Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第14572号 / 工博第3040号 / 新制||工||1453(附属図書館) / 26924 / UT51-2009-D284 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 杉村 博之, 教授 酒井 明, 准教授 山田 啓文 / 学位規則第4条第1項該当

>Magister Scientiae - MSc / In the current study, we give a report when oxalic acid was used as an electrolyte to synthesize an AAO template with hexagonal pore array. Optimum parameters were observed as 0.4 M of oxalic acid, anodizing voltage of 45 V, temperature of approximately 8 °C and the period of 120 minutes. Atomic force microscope (AFM) and High resolution scanning electron microscope (HRSEM) showed that template has an average pore diameter of 103 nm. Co and MnOx (x = 1,2) nanostructures were selectively deposited in the pores of the template using a novel atomic layer deposition (ALD) technique. The diameter sizes and the array of the nanostructures and the template were corresponding. Energy dispersive xrays (EDX) and X-ray photoelectron spectroscopy (XPS) confirmed the presence of Co and MnOx (x =1,2) on the samples while x-ray diffraction (XRD) provided an indication of their orientations. Magnetic force microscopy as main characterization tool showed the existence of multi-domains on both Co and MnOx (x =1,2) nanostructures. / South Africa

Les stents urétéraux et les sondes de néphrostomie sont constitués de silicone ou de polyuréthane thermoplastique (TPU). Afin de limiter les risques infectieux lors de leur implantation, une modification topographique par création de pores permettrait de limiter l’adhésion des bactéries et de former des réservoirs pour une libération in situ de substances antiinfectieuses. Ce travail vise à préparer des surfaces en polymère ayant un motif poreux tubulaire ordonné. Une réplication en deux temps à partir de surfaces ordonnées poreuses d’oxyde d’aluminium (PAAO) préparées par 2 méthodes (double anodisation douce et double anodisation dure/douce) a été mise en œuvre pour reproduire le motif initial sur des surfaces en silicone et TPU. Pour le moule intermédiaire trois matériaux ont été testés (acrylonitrile butadiène styrène, polystyrène et résine polyacrylate). Les surfaces ont toutes été caractérisées par des techniques microscopiques et spectroscopiques. Les surfaces en PAAO préparées par double anodisation douce possédaient des pores d’environ 50 nm de diamètre et 100 nm de profondeur, alors que celles obtenues après mise au point de la méthode dure/douce étaient de taille supérieure, d’environ 125 nm de diamètre et ayant des profondeurs de quelques centaines de nanomètres. La surface du moule intermédiaire est constituée de picots. Une adhésion latérale de ceux-ci a été observée pour certaines conditions. La meilleure réplication du motif a été obtenue pour le TPU. Les surfaces ainsi obtenues pourront être utilisées et optimisées lors de l'étude ultérieure de l'adhésion du biofilm. / Ureteral stents and nephrostomy catheters are made of silicone or thermoplastic polyurethane (TPU). A topographical modification creating an ordered porous surface could limit the infectious risks during their implantation, by reducing bacterial adhesion and creating a loading platform from which anti-infectious compounds could be released.In this work, a two-steps replication method was used to create ordered porous polymer surfaces (silicone or TPU) using porous anodic aluminium oxide (PAAO) as master template. The PAAO surfaces were prepared by double mild or double hard/mild anodization. Three intermediate mould materials were tested (acrylonitrile butadiene styrene, polystyrene, polyacrylate resin). The polymer material (silicone or TPU) was then moulded onto the intermediate mould surfaces that possessed freestanding pillar arrays, to imprint pores. The obtained surfaces were characterized by microscopic and spectroscopic methods. The initial PAAO surfaces prepared by double mild anodization possessed pores of about 50 nm diameter and 100 nm depth, whereas those prepared after development of the double hard/mild anodization method were bigger, of about 125 nm diameter and several hundred nanometers deep. The intermediate mould structure possessed freestanding arrays, but instabilities (lateral adhesion) were noted for certain conditions. The best pattern replication was observed for TPU. In conclusion, these novel porous polymeric surfaces could be optimized and tested for an anti-biofilm effect.

