Langmuir and langmuir-blodgett films of polyfluorenes and their use in polymer light-emitting diodes

The Langmuir and Langmuir-Blodgett (LB) film properties of two polyfluorene derivatives, namely poly(2,7-9,9'-dihexylfluorene-dyil) (PDHF) and poly(9,9 dihexylfluorene-dyil-vynilene-alt-1,4-phenylene-vyninele) (PDHF-PV), are reported. Surface pressure (Pi-A) and surface potential (Delta V-A) isotherms indicated that PDHF-PV forms true monolayers at the air/water interface, but PDHF does not. LB films could be transferred onto various types of substrate for both PDHF and PDHF-PV. Only the LB films from PDHF-PV could withstand deposition of a layer of evaporated metal to form a light-emitting diode (PLED), which had typical rectifying characteristics and emitted blue light. It is inferred that the ability of the polymer to form true monomolecular layers at the air/water interface seems to be associated with the viability of the LB films in PLEDs.

Microstructural, dielectric and ferroelectric properties of calcium-modified lead titanate thin films derived by chemical processes

Ferroelectric Pb1-xCaxTiO3 (x = 0.24) thin films were formed on a Pt/Ti/SiO2/Si substrate by the polymeric precursor method using the dip-coating technique for their deposition. Characterization of the films bq X-ray diffraction showed a perovskite single phase with a tetragonal structure after annealing at 700 degreesC. Atomic force microscopy (AFM) analyses showed that the film had a smooth and crack-free surface with low surface roughness. In addition, the PCT thin film had a granular structure with an 80 nm grain size. The thickness of the films observed by the scanning electron microscopy (SEM) is 550 nm and there is a good adhesion between the film and substrate. For the electrical measurements metal-ferroelectric-metal of the type capacitors were obtained, where the thin films showed good dielectric and ferroelectric properties. The dielectric constant and dissipation factor at 1 kHz and measured at room temperature were found to be 457 and 0.03. respectively. The remanent polarization and coercive field for the: deposited films were P-r = 17 muC/cm(2) and E-c = 75 kV/cm, respectively. Moreover. The 550-nm-thick film showed a current density in the order of 10(-8) A/cm(2) at the applied voltage of 2 V. The high values of the thin film's dielectric properties are attributed to its excellent microstructural quality and the chemical homogeneity obtained by the polymeric precursor method. (C) 2001 Elsevier science Ltd. All rights reserved.

Grazing incidence X-ray diffraction and atomic force microscopy analysis of BaBi2Ta2O9 thin films

Thin films of BaBi2Ta2O9 (BBT) composition were prepared through the metal organic decomposition method. The crystallinity, phase formation, crystallite size and morphology of the thin films were measured as a function of the type of substrate, stoichiometry of solution and process variables such as thickness and temperature. The thin films were investigated by grazing incidence X-ray diffractometry and atomic force microscopy (AFM) techniques. For the sample without excess of bismuth, diffraction peaks other than that of the BBT phase were observed. A well crystallized BBT single phase was observed for films prepared from a solution with 10% excess of bismuth, deposited on Si/Pt substrate, with a thickness up to 150 nm and sintered at temperatures of 700 degreesC. The thin BBT phase films heat-treated at 600 degreesC presented a diffraction pattern characteristic of samples with lower degree of crystallinity whereas for the thin films heat-treated at 800 degreesC, we observed the presence of other phases than the BBT. For the thin film deposited on the Sin+ substrate, we observe that the peaks corresponding to the BBT phase are broader than that observed on the samples deposited on the Pt and Si/Pt substrates. No variation of average crystallite size was observed as the excess of Bi increased from 10 to 20%. AFM images for the samples showed that the increasing the amount of bismuth promotes grain growth. The average surface roughness measured was in the range of 16-22 nm showing that the bismuth amount had no or little effect on the roughness of films. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Structural and electrical properties of SrBi2Nb2O9 thin films prepared by chemical aqueous solution at low temperature

