Anodisation is a surface treatment process, commonly used to form a protective oxide coating on the surface of metals like aluminium. Anodised coatings, being grown out of the base metal have excellent interface strength but are porous and brittle. Porosity of the coating reduces the hardness and the brittle nature of the oxide induces cracking. In practice, the pores are typically filled with organic dye and sealed. Under certain controlled electrochemical conditions, anodisation results in a highly ordered hexagonal porous structure in pure aluminium. In this work, we explore the possibility of using this ordered porous alumina to form a novel metal nanocomposite as a tribological coating. By optimizing the nonporous structure and tuning the electrodeposition process, we uniformly filled the ordered pores with copper. We have measured the hardness of the resulting ordered and aligned nanocomposite. We explore the possibility of using this composite coating for tribological applications by carrying out some preliminary reciprocating wear test. Ordered porous alumina layer is formed by a two-step anodisation process. By optimizing the anodisation conditions, we control the thickness of the coating and the pore size. The interface of the porous structure and aluminium substrate is defined by a non-conducting dense barrier oxide layer. However, to deposit metal into the pores, a conducting path should be established through the barrier layer. One possibility is to etch out the bottom of the pores at the cost of the interface strength and losing out on the main advantage of anodised coatings. To be able to fill metal without this sacrifice, we utilised the dendritic structure in the barrier layer formed by a step-wise reduction of voltage towards the end of anodisation process. Optimisation of this dendritic structure led to uniform deposition of metal into pores, achieved by pulsed electrodeposition. In pulse lectrodeposition, a positive pulse is applied to remove accumulated charge near to the bottom of pores, followed by a negative pulse to deposit metal and a delay to allow diffusion of ions. By optimising the pulse shape and duration, we have achieved uniform growth of metal into pores. Further, monitoring the deposition current helped us to identify and control different phases of growth of the nanowire. The properties of the porous alumina and the nanocomposite were measured by nanoindentation. The deformation characteristics were obtained by observing the indents in a FE-SEM. We find that dendritic modification of interface has very little effect on the hardness of the porous alumina layer. We also found that the porous alumina deformed either by compaction or by forming circumferential and radial cracks. When copper is filled in the nano pores, the hardness increased by 50% and no circumferential cracks were found up to the load of 10 mN for a film thickness of about 1 µm. Coefficient of friction of the coating reciprocated against steel in dry condition is found to be around 0.4. Minimal wear was observed from the SEM images of wear track. In summary, a novel nanocomposite coating with ordered porous alumina as matrix embedded with aligned metal nano rods has been developed. This was achieved by optimally modifying the barrier layer without sacrificing the interfacial strength. Uniform coating has been achieved over an area of 10 mm x 10 mm. The coating is found to have high hardness and high wear resistance.

Highly ordered nanoparticle arrays have been successfully fabricated by our group recently using ultra-thin porous alumina membranes as masks in the evaporation process. The sizes of the nanoparticles can be adjusted from 5-10 nm to 200 nm while the spacing between adjacent particles can also be adjusted from several nanometers to about twice the size of a nanoparticle. The configuration of the nanoparticles can be adjusted by changing the height of the alumina masks and the evaporation direction. Due to the high pore regularity and good controllability of the particle size and spacing, this method is useful for the ordered growth of nanocrystals. Different kinds of nanoparticle arrays have been prepared on silicon wafer including semiconductors (e.g., germanium) and metals (e.g., nickel). The germanium nanoparticle arrays have potential applications in memory devices while the nickel catalyst nanoparticle arrays can be used for the growth of ordered carbon nanotubes. / Singapore-MIT Alliance (SMA)