Les laboratoires sur puce visent à miniaturiser et à intégrer les fonctions couramment utilisées dans les laboratoires d'analyse afin de cibler des applications en santé avec un impact prometteur sur le diagnostic médical au lit du patient. Les membranes poreuses sont d'un grand intérêt pour la préparation et l'analyse d'échantillon sur puce car elles permettent la séparation par taille/charge de molécules, mais également leur pré-concentration. Parmi les matériaux disponibles pour constituer des membranes poreuses, le silicium poreux présente de nombreux avantages tels que le contrôle précis de la taille des pores et de la porosité, une chimie de surface pratique et des propriétés optiques uniques. Les membranes de silicium poreux sont généralement intégrées dans des puces fluidiques en les montant entre deux couches comportant des micro-canaux, formant ainsi des réseaux fluidiques à trois dimensions, peu pratiques et peu adaptés à l'observation directe par microscopie. Dans ces travaux de thèse, nous avons développé deux méthodes de fabrication de membranes de silicium à pores latéraux qui permettent leur intégration monolithique dans des systèmes microfluidiques planaires. Le premier procédé est fondé sur l'utilisation d'électrodes localement structurées afin de guider la formation de pores de manière horizontale, en combinaison avec des substrats type silicium sur isolant (SOI) pour localiser spatialement la formation de silicium poreux dans la profondeur du canal. La deuxième méthode repose sur le fait que la formation de silicium poreux par anodisation est fortement dépendante du type de dopant et de sa concentration. Bien que nous utilisons encore le même type d'électrodes structurées sur les parois latérales de la membrane pour injecter le courant lors de l'anodisation, le dopage par implantation permet de confiner la membrane, de façon analogue mais à la place de l'oxyde enterré du SOI. Des membranes à pores latéraux ont été fabriquées par ces deux méthodes et leur fonctionnalité a été démontrée en réalisant des expériences de filtrage. En plus de la filtration d'échantillon, les membranes ont été utilisées pour étudier la possibilité d'effectuer de la pré-concentration électrocinétique et de la détection interférométrique. La sélectivité ionique des membranes microporeuse permet la pré-concentration moléculaire avec des facteurs de concentration pouvant atteindre jusqu'à 103 en 10 min en appliquant moins de 9 V. Ces résultats sont comparables à ceux rapportés dans la littérature à l'aide par exemple de nanocanaux avec une consommation d'énergie beaucoup plus faible. Enfin, nous avons pu détecter une variation de l'indice de réfraction du silicium poreux par le décalage du spectre d'interférence lors du chargement de différents liquides injectés dans les membranes. Le travail présenté dans cette thèse constitue la première étape dans la démonstration de l'intérêt du silicium poreux pour la préparation d'échantillon et la biodétection dans des laboratoires sur puce planaires. / Lab on a chip devices aim at integrating functions routinely used in medical laboratories into miniaturized chips to target health care applications with a promising impact foreseen in point-of-care testing. Porous membranes are of great interest for on-chip sample preparation and analysis since they enable size- and charge-based molecule separation, but also molecule pre-concentration by ion concentration polarization. Out of the various materials available to constitute porous membranes, porous silicon offers many advantages, such as tunable pore properties, large porosity, convenient surface chemistry and unique optical properties. Porous silicon membranes are usually integrated into fluidic chips by sandwiching fabricated membranes between two layers bearing inlet and outlet microchannels, resulting in three-dimensional fluidic networks that lack the simplicity of operation and direct observation accessibility of planar microfluidic devices. To tackle this constraint, we have developed two methods for the fabrication of lateral porous silicon membranes and their monolithic integration into planar microfluidics. The first method is based on the use of locally patterned electrodes to guide pore formation horizontally within the membrane in combination with silicon-on-insulator (SOI) substrates to spatially localize the porous silicon within the channel depth. The second method relies on the fact that the formation of porous silicon by anodization is highly dependent on the dopant type and concentration. While we still use electrodes patterned on the membrane sidewalls to inject current for anodization, the doping via implantation enables to confine the membrane analogously to but instead of the SOI buried oxide box. Membranes with lateral pores were successfully fabricated by these two methods and their functionality was demonstrated by conducting filtering experiments. In addition to sample filtration, we have achieved electrokinetic pre-concentration and interferometric sensing using the fabricated membranes. The ion selectivity of the microporous membrane enables to carry out sample pre-concentration by ion concentration polarization with concentration factors that can reach more than 103 in 10 min by applying less than 9 V across the membrane[TL1]. These results are comparable to what has already been reported in the literature using e.g. nanochannels with much lower power consumption. Finally, we were able to detect a change of the porous silicon refractive index through the shift of interference spectrum upon loading different liquids into the membrane. The work presented in this dissertation constitutes the first step in demonstrating the interest of porous silicon for all-in-one sample preparation and biosensing into planar lab on a chip.

