Preparation of nanocrystalline titania films with different porosity by water-based chemical solution deposition

This study describes the synthesis of nanocrystalline titania layers on silicon and glass substrates by chemical solution deposition, using a water-based citratoperoxo-Ti(IV) precursor solution. The same aqueous solution–gel precursor is used for deposition of, both, thin dense layers by spin-coating and thicker porous layers by tape-casting. In the latter, the precursor solution is modified by the addition of polyvinyl alcohol (PVA), which acts as a thickener and pore-forming agent. Phase composition, film morphology, and the hydrophilic character of the films are studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV–VIS transmission measurements, variable angle spectroscopic ellipsometry (VASE), and by contact angle measurements. The thin 180 nm titania film, deposited from the unmodified precursor solution, shows a density of about 96%. Upon ultraviolet illumination, it acquires a highly hydrophilic surface. One hour of illumination is sufficient to obtain a water contact angle of almost 0°. Furthermore, the hydrophilisation process shows to be reversible. Tape-casting and thermal treatment of the modified precursor solution gives rise to the formation of a 500 nm thick, porous, pure anatase film. The nanocrystalline thick film is composed of 20–40 nm particles, and contains clearly defined pores of 20 nm, homogeneously distributed along the surface.     

Evolution of crystalline structure in SnS thin films prepared by chemical deposition

Crystal structure and morphology undergo significant evolution in thin films of tin(II) sulfide prepared by chemical deposition, over a narrow interval of bath temperature of 20–40 °C, but has not been recognized in previous studies. The chemical bath is constituted using tin(II) chloride, triethanolamine, ammonia(aq.) and thioacetamide. At bath temperature of 20 °C, the deposition rate of the film is 10 nm/h; and at 24 h, a film of thickness 260 nm is obtained. This film is compact and with a predominantly cubic (Cub-) crystalline structure. At 40 °C, the deposition rate is 25 nm/h, and a film of 600 nm in thickness is deposited in 24 h. However, this film has evolved into vertically stacked platelets of orthorhombic (OR-) crystalline structure. The transition from compact-to-platelet morphology as well as from Cub-to-OR-crystalline structure is observed near a deposition temperature, 35 °C. The Cub-SnS has a characteristic high optical band gap, 1.67 eV (direct gap; forbidden transitions) with an electrical conductivity, 10⁻⁷(Ω cm)⁻¹; both properties being un-affected when films are heated at 300 °C in a nitrogen ambient. In OR-SnS, the band gap is 1.1 eV (indirect gap; allowed transitions). The electrical conductivity of such films is notably higher, 10⁻⁴ (Ω cm)⁻¹, which increases further by an order of magnitude when the films have been heated at 300 °C in nitrogen.     

Ion dopants tuning the interband electronic structure for huge saturated ferroelectric polarization in bismuth ferrite films

Bismuth ferrite (BiFeO₃, BFO) as a prototype multiferroic has been extensively studied in past years; however, there are several key issues not to be clearly expressed. Especially, the relationship of structure and physical properties still remains obscure. In this case, the interband electronic structure of BFO was elaborately manipulated by appropriation dopants of Ni and Gd to realize the huge saturated ferroelectric polarization in the polycrystalline films. For instance, a huge saturated polarization P_S of 96?μC/cm² and remnant polarization Pr of 91?μC/cm² were achieved in Bi_0.925Gd_0.075Fe_0.95Ni_0.05O₃ film. The results and analysis show that the alteration in the interband electronic structure and the improvement of morphology derived from the ion doping effect indeed play key roles on the improved ferroelectric property of the doped BFO films. The decreased leakage current density and thereby the enhanced ferroelectric polarization in the doped BFO films should be attributed to the decrease in both Fermi level and Urbach energy closely related with the defects, as well as the improved surface uniformity and compactness of the films. Finally, the mechanism and relationship of structure and physical properties in BFO were systemically analyzed and discussed.

