Optimal catalyst thickness in titanium dioxide fixed film reactors: Mathematical modelling and experimental validation

The use of immobilised TiO2 for the purification of polluted water streams introduces the necessity to evaluate the effect of mechanisms such as the transport of pollutants from the bulk of the liquid to the catalyst surface and the transport phenomena inside the porous film. Experimental results of the effects of film thickness on the observed reaction rate for both liquid-side and support-side illumination are here compared with the predictions of a one-dimensional mathematical model of the porous photocatalytic slab. Good agreement was observed between the experimentally obtained photodegradation of phenol and its by-products, and the corresponding model predictions. The results have confirmed that an optimal catalyst thickness exists and, for the films employed here, is 5 μm. Furthermore, the modelling results have highlighted the fact that porosity, together with the intrinsic reaction kinetics are the parameters controlling the photocatalytic activity of the film. The former by influencing transport phenomena and light absorption characteristics, the latter by naturally dictating the rate of reaction.

Thickness-induced stabilization of ferroelectricity in SrRuO3/Ba0.5Sr0.5TiO3/Au thin film capacitors

Pulsed-laser deposition has been used to fabricate Au/Ba0.5Sr0.5TiO3/SrRuO3/MgO thin film capacitor structures. Crystallographic and microstructural investigations indicated that the Ba0.5Sr0.5TiO3 (BST) had grown epitaxially onto the SrRuO3 lower electrode, inducing in-plane compressive and out- of-plane tensile strain in the BST. The magnitude of strain developed increased systematically as film thickness decreased. At room temperature this composition of BST is paraelectric in bulk. However, polarization measurements suggested that strain had stabilized the ferroelectric state, and that the decrease in film thickness caused an increase in remanent polarization. An increase in the paraelectric-ferroelectric transition temperature upon a decrease in thickness was confirmed by dielectric measurements. Polarization loops were fitted to Landau-Ginzburg-Devonshire (LGD) polynomial expansion, from which a second order paraelectric-ferroelectric transition in the films was suggested at a thickness of similar to500 nm. Further, the LGD analysis showed that the observed changes in room temperature polarization were entirely consistent with strain coupling in the system. (C) 2002 American Institute of Physics.

Understanding thickness effects in thin film capacitors

Pulsed Laser Deposition (PLD) was used to make Au/(Ba0.5Sr0.5)TiO3/(La0.5Sr0.5) CoO3/MgO thin film capacitor structures. Functional properties were studied with changing BST thickness from similar to1265 nm to similar to63 nm. The dielectric constant was found to decrease, and migration of T-m (the temperature at which the dielectric constant is maximum) to lower temperatures occurred as thickness was reduced. Curie-Weiss plots of the as-obtained dielectric data, indicated that the Curie temperature was also systemmatically progressively depressed. Further, fitting to expressions previously used to describe diffuse phase transitions suggested increased diffuseness in transformation behaviour as film thickness decreased. This paper discusses the care needed in interpreting the observations given above. We make particular distinction between the apparent Curie-temperature derived from Curie-Weiss plots of as-measured data, and the inherent Curie temperature determined after correction for the interfacial capacitance. We demonstrate that while the apparent Curie temperature decreases as thickness decreases, the inherent Curie temperature is thickness independent. Thickness-invariant phase transition behaviour is confirmed from analysis of polarisation loops, and from examination of the temperature dependence of the loss-tangent. We particularly note that correction of data for interfacial capacitance does not alter the position of T-m. We must therefore conclude that the position of T-m is not related simply to phase transformation behaviour in BST thin films.