SrBi2Nb2O9 (SBN) thin films were prepared by the polymeric precursors method and deposited by dip coating onto Pt/Ti/SiO2/Si(100) substrates. The dip-coated films were specular and crack-free and crystallized during firing at 700 degrees C. Microstructure and morphological evaluation were followed by grazing incident X-ray diffraction (GIXRD), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The films exhibited somewhat porous grain structure with rounded grains of about 100 nm. For the electrical measurements, gold electrodes of 300 mu m in diameter were sputter deposited on the top surface, forming a metal-ferroelectric-metal (MFM) configuration. The remanent polarization (P-r) and coercive field (E-c) were 5.6 mu C/cm(2) and 100 kV/cm, respectively. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Thickness dependence of leakage current in BaBi2Ta2O9 thin films

BaBi2Ta2O9 thin films having a layered structure were fabricated by metalorganic solution deposition technique. The films exhibited good structural, dielectric, and insulating properties. The room temperature resistivity was found to be in the range of 10(12)-10(14) Omega cm up to 4 V corresponding to a field of 200 kV/cm across the capacitor for films annealed in the temperature range of 500-700 degrees C. The current-voltage (I-V) characteristics as a function of thickness for films annealed at 700 degrees C for 1 h, indicated bulk limited conduction and the log(I) vs V-1/2 characteristics suggested a space-charge-limited conduction mechanism. The capacitance-voltage measurements on films in a metal-insulator-semiconductor configuration indicated good Si/BaBi2Ta2O9 interface characteristics and a SiO2 thickness of similar to 5 nm was measured and calculated. (C) 1999 American Institute of Physics. [S0003-6951(99)00830-X].

Lignin from sugar cane bagasse: Extraction, fabrication of nanostructured films, and application

Four lignin samples were extracted from sugar cane bagasse using four different alcohols (methanol, ethanol, n-propanol, and 1-butanol) via the organosolv-CO2 supercritical pulping process. Langmuir films were characterized by surface pressure vs mean molecular area (Pi-A) isotherms to exploit information at the molecular level carrying out stability tests, cycles of compression/expansion (hysteresis), subphase temperature variations, and metallic ions dissolved into the water subphase at different concentrations. Briefly, it was observed that these lignins are relatively stable on the water surface when compared to those obtained via different extraction processes. Besides, the Pi-A isotherms are shifted to smaller molecular areas at higher subphase temperatures and to larger molecular areas when the metallic ions are dissolved into the subphase. The results are related to the formation of stable aggregates (domains) onto the water subphase by these lignins, as shown in the Pi-A isotherms. It was found as well that the most stable lignin monolayer onto the water subphase is that extracted with 1-butanol. Homogeneous Langmuir-Blodgett (LB) films of this lignin could be produced as confirmed by UV-vis absorption spectroscopy and the cumulative transfer parameter. In addition, FTIR analysis showed that this lignin LB film is structured in a way that the phenyl groups are organized preferentially parallel to the substrate surface. Further, these LB films were deposited onto gold interdigitated electrodes and ITO and applied in studies involving the detection of Cd+2 ions in aqueous solutions at low concentration levels throughimpedance spectroscopy and electrochemical measurements. FTIR spectroscopy was carried out before and after soaking the thin films into Cd+2 aqueous solutions, revealing a possible physical interaction between the lignin phenyl groups and the heavy metal ions. The importance of using nanostructured systems is demonstrated as well by comparing both LB and cast films.

Unusual interactions binding iron tetrasulfonated phthalocyanine and poly(allylamine hydrochloride) in layer-by-layer films

Molecular-level interactions are found to bind iron tetrasulfonated phthalocyanine (FeTsPc) and the polyelectrolyte poly(allylamine hydrochloride) (PAH) in electroactive layer-by-layer (LBL) films. These interactions have been identified by comparing Fourier transform infrared (FTIR) and Raman spectroscopy data from bulk samples of FeTsPc and PAH with those from FeTsPc/PAH LBL films. of particular importance were the SO3- -NH3 interactions that we believe to bind PAH and FeTsPc and the interactions between unprotonated amine groups of PAH and the coordinating metal of the phthalocyanine. The multilayer formation was monitored via UV-vis spectroscopy by measuring the increase in the Q band of FeTsPc at 676 nm. Film thickness estimated with profilometry was ca. I I Angstrom per bilayer for films adsorbed on glass. Reflection absorption infrared spectroscopy (RAIRS) revealed an anisotropy in the LBL film adsorbed on gold with FeTsPc molecules oriented perpendicularly to the substrate plane. Cyclic voltammograms showed reproducible pairs of oxidation-reduction peaks at 1.07 and 0.81 V, respectively, for a 50-bilayer PAH/FeTsPc film at 50 mV/s (vs Ag/Ag+). The peak shape and current dependence on the scan rate suggest that the process is a diffusion controlled charge transport. In the presence of dopamine, the electroactivity of FeTsPc/PAH LBL films vanishes due to a passivation effect. Dopamine activity is not detected either because the interaction between Fe atoms and NH2 groups prevents dopamine molecules from coordinating with the Fe atoms.

