Τα τελευταία χρόνια διεξάγεται µια έντονη ερευνητική προσπάθεια µε στόχο την ανά- πτυξη αποτελεσµατικών καταλυτών για την εκλεκτική οξείδωση του CO παρουσία περίσσειας H2. Το ενδιαφέρον για αυτήν την διεργασία εντοπίζεται στην εφαρµογή της για τον καθαρισµό από το περιεχόµενο CO, πλούσιων σε Η2 αέριων µιγµάτων τα οποία χρησιµοποιούνται ως καύσιµο σε κυψελίδες καυσίµου τύπου PEM. Στην παρούσα διδακτορική διατριβή εξετάστηκαν οι καταλυτικές ιδιότητες τριών συ- στηµάτων: Au/α-Fe2O3, Pt/γ-Al2O3 και CuO-CeO2, για την εν λόγω διεργασία. Η µελέτη εντοπί- στηκε, κατά κύριο λόγο, στους καταλύτες CuO-CeO2, οι οποίοι δε περιέχουν πολύτιµο µέταλλο. Στους εν λόγω καταλύτες, παράµετροι της µελέτης ήταν η µέθοδος παρασκευής, η φόρτιση των καταλυτών σε ενεργό φάση και η θερµοκρασία ενεργοποίησής τους. Σε κάθε περίπτωση εξετά- στηκε η ενεργότητα, εκλεκτικότητα και σταθερότητα των καταλυτών, καθώς και η ανθεκτικότητά τους στην παρουσία CO2 και Η2Ο στην τροφοδοσία. Για το χαρακτηρισµό των καταλυτών χρησι- µοποιήθηκαν: α) φασµατοσκοπία ατοµικής απορρόφησης, β) ρόφηση Ν2, γ) περίθλαση ακτίνων Χ, δ) ηλεκτρονική µικροσκοπία, ε) θερµοσταθµική ανάλυση, στ) φασµατοσκοπία φωτοηλεκτρο- νίων ακτίνων Χ και ζ) δυναµικά πειράµατα µε προγραµµατισµό θερµοκρασίας. Επιπλέον, κινητι- κές µελέτες πραγµατοποιήθηκαν σε επιλεγµένα δείγµατα CuO-CeO2. Οι καταλύτες CuO-CeO2 βρέθηκαν να έχουν σχεδόν ιδανική εκλεκτικότητα σε θερµο- κρασίες µικρότερες από 130οC. Ενεργοί και εξαιρετικά εκλεκτικοί καταλύτες CuO-CeO2 παρα- σκευάστηκαν µε διαφορετικές τεχνικές, και εµφάνισαν µεγάλη σταθερότητα µε το χρόνο αντί- δρασης και ικανοποιητική ανθεκτικότητα στην παρουσία Η2Ο και CO2. H σειρά ενεργότητας των καταλυτών, µε βάση τη µέθοδο παρασκευής τους, ήταν: (sol-gel) > (καύση) > (κιτρικά-υδρο- θερµική) > (συγκαταβύθιση) > (εµποτισµός). Ο βέλτιστος καταλύτης CuO-CeO2, ο οποίος παρα- σκευάστηκε µε τεχνική sol-gel, έδωσε ~99% µετατροπή του CO, µε ~87% εκλεκτικότητα, στους 175οC, σε συνθήκες εκλεκτικής οξείδωσης του CO (παρουσία CO2 και Η2Ο). Γενικά, η ένταση της αλληλεπίδρασης CuO-CeO2 βρέθηκε να εξαρτάται από τη θερµοκρασία ενεργοποίησης των καταλυτών. Σε χαµηλές θερµοκρασίες ενεργοποίησης η προω- θητική δράση της δηµήτριας εντοπίζεται στην αύξηση της ειδικής επιφάνειας των καταλυτών και στη δηµιουργία νέων ενεργών κέντρων, πιθανά στη διεπιφάνεια των δύο φάσεων. Απ’ την άλλη πλευρά, η ένταση της αλληλεπίδρασης ενισχύεται σε υψηλές θερµοκρασίες ενεργοποίησης, µε συνέπεια την αύξηση της εγγενούς ενεργότητας των ενεργών κέντρων. Στα περισσότερα καταλυ- τικά δείγµατα το οξείδιο του χαλκού βρισκόταν πολύ καλά διασπαρµένο στην επιφάνεια της δηµήτριας. Επιπλέον, η παρουσία και σταθεροποίηση ιόντων Cu1+ στους καταλύτες που παρα- σκευάστηκαν µε καύση, συγκαταβύθιση και sol-gel, και ενεργοποιήθηκαν σε υψηλές θερµοκρασίες, αποτελεί ένδειξη ισχυρής αλληλεπίδρασης ανάµεσα στο οξείδιο του χαλκού και στη δηµήτρια, µε αποτέλεσµα την εισχώρηση ιόντων Cu1+ στα πρώτα επιφανειακά στρώµατα της δηµήτριας. Κινητικά µοντέλα βασιζόµενα σε έναν οξειδοαναγωγικό µηχανισµό, µπορούν να περι- γράψουν τις αντιδράσεις οξείδωσης του CO και του Η2, τόσο στο καθαρό CuO, όσο και στους κα- ταλύτες CuO-CeO2. H αλληλεπίδραση ανάµεσα στο CuO και τη δηµήτρια έχει ως αποτέλεσµα την ευκολότερη αναγωγή των οξειδωµένων ενεργών κέντρων, σε σχέση µε το καθαρό CuO. Η ευχερέστερη αναγωγή αυτών των κέντρων από το CO, σε σχέση µε το Η2, είναι η αιτία της υψη- λής εκλεκτικότητας των καταλυτών CuO-CeO2. Η ενεργότητα των καταλυτών Au βρέθηκε να εξαρτάται από την επιφανειακή συγκέ- ντρωση του Au, γεγονός που καταδεικνύει τη σηµασία ύπαρξης καλώς διασπαρµένων νανοσωµα- τιδίων Au (µεγέθους ~3 nm), για την επίτευξη υψηλής καταλυτικής ενεργότητας. Την καλύτερη συµπεριφορά παρουσίασε το δείγµα µε 2.94 