En aquesta tesi es detalla la metodologia per obtindre sensors de gasos basats en òxid de tungstè nanoestructurat sobre suports micromecanitzats de silici. Aquesta nanoestructuració s’ha fet mitjançant una capa d’alúmina porosa como a motlle, pel que s’ha desenvolupat una metodologia per a compatibilitzar l'anodització de l’alumini, i altres metalls com el tungstè, amb els processos estàndards del silici. S’han desenvolupat dos tipus de capes nanoestructurades, nanotubs i nanopunts de WO3. Els nanotubs s’han obtingut depositant mitjançant polvorització catòdica reactiva la capa sensible sobre alúmina porosa recobrint les parets dels pors. Els nanopunts s’han obtingut anoditzant una bicapa d’alumini i tungstè, on la primera anodització crea la alúmina porosa i la segona fa créixer els nanopunts d’òxid de tungstè en la base dels pors. S’ha analitzat la composició, morfologia i funcionament com a sensors de gasos d’ambdós materials nanoestructurats i s’han comparat els resultats amb sensors basats en materials sense nanoestructuració. / En esta tesis se detalla la metodologia para obtener sensores de gases basados en óxido de tungsteno nanoestructurado sobre soportes micromecanizados de silicio. Dicha nanoestructuración se ha obtenido empleando una capa de alúmina porosa como molde, por lo que se desarrolla una metodología para compatibilizar la anodización del aluminio, y otros metales como el tungsteno, con los procesos estándares del silicio. Se han desarrollado dos tipos de capas nanoestructuradas, nanotubos y nanopuntos de WO3. Los nanotubos se han obtenido depositando por pulverización catódica reactiva la capa sensible sobre alúmina porosa recubriendo las paredes de sus poros. Los nanopuntos se han obtenido anodizando una bicapa de aluminio y tungsteno, donde la primera anodización crea la alúmina porosa y la segunda hace crecer los nanopuntos de óxido de tungsteno en la base de los poros. Se ha analizado la composición, morfología y funcionamiento como sensores de gases en ambos casos y se han comparado los resultados con los de sensores sin nanoestructuración. / This thesis shows the methodology to obtain nanostructured tungsten oxide layer as sensing material on silicon micromachined gas sensor devices. A porous anodised alumina layer was used as pattern to obtain it, so a technique has been developed to make compatible the anodising of aluminium and other metals like tungsten with the standard silicon processes. Two different nanostructuring approaches were developed, nanotube and nanodot based tungsten oxide layers. The WO3 nanotube layer has been obtained by the tungsten oxide deposition using reactive sputtering on the porous alumina layer. As a result a continuous sensing layer coats the pores without clogging them. WO3 nanodot layers were obtained by the anodising of an aluminium and tungsten bilayer, where the first anodising process grows the porous alumina layer and the second one generates the tungsten oxide nanodots in the end of the pores. Compositional and morphological studies and the study of their behaviour as gas sensors where conducted for the two nanomaterials. The results have been compared with the flat tungsten oxide layers on micromachined gas sensors.

Indium tin oxide (ITO) and molybdenum are substrates of choice in the manufacture of the CdS-CIS photovoltaic cell, which is the base for the leading thin-film solar cell technology. Substantial advancement in this technology is expected if these devices can be made in nanoporous alumina (AAO) templates. The first step to this endeavor is to learn to form AAO templates on molybdenum and ITO substrates. This was accomplished, and the results are reported in this thesis. Starting substrates were glass, coated with either a thin molybdenum layer or a thin ITO layer. Aluminum was deposited on top of this conducting substrate. Oxalic acid was used as the electrolyte for anodization. In the case of molybdenum substrates, average pore diameter was 45 nm when an anodization voltage of 40 volts was used for approximately 46 minutes; current density was approximately 23 amps/sq. m. In the case of ITO substrates, pores of 45 nm diameter were obtained for approximately 20 minute anodization at 40 V; current density was 40 amps/sq. m; annealing of aluminum layer prior to anodization, at 550 oC (degrees Centigrade) for 90 minutes was needed to obtain good pores. A one micrometer thick CdS layer was electrodeposited inside the AAO pores on top of the ITO substrate. In preliminary experiments, CdS/Cu2S photovoltaic heterojunctions with an open circuit voltage of 242 mV were formed inside the nanopores.

