Enhanced dielectric properties of LSCO-buffered Ba(Sn<Subscript>0.05</Subscript>Ti<Subscript>0.95</Subscript>)O<Subscript>3</Subscript> thin film prepared by sol–gel processing

Ferroelectric Ba(Sn_0.05Ti_0.95)O₃ (BTS) thin films were deposited onto Pt/Ti/SiO₂/Si substrates by sol–gel technique with a 100 nm thick LSCO buffer layer. The influence of buffer layer on the phase and microstructure of the thin films was examined. Dielectric properties of the thin films were investigated as a function of frequency and direct current (DC) electric field. The results show that the LSCO buffer layer had a marked effect on the dielectric properties of the BTS films. The BTS thin films with LSCO buffer layer had enhanced dielectric properties.     

UV assisted pyrolysis of solution deposited BiFeO<Subscript>3</Subscript> multiferroic thin films. Effects on microstructure and functional properties

BiFeO₃ thin films were processed on platinized silicon substrate via chemical solution deposition. Short wave UV assisted pyrolysis was conducted in oxygen atmosphere in order to obtain a fine and homogeneous grain structure. Phase pure thin films with a pronounced (100) texture were obtained at a fairly low annealing temperature of 600°C. For comparison specimens processed without UV assisted pyrolysis were also investigated. It is shown that UV assisted pyrolysis leads to a substantial improvement of leakage resistance properties. Polarization switching could also be obtained using capacitance-voltage (C-V) curves. The leakage current was investigated as a function of temperature. Interpretation in terms of Frenkel-Poole mechanism leads to a high trap depth in the range of 2.4 eV which is attributed to the creation of Fe²⁺ centres. For both microstructures investigated well saturated magnetization loops were obtained with a remnant magnetization of 2Mr = 5.4 emu/cm³ and a coercive fields in the range of 2Hc = 200 Oe. Slightly higher saturation magnetization 2Ms of 55.4 emu/cm³ was obtained for UV assisted pyrolysis in comparison to 45.8 emu/cm³ for the thin films processed without UV.     

Study of the crystallization pathway of Na0.5Bi0.5TiO3 thin films obtained by chemical solution deposition

Na_0.5Bi_0.5TiO₃ (NBT) thin films were fabricated by a chemical solution deposition (CSD) method. A route involving the reaction between sodium and bismuth acetates and titanium n-butoxide was used to synthesise the different precursor solutions. The thermal decomposition and crystallization pathways of different modified precursors have been studied by thermal analysis and X-ray diffraction techniques. As a consequence of the modification of the precursor solutions and their different thermal behaviour, the nucleation of the stable perovskite phase happens at different temperatures depending on each case but is found to be at temperatures as low as 500 °C. For the thin film processing, the drying and pyrolysis temperatures were chosen according to the thermogravimetric data to minimize the strain resulting from the shrinkage of the film during the elimination of solvents and organic ligands. The crystallization process was studied and the experimental results are discussed in terms of structural, microstructural and electrical features investigated by field-emission scanning electron microscopy, atomic force microscopy in tapping and piezo-force modes and X-ray diffraction.     

Enhanced ferroelectric properties of Ce-substituted BiFeO<Subscript>3</Subscript> thin films prepared by sol–gel process

Ce-substituted BiFeO₃ film (BCFO film) have been prepared by sol–gel process on F doped SnO₂ (FTO)/glass substrates. The effects of Ce substitution on the structural and electrical properties have been reported. X-ray diffraction data confirmed the R3c structure with the elimination of all secondary phases. We observed an increase in the remnant polarization (Pr) with Ce substitution and obtained a maximum value of ∼84 μC/cm² in 5% Ce-substituted film. The dielectric constant of the films was increased from 280 to about 420 for the BiFeO₃ film and 5% Ce-substituted BCFO film, respectively and the films showed excellent dielectric loss behavior. Moreover, the leakage current was substantially reduced by the Ce substitution.     

