Control of the thickness of mesoporous titania films for application in multiphase catalytic microreactors

A new method of sol-gel polymer template synthesis of mesoporous catalytic thin films has been proposed which allows controlling the chemical nature of the film, the porosity, thickness and loading with an active species. The mesoporous films with a long-order structure can be obtained in a narrow range of surfactant-to-metal precursor molar ratios from 0.006 to 0.009. The catalytic film thickness was varied from 300 to 1000 nm while providing a uniform catalyst distribution with a desired catalyst loading (1 wt. % Au nanoparticles) throughout the film. The films were characterized by TEM, SEM, ethanol adsorption and contact angle measurements. The calcination of the as-synthesized films at 573 K reduced Ti4+ sites to Ti3+. A 300 nm thick Au-containing film showed an initial TOF of 1.4 s(-1) and a selectivity towards unsaturated alcohols as high as 90% in the hydrogenation of citral. Thicker films demonstrated a high selectivity towards the saturated aldehyde (above 55%) and a lower intrinsic catalytic activity (initial TOF of 0.7-0.9 s(-1)) in the absence of internal diffusion limitations.

An investigation into the effect of thickness of titanium dioxide and gold-silver nanoparticle titanium dioxide composite thin-films on photocatalytic activity and photo-induced oxygen production in a sacrificial system

Thin films of titanium dioxide and titanium dioxide with incorporated gold and silver nanoparticles were deposited onto glass microscope slides, steel and titanium foil coupons by two sol-gel dip-coating methods. The film's photocatalytic activity and ability to evolve oxygen in a sacrificial solution were assessed. It was found that photocatalytic activity increased with film thickness (from 50 to 500 nm thick samples) for the photocatalytic degradation of methylene blue in solution and resazurin redox dye in an intelligent ink dye deposited on the surface. Contrastingly, an optimum film thickness of similar to 200 nm for both composite and pure films of titanium dioxide was found for water oxidation, using persulfate (S2O82-) as a sacrificial electron acceptor. The nanoparticle composite films showed significantly higher activity in oxygen evolution studies compared with plain TiO2 films.

Use of luminescent gold compounds in the design of thin-film oxygen sensors

The use of two gold compounds incorporated into thin plastic films as luminescence quenching oxygen sensors is described. The films are sensitive both to gaseous oxygen and to oxygen dissolved in nonaqueous media such as ethanol. The luminescence quenching of these sensors by oxygen obeys the Stern-Volmer equation and Stern-Volmer constants of 5.35 x 10(-3) and 0.9 x 10(-3) Torr(-1) are found, respectively, for the two dyes in a polystyrene polymer matrix. The sensitivity of the films is strongly influenced by the nature of the polymer matrix, and greatest sensitivity was found in systems based an the polymers polystyrene or cellulose acetate butyrate. Sensitivity was not found to be temperature dependent though raising the temperature hom 15 to 50 degrees C did result in a slight decrease in emission intensity and a hypsochromic shift in the emission wavelength. The rate of response and recovery of the sensors can be increased either by decreasing film thickness or by increasing the operating temperature. The operational and storage stability of these films is generally good though exposure to light should be avoided as one of the dyes tends to undergo photobleaching probably due to a photoinduced ligand substitution reaction.

MODELED DIFFUSION-CONTROLLED RESPONSE AND RECOVERY BEHAVIOR OF A NAKED OPTICAL FILM SENSOR WITH A HYPERBOLIC-TYPE RESPONSE TO ANALYTE CONCENTRATION

The diffusion-controlled response and recovery behaviour of a naked optical film sensor (i.e., with no protective membrane) with a hyperbolic-type response [i.e., S0/S = (1 + Kc), where S is the measured value of the absorbance or luminescence intensity of one form of the sensor dye in the presence of the analyte, S0 is the observed value of S in the absence of analyte and K is a constant] to changes in analyte concentration, c, in a system under test is approximated using a simple model, and described more accurately using a numerical model; in both models it is assumed that the system under test represents an infinite reservoir. Each model predicts the variations in the response and recovery times of such an optical sensor, as a function of the final external analyte concentration, the film thickness (I) and the analyte diffusion coefficient (D). From an observed signal versus time profile for a naked optical film sensor it is shown how values for K and D/I2 can be extracted using the numerical model. Both models provide a qualitative description of the often cited asymmetric nature of the response and recovery for hyperbolic-type response naked optical film sensors. It is envisaged that the models will help in the interpretation of the response and recovery behaviour exhibited by many naked optical film sensors and might be especially apposite when the analyte is a gas.