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The ferroelectric polarization for pure and doped BiFeO₃ films

     

Selective reaction and chemical anisotropy in epitaxial bismuth layer-structured ferroelectric thin films

Bismuth layer-structured ferroelectric thin films consisting of a stacking of pseudoperovskite and bismuth oxide blocks along the c-axis were epitaxially grown on single-crystal substrates by metalorganic chemical vapor deposition (MOCVD), and a selective reaction of the bismuth oxide layer with HCl was demonstrated. Epitaxial films with contrasting crystal orientations were used for the acid treatment in order to probe chemical anisotropy. For a/b-axis-oriented SrBi₂Ta₂O₉, Bi₄Ti₃O₁₂, and SrBi₄Ti₄O₁₅ films with sequential stacking of the two vertical blocks, notable structural selectivity of the reaction was observed only for SrBi₂Ta₂O₉. For this film, the pseudoperovskite block remained and the bismuth oxide block was removed, while both blocks of Bi₄Ti₃O₁₂ and SrBi₄Ti₄O₁₅ dissolved into the acid. In addition to the bismuth, the other cations in the pseudoperovskite blocks, strontium and titanium, also decreased for Bi₄Ti₃O₁₂ and SrBi₄Ti₄O₁₅. The selective reaction observed for a/b-axis-oriented SrBi₂Ta₂O₉, however, was not observed for c-axis-oriented SrBi₂Ta₂O₉ films in which the pseudoperovskite and bismuth oxide blocks were stacked horizontally. The results clearly show that SrBi₂Ta₂O₉ has sub-nano-order structural selectivity and chemical anisotropy in the unit cell in the reaction with HCl.     

Physical and chemical properties of silicon carbonitride nanocrystalline films

Nanocrystalline transparent films SiC_xN_y were obtained by plasma-enhanced chemical deposition within the temperature range 473–1173 K from low pressure gas phase from a mixture of hexamethyldisilazane vapor, ammonia, and helium. Physical chemical properties of the films obtained were studied by IR and Raman spectroscopy, ellipsometry, X-ray photoelectron spectroscopy, scanning electron microscopy, high resolution transmission electron spectroscopy and synchrotron radiation powder diffaction. Voltage-capacity and voltage-current measurements were also made. The dependence of chemical and phase composition of the films on deposition conditions was determined, and the formation of approximately 2 nm sized spherical nanocrystals within the films was established. The nanocrystals are formed by a phase similar to usual α-Si₃N₄, with silicon atoms partially substituted by carbon ones.     

Crystalline orientation of the InN films prepared by atmospheric pressure halide chemical vapor deposition

The structural analysis of the hexagonal InN film prepared on a Si(100) substrate by the AP-HCVD technique using InCl₃ and NH₃ as starting materials were carried out by the X-ray pole figure analysis. The deposited films consist of the hexagonal InN pillar crystals. It was found that the pillar crystals, which have random rotation around the 100 axis, were grown at an angle of 70–90° to the substrate.     

Characterization of zinc-modified lithium tantalate thin films fabricated by chemical solution deposition method

Zinc-substituted lithium tantalate thin films were fabricated for improving the electrical resistivity by compensating the valence of lattice defects in LiTaO₃ crystal. The films with the chemical composition of (Li_1.00-x Zn _x )TaO₃ were fabricated on (111)Pt/TiO₂/SiO₂/(100)Si substrate by a chemical solution deposition technique using metal-organic precursors. Dense films consisting of a ilumenite-type crystalline phase were deposited by spin coating on the substrates, followed by heat-treatment at 650°C for 5 min in air. The leakage current density of the LiTaO₃ film was reduced from approximately 10⁻⁴ to 10⁻⁶ A/cm² by substituting Zn²⁺ ions for Li⁺ ions in the LiTaO₃ films. Polarization–electric field hysteresis loop was improved significantly by partial substitution of Zn²⁺ for Li⁺ ions, which is based on the enhancement of electrical resistivity.     

Preparation and characterization of CuAlO2 transparent thin films prepared by chemical solution deposition method

CuAlO₂ thin films were prepared on quartz glass and sapphire substrates by chemical solution deposition method using copper acetate monohydrate, aluminum nitrate nonahydrate and 2-methoxyethanol as starting precursor and solvent. The effects of annealing temperature on the structural, morphological, electrical and optical properties have been studied. Via the optimized annealing treatment condition, CuAlO₂ film annealed at 850 °C in nitrogen flow of 400sccm under atmosphere pressure exhibits the best performance with the lowest room temperature resistivity of 3.6 × 10² Ω cm and the highest optical transmission in the visible region (>70% at around 600 nm wavelength). CuAl₂O₄ and CuO phases, not CuAlO₂ phase are obtained when annealing temperature is lower than 850 °C. However, a further increase of annealing temperature weakens the crystallization quality and deteriorates the surface morphology of CuAlO₂ films as the annealing temperature exceeds 850 °C, leading to an increase in the resistivity and a decrease of the optical transmission in the visible region of CuAlO₂ films.     