wt% Au, για το οποίο προσδιορίστηκε η µεγαλύτερη τιµή επιφανειακής συγκέντρωσης Au. Με αυτό το δείγµα επιτεύχθηκε µετατροπή του CO µεγαλύτερη από 99% (µε 52% εκλεκτικότητα), στους 100οC, σε ρεαλιστικές συνθήκες εκλεκτικής oξείδωσης του CO (παρουσία CO2 και Η2Ο). Η σύγκριση της καταλυτικής συµπεριφοράς καταλυτών Au/α-Fe2O3, Pt/γ-Al2O3 και CuOCeO2 έδειξε ότι σε σχετικά χαµηλές θερµοκρασίες λειτουργίας (<80oC) ο καταλύτης Au/α-Fe2O3 εµφανίζει τη βέλτιστη συµπεριφορά για την εκλεκτική οξείδωση του CO. Σε υψηλότερες θερµοκρασίες, καλύτερα αποτελέσµατα έδωσαν οι καταλύτες CuO-CeO2, ο οποίοι ήταν αντί- στοιχα ενεργοί, και σε κάθε περίπτωση πιο εκλεκτικοί από τον καταλύτη Pt/γ-Al2O3. Η παρουσία H2O και CO2 στο αντιδρόν µίγµα προκάλεσε σηµαντική µείωση στην ενεργότητα των καταλυτών Au/α-Fe2O3 και CuO-CeO2, αλλά δεν επηρέασε, τουλάχιστον αρνητικά, την ενεργότητα του Pt/γ- Al2O3. Οι καταλύτες CuO-CeO2 και Pt/γ-Al2O3 παρουσίασαν σταθερή καταλυτική συµπεριφορά για το χρονικό διάστηµα που εξετάστηκαν σε ρεαλιστικές συνθήκες αντίδρασης (7-8 ηµέρες), σε αντίθεση µε τον καταλύτη Au/α-Fe2O3. / The development of efficient catalysts for the selective oxidation of CO in the presence of excess H2 is the goal of intense research effort during the last years, due to the application of this process in removal of CO from H2-rich gas mixtures, which are used as fuel in PEM fuel cells. The catalytic properties of three systems: Au/α-Fe2O3, Pt/γ-Al2O3 και CuO-CeO2, were investigated for the title process of the present thesis. The study was focused mainly on the CuOCeO2 catalysts, which do not contain a noble metal. Parameters of the study were: the preparation method, the metal loading and the activation temperature. The activity, selectivity and stability of catalysts, and also their tolerance in the presence of CO2 and Η2Ο in the feed, were examined. The catalysts were characterized by: a) atomic adsorption spectroscopy, b) N2 adsorption, c) X-ray diffraction, d) electron microscopy, e) thermogravimetry, f) X-ray photoelectron spectroscopy and g) temperature-programmed dynamic tests. Additionally, kinetic studies were performed with selected CuO-CeO2 samples. CuO-CeO2 catalysts were found to be almost ideally selective in temperatures lower than 130οC. Active and selective CuO-CeO2 catalysts were prepared with various techniques, and showed high stability with time on stream and good resistance towards Η2Ο and CO2. Based on the preparation method, the activity ranking of the catalysts was: (sol-gel) > (combustion) > (citrate- hydrothermal) > (coprecipitation) > (impregnation). The best CuO-CeO2 catalyst, prepared with a sol-gel technique, showed ~99% CO conversion, with ~87% selctivity, at 175οC (in the presence of CO2 and Η2Ο). The interaction intensity between copper oxide and ceria was generally found to depend on the activation temperature of the catalysts. At low activation temperatures, the promoting effect of ceria causes enhancement of surface area and creation of additional active sites, probably at the interface of the two phases. On the other hand, the interaction is enhanced at high activation temperatures, resulting in increase of intrinsic activity of active sites. In most of the catalytic samples, copper oxide was well dispersed on the ceria surface. In addition, the presence and stabilization of Cu1+ ions in the catalysts that were prepared with combustion, coprecipitation and sol-gel, and were activated at high temperatures, indicates the presence of strong interaction between copper v oxide and ceria, resulting to the penetration of Cu1+ ions into the first surface layers of ceria. Kinetic models, based on the redox mechanism, can describe the oxidation reactions of CO and Η2, for both pure