Monodomain strained ferroelectric PbTiO(3) thin films: Phase transition and critical thickness study

This work demonstrates that instead of paraelectric PbTiO(3), completely c-oriented ferroelectric PbTiO(3) thin films were directly grown on (001)-SrTiO(3) substrates by pulsed-laser deposition with thickness up to 340 nm at a temperature well above the Curie temperature of bulk PbTiO(3). The influence of laser-pulse frequency, substrate-surface termination on growth, and functional properties were studied using x-ray diffraction, transmission electron microscopy, and piezoresponse force microscopy. At low growth rates (frequency 8 Hz) a domains were formed for film thickness above 20-100 nm. Due to coherency strains the Curie temperature (T(c)) of the monodomain films was increased approximately by 350 degrees C with respect to the T(c) of bulk PbTiO(3) even for 280-nm-thick films. Nonetheless, up to now this type of growth mode has been considered unlikely to occur since the Matthews-Blakeslee (MB) model already predicts strain relaxation for films having a thickness of only similar to 10 nm. However, the present work disputes the applicability of the MB model. It clarifies the physical reasons for the large increase in T(c) for thick films, and it is shown that the experimental results are in good agreement with the predictions based on the monodomain model of Pertsev et al. [Phys. Rev. Lett. 80, 1988 (1998)].

Quantum yield measurements for the photocatalytic oxidation of Acid Orange 7 (AO7) and reduction of 2,6-dichloroindophenol (DCIP) on transparent TiO2 films of various thickness

This work comprises the photoactivity assessment of transparent sol–gel TiO2 coatings of various thickness using two test systems. The initial rates of both photocatalytic reactions, namely the oxidative bleaching of Acid Orange 7 (AO7) and the reductive bleaching of 2,6-dichlorindophenol (DCIP) increase linearly with increasing titania film thickness as well as with increasing absorbed light flux. The latter work revealed quantum yields (QY) of 0.19% and 92% for the AO7 and DCIP test system, respectively. The low QY for the AO7 oxidation is due to the combination of a slow irreversible reduction of oxygen and also for the oxidation of AO7, thus favouring the high efficiency for electron–hole recombination that is typical for aqueous organic pollutants. In contrast, the very high QY for the photocatalysed reduction of DCIP is due to the presence of a vast excess of glycerol which traps the photogenerated holes efficiently and so allow time for the slower reduction of dye to take place. Furthermore, the oxidation of glycerol results in the generation of highly reducing R-hydroxyalkyl radicals that are able to also reduce DCIP. As a consequence of this ‘current doubling’ effect, the observed QY (92%) is much higher than the apparent theoretical value of 50%.

Dynamics of laser produced silver plasma under film deposition conditions studied using optical emission spectroscopy

Laser produced plasma from silver is generated using a Q-switched Nd:YAG laser. Optical emission spectroscopy is used to carry out time of flight (TOF) analysis of atomic particles. An anomalous double peak profile in the TOF distribution is observed at low pressure. A collection of slower species emerge at reduced pressure below 4 X lO-3 mbar and this species has a greater velocity spread. At high pressure the plasma expansion follows the shockwave model with cylindrical symmetry whereas at reduced pressure it shows unsteady adiabatic expansion (UAE). During UAE the species show a parabolic increases in the expansion time with radial distance whereas during shock wave expansion the exponent is less than one. The angular distribution of the ablated species in the plume is obtained from the measurement of optical density of thin films deposited on to glass substrates kept perpendicular to the plume. There is a sharp variation in the film thickness away from the film centre due to asymmetries in the plume.

