Η φωτοκαταλυτική παραγωγή H2 μέσω διεργασιών φωτοκαταλυτικής αναμόρφωσης, μελετήθηκε με χρήση νανοκρυσταλλικών υμενίων TiO2 εμπλουτισμένων με εναποτεθειμένα μέταλλα στην επιφάνειά τους. Το TiO2 παρασκευάστηκε με τη μέθοδο sol-gel παρουσία οξικού οξέος και ενός επιφανειακώς δραστικού μορίου, του Triton X-100. Τα υμένια που παρασκευάστηκαν ήταν κρυσταλλικής μορφής ανατάση, με μέσο μέγεθος των σωματιδίων 12 nm, αρκετά σημαντικές υδροφιλικές ιδιότητες και υψηλή προσροφητική ικανότητα, ενώ είναι και πολύ ικανοί φωτοκαταλύτες για την αντίδραση διάσπασης των προσροφημένων χρωστικών στην επιφάνειά τους. Η μελέτη της αντίδρασης παραγωγής H2 πραγματοποιήθηκε με χρήση του φωτοκαταλύτη Pt/TiO2, αφού ο Pt αύξησε τη φωτοκαταλυτική ενεργότητα του υλικού και τη φωτοκαταλυτική απόδοση της αντίδρασης περισσότερο από τα υπόλοιπα μέταλλα. Οι βέλτιστες συνθήκες εναπόθεσης του Pt, ήταν η προσρόφησή του για 30 min από υδατικά διαλύματα Na2PtCl4 συγκέντρωσης 5*10-4 Μ και φωτοβόληση του υλικού για 15 min ώστε να πραγματοποιηθεί η αναγωγή. Η χρήση αυτού του φωτοκαταλύτη έδωσε σημαντικά αποτελέσματα φωτοκαταλυτικής αποικοδόμησης αλκοολών και άλλων προϊόντων βιομάζας σε υδατικά διαλύματα. Από τις ενώσεις που μελετήθηκαν, η χρήση της αιθανόλης και της γλυκερόλης οδήγησε στη μεγαλύτερη αύξηση του ρυθμού φωτοκαταλυτικής παραγωγής H2. Η αντίδραση της φωτοκαταλυτικής αναμόρφωσης πραγματοποιήθηκε κυρίως με χρήση υπεριώδους ακτινοβολίας UVA (Black light, ~360 nm), παρουσία ενώσεων με γενικό χημικό τύπο CxHyOz. Κυριότερες κατηγορίες αυτών των ενώσεων είναι οι αλκοόλες, τα σάκχαρα, οι πολυόλες και τα οργανικά οξέα. Επίσης, τα φωτοκαταλυτικά υμένια Pt/TiO2 είναι ικανά να προκαλέσουν την φωτοκαταλυτική παραγωγή H2 μέσα από μικρογαλακτώματα διασποράς ελαίου σε νερό. Η συνολική διεργασία της φωτοκαταλυτικής αναμόρφωσης αποτελεί μια ιδιαίτερα ελκυστική διεργασία, η οποία πραγματοποιείται με αρκετά ικανοποιητική απόδοση, με την κατάλληλη χρήση του φωτοκαταλύτη Pt/TiO2, σε μορφή λεπτών υμενίων. / Nanocrystalline titanium dioxide films, with deposited noble metals on their surface were studied for the photocatalytic production of Η2, through the so-called “photocatalytic reforming” processes. These films were deposited on glass substrates by using sol-gel procedures, carried out in the presence of acetic acid and a surfactant template, Triton X-100. The titania films consist of anatase nanocrystals, of about 12 nm average particle size. They were highly hydrophilic and were strong adsorbers of positively charged organic substances. Photodegradation of adsorbed dyes was very efficient on these titania nanoparticulate films. Photocatalytic hydrogen production was studied by using nanocrystalline films of Pt/TiO2. Pt gave the best results concerning photocatalytic activity of titanium dioxide. The best conditions of platinum deposition, through its adsorption from aqueous solutions, were 30 min of adsorption in the dark from an aqueous solution of Na2PtCl4, having a concentration of 5*10-4 M, followed by the reduction of the adsorbed ions of Pt (II) by UV treatment. Using this type of photocatalyst lead to high efficiency of photodegradation of alcohols and generally products, derived from biomass in aqueous solutions. From all the compounds examined, ethanol and glycerol gave the highest photocatalytic hydrogen production rates. The photocatalytic reforming reaction, was carried out using UVA (black light, ~360 nm) radiation, that comes from low-energy black light sources and was applied on chemical compounds that have the general chemical structure of CxHyOz. Several categories of substances may have this structure, such as alcohols, saccharides, polyols and organic acids. Also, photocatalytic nanocrystalline films Pt/TiO2 led to substantially efficient process of hydrogen production, by using colloidal dispersions of oil-in-water microemulsion. The whole process of photocatalytic reforming of several substances can be a very attractive and very promising process, by employing nanocrystalline titania films, Pt/TiO2.