CuO and CuO-CeO2 catalysts. The interaction between CuO and ceria results in easier reduction of oxidized active sites, compared to pure CuO. The easier reduction of these sites from CO, compared to Η2, is the cause of high selectivity of CuO-CeO2 catalysts. The activity of gold catalysts was found to depend on the surface concentration of Au, implying that well-dipersed gold nanoparticles (size of ~3 nm) are essential for the achievement of high catalytic activity. The best performance was found for the sample with 2.94 wt% Au, which had the highest value of surface concentration of gold. In this case, CO conversion higher than 99% (with 52% selectivity) was obtained at 100οC, under realistic conditions of selective CO oxidation (in the presence of CO2 and Η2Ο). Comparison of the catalytic performance of Au/α-Fe2O3, Pt/γ-Al2O3 and CuO-CeO2 catalysts, showed that the Au/α-Fe2O3 catalyst is superior for the selective oxidation of CO at relatively low operation temperatures (<80oC). At higher temperatures, best results were obtained with the CuO-CeO2 catalysts, which proved to be comparably active, and in any case more selective than the Pt/γ-Al2O3 catalyst. The presence of H2O and CO2 in the reactant mixture caused a significant decrease in the catalytic activity of Au/α-Fe2O3 and CuO-CeO2 catalysts, but didn’t affect, at least negatively, the activity of Pt/γ-Al2O3. With the exception of Au/α-Fe2O3, the CuO-CeO2 and Pt/γ-Al2O3 catalysts exhibited a stable catalytic performance for at least 7-8 days under realistic reaction conditions.

This article has been published online on 21st May 2014, in Journal of Vacuum Science & Technology A: Vac (Vol.32, Issue 4): http://scitation.aip.org/content/avs/journal/jvsta/32/4/10.1116/1.4878815?aemail=author DOI: 10.1116/1.4878815 This article may be accessed via the issue's table of contents at this link: http://scitation.aip.org/content/avs/journal/jvsta/32/4?aemail=author The surface chemistry of the bis(tri-n-butylphosphane) copper(I) acetylacetonate, [(nBu3P)2Cu(acac)], and the thermal atomic layer deposition (ALD) of Cu2O using this Cu precursor as reactant and wet oxygen as co-reactant on SiO2 substrates are studied by in-situ X-ray photoelectron spectroscopy (XPS). The Cu precursor was evaporated and exposed to the substrates kept at temperatures between 22 °C and 300 °C. The measured phosphorus and carbon concentration on the substrates indicated that most of the [nBu3P] ligands were released either in the gas phase or during adsorption. No disproportionation was observed for the Cu precursor in the temperature range between 22 °C and 145 °C. However, disproportionation of the Cu precursor was observed at 200 °C, since C/Cu concentration ratio decreased and substantial amounts of metallic Cu were present on the substrate. The amount of metallic Cu increased, when the substrate was kept at 300 °C, indicating stronger disproportionation of the Cu precursor. Hence, the upper limit for the ALD of Cu2O from this precursor lies in the temperature range between 145 °C and 200 °C, as the precursor must not alter its chemical and physical state after chemisorption on the substrate. 500 ALD cycles with the probed Cu precursor and wet O2 as co reactant were carried out on SiO2 at 145 °C. After ALD, in situ XPS analysis confirmed the presence of Cu2O on the substrate. Ex-situ spectroscopic ellipsometry indicated an average film thickness of 2.5 nm of Cu2O deposited with a growth per cycle of 0.05 Å/cycle. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) investigations depicted a homogeneous, fine, and granular morphology of the Cu2O ALD film on SiO2. AFM investigations suggest that the deposited Cu2O film is continuous on the SiO2 substrate.