A sol-gel route for the development of rare-earth aluminum borate nanopowders and transparent thin films

A new sol-gel route was applied to obtain Y_0.9Er_0.1Al₃(BO₃)₄ crystalline powders and amorphous thin films by using Al(acac)₃, B(OPrⁱ)₃, Y(NO₃)₃·6H₂O, and Er(NO₃)₃·5H₂O as starting materials dissolved in propionic acid and ethyl alcohol mixtures. Our study shows that propionic acid acts as good chelant agent for yttrium and erbium ions while ethyl alcohol allows to dissolve Al(acac)₃. This process makes the resulting sols very stable to obtain homogeneous gels and transparent amorphous thin films. In addition, the propionic acid prevents the sol precipitation, making easy porous- and crack-free thin film depositions. Chemical reactions involved in the complexation were discussed. As-prepared powders and films are amorphous and present a good thermal stability due to their high glass transition (746 °C) and crystallization temperatures (830 °C). This new sol-gel route showed to be adequate to obtain dense and crack-free thin films free of organic and hydroxyl groups that can be considered as promising materials to be used in integrated optical systems.     

Deposition and investigation of lanthanum-cerium hexaboride thin films

Thin films of lanthanum-cerium hexaboride, the promising thermoelectric material for low-temperature applications, are deposited on various substrates by the electron-beam evaporation, pulsed laser deposition and magnetron sputtering. The influence of the deposition conditions on the films X-ray characteristics, composition, microstructure and physical properties, such as the resistivity and Seebeck coefficient, is studied. The preferred (100) orientation of all films is obtained from XRD traces. In the range of 780-800 °C deposition temperature the highest intensity of diffractions peaks and the highest degree of the preferred orientation are observed. The temperature dependence of the resistivity and the Seebeck coefficient of films are investigated in the temperature range of 4-300 K. The features appropriate to Kondo effect in the dependences ρ(T) and S(T) are detected at temperatures below 20 K. Interplay between the value of the Seebeck coefficient, metallic parameters and Kondo scattering of investigated films is discussed.     

Deposition and dielectric characterization of strontium and tantalum-based oxide and oxynitride perovskite thin films

We have synthesized the composition x = 0.01 of the (Sr_1-xLa_x)₂(Ta_1-xTi_x)₂O₇ solid solution, mixing the ferroelectric perovskite phases Sr₂Ta₂O₇ and La₂Ti₂O₇. Related oxide and oxynitride materials have been produced as thin films by magnetron radio frequency sputtering. Reactive sputter deposition was conducted at 750 °C under a 75 vol.% (Ar) + 25 vol.% (N₂,O₂) mixture. An oxygen-free plasma leads to the deposition of an oxynitride film (Sr_0.99La_0.01) (Ta_0.99Ti_0.01)O₂N, characterized by a band gap E_g = 2.30 eV and a preferential (001) epitaxial growth on (001) SrTiO₃ substrate. Its dielectric constant and loss tangent are respectively Epsilon' = 60 (at 1 kHz) and tanDelta = 62.5 × 10⁻³. In oxygen-rich conditions (vol.%N₂ ≤ 15%), (110) epitaxial (Sr_0.99La_0.01)₂(Ta_0.99Ti_0.01)₂O₇ oxides films are deposited, associated to a larger band gap value (E_g = 4.55 eV). The oxide films permittivity varies from 45 to 25 (at 1 kHz) in correlation with the decrease in crystalline orientation; measured losses are lower than 5.10⁻³. For 20 ≤ vol.% N₂ ≤ 24.55, the films are poorly crystallized, leading to very low permittivities (minimum Epsilon' = 3). A correlation between the dielectric losses and the presence of an oxynitride phase in the samples is highlighted.     