Effects of chemical structure and precursor on optical properties,thermo-mechanical properties,and molecular orientation and order of thin films of stiff aromatic polyimides

Thin films of rigid poly(p-phenylene pyromellitimide) (PMDA-PDA) and semi-rigid poly(p-phenylene biphenyltetracarboximide) (BPDA-PDA), prepared by thermal imidization of the respective poly(amic acid) and poly(amic ethyl ester) precursors, were characterized with respect to their optical, thermomechanical and structural properties. Both polyimides exhibit an unusually large anisotropy between the in-plane and out-of-plane refractive indices, with n ranging from 0.198 to 0.216 for PMDA-PDA and from 0.230 to 0.242 for BPDA-PDA, nearly independent of the nature of the initial polyimide precursor, film thickness, and film preparation method. PMDA-PDA films exhibit low coefficients of thermal expansion (CTE's) of 6.5 and 8.2 ppm/C for the acid-derived and the ester-derived polyimides, respectively. In comparison, the BPDA-PDA films show CTE values of 4.3 and 18.0 for the acid-derived and ester-derived samples, respectively, despite the small differences in their optical anisotropies. Wide-angle x-ray diffraction patterns obtained in reflection and transmission for the various samples reveal a strong in-plane chain orientation for both PMDA-PDA and BPDA-PDA polyimides, with somewhat better intermolecular packing order for the ester-derived polyimide films. These effects of chemical structure and precursor on properties and structures of the polyimide films are discussed in light of recent theoretical considerations of semiflexible polymers.Dedicated to Prof E. W. Fischer on the occasion of his 65th birthday     

Synthesis, electrical properties, and structural features of copper-containing chalcogenide films produced by the chemical deposition method

Multicomponent copper-containing CuI-AsI₃-As₂Se₃ and CuI-Sb₃I-As₂Se₃ chalcogenide films were produced by chemical deposition from solutions of chalcogenide glasses in n-butylamine and their electrical conductivity was studied. It was shown that the electrical properties of chalcogenide glasses and films based on these glasses have the same values within experimental error. It was found sing Mossbauer spectroscopy that antimony atoms are in the Sb(III) state in the environment of three selenium atoms, and copper ions in the Cu(I) state and are surrounded by iodine atoms. The chalcogenide films can be used to fabricate ion-selective electrodes sensitive to copper cations.     

Chemical composition and properties of films produced from hexamethyldisilazane by plasma-enhanced chemical vapor deposition

Relationships between the chemical composition of the gas phase and the properties of SiC_xN_yH_z films produced from hexamethyldisilazane by plasma-enhanced chemical vapor deposition have been studied. The plasma composition has been examined by optical emission spectroscopy. Thermal analysis of the films with simultaneous mass spectrometric detection of released gases has been performed. On the basis of the results and published data, mechanisms for the formation of films by plasma polymerization have been proposed and the film growth at a low plasma power and high reactor temperatures has been found to follow the heterogeneous mechanism.     

Application of thermal analysis and kinetic predictions to YBCO films prepared by chemical solution deposition methods

Journal of Thermal Analysis and Calorimetry - Low-temperature DSC on a wide range of opal-A and opal-CT samples was carried out to estimate the proportion of crystallisable water and to determine...     

Polarized Raman study on the lattice structure of BiFeO3 films prepared by pulsed laser deposition

Polarized Raman spectroscopy was used to study the lattice structure of BiFeO₃ films on different substrates prepared by pulsed laser deposition. Interestingly, the Raman spectra of BiFeO₃ films exhibit distinct polarization dependences. The symmetries of the fundamental Raman modes in 50–700 cm⁻¹ were identified based on group theory. The symmetries of the high order Raman modes in 900–1500 cm⁻¹ of BiFeO₃ are determined for the first time, which can provide strong clarifications to the symmetry of the fundamental peaks in 400–700 cm⁻¹ in return. Moreover, the lattice structures of BiFeO₃ films are identified consequently on the basis of Raman spectroscopy. BiFeO₃ films on SrRuO₃ coated SrTiO₃ (0 0 1) substrate, CaRuO₃ coated SrTiO₃ (0 0 1) substrate and tin-doped indium oxide substrate are found to be in the rhombohedral structure, while BiFeO₃ film on SrRuO₃ coated Nb: SrTiO₃ (0 0 1) substrate is in the monoclinic structure. Our results suggest that polarized Raman spectroscopy would be a feasible tool to study the lattice structure of BiFeO₃ films.     