The lap shear strength of chromic acid anodized, primed, Ti-6Al-4V alloy bonded with a high performance FM-5 polyimide adhesive has been investigated as a function of thermal treatment for selected times at various temperatures in air. The research findings indicate that the lap shear strength decreases with the increase in duration of the thermal treatment at constant temperature and with the increase in temperature at constant time. The bond fails increasingly in the oxide coating with increasing treatment temperature and time of treatment. Surface analysis results for debonded specimens suggest that the process leading to failure is the formation of fluorine-containing materials within the oxide, which weakens the adherend-adhesive bond. The formation of the fluorine components is facilitated by treatment at elevated temperatures. This study suggests that the presence of fluoride ions in the anodic oxide coating, prior to bonding, is detrimental to the bond strength of adhesively bonded Ti-alloy when exposed to high temperatures. The wedge test configuration was used to investigate the influence of temperature on the bond durability of adhesively bonded chromic acid anodized Ti-6Al-4V alloy in air. Based on the average crack length vs. exposure time data, the bond durability varied in the order -25°C > 24°C > 177°C. In each case, the bonded joint failed cohesively within the adhesive, irrespective of the temperature of exposure. XPS analysis and scanning electron photomicrographs of failure surfaces revealed that the failure occurred at the scrim cloth/adhesive interface. The influence of thermal treatment history on the bond durability of adhesively bonded chromic acid anodized Ti-6Al-4V alloy immersed in boiling water was also investigated. The average crack length vs. immersion time indicated no significant differences for specimens that were thermally treated and then bonded compared to the non-thermally treated specimens. In addition, the failure mode was cohesive within the adhesive for specimens prepared using various thermal treatment conditions. The crack growths for samples treated for 0.5 hour and 1.0 hour and for non-thermally treated specimens for any given exposure time were equivalent. In addition, cohesive failure (failure within adhesive) was observed for each specimen under each treatment condition. The specimens that were bonded and then thermally treated for 3 hours, failed in the oxide coating immediately upon insertion of the wedge. Surface analysis results for debonded specimens suggest that the process leading to failure is the formation of fluorine-containing materials within the oxide. The measured average activation energy for the formation of aluminum fluoride species is 149 kJ/mol. The high activation energy suggests that the rate of aluminum fluoride formation is substantial only at high temperatures. In summary, the presence of fluorides in the anodic oxide coatings prior to bonding is detrimental to the overall strength and durability of adhesively bonded chromic acid anodized Ti-6Al-4V joints which have been exposed to high temperatures (350°C-399°C). / Ph. D.

When bonded joints are subjected to harsh environmental conditions, the interphase, the three-dimensional region surrounding the adhesive/substrate interface, becomes critically important. Frequently, failure occurs in this region after adhesively bonded systems are subjected to elevated temperature oxidative aging. In a previous study, this was found to be the case with a polyimide adhesive bonded to chromic acid anodized (CAA) Ti-6Al-4V. The objective of the current research has been twofold: 1) to investigate the effect of thermal aging on the interphase region of polyimide/titanium adhesive joints, and 2) to evaluate the method used in the current study for durability characterization of other adhesive/substrate systems. The method used in this research has been to characterize the effect of elevated temperature aging on the following systems: 1) Notched coating adhesion (NCA) specimens and 2) bulk samples of dispersed substrate particles in an adhesive matrix. The NCA test has the advantages of an accelerated aging geometry and a mode mix that leads to failure through the interphase, the region of interest. The bulk samples have the advantage of an increased interphase volume and allow for the application of bulk analysis techniques to the interphase, a region that is traditionally limited to surface analysis techniques. The adhesive systems studied consisted of one of two polyimide adhesives, LaRC© PETI-5 or Cytec Fiberite© FM-5, bonded to CAA Ti-6Al-4V. The model filled system consisted of a PETI-5 matrix with amorphous titanium dioxide filler. Through the use of the NCA test, it was determined that bonded specimens made with FM-5 lose approximately 50% of their original fracture energy when aged in air at 177°C for 30 days. This aging temperature is well below the glass transition temperature of the adhesive, 250°C. At the same time, the failure location moves from the anodized oxide layer to the adhesive that is directly adjacent to the substrate surface, the interphase region. Through surface analysis of this region, it is determined that the adhesive penetrates the pores of the CAA surface to a depth of 70 to 100 nm, promoting adhesion at the interface. With aging, the adhesive in the interphase region appears to be weakening, although analysis of the bulk adhesive after aging shows little change. This indicates that adhesive degradation is enhanced in the interphase compared to the bulk. Analysis of the model filled system gave similar information. Specimens containing titanium dioxide filler had glass transition temperatures that were approximately 20°C lower than the neat polyimide samples. In addition, the filled samples contained a significant portion of low molecular weight extractable material that was not present in the neat specimens. The tan delta spectra from dynamic mechanical thermal analysis of the filled specimens exhibited a shoulder on the high-temperature side of the glass transition peak. This shoulder is attributed to the glass transition of the interphase, a distinct phase of the polyimide which is constrained by adsorption onto the filler particle surfaces. As a function of aging time at 177° or 204°C, the shoulder decreases substantially in magnitude, which may relate to loss of adhesive strength between the polyimide and the filler particles. From this research, it has been illustrated that information relating to the durability of adhesively bonded systems is gained using an interfacially debonding adhesive test and a model system of substrate particles dispersed in an adhesive matrix / Ph. D.