No description available.

<p>When the amorphous silicon (a-Si) dangling bonds are bonded to hydrogen the concentration of the dangling bond is decreased. The resulting film is called hydrogenated amorphous silicon (a-Si:H). The reduction in the dangling bonds concentration improves the optoelectrical properties of the film. The improved properties of a-Si:H makes it possible to manufacture electronic devices including a solar cell. A solar cell device based on the hydrogenated amorphous silicon (a-Si:H) was fabricated using the Hot-Wire Chemical Vapour Deposition (HWCVD). When an n-i-p solar cell configuration is grown, the norm is that the p-doped layer is deposited from a mixture of silane (SiH4) gas with diborane (B2H6). The boron atoms from diborane bonds to the silicon atoms and because of the number of the valance electrons, the grown film becomes a p-type film. Aluminium is a group 3B element and has the same valence electrons as boron, hence it will also produce a p-type film when it bonds with silicon. In this study the p-doped layer is grown from the co-deposition of a-Si:H from SiH4 with aluminium evaporation resulting in a crystallized, p-doped thin film. When this thin film is used in the n-i-p cell configuration, the device shows photo-voltaic activity. The intrinsic layer and the n-type layers for the solar cell were grown from SiH4 gas and Phosphine (PH3) gas diluted in SiH4 respectively. The individual layers of the solar cell device were characterized for both their optical and electrical properties. This was done using a variety of experimental techniques. The analyzed results from the characterization techniques showed the films to be of device quality standard. The analysed results of the ptype layer grown from aluminium showed the film to be successfully crystallized and doped. A fully functional solar cell was fabricated from these layers and the cell showed photovoltaic activity.<br /> &nbsp / </p>

It has been debated that among all the renewable energy alternatives, only solar energy offers sufficient resources to meet energy demands. Silicon thin film solar cells are at the frontier of commercial solar technology. Hot wire chemical vapour deposition (HWCVD) is the technique of choice for silicon thin film deposition due to the absence of ion bombardment and its independence toward geometry or electromagnetic properties of the substrate, as seen by plasma enhanced chemical vapour deposition (PECVD). With the implementation of nanostructures in a multi-band gap tandem solar cell, considerable improvement has been achieved over the single junction solar cells. Defect assisted tunnelling processes at the junctions between individual solar cells in a tandem structure solar cell largely affect the efficiency of these solar cells. In this contribution, the investigation toward the improvement of silicon thin films for tandem solar cell application is initiated. This study reports on the effects of hydrogen dilution and deposition time on six silicon thin films deposited at six specific deposition regimes. The thin film properties are investigated via X-Ray diffraction analysis, Raman spectroscopy, Fourier transform infra-red spectroscopy, elastic recoil detection analysis, scanning and transmission electron microscopy and UV-visible spectroscopy. This investigation revealed the dominating etching effect of atomic hydrogen with the increase in hydrogen dilution and a bonded hydrogen content (CH) exceeding 10 at.% for each of the six thin films. The optically determined void volume fraction and static refractive index remain constant, for each thin film, with the change in CH. A new deposition procedure, utilising the deposition conditions of the previously investigated thin films, is performed by HWCVD to deposit two silicon thin films. This deposition procedure involved either increasing (protocol 1) or decreasing (protocol 2) hydrogen dilution during deposition. Structural and optical variation with depth was observed for the dynamically deposited silicon thin films, with nano-voids existing across the entire cross section and bond angle variations which are indicative of good structural order. The optical absorption curves differ for the two silicon thin films whereas the optical density remains constant for both. / >Magister Scientiae - MSc