Optimization of the photocatalytic activity of CdO + CdTiO3 coupled oxide thin films obtained by sol-gel technique

In the preparation of CdO + CdTiO₃ polycrystalline thin films by the sol-gel method, the optical, structural and crystalline properties, as well as the photocatalytic activity (PA) depends strongly on the sintering temperature (Ts) of the films and of the Ti/Cd ratio used in the precursor solution. In this work, CdO + CdTiO₃ thin films were prepared using a Ti/Cd constant ratio in the precursor solution. The films were sintered at six different Ts in the 450-550 °C range, in an open atmosphere. The structure of the films was characterized by X-ray diffraction and the PA was evaluated by the photobleaching of methylene blue in an aqueous solution using a UV-vis spectrometer. The relative intensity of the diffraction peaks associated with CdO and CdTiO₃, change with the Ts. The better photocatalytic activities were obtained for the films sintered at 490 °C and 550 °C. When the CdO was removed from the films by chemical etching the PA decreased, showing the importance of coupling both oxides.     

Process optimization and characterization of thin films of SrFeO3-x by the pechini method

Nanostructured coatings have recently attracted increasing interest because of the possibilities of synthesizing materials with unique physical-chemical properties. Highly sophisticated surface related properties, such as optical, magnetic, electronic, catalytic, mechanical, chemical and tribological properties can be obtained by advanced nanostructured coatings, making them attractive for various industrial applications. In this report we describe our efforts at developing methodology for the fabrication of SrFeO_3-x based thin films using a modified Pechini method. Thin films of SrFeO_3-x were fabricated using spin coating and a drop coating method developed in-house on Al₂O₃ and Si- substrates. The films annealed at 600°C for one hour show a perovskite phase. The grain size increases with increase in annealing temperature. The influence of various variables such as metal to chelant ratio, drying control reagents, calcination conditions, substrate type and mode of film formation were studied using XRD, optical microscopy, SEM and AFM.     

Optical constants,dispersion energy parameters and dielectric properties of ultra-smooth nanocrystalline BiVO4 thin films prepared by rf-magnetron sputtering

BiVO₄ thin films have been prepared through radio frequency (rf) magnetron sputtering of a pre-fabricated BiVO₄ target on ITO coated glass (ITO-glass) substrate and bare glass substrates. BiVO₄ target material was prepared through solid-state reaction method by heating Bi₂O₃ and V₂O₅ mixture at 800 °C for 8 h. The films were characterized by X-ray diffraction, UV–Vis spectroscopy, LCR meter, field emission scanning electron microscopy, transmission electron microscopy and atomic force microscopy. BiVO₄ thin films deposited on the ITO-glass substrate are much smoother compared to the thin films prepared on bare glass substrate. The rms surface roughness calculated from the AFM images comes out to be 0.74 nm and 4.2 nm for the films deposited on the ITO-glass substrate and bare glass substrate for the deposition time 150 min respectively. Optical constants and energy dispersion parameters of these extra-smooth BiVO₄ thin films have been investigated in detail. Dielectric properties of the BiVO₄ thin films on ITO-glass substrate were also investigated. The frequency dependence of dielectric constant of the BiVO₄ thin films has been measured in the frequency range from 20 Hz to 2 MHz. It was found that the dielectric constant increased from 145 to 343 at 20 Hz as the film thickness increased from 90 nm to 145 nm (deposition time increased from 60 min to 150 min). It shows higher dielectric constant compared to the literature value of BiVO₄.     

Dielectric properties of Ca(Zr0.05Ti0.95)O3 thin films prepared by chemical solution deposition

Ca(Zr_0.05Ti_0.95)O₃ (CZT) thin films were grown on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by the soft chemical method. The films were deposited from spin-coating technique and annealed at 928 K for 4 h under oxygen atmosphere. CZT films present orthorhombic structure with a crack free and granular microstructure. Atomic force microscopy and field-emission scanning electron microscopy showed that CZT present grains with about 47 nm and thickness about 450 nm. Dielectric constant and dielectric loss of the films was approximately 210 at 100 kHz and 0.032 at 1 MHz. The Au/CZT/Pt capacitor shows a hysteresis loop with remnant polarization of , and coercive field of 18 kV/cm, at an applied voltage of 6 V. The leakage current density was about at 3 V. Dielectric constant-voltage curve is located at zero bias field suggesting the absence of internal electric fields.     