No description available.

Ce travail de thèse se compose de deux parties : tout d’abord nous avons caractérisé sur le plan morphologique des motifs de TiOx réalisés par anodisation localisée par AFM (LAO) dans des couches pleines plaques de 5 nm de titane. Nous avons étudié l’influence de la tension d’oxydation, de la vitesse de balayage de la pointe AFM, de l’humidité relative de l’environnement, du mode AFM (contact ou intermittent) et du type de pointe. Les motifs les plus fins atteignent une largeur à mi-hauteur de 21 nm pour 2.2 nm de hauteur, ils sont obtenus avec une pointe PtSi utilisée en mode intermittent sous une tension de polarisation de -7V, une vitesse de balayage de 0.4 µm.s-1 et dans un environnement comportant une humidité de 43%. La deuxième partie de notre travail a été consacrée à l’élaboration et à la caractérisation de jonctions planaires MIM Ti/TiOx/Ti. Ces jonctions sont des motifs TLM de titane comportant une ligne transverse de TiOx réalisée par LAO. Lorsque les jonctions sont stressées électriquement sous air, une transformation morphologique irréversible se produit pour une densité de courant et un champ électrique atteignant de l’ordre de 7.1010 A.m-2 et 3.107 V.m-1 respectivement. Des analyses chimiques et structurales basées sur la microscopie électronique à transmission ont montré que la ligne initiale de TiOx amorphe s’était considérablement élargie et est constituée d’une zone de TiOx cristallin. Cette transformation peut être évitée en appliquant le stress électrique sous vide. Enfin des mesures électriques en température ont permis d’élucider les mécanismes de conduction : émission Schottky sous vide et conduction ionique sous air. / This work is divided in two specific parts: first of all we caracterized oxide patterns made by local anodic oxidation using an AFM on 5nm titanium wafers. We caracterized the morphology of the patterns. We studied the influence of several parameters such as oxidation voltage, writing speed of the AFM tip, relative humidity of the environment, AFM modes (contact or tapping)and the type of the tips we used. Most thinnest pattern we made reaches a full width at half maximum of 21nm with a 2.2nm height. It was obtained using a PtSi coating tip in tapping mode with an oxidation voltage of -7V, a writing speed of 0.4 um/s and a relative humidity of 43%. The second part of our work was dedicated to the realization and the characterization of planar MIM junction Ti/TiOx/Ti. These junctions are TLM patterns with a TiOx line cross-ways over the microwire of the TLM pattern. When the junctions are stressed electrically under ambient atmosphere, an irreversible morphological transformation is happenning for a current density and an electric field of 7.1010 A/m² and 3.107 V/m respectively. Chemical and structural analysis based on transmission electronic microscopy have shown that the initial amorphous TiOx junction have grown importantly with an area of crystalline TiOx. This transformation can be avoided by applying the electric stress under vacuum. Finally, electrical measurements in temperature highlighted the transport mecanisms within the junction: Schottky emission under vacuum and ionic conduction under ambient atmosphere.