Austenitic stainless steels are commonly used in nuclear reactors and have been considered as potential structural materials in fusion reactors due to their excellent corrosion resistance, good creep and fatigue resistance at elevated temperatures, but their relatively low yield strength and poor radiation tolerance hinder their applications in high dose radiation environments. High angle grain boundaries have long been postulated as sinks for radiation-induced defects, such as bubbles, voids, and dislocation loops. Here we provide experimental evidence that high angle grain boundaries can effectively remove radiation-induced defects. The equal channel angular pressing (ECAP) technique was used to produce ultrafine grained Fe-Cr-Ni alloy. Mechanical properties of the alloy were studied at elevated temperature by tensile tests and in situ neutron scattering measurements. Enhanced dynamic recovery process at elevated temperature due to dislocation climb lowers the strain hardening rate and ductility of ultrafine grained Fe-Cr-Ni alloy. Thermal stability of the ultrafine grained Fe-Cr-Ni alloy was examined by ex situ annealing and in situ heating within a transmission electron microscope. Abnormal grain growth at 827 K (600°C) is attributed to deformation-induced martensite, located at the triple junctions of grains. Helium ion irradiation studies on Fe-Cr-Ni alloy show that the density of He bubbles, dislocation loops, as well as irradiation hardening are reduced by grain refinement. In addition, we provide direct evidence, via in situ Kr ion irradiation within a transmission electron microscope, that high angle grain boundaries in nanocrystalline Ni can effectively absorb irradiation-induced dislocation loops and segments. The density and size of dislocation loops in irradiated nanocrystalline Ni were merely half of those in irradiated coarse grained Ni. The results imply that irradiation tolerance in bulk metals can be effectively enhanced by microstructure refinement.