Study of the optimal condition for electroplating of Bi2S3 thin films and their photoelectrochemical characteristics

Bismuth sulfide (Bi₂S₃) thin films were electrodeposited from non-aqueous dimethyl sulfoxide medium containing Bi(NO₃)₃ and thiourea as the precursor salts, triethanol amine as the complexing agent, and TritonX-100 as the surface active agent. The prepared films were subjected to rigorous experimentation in order to validate their potential candidature for solar cells. The films exhibited band gap energy of ∼1.3 eV and resistivity of the order of 2 × 10⁶ Ω cm at room temperature as was obtained from UV–Vis spectroscopy and four-probe measurements, respectively. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and energy dispersive analysis of X-ray were employed to reveal the morphology, structure, and chemical composition of the film matrix. The Bi₂S₃ films were found to be non-decomposable up to the temperature of 1,000 °C with the help of thermogravimetry–differential thermal analysis. The Nyquist and Mott–Schottky plots derived from electrochemical impedance spectroscopy measurements provided important information regarding electrical and semiconducting properties of the films. The n-type film with a donor density of the order of ∼10²³ m⁻³ displayed reasonable photoactivity under illumination and is recommended as a promising candidate for potential photoelectrochemical applications.     

Structural and impedance studies on LaF3 thin films prepared by vacuum evaporation

Lanthanum fluoride thin film has been deposited on glass substrates by PVD method at various deposition temperatures (T_s), viz, 300, 473, 573 and 673 K. The hexagonal phase LaF₃ film has been detected by using glancing angle XRD analysis. The structural parameters such as lattice constants, grain size and micro-strain has been calculated from the XRD data. The F⁻ ion conduction through the grain and grain boundary has been analyzed using impedance analysis. The modulus spectra reveals the non-Debye nature and the distribution of relaxation times of the film.     

Surface modification of thermoplastics by atomic layer deposition of Al2O3 and TiO2 thin films

Al₂O₃ and TiO₂ thin films were deposited by atomic layer deposition at 80-250 °C on various polymeric substrates such as polymethylmethacrylate (PMMA), polyetheretherketone (PEEK), polytetrafluoroethylene (PTFE) and ethylenetetrafluoroethylene (ETFE). The films were studied with FESEM, EDX, XRD, contact angle measurements and adhesion tests. The film growth rates on the thermoplastics were close to the corresponding growth rates on Si substrates. The adhesion of the films was good on PEEK and poor on PTFE. All coated surfaces showed lower water contact angles than the uncoated thermoplastics. Furthermore, the water contact angles on all TiO₂-coated surfaces decreased upon UV illumination, most efficiently with crystalline TiO₂ coatings.     

Anatase TiO2 porous thin films prepared by sol-gel method using CTAB surfactant

Anatase TiO₂ porous thin films were prepared on glass substrates by sol-gel method with Cetyltrimethylammonium Bromide (CTAB) as a pore-forming agent, Tetrabutylorthotitanate as Ti precursor, ethanol as solvent and diethanolamine as chelating agent respectively. IR, TG-DSC, XRD and SEM analyzed the chemical and physical changes during sol-gel process and characteristics of the films. Effects of the amount of CTAB, alkane and water on morphology of the films were discussed and the principle of forming porous structure was proposed. It was shown that the diameter of pores was changed in the range of 30–400 nm.     

Investigation on the growth of CaCu3Ti4O12 thin film and the origins of its dielectric relaxations

Using the radio frequency magnetron sputtering, CaCu₃Ti₄O₁₂ (CCTO) thin films were deposited on platinized silicon substrates. The influence of annealing temperature on structures and morphologies of the thin films was investigated. The high annealing temperature increased the crystallinity of the films. Temperature dependence of the dielectric constant revealed an amazing different characteristic of the dielectric relaxation at ∼10 MHz, whose characteristic frequency abnormally increased with the decrease of the measuring temperature unlike the relaxations due to extrinsic origins. Meanwhile, the dielectric constant at high frequencies was close to the value derived from the first principle calculation. All these gave the evidences to ascribe this relaxation to the intrinsic mechanism.     