Synopsis of the thesis entitled “Titanium Nitride-Based Electrode Materials for Oxidation of Small Molecules: Applications in Electrochemical Energy Systems” submitted by Muhammed Musthafa O. T under the supervision of Prof. S. Sampath at the Department of Inorganic and Physical Chemistry of the Indian Institute of Science for the Ph.D degree in the faculty of science. Fuel cells have been the focus of interest for many decades because of the ever increasing demands in energy. Towards this direction, there have been considerable efforts to find efficient electrocatalysts to oxidize small organic molecules (SOMs) such as methanol, ethanol, glycerol, hydrazine and borohydride that are of potential interest in direct fuel cells. Most studies revolve around platinum which is the best electrocatalyst known for the oxidation of many SOMs. However, platinum is extremely susceptible to carbon monoxide (CO) poisoning which is an intermediate in the electrooxidation of aliphatic alcohols. The best known catalyst, platinum-ruthenium alloy (PtRu), suffers from leaching of Ru during cycling resulting in decrease in efficiency in addition to loss of precious metal. Another important aspect of fuel cell catalyst degradation is corrosion of widely-used carbon support, under fuel cell conditions. Corrosion of carbon support weakens the adherence of catalyst particles on the support and in turn results in loss of catalyst and also in its easy oxidation. Carbon corrosion is also reported to decrease the electronic continuity of the catalyst layer. Hence, replacement of carbon support with durable material is required. The present research explores the use of non-carbonaceous, transition metal nitride for anchoring catalytic particles. The favorable physicochemical properties of titanium nitride (TiN) such as extreme hardness, excellent corrosion resistance in aggressive electrolytes, resistance to nearly all chemicals, salt and humidity, very good support for the adherence of fuel cell catalysts and excellent electronic conductivity motivated us to use this material for anchoring fuel cell catalysts such as Pt, PtRu and Pd. In the present studies, TiN coated on stainless steel (SS 304) surface is used as an electrode material. Catalysts such as Pt, Pd and PtRu are anchored on to TiN and used for the oxidation of methanol and ethanol in acidic as well as in alkaline media. Use of bare TiN is explored for the oxidation of sodium borohydride. The efficiency of TiN supported catalysts are compared with carbon supported ones. Preliminary studies on the use of TiN supported catalysts in fuel cells have been conducted as well. Figure 1 shows the topographic atomic force microscopic (AFM) image in combination with scanning Kelvin probe (SKP) image of platinized TiN (Pt-TiN) surface. Since Pt particles are metallic, they are expected to show lower work function values than that of TiN domains which is indeed observed in figure 1B where the location of Pt particles is shown as dip in the work function. Very interestingly, the interface of Pt-TiN possesses very different work function values confirming the existence of metal-support interaction and this is expected to have positive implications in fuel cell catalysis. Figure 1. Contact mode AFM (A) and the corresponding scanning Kelvin probe image (B) of Pt-TiN surface. Figure 2. Cyclic voltammograms of Pt-TiN and Pt-C electrodes in 0.5 M H2SO4 containing 0.5 M methanol at a scan rate of 10 mV/s. Loading of the catalyst used is 1 mg of Pt/cm2. The performance of Pt-TiN and PtRu-TiN are compared with the corresponding carbon supported catalysts (Pt-C, PtRu-C) for the electrooxidation of methanol. Figure 2 shows the voltammograms obtained on Pt-TiN and Pt-C in presence of acidified methanol. TiN supported catalyst performs better than carbon supported catalyst in terms of high currents at low over voltages (based on I-t measurements), long term stability and high exchange current densities (based on Tafel studies). The electrochemical characteristics of methanol oxidation on Pt-TiN and Pt-C catalysts are given in table 1. The current densities observed on TiN supported catalyst are almost three times higher than that of carbon supported catalyst confirming the promoting effect of TiN support towards methanol oxidation reaction. The performance of Pt-TiN electrocatalyst