Synthesis of anatase TiO2 supported on porous solids by chemical vapor deposition

Coating anatase TiO2 onto three different particle supports, activated carbon (AC), gamma -alumina (Al2O3) and silica gel (SiO2), by chemical vapor deposition (CVD) was studied. The effect of the CVD synthesis conditions on the loading rate of anatase TiO2 was investigated. It was found that introducing water vapor during CVD or adsorbing water before CVD was crucial to obtain anatase TiO2 on the surface of the particle supports. The evaporation temperature of precursor, deposition temperature in the reactor, flow rate of carrier gas, and the length of coating time were also important parameters to obtain more uniform and repeatable TiO2 coating. High inflow precursor concentration, high CVD reactor temperature and long coating time tended to cause block problem. Coating TiO2 onto small particles by CVD involved both chemical vapor deposition and particle deposition. It was believed that the latter was the reason for the block problem. In addition, the mechanism of CVD process in this study included two parts, pyrolysis and hydrolysis, and one of them was dominant in the CVD process under different synthesis route. Among the three types of materials, silica gel, with higher surface hydroxyl groups and macropore surface area, was found to be the most efficient support in terms of both anatase TiO2 coating and photocatalytic reaction. (C) 2001 Elsevier Science B.V. All rights reserved.

Investigations on doping of amorphous and nano-crystalline silicon films deposited by catalytic chemical vapour deposition

Hydrogenated amorphous and nanocrystalline silicon, deposited by catalytic chemical vapour deposition, have been doped during deposition by the addition of diborane and phosphine in the feed gas, with concentrations in the region of 1%. The crystalline fraction, dopant concentration and electrical properties of the films are studied. The nanocrystalline films exhibited a high doping efficiency, both for n and p doping, and electrical characteristics similar to those of plasma-deposited films. The doping efficiency of n-type amorphous silicon is similar to that obtained for plasma-deposited electronic-grade amorphous silicon, whereas p-type layers show a doping efficiency of one order of magnitude lower. A higher deposition temperature of 450°C was required to achieve p-type films with electrical characteristics similar to those of plasma-deposited films.

Polymer surface modification by atomic layer deposition

Current industrial atomic layer deposition (ALD) processes are almost wholly confined to glass or silicon substrates. For many industrial applications, deposition on polymer substrates will be necessary. Current deposition processes are also typically carried out at temperatures which are too high for polymers. If deposition temperatures in ALD can be reduced to the level applicable for polymers, it will open new interesting areas and applications for polymeric materials. The properties of polymers can be improved for example by coatings with functional and protective properties. Although the ALD has shown its capability to operate at low temperatures suitable for polymer substrates, there are other issues related to process efficiency and characteristics of different polymers where new knowledge will assist in developing industrially conceivable ALD processes. Lower deposition temperature in ALD generally means longer process times to facilitate the self limiting film growth mode characteristic to ALD. To improve process efficiency more reactive precursors are introduced into the process. For example in ALD oxide processes these can be more reactive oxidizers, such as ozone and oxygen radicals, to substitute the more conventionally used water. Although replacing water in the low temperature ALD with ozone or plasma generated oxygen radicals will enable the process times to be shortened, they may have unwanted effects both on the film growth and structure, and in some cases can form detrimental process conditions for the polymer substrate. Plasma assistance is a very promising approach to improve the process efficiency. The actual design and placement of the plasma source will have an effect on film growth characteristics and film structure that may retard the process efficiency development. Due to the fact that the lifetime of the radicals is limited, it requires the placement of the plasma source near to the film growth region. Conversely this subjects the substrate to exposure byother plasma species and electromagnetic radiation which sets requirements for plasma conditions optimization. In this thesis ALD has been used to modify, activate and functionalize the polymer surfaces for further improvement of polymer performance subject to application. The issues in ALD on polymers, both in thermal and plasma-assisted ALD will be further discussed.