Thick Fe2O3, Fe3O4 films prepared by the chemical solution deposition method

Fe₂O₃, Fe₃O₄ films have been prepared from Fe(OCH₂CH(CH₃)₂)₃–(CH₃)₂CHCH₂OH–2.2′-diethanola- mine (DEA)–poly(vinylpyrrolidone) (PVP) solutions by the spin-(SC) and dip-coating (DC) technique on SiO₂ and Si substrates. The maximum film thickness achieved without crack formation has been increased by incorporation of PVP (relative molecular weights 40000 and 360000) into the precursor solution. The stability of the precursor solutions was remarkably increased by addition of DEA. Compact, dense, and crack-free Fe₂O₃ films with thicknesses 900 nm (DC), 450 nm (SC), have been obtained via single-step deposition cycle. Higher-molecular-weight PVP has been more effective in increasing the thickness. The minimum concentration of DEA, which results in pronounced increase of solutions stability, is about R _P (n(DEA)/n(Fe) = 0.1). The high content of carboneous residue in the pyrolysed Fe₂O₃ films promotes the formation of Fe₃O₄ films via reduction in a gas flow of H₂/N₂ gas mixture. Microstructure, surface morphology, and magnetic properties of the films have been also investigated using SEM, AFM, and SQUID, respectively.     

Nanostructured Bi2Te3 synthesized by low temperature aqueous chemical route

Chemical and physical reactions during the low temperature aqueous chemical synthesis of nanostructured Bi₂Te₃ powders were investigated in-situ by pH measurement, color observation of the solution and X-ray diffraction analysis of the powders. It was found that Bi₂Te₃ could be synthesized only in a strong alkaline solution. Bi₂Te₃ nanocapsules were synthesized by the aqueous chemical route at 65 °C with the addition of disodium ethylenediaminetetraacetate salt. High-resolution transmission electron microscopy observation indicates that the nanocapsules are hollow-structured with a wall thickness of about 6 nm. __________ Translated from CHIMICA SINICA, 2005, 63(16)(in Chinese)     

Fabrication and morphology control of BaWO4 thin films by microwave assisted chemical bath deposition

Highly crystallized barium tungstate (BaWO₄) thin films with dumbbell-like, kernel-like, bowknot-like and cauliflower-like microstructure were synthesized from an aqueous solution containing barium nitrate, ethylenediamine tetraacetate acid disodium and sodium tungstate, via mild microwave assisted chemical bath deposition process. The resulting BaWO₄ films with different morphologies were characterized by X-ray diffraction spectrum, scanning electron microscope, Raman and photoluminescence spectra. The results indicate that the morphologies of final products significantly depend on the reaction conditions including the reaction time, the initial concentration of precursor reagent and the physicochemical characteristics of the substrates. Furthermore, the oriented aggregation mechanism is proposed as a possible formation mechanism of the films with specific morphologies.     

Ultrasensitive fluorometric determination of hydrogen peroxide and glucose by using multiferroic BiFeO3 nanoparticles as a catalyst

BiFeO₃ magnetic nanoparticles (BFO MNPs) are used as a catalyst to develop an ultrasensitive method for the determination of H₂O₂. It is found that BFO MNPs can catalyze the decomposition of H₂O₂ to produce OH radicals, which in turn oxidize the weakly fluorescent benzoic acid to a strongly fluorescent hydroxylated product with a maximum emission at 405 nm. This makes it possible to sensitively quantify traces of H₂O₂. Under optimized conditions, the fluorescence intensity is observed to be well linearly correlated with H₂O₂ concentration from 2.0 × 10⁻⁸ to 2.0 × 10⁻⁵ mol L⁻¹ with a detection limit of 4.5 × 10⁻⁹ mol L⁻¹ (S/N = 3). In addition, a selective method for glucose determination is developed by using both glucose oxidase and BFO MNPs, which has a linear range for glucose concentration from 1.0 × 10⁻⁶ to 1.0 × 10⁻⁴ mol L⁻¹ with a detection limit of 5.0 × 10⁻⁷ mol L⁻¹. These new methods have been successfully applied for the determination of H₂O₂ in rainwater and glucose in human serum samples.