under fuel cell conditions reveals peak power densities close to 396 mW/cm2 at a current density of 375 mA/cm2, at 90C. Table 1. Characteristics of methanol oxidation on TiN and carbon supported catalysts in acidic medium. Material Onset Ep (mV) Ip EAA Ip Ip/Ib E=Ep-Eb potential (mA/mg (cm2/mg)b (mA/cm2 (mV) of Pt)a of Pt)c (mV) Pt-TiN 170 720 56 78.4 0.714 1.24 82 Pt-C 250 700 18 68.6 0.262 0.98 106 a Mass activity; Ip is the forward peak current and Ib is the reverse peak current; Ep and Eb are forward and reverse peak potentials. b Electrochemically active area (EAA) c Current density normalized for EAA Figure 3. In-situ FTIR spectra on bare TiN surface as a function of applied DC bias vs.SCE. The spectra are shown in regions of 1000 to 2000 cm-1 (A) and 2500 to 4000 cm-1 (B). Electrolyte used is 0.5 M methanol in 0.5 M H2SO4. Reference spectrum is obtained at 0 V. In-situ FTIR spectroelectrochemical measurements have been carried out to understand the intermediates and products formed during methanol oxidation. TiN surface is highly reflective and is quite amenable for reflectance IR studies. Figure 3 shows the potential dependant spectral characteristics of TiN in methanolic sulphuric acid. The bands observed at 1600 and 3600 cm-1 correspond to –OH bending and stretching vibrations of adsorbed water molecules. Interestingly, bands corresponding to adsorbed water are observed even at remarkably low over potentials of around 0.1 V vs. SCE where CO poisoning of Pt can be very severe. This experiment confirms the ability of inexpensive TiN to function like expensive Ru in fuel cell catalysis. Similar studies have been carried out for ethanol electrooxidation on TiN supported catalysts such as Pd, Pt and PtRu in acidic as well as alkaline conditions. Adherence of fuel cell catalyst on to TiN and carbon support is followed by cycling the electrode potential continuously as shown in figure 4. The adherence of Pd on TiN surface is very good and the stability tests reveal that Pd adheres and remains on TiN for a long time as compared to carbon support. Figure 4. Cyclic voltammograms of Pd-C (A) and Pd-TiN (B) in 1 M KOH at 100 mV/s. Pd loading used is 83 µg/cm2. In the chapter on borohydride oxidation, bare TiN electrode is used for the electrochemical oxidation of sodium borohydride. In direct borohydride fuel cells (DBFC), H2 evolution that occurs at low over voltages decreases the apparent number of electrons transferred and consequently the fuel cell efficiency. TiN has been shown to be a relatively H2 evolution-free electrocatalyst for borohydride oxidation (figure 5A). As shown in figure 5A, no H2 oxidation is observed (below -0.5 V) on TiN surface with increase in concentration of borohydride. This point to the fact that direct oxidation of borohydride is very favourable on TiN electrode and is confirmed by fuel cell measurements as shown in figure 5B. Non-platinum DBFCs using TiN as the anode (borohydride oxidation) and prussian blue supported carbon (PB-C) as the cathode (oxygen or hydrogen peroxide) electrocatalysts (figure 5B) reveal peak power density of 107 mW/cm2 for a current density 130 mA/cm2, at 80C. Figure 5. Cyclic voltammograms of TiN in 1 M NaOH containing varying concentrations of borohydride at a scan rate of 20 mV/s (A). Polarization studies of DBFC with TiN anode catalyst and PB-C (prussian blue supported on carbon) cathode catalyst (B). Anolyte is 0.79 M borohydride in 5 M NaOH and catholyte is 2.2 M acidified H2O2. The second aspect of the thesis is related to the use of TiN to prepare visible light active, nitrogen doped TiO2 (N-TiO2). This is carried out by electrochemical anodization of TiN in 0.5 M HNO3 at 1.4 V. The X-ray photoelectron spectroscopy (XPS) suggests the formation of oxide phase on anodized TiN surface (figure 6A) and is confirmed by reflectance UV-Visible spectroscopy. The visible light activity is used for the sunlight induced reduction of graphene oxide to reduced graphene oxide. As shown in the Raman spectra (figure 6B), a negative shift of the D and G band positions by about 20 cm-1 and the intensity ratio reversal after reduction confirms the formation of reduced graphene oxide on N-TiO2. Figure 6. (A) Ti (2p) region of XPS of fresh TiN and anodized TiN. Anodization has been carried out at 1.4 V vs. SCE in 0.5 M HNO3. (B) Raman spectra of exfoliated graphene oxide on anodized TiN before and after sunlight induced reduction. In summary, TiN has been shown to be an active support material for fuel cell catalysts in the present studies. The appendix details the basic electrochemical studies on TiN using various redox couples, electroploymerization of aniline and the formation of nanostructures on TiN surface. (For figures pl refer the abstract pdf file)