Low-voltage driven ZnS:Mn MIS and MISIM thin film electroluminescent devices with Eu2O3 insulator layer

AC thin film electroluminescent devices of MIS and MISIM have been fabricated with a novel dielectric layer of Eu2O3 as an insulator. The threshold voltage for light emission is found to depend strongly on the frequency of excitation source in these devices. These devices are fabricated with an active layer of ZnS:Mn and a novel dielectric layer of Eu2O3 as an insulator. The observed frequency dependence of brightness-voltage characteristics has been explained on the basis of the loss characteristic of the insulator layer. Changes in the threshold voltage and brightness with variation in emitting or insulating film thickness have been investigated in metal-insulator-semiconductor (MIS) structures. It has been found that the decrease in brightness occurring with decreasing ZnS layer thickness can be compensated by an increase in brightness obtained by reducing the insulator thickness. The optimal condition for low threshold voltage and higher stability has been shown to occur when the active layer to insulator thickness ratio lies between one and two.

Physicochemical characterization of collagen fibers and collagen powder for self-composite film production

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

Cracks developed during SrTiO3 thin-film preparation from polymeric precursors

Strontium titanate (SrTiO3) thin films were prepared by dip-coating Si(111) single-crystal substrates in citrate solutions of ethylene glycol, considering several citric acid/ethylene glycol (CA/EG) ratios. Measurements of intrinsic viscosity indicate that increasing the amount of EG increases the precursors' polymeric chains and increases the weight loss. After deposition the substrates were dried on a hotplate (approximate to 150 degrees C); this was followed by heat treatment at temperatures ranging from 500 to 700 degrees C using heating and cooling rates of 1 degrees C min(-1). SEM and optical microscopy investigations of the sintered films obtained from different CA/EG ratios indicate that there is a critical thickness above which the films present cracks. This critical thickness for SrTiO3 films deposited on the Si(111) substrate is about 150 nm, Measurements of crack spacing as a function of film thickness indicate that the origin of cracks cannot be explained by the elastic behavior of the film but rather by the viscoelastic relaxation of the film during pyrolysis and sintering. Copyright (C) 1999 John Wiley & Sons, Ltd.

Effect of thickness on the electrical and optical properties of Sb doped SnO2 (ATO) thin films

This work reports the preparation and characterization of (SnO2) thin films doped with 7 mol% Sb2O3. The films were prepared by the polymeric precursor method, and deposited by spin-coating, all of them were deposited on amorphous silica substrate. Then, we have studied the thickness effect on the microstrutural, optical and electric properties of these samples. The microstructural characterization was carried out by X-ray diffraction (XRD) and scanning tunneling microscopy (STM). The electrical resistivity measurements were obtained by the van der Pauw four-probe method. UV-visible spectroscopy and ellipsometry were carried out for the optical characterization. The films present nanometric grains in the order of 13 nm, and low roughness. The electrical resistivity decreased with the increase of the film thickness and the smallest measured value was 6.5 x 10(-3) Omega cm for the 988 nm thick film. The samples displayed a high transmittance value of 80% in the visible region. The obtained results show that the polymeric precursor method is effective for the TCOs manufacturing.

Effect of the fluorination of DLC film on the corrosion protection of aluminum alloy (AA 5052)