Investigation of phenol degradation : True reaction kinetics on fixed film titanium dioxide photocatalyst

This study of photocatalytic oxidation of phenol over titanium dioxide films presents a method for the evaluation of true reaction kinetics. A flat plate reactor was designed for the specific purpose of investigating the influence of various reaction parameters, specifically photocatalytic film thickness, solution flow rate (1–8 l min−1), phenol concentration (20, 40 and 80 ppm), and irradiation intensity (70.6, 57.9, 37.1and 20.4 W m−2), in order to further understand their impact on the reaction kinetics. Special attention was given to the mass transfer phenomena and the influence of film thickness. The kinetics of phenol degradation were investigated with different irradiation levels and initial pollutant concentration. Photocatalytic degradation experiments were performed to evaluate the influence of mass transfer on the reaction and, in addition, the benzoic acid method was applied for the evaluation of mass transfer coefficient. For this study the reactor was modelled as a batch-recycle reactor. A system of equations that accounts for irradiation, mass transfer and reaction rate was developed to describe the photocatalytic process, to fit the experimental data and to obtain kinetic parameters. The rate of phenol photocatalytic oxidation was described by a Langmuir–Hinshelwood type law that included competitive adsorption and degradation of phenol and its by-products. The by-products were modelled through their additive effect on the solution total organic carbon.

Thickness-dependent fcc-hcp phase transformation in polycrystalline titanium thin films

Polycrystalline Ti thin films are shown to gradually transform from face-centered cubic (fcc) to hexagonal close-packed structure (hcp) with increasing film thickness. Diffraction stress analysis revealed that the fcc phase is formed in a highly compressive hcp matrix (>= 2 GPa), the magnitude of which decreases with increasing film thickness. A correlation between stress and crystallographic texture vis-a-vis the fcc-hcp phase transformation has been established. The total free energy change of the system upon phase transformation calculated using the experimental results shows that the fcc-hcp transformation is theoretically possible in the investigated film thickness regime (144-720 nm) and the hcp structure is stable for films thicker than 720 nm, whereas the fcc structure can be stabilized in Ti films much thinner than 144 nm. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Recent Advances in Low CTE and High Density System-on-a-Package (SOP) Substrate with Thin Film Component Integration

The Packaging Research Center has been developing next generation system-on-a-package (SOP) technology with digital, RF, optical, and sensor functions integrated in a single package/module. The goal of this effort is to develop a platform substrate technology providing very high wiring density and embedded thin film passive and active components using PWB compatible materials and processes. The latest SOP baseline process test vehicle has been fabricated on novel Si-matched CTE, high modulus C-SiC composite core substrates using 10mum thick BCB dielectric films with loss tangent of 0.0008 and dielectric constant of 2.65. A semi-additive plating process has been developed for multilayer microvia build-up using BCB without the use of any vacuum deposition or polishing/CMP processes. PWB and package substrate compatible processes such as plasma surface treatment/desmear and electroless/electrolytic pulse reverse plating was used. The smallest line width and space demonstrated in this paper is 6mum with microvia diameters in the 15-30mum range. This build-up process has also been developed on medium CTE organic laminates including MCL-E-679F from Hitachi Chemical and PTFE laminates with Cu-Invar-Cu core. Embedded decoupling capacitors with capacitance density of >500nF/cm2 have been integrated into the build-up layers using sol-gel synthesized BaTiO3 thin films (200-300nm film thickness) deposited on copper foils and integrated using vacuum lamination and subtractive etch processes. Thin metal alloy resistor films have been integrated into the SOP substrate using two methods: (a) NiCrAlSi thin films (25ohms per square) deposited on copper foils (Gould Electronics) laminated on the build-up layers and two step etch process for resistor definition, and (b) electroless plated Ni-W-P thin films (70 ohms to few Kohms per square) on the BCB dielectric by plasma surface treatment and activation. The electrical design and build-up layer structure along- - with key materials and processes used in the fabrication of the SOP4 test vehicle were presented in this paper. Initial results from the high density wiring and embedded thin film components were also presented. The focus of this paper is on integration of materials, processes and structures in a single package substrate for system-on-a-package (SOP) implementation

Stability of developing film flow down an inclined surface

Film flows on inclined surfaces are often assumed to be of constant thickness, which ensures that the velocity profile is half-Poiseuille. It is shown here that by shallow water theory, only flows in a portion of Reynolds number-Froude number (Re-Fr) plane can asymptotically attain constant film thickness. In another portion on the plane, the constant thickness solution appears as an unstable fixed point, while in other regions the film thickness seems to asymptote to a positive slope. Our simulations of the Navier-Stokes equations confirm the predictions of shallow water theory at higher Froude numbers, but disagree with them at lower Froude numbers. We show that different regimes of film flow show completely different stability behaviour from that predicted earlier. Supercritical decelerating flows are shown to be always unstable, whereas accelerating flows become unstable below a certain Reynolds number for a given Froude number. Subcritical flows on the other hand are shown to be unstable above a certain Reynolds number. In some range of parameters, two solutions for the base flowexist, and the attached profile is found to be more stable. All flows except those with separation become more stable as they proceed downstream. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4758299]