Στην παρούσα διδακτορική διατριβή μελετάται η ανάπτυξη λεπτών υμενίων πορωδών ανοδικών οξειδίων του αλουμινίου (αναφέρονται και ως πορώδης ανοδική αλουμίνα) σε υπόστρωμα πυριτίου. Επιπλέον, εξετάζεται η ανάπτυξη εφαρμογών που αφορούν τη χρήση της πορώδους αλουμίνας ως μάσκα και ως μήτρα για την δημιουργία νανονημάτων ή κβαντικών τελειών (νανονησίδων) στο Si. Το πρώτο κεφάλαιο πραγματεύεται τη θεωρία και τους μηχανισμούς που διέπουν την ανάπτυξη πορωδών υμενίων, που προέρχονται από ανοδική οξείδωση (ανοδίωση) τόσο φύλλων αλουμινίου, όσο και υμενίων αλουμινίου σε υπόστρωμα πυριτίου. Επιπροσθέτως, παρατίθεται ο ρόλος που διαδραματίζουν οι ηλεκτροχημικές συνθήκες ανοδίωσης, όπως το pH, η θερμοκρασία και η εφαρμοζόμενη τάση, στα τελικά δομικά χαρακτηριστικά των πορωδών υμενίων. Στο δεύτερο κεφάλαιο παρουσιάζονται τα τεχνολογικά βήματα διεργασιών που αφορούν την προετοιμασία των δειγμάτων τα οποία πρόκειται να ανοδιωθούν, και δίνονται λεπτομέρειες για την πειραματική διάταξη η οποία χρησιμοποιείται κατά την ανοδίωση. Στο τρίτο κεφάλαιο μελετώνται εκτενώς, τρεις παράγοντες που έχουν σημαντική επίδραση στα τελικά δομικά χαρακτηριστικά των πορωδών υμενίων. Κατά τους δύο πρώτους, εξετάζεται η επίδραση του πάχους του προς ανοδίωση υμενίου αλουμινίου πάνω στο Si, καθώς και ο περιορισμός του σε επιφάνειες μερικών τετραγωνικών μικρομέτρων πάνω στο Si, στο μέγεθος και την πυκνότητα των πόρων. Ο τρίτος παράγοντας αφορά το ρόλο της ανοδίωσης του υμενίου του αλουμινίου σε δύο και τρία στάδια σε συνδυασμό με τη χημική εγχάραξή του μετά από κάθε στάδιο ανοδίωσης, στην ανάπτυξη εξαγωνικής συμμετρίας στην κατανομή των πόρων. Το τέταρτο κεφάλαιο, πραγματεύεται την ανάπτυξη εφαρμογών που συνδέονται με τη χρήση της πορώδους αλουμίνας ως μάσκα και ως μήτρα για τη δημιουργία νανοδομών επάνω στο πυρίτιο. Ως εκ τούτου παρουσιάζεται η δημιουργία νανονησίδων Cr, Ti, νανοστηλών Si, και νανονημάτων Au, πάνω στο Si, εφαρμογές στις οποίες τα πορώδη ανοδικά υμένια χρησιμοποιήθηκαν ως ενδιάμεσο στάδιο. Στο πέμπτο κεφάλαιο παρατίθεται η ανάπτυξη διαμέσου της πορώδους αλουμίνας, εξαγωνικά διατεταγμένων νανονησίδων SiO2 στο Si. Επίσης, παρουσιάζεται ο ηλεκτρικός χαρακτηρισμός διατάξεων οι οποίες αποτελούνται από την εν λόγω δομή. Σε ένα επιπλέον βήμα, οι νανονησίδες SiO2 χρησιμοποιούνται για την ανάπτυξη νανοκρυσταλλιτών Si στο εσωτερικό τους μέσω της τεχνικής της ιοντικής σύνθεσης. Τα σημαντικότερα αποτελέσματα και συμπεράσματα που προέκυψαν από την εκπόνηση της παρούσας διδακτορικής διατριβής συνοψίζονται στα εξής: • Βελτίωση της εξαγωνικής συμμετρίας στην κατανομή των πόρων, μέσω ανοδίωσης σε δύο ή τρία στάδια σε συνδυασμό με χημική εγχάραξη του προς ανοδίωση αλουμινίου έπειτα από κάθε στάδιο ανοδίωσης. • Αύξηση της πυκνότητας των πόρων των ανοδικών υμενίων κατά μία τάξη μεγέθους, με περιορισμό του προς ανοδίωση αλουμινίου σε προεπιλεγμένες περιοχές στο Si, επιφάνειας μερικών τετραγωνικών μικρομέτρων. • Ανάπτυξη διατεταγμένων νανοδομών Ti και Cr σε υπόστρωμα Si χρησιμοποιώντας λεπτά υμένια πορώδους αλουμίνας πάνω σε Si. Ιδιαίτερα οι δομές Cr, μπορούν να χρησιμοποιηθούν ως μεταλλική νανοδομημένη μάσκα για την εγχάραξη με ενεργά ιόντα του υποστρώματος Si και τη δημιουργία νανοστηλών Si πάνω σε αυτό. Η δημιουργία νανοστηλών Si, βρίσκει πληθώρα εφαρμογών στη Νανοηλεκτρονική, σε αισθητήρες, Nανοφωτονική, μνήμες κ.τ.