The study of ultra-low energy deposition of hydrogenated amorphous carbon thin films

This thesis is dedicated to the production and analysis of thin hydrogenated amorphous carbon films. A cascaded arc plasma source was used to produce a high density plasma of hydrocarbon radicals that deposited on a substrate at ultra low energies. The work was intended to create a better understanding of the mechanisms responsible for the film formation, by an extensive analysis on the properties of the films in correlation with the conditions used in the plasma cell. Two different precursors were used: methane and acetylene. They revealed a very different picture for the mechanism of film formation and properties. Methane was less successful, and the films formed were soft, with poor adhesion to the substrate and decomposing with time. Acetylene was the better option, and the films formed in this case were harder, with better adhesion to the substrate and stable over time. The plasma parameters could be varied to change the character of films, from polymer-like to diamond-like carbon. Films deposited from methane were grown at low deposition rates, which increased with the increase in process pressure and source power and decreased with the increase in substrate temperature and in hydrogen fraction in the carrier gas. The films had similar hydrogen content, sp3 fractions, average roughness (Ra) and low hardness. Above a deposition temperature of 350°C graphitization occurred - an increase in the sp2 fraction. A deposition mechanism was proposed, based upon the reaction product of the dissociative recombination of CH4+. There were small differences between the chemistries in the plasma at low and high precursor flow rates and low and high substrate temperatures; all experimental conditions led to formation of films that were either polymer-like, soft amorphous hydrogenated carbon or graphitic-like in structure. Films deposited from acetylene were grown at much higher deposition rates on different substrates (silicon, glass and plastics). The film quality increased noticeably with the increase of relative acetylene to argon flow rate, up to a certain value, where saturation occurred. With the increase in substrate temperature and the lowering of the acetylene injection ring position further improvements in film quality were achieved. The deposition process was scaled up to large area (5 x 5 cm) substrates in the later stages of the project. A deposition mechanism was proposed, based upon the reaction products of the dissociative recombination of C2H2 +. There were large differences between the chemistry in the plasma at low and medium/high precursor flow rates. This corresponded to large differences in film properties from low to medium flow rates, when films changed their character from polymer-like to diamond-like, whereas the differences between films deposited at medium and high precursor flow rates were small. Modelling of the film growth on silicon substrates was initiated and it explained the formation of sp2 and sp3 bonds at these very low energies. However, further improvements to the model are needed.

Tin oxide based composites derived using electrostatic spray deposition technique as anodes for lithium-ion batteries

Recent advances in the electric & hybrid electric vehicles and rapid developments in the electronic devices have increased the demand for high power and high energy density lithium ion batteries. Graphite (theoretical specific capacity: 372 mAh/g) used in commercial anodes cannot meet these demands. Amorphous SnO2 anodes (theoretical specific capacity: 781 mAh/g) have been proposed as alternative anode materials. But these materials have poor conductivity, undergo a large volume change during charging and discharging, large irreversible capacity loss leading to poor cycle performances. To solve the issues related to SnO2 anodes, we propose to synthesize porous SnO2 composites using electrostatic spray deposition technique. First, porous SnO2/CNT composites were fabricated and the effects of the deposition temperature (200, 250, 300 °C) & CNT content (10, 20, 30, 40 wt %) on the electrochemical performance of the anodes were studied. Compared to pure SnO2 and pure CNT, the composite materials as anodes showed better discharge capacity and cyclability. 30 wt% CNT content and 250 °C deposition temperature were found to be the optimal conditions with regard to energy capacity whereas the sample with 20% CNT deposited at 250 °C exhibited good capacity retention. This can be ascribed to the porous nature of the anodes and the improvement in the conductivity by the addition of CNT. Electrochemical impedance spectroscopy studies were carried out to study in detail the change in the surface film resistance with cycling. By fitting EIS data to an equivalent circuit model, the values of the circuit components, which represent surface film resistance, were obtained. The higher the CNT content in the composite, lower the change in surface film resistance at certain voltage upon cycling. The surface resistance increased with the depth of discharge and decreased slightly at fully lithiated state. Graphene was also added to improve the performance of pure SnO2 anodes. The composites heated at 280 °C showed better energy capacity and energy density. The specific capacities of as deposited and post heat-treated samples were 534 and 737 mAh/g after 70 cycles. At the 70th cycle, the energy density of the composites at 195 °C and 280 °C were 1240 and 1760 Wh/kg, respectively, which are much higher than the commercially used graphite electrodes (37.2–74.4 Wh/kg). Both SnO2/CNTand SnO2/grapheme based composites with improved energy densities and capacities than pure SnO2 can make a significant impact on the development of new batteries for electric vehicles and portable electronics applications.