Enhancement in threshold voltage with thickness in memory switch fabricated using GeSe1.5S0.5 thin films

Investigations on the electrical switching, structural, optical and photoacoustic analysis have been undertaken on chalcogenide GeSe1.5S0.5 thin films of various thicknesses prepared by vacuum evaporation technique. The decrease of band gap energy with increase in film thickness has been explained using the `density of states model'. The structural units of the films are characterized using Raman spectroscopy and the deconvoluted Raman peaks obtained from Gaussian fit around 188 cm(-1), 204 cm(-1) and 214 cm(-1) favors Ge-chalcogen tetrahedral units forming corner and edge sharing tetrahedra. All the thin films samples have been exhibited memory-type electrical switching behavior. An enhancement in the threshold voltages of GeSe1.5S0.5 thin films have been observed with increase in film thickness. The thickness dependence of switching voltages provide an insight into the switching mechanism and it is explained by the Joule heating effect. (C) 2014 Elsevier B.V. All rights reserved.

Investigation of the Mechanical Properties of Thin Films by Nanoindentation, Considering the Effects of Thickness and Different Coating-Substrate Combinations

In order to further investigate nanoindentation data of film-substrate systems and to learn more about the mechanical properties of nanometer film-substrate systems, two kinds of films on different substrate systems have been tested with a systematic variation in film thickness and substrate characteristics. The two kinds of films are aluminum and tungsten, which have been sputtered on to glass and silicon substrates, respectively. Indentation experiments were performed with a Nano Indent XP II with indenter displacements typically about two times the nominal film thicknesses. The resulting data are analyzed in terms of load-displacement curves and various comparative parameters, such as hardness, Young's modulus, unloading stiffness and elastic recovery. Hardness and Young's modulus are investigated when the substrate effects are considered. The results show how the composite hardness and Young's modulus are different for different substrates, different films and different film thicknesses. An assumption of constant Young's modulus is used for the film-substrate system, in which the film and substrate have similar Young's moduli. Composite hardness obtained by the Joslin and Oliver method is compared with the directly measured hardness obtained by the Oliver and Pharr method.

Size Effect and Geometrical Effect of Polycrystals and Thin Film/Substrate System in Micro-indentation Test

Micro-indentation test at scales on the order of sub-micron has shown that the measured hardness increases strongly with decreasing indent depth or indent size, which is frequently referred to as the size effect. Simultaneously, at micron or sub-micron scale, the material microstructure size also has an important influence on the measured hardness. This kind of effect, such as the crystal grain size effect, thin film thickness effect, etc., is called the geometrical effect by here. In the present research, in order to investigate the size effect and the geometrical effect, the micro-indentation experiments are carried out respectively for single crystal copper and aluminum, for polycrystal aluminum, as well as for a thin film/substrate system, Ti/Si3N4. The size effect and geometrical effect are displayed experimentally. Moreover, using strain gradient plasticity theory, the size effect and the geometrical effect are simulated. Through comparing experimental results with simulation results, length-scale parameter appearing in the strain gradient theory for different cases is predicted. Furthermore, the size effect and the geometrical effect are interpreted using the geometrically necessary dislocation concept and the discrete dislocation theory. Member Price: $0; Non-Member Price: $25.00

