延长至10 d左右;同时复合薄膜可减缓姬松茸贮藏过程中的自溶和褐变等现象,常温下将姬松茸的保质期从2 d延长至4 d左右,其包装保鲜效果良好。     

Crystallinity, magnetic and electrochemical studies of PVDF/Co3O4 polymer electrolyte

Organic-inorganic nanocomposites are gaining importance in the recent times as polymer electrolyte membranes. In the present work, composites were prepared by combining nano sized Co₃O₄ and poly(vinyledene fluoride) (PVDF), using spin coating technique. The surface of the PVDF/Co₃O₄ system characterized through field emission scanning electron microscopy (FESEM) revealed a porous structure of the films. The nanoparticles tend to aggregate on the surface and inside the pores, leading to a decrease in the porosity with an increase in Co₃O₄ content. Co₃O₄ nanoparticles prohibit crystallization of the polymer. Differential scanning calorimetry (DSC) studies revealed a decrease in crystallinity of PVDF/Co₃O₄ system with an increase in the oxide content. Magnetic property studies of the composite films revealed that with an increase in Co₃O₄ content, the saturation magnetization values of the nanocomposites increased linearly, showing successful incorporation of the nanoparticles in the polymer matrix. Further, ionic conductivity of the composite films was evaluated from electrochemical impedance spectroscopy. Addition of Co₃O₄ nanoparticles enhanced the conductivity of PVDF/Co₃O₄ system.     

Ascorbate electro-oxidation by modified electrodes: Polypyrrole and polypyrrole/Ni(OH)2 composite thin films

The present paper describes the utilization of polypyrrole and the composite of polypyrrole doped with nickel hydroxide modified electrodes toward the catalytic oxidation of ascorbate. Films were potentiostatically deposited onto a glassy carbon surface and Fluor-doped tin oxide glass for different times. The physical characterization was performed using the low angle X-ray diffraction technique. Furthermore, the films were electrochemically characterized using cyclic voltammetry. The X-ray diffraction results show the existence of different polymorphic phases of nickel hydroxide in the polymer matrix, and the β-Ni(OH)₂ phase appears to be dominant. The cyclic voltammetry profile in KOH solution shows the presence of two redox peaks that are related to the Ni^II/Ni^III and Ni^III/Ni^II couples, at approximately 0.5 and 0.35 V, respectively. The reversible electro-oxidation of ascorbate was observed on the surface of the polypyrrole and composite films. The analytical curves obtained using voltammetric techniques show a linear relationship between the faradaic current and the increase of the ascorbic acid concentration. The sensitivity of these films, which is obtained from the slope of the analytical curves, shows that the composite film is more electroactive than the polypyrrole film: 133.4 mA L mol^− 1 cm^− 2 and 83.8 mA L mol^− 1 cm^− 2, respectively. The rate constants of the catalytic ascorbate electro-oxidation were also reported, where the mean values were found to be 217.74 M^− 1 s^− 1 and 54.37 M^− 1 s^− 1, for the composite and polypyrrole films, respectively. The low cost of polypyrrole doped with Ni(OH)₂ composite electrodes presents a more selective and high sensitivity to determine ascorbic acid concentration.     

Ferroelectric properties of Mn-Doped Bi3.15Nd0.85Ti3O12 thin films prepared under different annealing conditions

Mn-doped Bi_3.15Nd_0.85Ti₃O₁₂ (BNTM) thin films were fabricated on Pt/Ti/SiO₂/Si(100) substrates by a chemical solution deposition technique and annealed at different temperatures from 650 to 800 °C. The structures of the films were analyzed using X-ray diffraction, which showed that the BNTM films exhibit polycrystalline structures and random orientations. The surface morphologies of the samples were investigated using scanning electron microscopy. The average grain size of the films increases with increasing annealing temperature. Electrical properties such as remanent polarization (2P_r) are quite dependent on the annealing temperature of BNTM films. It is found that the film annealed at 750 °C exhibits excellent ferroelectricity with a remanent polarization of 2P_r = 89.3 μC/cm² and a coercive field of E_c = 99.2 kV/cm respectively.     

The Influence of Neutron Irradiation on (B0.65C0.35)Ba1.4Sr0.6Ca2Cu3Oz Superconducting Phase: The Role of the Grain Edge

Using the transport and magnetization measurements, the influence of neutron irradiation at a fluence of 5 × 10¹⁷ n cm⁻² on (B_0.65C_0.35)Ba_1.4Sr_0.6Ca₂Cu₃O _z has been investigated. The neutron irradiation was found to decrease critical temperature and transport critical current density, increase the residual and normal state resistivity, and improve the intragranular critical current density with 1.6 × 10⁵ A/cm² (at 77.3 K and in the applied field up to 160 kA m) and ΔM _irr/ΔM _nonirr ratio (up to factor of 3) at highest field used for investigation. The field dependence of this ratio, which is below the unity at very low field but higher than 1 at high fields, correlated with the shape of the hysteretic loops as well as with the change of the transport parameters after irradiation suggests the role of the irradiation-induced effects on the grain edges. We discuss these effects in the framework of the Bean-Livingstone surface barriers and geometrical barriers.     

Preparation and super-hydrophilic properties of TiO2/SnO2 composite thin films

SnO₂-TiO₂ composite thin films were fabricated on soda-lime glass with sol-gel technology. By measuring the contact angle of the film surface and the degradation of methyl orange, we studied the influence of SnO₂ doping concentration, heat-treatment temperature and film thickness on the super-hydrophilicity and photocatalytic activity of the composite films. The results indicate that the doping of SnO₂ into TiO₂ can improve their hydrophilicity and photocatalytic activity, and the composite film with 1-5 mol% SnO₂ and heat-treated at 450°C is of super-hydrophilicity. The optimal SnO₂ concentration for the photocatalytic activity is 10 mol% and larger film thickness is helpful to reduce the contact angle of the composite films.     

Cathodoluminescence of CaWO4 and SrWO4 thin films prepared by spray pyrolysis

Thin films of CaWO₄ and SrWO₄ were prepared on glass substrates by spray pyrolysis. The effects of preparation conditions and monovalent, bivalent and trivalent cation doping on cathodoluminescence (CL) properties of the films were studied. Polycrystalline CaWO₄ and SrWO₄ films formed a scheelite structure after being annealed above 300°C. They exhibited analogous cathodoluminescence consisting of a blue emission band at 447 nm and a blue-green emission band at 487 nm. The blue and blue-green emission intensities increased with substrate and annealing temperature. Annealing atmosphere and doping with Ag⁺, Pb²⁺ and La³⁺ did not influence the characteristics of the blue and blue-green emissions, whereas Eu³⁺ did. The results indicated both the blue and blue-green emissions originated from the WO₄²⁻ molecular complex. The luminance and efficiency for CaWO₄ film were 150 cd/m² and 0.7 lm/W at 5 kV and 57 μA/cm².