Deposition of Intrinsic a-Si:H by ECR-CVD to Passivate the Crystalline Silicon Heterointerface in HIT Solar Cells

We have deposited intrinsic amorphous silicon (a-Si:H) using the electron cyclotron resonance (ECR) chemical vapor deposition technique in order to analyze the a-Si:H/c-Si heterointerface and assess the possible application in heterojunction with intrinsic thin layer (HIT) solar cells. Physical characterization of the deposited films shows that the hydrogen content is in the 15-30% range, depending on deposition temperature. The optical bandgap value is always comprised within the range 1.9- 2.2 eV. Minority carrier lifetime measurements performed on the heterostructures reach high values up to 1.3 ms, indicating a well-passivated a-Si:H/c-Si heterointerface for deposition temperatures as low as 100°C. In addition, we prove that the metal-oxide- semiconductor conductance method to obtain interface trap distribution can be applied to the a-Si:H/c-Si heterointerface, since the intrinsic a-Si:H layer behaves as an insulator at low or negative bias. Values for the minimum of D_it as low as 8 × 10^10 cm^2 · eV^-1 were obtained for our samples, pointing to good surface passivation properties of ECR-deposited a-Si:H for HIT solar cell applications.

Tin Oxide Based Composites Derived Using Electrostatic Spray Deposition Technique as Anodes for Li-Ion Batteries

Recent advances in the electric & hybrid electric vehicles and rapid developments in the electronic devices have increased the demand for high power and high energy density lithium ion batteries. Graphite (theoretical specific capacity: 372 mAh/g) used in commercial anodes cannot meet these demands. Amorphous SnO2 anodes (theoretical specific capacity: 781 mAh/g) have been proposed as alternative anode materials. But these materials have poor conductivity, undergo a large volume change during charging and discharging, large irreversible capacity loss leading to poor cycle performances. To solve the issues related to SnO2 anodes, we propose to synthesize porous SnO2 composites using electrostatic spray deposition technique. First, porous SnO2/CNT composites were fabricated and the effects of the deposition temperature (200,250, 300 oC) & CNT content (10, 20, 30, 40 wt %) on the electrochemical performance of the anodes were studied. Compared to pure SnO2 and pure CNT, the composite materials as anodes showed better discharge capacity and cyclability. 30 wt% CNT content and 250 oC deposition temperature were found to be the optimal conditions with regard to energy capacity whereas the sample with 20% CNT deposited at 250 oC exhibited good capacity retention. This can be ascribed to the porous nature of the anodes and the improvement in the conductivity by the addition of CNT. Electrochemical impedance spectroscopy studies were carried out to study in detail the change in the surface film resistance with cycling. By fitting EIS data to an equivalent circuit model, the values of the circuit components, which represent surface film resistance, were obtained. The higher the CNT content in the composite, lower the change in surface film resistance at certain voltage upon cycling. The surface resistance increased with the depth of discharge and decreased slightly at fully lithiated state. Graphene was also added to improve the performance of pure SnO2 anodes. The composites heated at 280 oC showed better energy capacity and energy density. The specific capacities of as deposited and post heat-treated samples were 534 and 737 mAh/g after 70 cycles. At the 70th cycle, the energy density of the composites at 195 °C and 280 °C were 1240 and 1760 Wh/kg, respectively, which are much higher than the commercially used graphite electrodes (37.2-74.4 Wh/kg). Both SnO2/CNTand SnO2/grapheme based composites with improved energy densities and capacities than pure SnO2 can make a significant impact on the development of new batteries for electric vehicles and portable electronics applications.

Lightweight amorphous silicon photovoltaic modules on flexible plastic substrate

Solar cells on lightweight and flexible substrates have advantages over glass-or wafer-based photovoltaic devices in both terrestrial and space applications. Here, we report on development of amorphous silicon thin film photovoltaic modules fabricated at maximum deposition temperature of 150 degrees C on 100 mu m thick polyethylene-naphtalate plastic films. Each module of 10 cm x 10 cm area consists of 72 a-Si:H n-i-p rectangular structures with transparent conducting oxide top electrodes with Al fingers and metal back electrodes deposited through the shadow masks. Individual structures are connected in series forming eight rows with connection ports provided for external blocking diodes. The design optimization and device performance analysis are performed using a developed SPICE model.

Optical absorption and graphitic clusters of hydrogenated amorphophous carbon thin films

The optical absorption of hydrogenated amorphous carbon films (a‐C:H) was measured by spectroscopic ellipsometry. The a‐C:H films were deposited at different substrate temperatures by rf‐plasma of methane. A volume distribution of graphitic cluster size was assumed to reproduce the experimental spectra of the absorption coefficient. The changes in the absorption coefficient and the optical gap, induced by deposition temperature, have been interpreted in terms of changes in the graphitic cluster size of the network. The increase in the deposition temperature produces an increase in the size of the graphitic clusters.