Barium strontium titanate nanocrystalline thin films prepared by soft chemical method

Barium strontium titanate (Ba0.65Sr0.35TiO3) nanocrystalline thin films, which were produced by the soft chemical method, were crystallized at low temperature using a domestic microwave oven. A SiC susceptor were used to absorb the microwave energy and rapidly transfer the heat to the film. Low microwave power and short time have been used. The films obtained are crack-free, well-adhered, and fully crystallized. The microstructure displayed a polycrystalline nature with nanograin size. The metal-BST-metal structure of the thin films treated at 700 degrees C show food electric properties. The ferroelectric nature of the BST35 thin film was indicated by buttertly- shaped C-V curves. The capacitance-frequency curves reveal that the dielectric constant may reach a value up to 800 at 100kHz. The dissipation factor was 0.01 at 100kHz. The charge storage density as function of applied voltage graph showed that the charge storage densities are suitable for use in trench type 64 Mb ( 1-5 mu C/cm(2) and 265 Mb (2-11 mu C/cm(2)) DRAMs. (C) 2007 Elsevier Ltd. All rights reserved.

Use of diffusive gradients in thin films and tangential flow ultrafiltration for fractionation of Al(III) and Cu(II) in organic-rich river waters

Diffusive gradients in thin films (DGT) and tangential-flow ultrafiltration (TF-UF) were combined for fractionation of Al and Cu in river water containing high content of dissolved organic carbon. A procedure based on ultrafiltration data is proposed to determine diffusion coefficients of the analytes in water samples and model solutions containing both free metal (M) and complex (metal - humic substance). Aiming to evaluate the accuracy of the proposed approach, the DGT results were compared with those from a protocol for determination of labile Al and Cu based on solid phase extraction (SPE). Good agreement between data from DGT and SPE were attained for model solutions. For analysis of real organic-rich water samples, differences between DGT and SPE measurements were consistent with the time-scales of the techniques. The concentration of labile Al determined by DGT were lower than the total dissolved concentrations (determined by inductively coupled plasma mass spectrometry) and exceeded the ultrafiltered concentration, indicating that inorganic Al species (species small enough to pass through 1 kDa membrane) were minor species as compared with Al organic complexes. For both Al and Cu, there were species not measured by DGT as they are not sufficiently labile. (C) 2007 Elsevier B.V. All rights reserved.

An investigation of metal oxides which are photoluminiscent at room temperature

Amorphous thin films, based on different network formers, were processed by a soft chemical process called the polymeric precursor method. The resultant amorphous metal oxides, displayed intense photoluminescence (PL) at room temperature. Heat treatment increases the PL intensity of these materials. Theoretical ab initio calculations are correlated with the observed experimental trends. (C) 2004 Elsevier B.V. All rights reserved.