Οι μονοδιάστατες μεταλλικές νανοδομές, όπως νανοσύρματα και νανοσωλήνες, έχουν ελκύσει το ενδιαφέρον της επιστημονικής κοινότητας τα τελευταία χρόνια λόγο του σημαντικού ρόλου που παίζουν στην κατασκευή νανοσυσκευών, όπως ανιχνευτές, ηλεκτρονικά και οπτικά συστήματα και συστήματα αποθήκευσης πληροφορίας. Μια απλή και αποτελεσματική τεχνική για την κατασκευή μεγάλου αριθμού νανοσυρμάτων και νανοσωλήνων με μεγάλη αναλογία μήκους προς διάμετρο είναι η ονομαζόμενη «σύνθεση μήτρας», η οποία βασίζεται στην ηλεκτροχημική εναπόθεση μετάλλου μέσα στους πόρους κατάλληλου υλικού το οποίο λειτουργεί σαν μήτρα. Η πορώδης αλουμίνα είναι ένα υλικό που χρησιμοποιείται ευρέως για τον σκοπό αυτό λόγο της χημικής και μηχανικής της σταθερότητας και της αντοχής της σε υψηλές θερμοκρασίες. Επίσης, τα γεωμετρικά της χαρακτηριστικά μπορούν να ελέγχουν εύκολα κατά την διάρκεια της διαδικασίας παρασκευής της. Στην εργασία περιγράφεται η διαδικασία κατασκευής μεμβρανών πορώδους αλουμίνας με εξαγωνική κατανομή πόρων, ανοιχτών και στις δύο επιφάνειες και με συγκεκριμένα γεωμετρικά χαρακτηριστικά. Για να κατασκευασθούν οι μήτρες οι οποίες θα χρησιμοποιηθούν στην ηλεκτροεναπόθεση και για άλλες εφαρμογές εξήχθη η σχέση μεταξύ του ρυθμού ανάπτυξης της μεμβράνης πορώδους αλουμίνας και των παραμέτρων της ανοδίωσης (πυκνότητα ρεύματος, θερμοκρασία) για ανοδίωση σε υδατικό διάλυμα με περιεκτικότητα 0.3Μ οξαλικό οξύ. Επιπλέον, μελετήθηκε ο απαραίτητος χρόνος για την διάλυση του συμπαγούς διαχωριστικού στρώματος (barrier layer) της πορώδους αλουμίνας με την χρήση υδατικού διαλύματος 5%wt. φωσφορικού οξέος. Τέλος, στην εργασία αυτή μελετήθηκε η ανάπτυξη νανοσυρμάτων νικελίου σε πορώδης αλουμίνα με μέση διάμετρο πόρων 240nm. Για την καλύτερη κατανόηση των μηχανισμών ανάπτυξης των νανοσυρμάτων μελετήθηκε η σχέση της κρυσταλλογραφικής δομής των νανοσυρμάτων με την εφαρμοζόμενη τάση κατά την ανάπτυξη τους με την χρήση της τεχνικής dc ηλεκτροεναπόθεσης. Κατά την μελέτη αυτή αναπτύχθηκαν μονοκρυσταλλικά νανοσύρματα νικελίου προσανατολισμένα κατά την διεύθυνση [110] και πολυκρυσταλλικά νανοσύρματα με ισχυρό προσανατολισμό κατά την διεύθυνση [111]. / One-dimensional metallic nanostructured materials, like nanowires and nanotubes, have attracted extensive attention in recent years because of their importance in the fabrication of nanometer-scale devices such as sensors, electronics, and optics and information storage systems. A simple and effective technique to fabricate large number of metallic nanowires and nanotubes with high aspect ratio is the so called “template synthesis”, which involves electrochemically depositing metal into nanopores of a suitable material used as a template. Porous alumina membrane is a commonly used material for this purpose because of its chemical and mechanical stability and durability at high temperatures. Moreover, its geometrical characteristics are easily controlled during the fabrication process. In this work the fabrication process of free- standing porous alumina membranes with highly organized hexagonal structure and with specific geometrical characteristics is described. In order to fabricate templates for use in electrodeposition and other applications the dependence relation between the thickness growth rate and the anodization parameters (current density and temperature) for anodization in aqueous solution of 0.3M oxalic acid was derived. Furthermore, the time needed for barrier layer dissolution of porous alumina membrane with the use of hydrate solution of 5%wt. phosphoric acid. Finally, nickel nanowires were fabricated inside porous alumina membranes with mean pore diameter of 240nm. For better understanding of the nanowires growth mechanism the dependence of the crystal structure of nickel nanowire fabricated with dc electrodeposition from the applied voltage was studied. As a result, single crystal nickel nanowires oriented along [110] and polycrystalline nickel nanowires with a strong orientation along [111] have been fabricated.