λ. • Οι πυκνότητες διεπιφανειακών καταστάσεων που προέκυψαν από τον ηλεκτρικό χαρακτηρισμό της διεπιφάνειας υμενίων πορώδους αλουμίνας με το πυρίτιο, και της διεπιφάνειας πορώδους αλουμίνας – νανονησίδων SiO2 με το πυρίτιο. Οι τιμές που υπολογίστηκαν είναι ενθαρρυντικές, αν ληφθεί υπόψη ο ηλεκτροχημικός τρόπος παρασκευής των εν λόγω σύνθετων υμενίων πάνω στο πυρίτιο. • Ανάπτυξη μεμονωμένων νανοκρυσταλλιτών Si ενσωματωμένων σε νανονησίδες SiO2. Για το σκοπό αυτό συνδυάστηκαν δύο διαφορετικές τεχνολογίες, εκείνη της ιοντικής σύνθεσης και εκείνη της ανάπτυξης νανονησίδων SiO2 διαμέσου λεπτών υμενίων πορώδους αλουμίνας απευθείας σε υπόστρωμα Si. Τέτοιες δομές νανοκρυσταλλιτών έχουν εφαρμογές σε διατάξεις μη πτητικών μνημών, όπου η κατανεμημένη αποθήκευση φορτίου στους νανοκρυσταλλίτες ευνοεί τη χρήση λεπτότερων οξειδίων πύλης και τη δυνατότητα σμίκρυνσης του πάχους των οξειδίων αυτών χωρίς να μειώνεται ο χρόνος αποθήκευσης φορτίου. / In the present thesis, the growth of porous anodic alumina films on Si substrate was studied extensively. Potential applications of porous anodic alumina films formed directly on Si, regarding the use of porous membranes as mask or template for various nanostructures growth directly on Si, are discussed. Chapter one deals with the theory and mechanisms governing porous anodic alumina film growth, either on porous anodic films formed by anodization of aluminum foils, or on porous anodic films developed on Si substrates. Additionally, the effect of different factors (pH, temperature, applied voltage) on the final structural characteristics is presented. In chapter two, the preliminary processing steps regarding sample preparation before the anodization procedure are quoted. Moreover, details about the experimental set-up and the electrochemical conditions used during the sample anodization in the current work are given. In chapter three, the influence of three different factors, in the final structural characteristics, is investigated. Primarily, the impact of the initial aluminum thickness deposited on Si substrate, and secondly the confinement of the aluminum film in areas of a few μm2, in the pore size and pore density are studied. Finally, the influence of the third factor is associated with a three-step instead of a two-step anodization, in combination with an in-between step of aluminum chemical etching, on the ordering and the uniformity of the pores. The deposition of Ti and Cr nanodots arrays on Si, using the porous alumina membrane as a masking layer, is investigated in chapter four. Furthermore, the Ti nanodots are used for the electrodeposition of Au nanodots and nanowires inside the porous alumina films. Additionally, the Cr dots are used as metallic nanostructured mask for the Si etching by reactive ion etching process, that leads to the formation of Si nanopillars on Si substrate. In chapter five the growth of hexagonally ordered SiO2 dots on Si through porous anodic alumina membranes, in various acidic electrolytes, is studied. Moreover, the electrical characterization of the interface of porous alumina film/Si and porous alumina film with SiO2 dots in pore bottoms/ Si is presented. Finally, in the present thesis the technology of fabrication of Si nanocrystals embedded in SiO2 dots arrays through porous alumina membranes on Si substrate is developed for the first time. This was achieved by the combination of ion beam synthesis with the already existing technology of porous anodic alumina growth on Si substrates. The nanocrystals are electrically isolated from the substrate. This technique is promising as an application in non-volatile memory devices. The main achievements accomplished through this study are summarized as follows: • The optimization of pores ordering by developing the porous alumina membrane in two or three processing steps in combination with the chemical etching of Al film, lying above the porous membrane, following each anodization cycle. • The increase of porous density by the confinement of porous alumina film in areas of a few μm2 on Si. • The development of Ti, Cr and nanodots arrays, directly on Si, through porous alumina membranes. The use of Cr nanodots as nanostructured masking layer for the formation of Si nanopillars, formed by etching of Si substrate with RIE, on Si. • The density of interface stages results from the electrical characterization of porous alumina with or without SiO2 dots at each pore bottom, with the Si substrate. The results are encouraging, keeping in mind that the pore membranes and SiO2 dots were electrochemically grown directly on Si substrate. • The development of distinct Si nanocrystalls, embedded in SiO2 dots, combining for the first time two different technologies, that is the fabrication of porous anodic alumina films directly on Si substrate, as well as the ion beam synthesis technique. The proposed technique is promising for the fabrication of non-volatile memory devices.