ZnO film based surface acoustic wave micro-pump

In this study, a micro-pump unit based on surface acoustic wave (SAW) on piezoelectric ZnO film is designed and fabricated as a micro-fluidic device. It employs a mechanical wave, which is generated electrically using an aluminum interdigital transducer (IDT), and propagates on the surface of the ZnO film. The ZnO film was used in this study because it has a high electromechanical coefficient and an excellent bonding with various substrate materials, in particular silicon. The sputtering parameters for ZnO film deposition have been optimized, and the ZnO films with different thickness from 1 micron to 5.5 microns were prepared. The film properties have been characterized using different methods, such as scanning electron microscopy, X-ray diffraction and atomic force microscopy. Aluminum IDT with a finger width and spacing of 8 microns was patterned on the ZnO film using a lift-off process. The frequency generated was measured using a network analyzer, and it varies from 130 MHz to 180 MHz as a function of film thickness. A signal generator was used to generate the frequency with a power amplifier to amplify the signal, which was then applied to aluminum IDT to generate the surface acoustic wave. If a liquid droplet exists on the surface carrying the acoustic wave, the energy and the momentum of the SAW will be coupled into the fluid, causing the liquid to vibrate and move on film surface. The strength of this movement is determined by the applied voltage and frequency. The volume of the liquid drop loaded on the SAW device in this study is of several hundreds of nanoliters. The movement of the liquid inside the droplet and also on the ZnO film surface can be demonstrated. The performance of ZnO SAW device was characterized as a function of film thickness. © 2007 IOP Publishing Ltd.

Thickness And Component Distributions Of Yttrium-Titanium Alloy Films In Electron-Beam Physical Vapor Deposition

Thickness and component distributions of large-area thin films are an issue of international concern in the field of material processing. The present work employs experiments and direct simulation Monte Carlo (DSMC) method to investigate three-dimensional low-density, non-equilibrium jets of yttrium and titanium vapor atoms in an electron-beams physical vapor deposition (EBPVD) system furnished with two or three electron-beams, and obtains their deposition thickness and component distributions onto 4-inch and 6-inch mono-crystal silicon wafers. The DSMC results are found in excellent agreement with our measurements, such as evaporation rates of yttrium and titanium measured in-situ by quartz crystal resonators, deposited film thickness distribution measured by Rutherford backscattering spectrometer (RBS) and surface profilometer and deposited film molar ratio distribution measured by RBS and inductively coupled plasma atomic emission spectrometer (ICP-AES). This can be taken as an indication that a combination of DSMC method with elaborate measurements may be satisfactory for predicting and designing accurately the transport process of EBPVD at the atomic level.

Determination of interface properties between micron-thick metal film and ceramic substrate using peel test

Peel test measurements have been performed to estimate both the interface toughness and the separation strength between copper thin film and Al2O3 substrate with film thicknesses ranging between 1 and 15 mu m. An inverse analysis based on the artificial neural network method is adopted to determine the interface parameters. The interface parameters are characterized by the cohesive zone (CZ) model. The results of finite element simulations based on the strain gradient plasticity theory are used to train the artificial neural network. Using both the trained neural network and the experimental measurements for one test result, both the interface toughness and the separation strength are determined. Finally, the finite element predictions adopting the determined interface parameters are performed for the other film thickness cases, and are in agreement with the experimental results.

Small scale, grain size and substrate effects in nano-indentation experiment of film-substrate systems

The mechanical properties of film-substrate systems have been investigated through nano-indentation experiments in our former paper (Chen, S.H., Liu, L., Wang, T.C., 2005. Investigation of the mechanical properties of thin films by nano-indentation, considering the effects of thickness and different coating-substrate combinations. Surf. Coat. Technol., 191, 25-32), in which Al-Glass with three different film thicknesses are adopted and it is found that the relation between the hardness H and normalized indentation depth h/t, where t denotes the film thickness, exhibits three different regimes: (i) the hardness decreases obviously with increasing indentation depth; (ii) then, the hardness keeps an almost constant value in the range of 0.1-0.7 of the normalized indentation depth h/t; (iii) after that, the hardness increases with increasing indentation depth. In this paper, the indentation image is further investigated and finite element method is used to analyze the nano-indentation phenomena with both classical plasticity and strain gradient plasticity theories. Not only the case with an ideal sharp indenter tip but also that with a round one is considered in both theories. Finally, we find that the classical plasticity theory can not predict the experimental results, even considering the indenter tip curvature. However, the strain gradient plasticity theory can describe the experimental data very well not only at a shallow indentation depth but also at a deep depth. Strain gradient and substrate effects are proved to coexist in film-substrate nano-indentation experiments. (c) 2006 Elsevier Ltd. All rights reserved.