Thesis (Ph. D.)--Ohio State University, 2007. / Title from first page of PDF file. Includes bibliographical references (p. 166-181).

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-11-11T17:33:21Z No. of bitstreams: 0 / Made available in DSpace on 2016-11-11T17:33:21Z (GMT). No. of bitstreams: 0 / O desenvolvimento de sistemas laser com pulsos ultracurtos trouxe a possibilidade de usinagem de estruturas muito pequenas em praticamente qualquer tipo de material. Neste trabalho foi dada continuidade a estudos já iniciados no Centro de Lasers e Aplicações (CLA) com os materiais dielétricos, introduzindo a largura temporal dos pulsos laser como mais uma variável e utilizando os conhecimentos adquiridos para a determinação de limiares de ablação e parâmetros de incubação em alguns metais como: aço AISI 1045, aço inoxidável VI138, cobre eletrolítico e molibdênio. A ausência de calor no processo de ablação dos metais torna-se muito difícil, pois a criação de uma camada de íons é muito prejudicada pela mobilidade eletrônica ao seu redor. Assim a ablação de metais com pulsos ultracurtos, tem como principal mecanismo a explosão de fase associada a outros processos que também contribuem na ablação, porém em menor escala, como a explosão coulombiana e a fusão ultrarrápida. Além disso, propriedades como a constante de acoplamento elétron-fônon e a condutividade térmica assumem um papel importante e devem ser levadas em conta na investigação do processo de ablação dos metais. Este trabalho possibilitou a obtenção de parâmetros de operação nos quais o calor transferido para a rede é minimizado, possibilitando a microusinagem de precisão e alterações controladas na morfologia da superfície de diversos metais. Os resultados propiciaram assim condições para novos desenvolvimentos e aplicações práticas de usinagem com pulsos ultracurtos. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

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Binary oxides constitute an outstanding class of functional materials with potential applications in many fields such as catalysis, gas sensing, field emission, solar cells, photodetection, etc. Due to the difference in their physical/chemical properties, different oxides have been explored for different applications. For examples, SnO2, Cr2O3 and ZnO are being explored for gas sensing due to their high adsorption capacity for volatile gases, ZnO, Cu2O etc. are being explored in solar cells because of high adsorption coefficient in UV/visible region and so on. Various techniques are available for synthesis of binary oxides and tuning their properties. Most of the physical or chemical synthesis techniques are expensive, need high cost instruments and produces hazardous chemical waste. We need a simple, cost effective and ecofriendly techniques for the synthesis of binary oxides. In present work, a simple and facile thermal oxidation strategy has been employed for the synthesis of various binary oxides (Cu2O, GeO2 and ZnO). For example, CuO nanorods are obtained when Cu is heated around ~ 500 oC, which then heated in Ar atmosphere to obtain a film of porous Cu2O. Similarly, GeO2 with different morphologies and green-luminescent ZnO are obtained by controlling the reaction parameters. These oxides have then been explored for various applications including white light phosphors, catalysis for the degradation of dyes and non-contact thermometry. Overall, we present a thermal oxidation strategy for the synthesis of various binary oxides and explore potential applications in various fields.