Synthesis, ferroelectric and optical properties of (Pb,Ca)TiO3 thin films by soft solution processing

Calcium modified lead titanate sol was synthesized using a soft solution processing, the so-called polymeric precursor method. In soft chemistry method, soluble precursors such as lead acetate trihydrate, calcium carbonate and titanium isopropoxide, as starting materials, were mixed in aqueous solution. Pb0.7Ca0.3TiO3 thin films were deposited on platinum-coated silicon and quartz substrates by means of the spinning technique. The surface morphology and crystal structure, dielectric and optical properties of the thin films were investigated. The electrical measurements were conducted on metal-ferroelectric-metal (MFM) capacitors. The typical measured small signal dielectric constant and dissipation factor at a frequency of 100 kHz were 299 and 0.065, respectively, for a thin film with 230 nm thickness annealed at 600degreesC for 2 h. The remanent polarization (2P(r)) and coercive field (E-c) were 32 muC/cm(2) and 100 kV/cm, respectively. Transmission spectra were recorded and from them, refractive index, extinction coefficient, and band gap energy were calculated. Thin films exhibited good optical transmissivity, and had optical direct transitions. The present study confirms the validity of the DiDomenico model for the interband transition, with a single electronic oscillator at 6.858 eV. The optical dispersion behavior of PCT thin film was found to fit well the Sellmeir dispersion equation. The band gap energy of the thin film, annealed at 600degreesC, was 3.56 eV. The results confirmed that soft solution processing provides an inexpensive and environmentally friendly route for the preparation of PCT thin films.

Langmuir-Blodgett films incorporating an ionic europium complex

Langmuir-Blodgett (LB) technique is a powerful tool to fabricate ultrathin films with highly ordered structures and controllable molecular array for efficient energy and electron transfer, allowing the construction of devices at molecular level. One method to obtain LB films consists in the mixture of classical film-forming molecules, for example Stearic Acid (SA) and functional metal complex. In this work NH(4)[Eu(bmdm)(4)], where the organic ligand bmdm is (butyl methoxy-dibenzoyl-methane) or (1-(4-methoxyphenyl)-3-(4-tert-butylphenyl)propane-1,3-dione) was used to build up Langmuir and LB films. Langmuir isotherms were obtained from (i) NH(4)[Eu(bmdm)(4)] complex and (ii) NH(4)[Eu(bmdm)(4)]/SA (1:1). Results indicated that (i) form multilayer structure; however the surface pressure was insufficient to obtain LB films, and (ii) can easily reproduce and build LB films. The dependence of number of layers in the UV absorption spectra suggest that the complex did not hydrolyze or show decomposition, UV spectral differences observed between the solution and the LB film indicate that the complex has a highly ordered arrangement in the film and the complex has an interaction with SA. Excitation spectra confirm a ligand-europium energy transfer mechanism. The transition lines of Eu(3+) ion were observed in emission spectra of all films, the photoluminescence spectra indicate a fluorescence enhanced effect with the number of LB layers. (C) 2009 Elsevier B.V. All rights reserved.

Developments in hot-filament metal oxide deposition (HFMOD)

Hot-filament metal oxide deposition (HFMOD) is a variant of conventional hot-filament chemical vapor deposition (HFCVD) recently developed in our laboratory and successfully used to obtain high-quality, uniform films of MOx WOx and VOx. The method employs the controlled oxidation of a filament of a transition metal heated to 1000 degrees C or more in a rarefied oxygen atmosphere (typically, of about 1 Pa). Metal oxide vapor formed on the surface of the filament is transported a few centimetres to deposit on a suitable substrate. Key system parameters include the choice of filament material and diameter, the applied current and the partial pressures of oxygen in the chamber. Relatively high film deposition rates, such as 31 nm min(-1) for MoOx, are obtained. The film stoichiometry depends on the exact deposition conditions. MoOx films, for example, present a mixture of MoO2 and MoO3 phases, as revealed by XPS. As determined by Li+ intercalation using an electrochemical cell, these films also show a colouration efficiency of 19.5 cm(2) C-1 at a wavelength of 700 nm. MOx and WOx films are promising in applications involving electrochromism and characteristics of their colouring/bleaching cycles are presented. The chemical composition and structure of VOx films examined using IRRAS (infrared reflection-absorption spectroscopy), RBS (Rutherford backscattering spectrometry) and XPS (X-ray photoelectron spectrometry) are also presented. (c) 2007 Elsevier B.V. All rights reserved.

Paper-based diffusive gradients in thin films technique coupled to energy dispersive X-ray fluorescence spectrometry for the determination of labile Mn, Co, Ni, Cu, Zn and Pb in river water

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effects of thermal annealing on the semi-insulating properties of radio frequency magnetron sputtering-produced germanate thin films

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)