Στην παρούσα ειδική ερευνητική εργασία μελετήθηκε η αγωγιμότητα σκότους και η μεταβατική φωτοαγωγιμότητα στο κενό και στον αέρα δειγμάτων υπό μορφή δισκίων συμπιεσμένης σκόνης διοξειδίου του τιτανίου (με την εμπορική ονομασία Evonik-Degussa (P25)) και δειγμάτων UP25 που προέκυψαν μετά από ανάμιξη σκόνης P25 και ουρίας (urea NH2CONH2) σε αναλογία βάρους 1:1, και τα οποία ψήθηκαν για 1 ώρα στους 450oC. Κατά το ψήσιμο καίγεται η ουρία και τροποποιεί την επιφάνεια του TiO2. Η αγωγιμότητα σκότους του δείγματος UP25 είναι μεγαλύτερη στο κενό από την αντίστοιχη του P25, γεγονός που αποδίδεται στην παρουσία της ουρίας, η οποία εισάγει κενές θέσεις οξυγόνου που δρουν σαν δότες ηλεκτρονίων. Στον αέρα η αγωγιμότητα σκότους του δείγματος UP25 είναι μικρότερη από την αντίστοιχη του P25 και αυτό οφείλεται στην προσρόφηση μορίων οξυγόνου στην επιφάνεια του TiO2, τα οποία δεσμεύουν ηλεκτρόνια και στην παρουσία αζώτου (από την ουρία), το οποίο εμποδίζει την προσρόφηση υγρασίας. Η φωτοαγωγιμότητα στο κενό φθάνει σε υψηλές τιμές και στα δυο δείγματα και εμφανίζεται ιδιαίτερα ευαίσθητη στο περιβάλλον. Η μεταβατική φωτοαγωγιμότητα αυξάνει με αργό ρυθμό στο κενό, φθάνοντας στον κόρο μετά από ημέρες και είναι σημαντικά μεγαλύτερη από αυτήν στον αέρα. Η «αύξηση» και η «μείωση» της φωτοαγωγιμότητας στον αέρα είναι πιο γρήγορη από την αντίστοιχη στο κενό και στα δυο δείγματα λόγω επανασύνδεσης. Στον αέρα η διαδικασία της επανασύνδεσης είναι ιδιαίτερα έντονη στο δείγμα UP25, καθώς η παρουσία του αζώτου μειώνει δραματικά την φωτοαγωγιμότητα λόγω της δημιουργίας μεγάλου αριθμού κέντρων επανασύνδεσης. / In the present master thesis, dark conductivity and transient photoconductivity in vacuum and in air were studied in samples of titania powder P25, which is a commercial product of Evonik-Degussa, and of UP25, prepared by mixing P25 and urea (NH2CONH2) powders in 1:1 weight ratio and consequent calcinations at 450 oC for 1 hour, in the form of pellet. The dark conductivity of UP25 is greater in vacuum than the corresponding one of P25 and this effect is attributed to urea’s presence, which introduces oxygen vacancies, that behave like electron donors. The dark conductivity in air of UP25 is lower than the corresponding one of P25, which is attributed to oxygen molecules adsorption on TiO2’s surface, which act as electron scavenger and nitrogen’s presence (by urea), which prevents water’s absorption. Photoconductivity in vacuum reaches very high values in both samples and is sensitive on the environment. Transient photoconductivity rises slowly in vacuum, saturating in days, and is much larger than that in air. The rise and the decay of the photoconductivity in air are faster than in vacuum for both samples, due to recombination. In air, the recombination process is significant mainly in sample UP25 since the nitrogen presence creates a large amount of recombination centers causing an important decrease of photoconductivity.

>Magister Scientiae - MSc / This study reports on the effects of hydrogen dilution and deposition time on six silicon thin films deposited at six specific deposition regimes. The thin film properties are investigated via X-Ray diffraction analysis, raman spectroscopy, fourier transform infra-red spectroscopy, elastic recoil detection analysis, scanning and transmission electron microscopy and UV-visible spectroscopy. This investigation revealed the dominating etching effect of atomic hydrogen with the increase in hydrogen dilution and a bonded hydrogen content (CH) exceeding 10 at.% for each of the six thin films. The optically determined void volume fraction and static refractive index remain constant, for each thin film, with the change in CH

Orientadores: Vitor Baranauskas, Alfredo Carlos Peterlevitz / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e de Computação / Made available in DSpace on 2018-08-12T10:56:53Z (GMT). No. of bitstreams: 1 Manne_GustavoAndreMograo_M.pdf: 4900447 bytes, checksum: 96ac39c8d4903a68da74c3db411b33b1 (MD5) Previous issue date: 2008 / Resumo: Esta tese apresenta um estudo do crescimento e caracterização do diamante nanocristalino crescido por deposição química a partir da fase vapor (diamante CVD), com a introdução de boro durante o crescimento. Nosso objetivo foi de produzir amostras com boas propriedades para emissão de elétrons para o vácuo por efeito do campo elétrico (FEE). As amostras foram caracterizadas por Microscopia Eletrônica de Varredura de Emissão por Campo (FESEM), micro-espectroscopia Raman e emissão de elétrons por campo elétrico. Os resultados destas caracterizações são apresentados e discutidos. / Abstract: This thesis presents a study of the growth and characterization of nano crystalline diamonds produced by the hot-filament chemical vapor deposition (CVD) with the introduction of boron during the growth process. Our objective was to produce samples with good electrical properties for field induced emission of electrons (FEE) to the vacuum. Characterization of the samples by electron microscopy, Raman micro-spectroscopy, and Field Emission measurements are presented and discussed. / Mestrado / Eletrônica, Microeletrônica e Optoeletrônica / Mestre em Engenharia Elétrica