Fabrication of ordered anodic alumina nanopore arrays and anodization parameters including electrolyte, concentration, voltage, temperature and time have been investigated. Cobalt nanoparticles were electrodeposited at the bottom of the pores. Vertically aligned, open-tipped multi-walled carbon nanotube arrays of high density and uniformity were synthesized via a flame method on silicon substrates using a nanoporous template of anodized aluminum oxide. The diameter and length of the nanotubes are controlled by the geometry of the aluminum oxide template. It is the cobalt catalyst particles, not the porous aluminum templates, help the growth of carbon nanotubes through graphitization and bonding of carbon nanotubes to the silicon substrates. Fabrication of nano-structures has been demonstrated. Nano-trenches of 20 nm have been achieved using single-walled nanotube bundles as shadow masks, which were aligned across electrodes under high frequency AC voltage.

In this research work, porous films on aluminum foil, with vertical through and through pores, were fabricated. The films were anodized at different applied voltages and the conditions were reported. In some cases, aluminum foil films were anodized under constant current conditions. Thicker aluminum films, referred to as aluminum tape in this thesis, were also anodized to get good porous films. While the porous alumina films using aluminum tape produced pores with good uniformity, the films did not produce through and through pores. Porous alumina films were also prepared on aluminum evaporated ITO substrate. The films on ITO substrate were different from the porous alumina films using aluminum foil/tape. In case of ITO substrate based films, an additional condition, temperature was also varied. The anodization process on ITO substrate based films was done at lower temperatures in order to reduce the effect of high currents on the process. The SEM images for different anodization conditions were compared and the porosity of films was calculated. CdS was electrodeposited inside porous alumina. D.C as well as a.c. voltages were applied and duration of the process was varied to study their effect on film morphology and the thickness of the deposited CdS. The current-voltage characteristics of the CdS-deposited alumina films were plotted and the phase of the electrodeposited CdS was found to be hexagonal using XRD.

Nano structured solar cells provide an opportunity for increased open circuit voltages and and short circuit currents in solar cells due to quantum confinement of the window and absorber materials and an increase in the optical path length for the incident light. In this study, both bulk and nano heterojunctions of CIS/CdS and Cu2S/CdS devices have been fabricated and studied on plain glass substrates and inside porous alumina templates to compare their performance. The devices have also been characterized SEM, XRD and JV measurements. The J-V curves have also been analyzed for series resistance, diode ideality factor and reverse saturation current density.

Multi walled carbon nanotubes (MWCNT) grown in highly ordered porous alumina templates were incorporated into a resistive gas sensor design and were evaluated for their sensitivities. The material characteristics and electrical properties of the nanotubes were analyzed. A study was undertaken to elucidate the effect of UV light on desorption characteristics and the dependence of sensitivity on (i) thickness of amorphous carbon layers and (ii) flow rates of analyte gases. These sensors were highly responsive to both oxidizing and reducing gases with steady state sensitivities of 5% and 10% for 100ppm of NH3 and NO2 respectively, at room temperature. As part of a comparative study, thick films of MWCNTs grown on Si/SiO2 substrates were integrated into various nano-composite based sensors and were evaluated for their response. Steady state sensitivities as high as 10% and 11% were achieved for 100ppm of NH3 and NO2 respectively, at room temperature. MWCNTs were characterized for their electrical properties by I–V measurements at room temperatures. A typical I-V curve with an ohmic behavior was observed for a device with high work function metals (example: Au, Pt); Schottky behavior was observed for devices with metal contacts having low work functions (example: Al, Cu).

Μελέτη με μετρήσεις ανακλαστικότητας ακτίνων-Χ προσρόφησης μορίων μικρού σχετικά μήκους (~ 2 nm) εντός πορώδους υμενίου αλουμίνας. Σκοπός της εργασίας είναι να διερευνηθεί καταρχήν η δυνατότητα της τεχνικής της ανακλαστικότητας να δώσει πληροφορίες για πορώδη υμένια, υμένια δηλαδή που η επιφάνειά τους παρουσιάζει μεγάλη τραχύτητα και κατόπιν να μελετηθεί η διείσδυση εντός των πόρων μορίων μικρού σχετικά μήκους. / Study with measurements of X-ray reflectivity, small molecules adsorption on length (~ 2 nm) in porous alumina film. The purpose of this paper is to explore the possibility of the reflectivity technique to provide information for porous films, films that the surface roughness is highly and then studied the penetration of molecules within the resources of a relatively small length.