Electrical and optical properties of Zn-In-Sn-O transparent conducting thin films

Indium tin oxide (ITO) is one of the widely used transparent conductive oxides (TCO) for application as transparent electrode in thin film silicon solar cells or thin film transistors owing to its low resistivity and high transparency. Nevertheless, indium is a scarce and expensive element and ITO films require high deposition temperature to achieve good electrical and optical properties. On the other hand, although not competing as ITO, doped Zinc Oxide (ZnO) is a promising and cheaper alternative. Therefore, our strategy has been to deposit ITO and ZnO multicomponent thin films at room temperature by radiofrequency (RF) magnetron co-sputtering in order to achieve TCOs with reduced indium content. Thin films of the quaternary system Zn-In-Sn-O (ZITO) with improved electrical and optical properties have been achieved. The samples were deposited by applying different RF powers to ZnO target while keeping a constant RF power to ITO target. This led to ZITO films with zinc content ratio varying between 0 and 67%. The optical, electrical and morphological properties have been thoroughly studied. The film composition was analysed by X-ray Photoelectron Spectroscopy. The films with 17% zinc content ratio showed the lowest resistivity (6.6 × 10 - 4 Ω cm) and the highest transmittance (above 80% in the visible range). Though X-ray Diffraction studies showed amorphous nature for the films, using High Resolution Transmission Electron Microscopy we found that the microstructure of the films consisted of nanometric crystals embedded in a compact amorphous matrix. The effect of post deposition annealing on the films in both reducing and oxidizing atmospheres were studied. The changes were found to strongly depend on the zinc content ratio in the films.

Growth and Characterisation of Radio Frequency Magnetron Sputttered Indium Tin Oxide Thin Films

The increasing interest in the interaction of light with electricity and electronically active materials made the materials and techniques for producing semitransparent electrically conducting films particularly attractive. Transparent conductors have found major applications in a number of electronic and optoelectronic devices including resistors, transparent heating elements, antistatic and electromagnetic shield coatings, transparent electrode for solar cells, antireflection coatings, heat reflecting mirrors in glass windows and many other. Tin doped indium oxide (indium tin oxide or ITO) is one of the most commonly used transparent conducting oxides. At present and likely well into the future this material offers best available performance in terms of conductivity and transmittivity combined with excellent environmental stability, reproducibility and good surface morphology. Although partial transparency, with a reduction in conductivity, can be obtained for very thin metallic films, high transparency and simultaneously high conductivity cannot be attained in intrinsic stoichiometric materials. The only way this can be achieved is by creating electron degeneracy in a wide bandgap (Eg > 3eV or more for visible radiation) material by controllably introducing non-stoichiometry and/or appropriate dopants. These conditions can be conveniently met for ITO as well as a number of other materials like Zinc oxide, Cadmium oxide etc. ITO shows interesting and technologically important combination of properties viz high luminous transmittance, high IR reflectance, good electrical conductivity, excellent substrate adherence and chemical inertness. ITO is a key part of solar cells, window coatings, energy efficient buildings, and flat panel displays. In solar cells, ITO can be the transparent, conducting top layer that lets light into the cell to shine the junction and lets electricity flow out. Improving the ITO layer can help improve the solar cell efficiency. A transparent ii conducting oxide is a material with high transparency in a derived part of the spectrum and high electrical conductivity. Beyond these key properties of transparent conducting oxides (TCOs), ITO has a number of other key characteristics. The structure of ITO can be amorphous, crystalline, or mixed, depending on the deposition temperature and atmosphere. The electro-optical properties are a function of the crystallinity of the material. In general, ITO deposited at room temperature is amorphous, and ITO deposited at higher temperatures is crystalline. Depositing at high temperatures is more expensive than at room temperature, and this method may not be compatible with the underlying devices. The main objective of this thesis work is to optimise the growth conditions of Indium tin oxide thin films at low processing temperatures. The films are prepared by radio frequency magnetron sputtering under various deposition conditions. The films are also deposited on to flexible substrates by employing bias sputtering technique. The films thus grown were characterised using different tools. A powder x-ray diffractometer was used to analyse the crystalline nature of the films. The energy dispersive x-ray analysis (EDX) and scanning electron microscopy (SEM) were used for evaluating the composition and morphology of the films. Optical properties were investigated using the UVVIS- NIR spectrophotometer by recording the transmission/absorption spectra. The electrical properties were studied using vander Pauw four probe technique. The plasma generated during the sputtering of the ITO target was analysed using Langmuir probe and optical emission spectral studies.