Philosophiae Doctor - PhD / When the amorphous silicon (a-Si) dangling bonds are bonded to hydrogen the concentration of the dangling bond is decreased. The resulting film is called hydrogenated amorphous silicon (a-Si:H). The reduction in the dangling bonds concentration improves the optoelectrical properties of the film. The improved properties of a-Si:H makes it possible to manufacture electronic devices including a solar cell. A solar cell device based on the hydrogenated amorphous silicon (a-Si:H) was fabricated using the Hot-Wire Chemical Vapour Deposition (HWCVD). When an n-i-p solar cell configuration is grown, the norm is that the p-doped layer is deposited from a mixture of silane (SiH4) gas with diborane (B2H6). The boron atoms from diborane bonds to the silicon atoms and because of the number of the valance electrons, the grown film becomes a p-type film. Aluminium is a group 3B element and has the same valence electrons as boron, hence it will also produce a p-type film when it bonds with silicon. In this study the p-doped layer is grown from the co-deposition of a-Si:H from SiH4 with aluminium evaporation resulting in a crystallized, p-doped thin film. When this thin film is used in the n-i-p cell configuration, the device shows photo-voltaic activity. The intrinsic layer and the n-type layers for the solar cell were grown from SiH4 gas and Phosphine (PH3) gas diluted in SiH4 respectively. The individual layers of the solar cell device were characterized for both their optical and electrical properties. This was done using a variety of experimental techniques. The analyzed results from the characterization techniques showed the films to be of device quality standard. The analysed results of the ptype layer grown from aluminium showed the film to be successfully crystallized and doped. A fully functional solar cell was fabricated from these layers and the cell showed photovoltaic activity. / South Africa

Philosophiae Doctor - PhD / When the amorphous silicon (a-Si) dangling bonds are bonded to hydrogen the concentration of the dangling bond is decreased. The resulting film is called hydrogenated amorphous silicon (a-Si:H). The reduction in the dangling bonds concentration improves the optoelectrical properties of the film. The improved properties of a-Si:H makes it possible to manufacture electronic devices including a solar cell.A solar cell device based on the hydrogenated amorphous silicon (a-Si:H) was fabricated using the Hot-Wire Chemical Vapour Deposition (HWCVD). When an n-i-p solar cell configuration is grown, the norm is that the p-doped layer is deposited from a mixture of silane (SiH4) gas with diborane (B2H6). The boron atoms from diborane bonds to the silicon atoms and because of the number of the valance electrons, the grown film becomes a p-type film. Aluminium is a group 3B element and has the same valence electrons as boron, hence it will also produce a p-type film when it bonds with silicon.In this study the p-doped layer is grown from the co-deposition of a-Si:H from SiH4 with aluminium evaporation resulting in a crystallized, p-doped thin film. When this thin film is used in the n-i-p cell configuration, the device shows photo-voltaic activity.The intrinsic layer and the n-type layers for the solar cell were grown from SiH4 gas and Phosphine (PH3) gas diluted in SiH4 respectively. The individual layers of the solar cell device were characterized for both their optical and electrical properties. This was done using a variety of experimental techniques. The analyzed results from the characterization techniques showed the films to be of device quality standard. The analysed results of the ptype layer grown from aluminium showed the film to be successfully crystallized and doped.A fully functional solar cell was fabricated from these layers and the cell showed photovoltaic activity.