Biaxial orientation characterization on-line and off-line and structure properties correlations in films

In this paper, biaxial orientation characterization techniques are briefly reviewed. Results obtained using birefringence and Fourier Transform Infrared Spectroscopy (FTIR) techniques are presented for different applications: On-line monitoring of birefringence for an amorphous polymer (polystyrene); On-line and off-line determination of orientation (birefringence) of polyethylene terephthalate (PET) and finally off-line measurement of orientation on polyethylene (LDPE) films using FTIR. Some typical morphologies of blown LDPE films are reported and discussed. Finally, correlations between orientation on one hand and shrinkage and tear strength on the other are attempted.     

Photophysics, photoelectrical properties and photoconductivity relaxation dynamics of quantum-sized bismuth(III) sulfide thin films

Electrical and photoelectrical properties (including both the stationary photoresponse and the photocarriers' relaxation dynamics) of nanocrystalline semiconducting bismuth(III) sulfide thin films were investigated. The experimental design of photoelectrical properties was achieved by controlling the chemistry of the deposition process (varying the reagent concentration in the reaction system) and also by physical means (controlling the crystal dimensions by post-deposition annealing). The band gap energy of thin films characterized by most pronounced photoelectrical properties was calculated, on the basis of measured photoconductivity spectral response curves, by several approaches. All of the obtained values are in very good agreement with the corresponding ones obtained from optical spectroscopy data within the framework of parabolic approximation for dispersion relation. On the basis of measured temperature dependence of dark electrical resistivity of nanocrystalline bismuth(III) sulfide films, the thermal band gap energy and the ionization energy of the impurity level (of donor type) were calculated. The corresponding values are 1.50 and 0.42 eV. Dynamics of non-equilibrium charge carriers' relaxation processes was studied with the oscilloscopic method. By analysis of the photoconductivity decay kinetics data it is found that recombination of non-equilibrium charge carriers is carried out according to the linear mechanism. The calculated relaxation time of photoexcited charge carriers is 1.58 ms, the relaxation processes occurring via local trapping centers. Recombination processes occurring via a single-type trapping center can be described within the framework of the Schockley-Read model. The practically linear regime detected in the measured lux-ampere characteristics of the studied films (Δσ∼Φ^0.98) indicate as well a linear recombination mechanism of the photoexcited charge carriers.     

Magnetic,optical and electrical properties of Mn-doped CuCrO<Subscript>2</Subscript> thin films prepared by chemical solution deposition method

CuCrO₂ and CuCrO₂:Mn thin films were prepared on sapphire substrates by chemical solution deposition method. The effects of the annealing temperatures and Mn concentration on the structural, electrical and optical properties were investigated. The X-ray diffraction measurement was used to confirm the c-axis orientation of CuCrO₂ and CuCrO₂:Mn thin films. The maximum transmittances of the films in the visible region are about 65% with direct band gaps of 3.25 eV. All films showed the p-type conduction and semiconductor behavior. The electrical conductivity decreases rapidly with the increase of Mn content, the maximum of the electrical conductivity of 1.35 × 10⁻² S cm⁻¹ is CuCrO₂ film deposited at 600 °C temperature in 10⁻³ Torr vacuum, which is about four orders of magnitude higher than that of the Mn-doped CuCrO₂ thin film. The energy band of the samples is constructed based on the grain-boundary scattering in order to investigate the conduction mechanism. Moreover, the samples exhibit a clear ferromagnetism, which was likely ascribed to originating from the double-exchange interaction between the Mn³⁺ and Cr³⁺ ions.     

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.     

X-ray diffraction area mapping of preferred orientation and phase change in TiO2 thin films deposited by chemical vapor deposition

This paper reports on an investigation into the formation of TiO(2) thin films, whereby X-ray diffraction is used to map systematic changes in preferred orientation and phase observed throughout the films. The key to this strategy is the recording of X-ray diffraction patterns of specific and isolated areas of a substrate, ensuring this specificity by the use of a small X-ray sample illumination area (approximately 3-5 mm(2)). A map of the variation in film composition can then be built up by recording such diffraction patterns at regular intervals over the whole substrate. Two titania films will be presented, grown using atmospheric pressure chemical vapor deposition, at 450 and 600 degrees C, from TiCl(4) and ethyl-acetate precursors. The film grown at 450 degrees C showed a systematic change in preferred orientation, while the film grown at 600 degrees C was composed of a mixture of the rutile and anatase phases of TiO(2) with the ratio of these phases altering with position on the substrate. The results of physical property measurements and electron microscopy carried out on the films are also reported, conducted at locations identified by the X-ray diffraction mapping procedure as having different compositions, and hence different physical responses. We found that the photocatalytic activity and hydrophobicity were dependent on the rutile:anatase ratio at any given location on the film.