<div>Thermal desalination of high salinity water resources is crucial for increasing freshwater supply, but efficiency enhancements are badly needed. Nanomaterial enhancements and novel condensation regimes offer enormous potential for improving promising technologies like membrane distillation (MD). In this work, we first examined nanofluids for MD, including the role of nanoscale physics, and model system-level energy efficiency enhancements. Our model included the dominant micro-mixing from Brownian motion in fine particle nanofluids (copper oxide) and the unusually high axial conduction from phonon resonance through Van der Waals interaction in carbon nanotube nanofluids. Carbon nanotubes resulted in a consistent, wide range of improvements; while copper oxide particles showcased diminishing returns after a concentration of 0.7%, where Brownian motion effects reduced. However, the enhancements at higher concentrations from liquid layering around nanoparticles were impractical in MD, since the related high surfactant levels compromised the membrane hydrophobicity and promoted fouling. Dilute solutions of metallic nanofluids can be actively integrated to enhance the performance of MD, whereas stronger nanofluid solutions should be limited to heat exchangers that supply thermal energy to MD systems. We then investigated slippery liquid infused porous surfaces (SLIPS) for enhanced condensation rates in MD. Dropwise condensation heat transfer was modelled considering the effects of the departing, minimum droplet radii and the interfacial thermal resistances. Effective droplet shedding from these surfaces led to an experimental thermal efficiency of 95%. Alternatively, porous condensers with superior wicking properties and conductive heat transfer offered a robust solution to high salinity desalination. We modelled the onset of flooding in porous condensers using Darcy’s law for porous media, including the effects of the condenser permeability and determined the optimal condenser thickness at varying system length scales. The increased active area of condensation resulted in a significant enhancement (96.5%) in permeate production and 31.7% improvement in experimental thermal efficiency. However, porous condensers were only compatible with flat plate module designs limiting their practicality.</div>

No / A new dual-log spiral geometry is proposed for microstrip resonators, offering substantial advantages in performance and size reduction at subgigahertz frequencies when realized in superconducting materials. The spiral is logarithmic in line spacing and width such that the width of the spiral line increases smoothly with the increase of the current density, reaching its maximum where the current density is maximum (in its center for ¿/2 resonators). Preliminary results of such a logarithmic ten-turn (2 × 5 turns) spiral, realized with double-sided YBCO thin film, showed a Q.-factor seven times higher than that of a single ten-turn uniform spiral made of YBCO thin film and 64 times higher than a copper counterpart. The insertion loss of the YBCO dual log-spiral has a high degree of independence of the input power in comparison with a uniform Archimedian spiral, increasing by only 2.5% for a 30-dBm increase of the input power, compared with nearly 31% for the uniform spiral. A simple approximate method, developed for prediction of the resonant frequency of the new resonators, shows a good agreement with the test results.

In this work, an approach for copper atomic layer deposition (ALD) via reduction of CuxO films was investigated regarding applications in ULSI interconnects, like Cu seed layers directly grown on diffusion barriers (e. g. TaN) or possible liner materials (e. g. Ru or Ni) as well as non-ferromagnetic spacer layers between ferromagnetic films in GMR sensor elements, like Ni or Co. The thermal CuxO ALD process is based on the Cu (I) β-diketonate precursor [(nBu3P)2Cu(acac)] and a mixture of water vapor and oxygen ("wet O2") as co-reactant at temperatures between 100 and 130 °C. Highly efficient conversions of the CuxO to metallic Cu films are realized by a vapor phase treatment with formic acid (HCOOH), especially on Ru substrates. Electrochemical deposition (ECD) experiments on Cu ALD seed / Ru liner stacks in typical interconnect patterns are showing nearly perfectly filling behavior. For improving the HCOOH reduction on arbitrary substrates, a catalytic amount of Ru was successful introduced into the CuxO films during the ALD with a precursor mixture of the Cu (I) β-diketonate and an organometallic Ru precursor. Furthermore, molecular and atomic hydrogen were studied as promising alternative reducing agents.

Copper films with a thickness in the nanometer range are required as seed layers for the electrochemical Cu deposition to form multilevel interconnects in ultralarge-scale integrated (ULSI) electronic devices. Continuously shrinking device dimensions and increasing aspect ratios of the dual-damascene structures in the copper-based metallization schemes put ever more stringent requirements on the films with respect to their conformality in nanostructures and thickness homogeneity across large wafers. Due to its intrinsic self-limiting film growth characteristic, atomic layer deposition (ALD) appears appropriate for homogeneously coating complex substrates and to replace conventional physical vapor deposition (PVD) methods beyond the 32 nm technology node. To overcome issues of direct Cu ALD, such as film agglomeration at higher temperatures or reduced step coverage in plasma-based processes, an ALD copper oxide film may be grown under mild processing conditions, while a subsequent reduction step converts it to metallic copper. In this poster, which was presented at the AVS 9th International Conference on Atomic Layer Deposition (ALD 2009), held in Monterey, California from 19 to 22 July 2009, we report detailed film growth studies of ALD copper oxide in the self-limiting regime on SiO2, TaN and Ru. Applications in subsequent electrochemical deposition processes are discussed, comparing Cu plating results on as-deposited PVD Ru as well as with PVD and reduced ALD Cu seed layer.