Multicamadas Ferromagnéticas Nanométricas Periódicas e Quasiperiódicas

We present a study of nanostructured magnetic multilayer systems in order to syn- thesize and analyze the properties of periodic and quasiperiodic structures. This work evolved from the deployment and improvement of the sputtering technique in our labora- tories, through development of a methodology to synthesize single crystal ultrathin Fe (100) films, to the final goal of growing periodic and quasiperiodic Fe/Cr multilayers and investi- gating bilinear and biquadratic exchange coupling between ferromagnetic layer dependence for each generation. Initially we systematically studied the related effects between deposition parameters and the magnetic properties of ultrathin Fe films, grown by DC magnetron sput- tering on MgO(100) substrates. We modified deposition temperature and film thickness, in order to improve production and reproduction of nanostructured monocrystalline Fe films. For this set of samples we measured MOKE, FMR, AFM and XPS, with the aim of investi- gating their magnocrystalline and structural properties. From the magnetic viewpoint, the MOKE and FMR results showed an increase in magnetocrystalline anisotropy due to in- creased temperature. AFM measurements provided information about thickness and surface roughness, whereas XPS results were used to analyze film purity. The best set of parame- ters was used in the next stage: investigation of the structural effect on magnetic multilayer properties. In this stage multilayers composed of interspersed Fe and Cr films are deposited, following the Fibonacci periodic and quasiperiodic growth sequence on MgO (100) substrates. The behavior of MOKE and FMR curves exhibit bilinear and biquadratic exchange coupling between the ferromagnetic layers. By computationally adjusting magnetization curves, it was possible to determine the nature and intensity of the interaction between adjacent Fe layers. After finding the global minimum of magnetic energy, we used the equilibrium an- gles to obtain magnetization and magnetoresistance curves. The results observed over the course of this study demonstrate the efficiency and versatility of the sputtering technique in the synthesis of ultrathin films and high-quality multilayers. This allows the deposition of magnetic nanostructures with well-defined magnetization and magnetoresistance parameters and possible technological applications

Crescimento de filmes nanométricos monocristalinos de Fe/MgO(100) por "SPUTTERING" DC

The research behind this master dissertation started with the installation of a DC sputtering system, from its first stage, the adaptation of a refrigerating system, passing by the introduction of a heating system for the chamber using a thermal belt, until the deposition of a series of Fe/MgO(100) single crystal nanometric film samples. The deposition rates of some materials such as Fe, Py and Cu were investigated through an Atomic Force Microscope (AFM). For the single crystal samples, five of them have the same growth parameters and a thickness of 250Å, except for the temperature, which varies from fifty degrees from one to another, from 100ºC to 300ºC. Three other samples also have the same deposition parameters and a temperature of 300ºC, but with thickness of 62,5Å, 150Å, and 250Å. Magneto-optical Kerr Effect (MOKE) of the magnetic curves measurements and Ferromagnetic Resonance (FMR) were made to in order to study the influence of the temperature and thickness on the sample s magnetic properties. In the present dissertation we discuss such techniques, and the experimental results are interpreted using phenomenological models, by simulation, and discussed from a physical point of view, taking into account the system s free magnetic energy terms. The results show the growth of the cubic anisotropy field (Hac) as the sample s deposition temperature increases, presenting an asymptotic behavior, similar to the characteristic charging curve of a capacitor in a RC circuit. A similar behavior was also observed for the Hac due to the increase in the samples thicknesses. The 250˚A sample, growth at 300°C, presented a Hac field close to the Fe bulk value

Propriedades fisicas do monocristal fe/mgo(100) e estudo da expansao termica da superficie da ag(100)

In this work we have developed a way to grow Fe/MgO(100) monocrystals by magnetron sputtering DC. We investigated the growing in a temperature range among 100 oC and 300 oC. Structural and magneto-crystalline properties were studied by different experimental techniques. Thickness and surface roughness of the films were investigated by atomic force microscopy, while magneto-crystalline properties were investigated by magneto-optical Kerr effect and ferromagnetic resonance. Our results show that as we increase the deposition temperature, the magneto-crystalline anisotropy of the films also increases, following the equation of Avrami. The best temperature value to make a film is 300 oC. As the main result, we built a base of magnetoresistence devices and as an aplication, we present measurements of Fe/Cr/Fe trilayer coupling. In a second work we investigated the temperature dependence of the first three interlayer spacings of Ag(100) surface using low energy electron diffraction. A linear expansion model of crystal surface was used and the values of Debye temperatures of the first two layers and thermal expansion coefficient were determinated. A relaxation of 1% was found for Ag(100) surface and these results are matched with faces (110) and (111) of the silver. iv

Resistive-Switching Behavior in Polycrystalline CaCu3Ti4O12 Nanorods

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