It is presented a study conducted on the physical and electrochemical properties of fluorinated a-C:H films deposited onto a commercial aluminum alloy (AA 5052). The coatings were deposited from mixtures of 91% of acetylene and 9% of argon by plasma immersion ion implantation and deposition technique, PIIID. Total gas pressure was 44 Pa and deposition time (t(dep)) was varied from 300 to 1200 s. The depositing plasmas were generated by the application of radiofrequency power (13.56 MHz, 100W) to the upper electrode and high voltage negative pulses (2400 V. 300 Hz) to the sample holder. Fluorine was incorporated in a post-deposition plasma treatment (13.56 MHz, 70W, 13 Pa) generated from sulfur hexafluoride atmosphere. Chemical structure and composition of the films were investigated using infrared reflectance/absorbance spectroscopy and X-ray photoelectron spectroscopy. The corrosion resistance of the layers was determined by electrochemical impedance spectroscopy (EIS) in a 3.5% NaCl solution, at room temperature. Films presented good adhesion to the substrates and are classified as hydrogenated amorphous carbon (a-C:H) with oxygen traces. Fluorine was detected in all the samples after the post-deposition treatment being its proportion independent on the deposition time. Film thickness presented different tendencies with t(dep), revealing the variation of the deposition rate as a function of the deposition time. Such fluorinated a-C:H films improved the corrosion resistance of the aluminum surface. In a general way the corrosion resistance was higher for films prepared with lower deposition times. The variation of sample temperature with t(dep) was found to be decisive for the concentration of defects in the films and, consequently, for the performance of the samples in electrochemical tests. Results are interpreted in terms of the energy delivered to the growing layer by ionic bombardment. (C) 2010 Elsevier B.V. All rights reserved.

One-dimensional analytical model for oxide thin film growth on Ti metal layers during laser heating in air

This paper presents the theoretical and experimental results for oxide thin film growth on titanium films previously deposited over glass substrate. Ti films of thickness 0.1 μm were heated by Nd:YAG laser pulses in air. The oxide tracks were created by moving the samples with a constant speed of 2 mm/s, under the laser action. The micro-topographic analysis of the tracks was performed by a microprofiler. The results taken along a straight line perpendicular to the track axis revealed a Gaussian profile that closely matches the laser's spatial mode profile, indicating the effectiveness of the surface temperature gradient on the film's growth process. The sample's micro-Raman spectra showed two strong bands at 447 and 612 cm -1 associated with the TiO 2 structure. This is a strong indication that thermo-oxidation reactions took place at the Ti film surface that reached an estimated temperature of 1160 K just due to the action of the first pulse. The results obtained from the numerical integration of the analytical equation which describes the oxidation rate (Wagner equation) are in agreement with the experimental data for film thickness in the high laser intensity region. This shows the partial accuracy of the one-dimensional model adopted for describing the film growth rate. © 2001 Elsevier Science B.V.

Thickness dependence of structure and piezoelectric properties at nanoscale of polycrystalline PZT thin films

Lead zirconate titanate Pb(Zr 0.50Ti 0.50)O 3 (PZT) thin films were deposited by a polymeric chemical method on Pt(111)/Ti/SiO2/Si substrates to understand the mechanisms of phase transformations and the effect of film thickness on the structure, dielectric and piezoelectric properties in these films. PZT films pyrolyzed at temperatures higher than 350 °C present a coexistence of pyrochlore and perovskite phases, while only perovskite phase grows in films pyrolyzed at temperatures lower than 300 °C. For pyrochlore-free PZT thin films, a small (100) orientation tendency near the film-substrate interface was observed. Finally, we demonstrate the existence of a self-polarization effect in the studied PZT thin films. Results suggest that Schottky barriers and/or mechanical coupling near the filmsubstrate interface are not primarily responsible for the observed self-polarization effect in our films. © 2012 IEEE.

Thickness dependence of structure and piezoelectric properties at nanoscale of polycrystalline lead zirconate titanate thin films

Lead zirconate titanate Pb(Zr0.50Ti0.50)O3 (PZT) thin films were deposited by a polymeric chemical method on Pt(111)/Ti/SiO2/Si substrates to understand the mechanisms of phase transformations and the effect of film thickness on the structure, dielectric, and piezoelectric properties in these films. PZT films pyrolyzed at temperatures higher than 350 °C present a coexistence of pyrochlore and perovskite phases, while only perovskite phase grows in films pyrolyzed at temperatures lower than 300 °C. For pyrochlore-free PZT thin films, a small (100)-orientation tendency near the film-substrate interface was observed. Finally, we demonstrate the existence of a self-polarization effect in the studied PZT thin films. The increase of self-polarization with the film thickness increasing from 200 nm to 710 nm suggests that Schottky barriers and/or mechanical coupling near the film-substrate interface are not primarily responsible for the observed self-polarization effect in our films. © 2013 AIP Publishing LLC.