Le titanate de baryum et de strontium (BaSrTiO3) est un matériau diélectrique de synthèse à forte permittivité possédant la propriété d'être accordable lorsqu'il est soumis à un champ électrique. Ceci est lié à sa structure cristalline à maille perovskite. Son intégration dans des dispositifs capacitifs est donc prometteuse pour l'industrie de la microélectronique. Il est déposé en couches minces par pulvérisation cathodique à partir de cibles pressées à froid au sein du laboratoire. L'étude de la croissance du matériau, dopé ou non, et de ses propriétés électriques à 100 khz ont permis d'envisager une montée en fréquence. Les évolutions de la permittivité diélectrique complexe et de l'accordabilité du matériau ont ainsi pu être étudiées sur un dispositif spécifique dans une gamme de fréquences allant de 1 à 60 ghz. L'utilisation d'un logiciel de simulation numérique par éléments finis (ELFI) dans le cadre de l'étude à haute fréquence permet de remonter aux caractéristiques propres du matériau, et ainsi d'interpréter plus finement les résultats issus de l'étude en basse fréquence. L'ensemble des connaissances acquises permet finalement de développer des dispositifs à capacité variable qui sont actuellement en cours d'élaboration au sein du laboratoire.

Oxides form a class of material which covers almost all the spectra of functionalities : dielectricity, semiconductivity, metallicity superconductivity, non-linear optics, acoustics, piezoelectricity, ferroelectricity, ferromagnetism...In this thesis, crystalline oxides have beenintegrated on the workhorse of the semiconductor industry, the silicon, by Molecular Beam Epitaxy (MBE).The first great interest of the epitaxial growth of crystalline oxides on silicon consists in the application of "high-k" dielectric for future sub-22nm CMOS technology. Gadoliniumoxide was explored in detail as a promising candidate of the alternative of SiO2. The pseudomorphic epitaxial growth of Gd2O3 on Si (111) was realized by identifying the optimal growth conditions. The Gd2O3 films show good dielectric properties and particularly an EOTof 0.73nm with a leakage current consistent with the requirements of ITRS for the sub-22nmnodes. In addition, the dielectric behavior of Gd2O3 thin films was further improved by performing PDA treatments. The second research interest on crystalline oxide/Si platform results from its potential application for the "More than Moore" and "Heterogeneous integration" technologies. TheSrTiO3/Si (001) was intensively studied as a paradigm of the integration of oxides on semiconductors. The crystallinity, interface and surface qualities and relaxation process of the STO films on silicon grown at the optimal conditions were investigated and analyzed. Several optimized growth processes were carried out and compared. Finally a "substrate-like" STO thin film was obtained on the silicon substrate with good crystallinity and atomic flat surface. Based on the Gd2O3/Si and SrTiO3/Si templates, diverse functionalities were integrated on the silicon substrate, such as ferro-(piezo-)electricity (BaTiO3, PZT and PMN-PT),ferromagnetism (LSMO) and optoelectronics (Ge). These functional materials epitaxially grown on Si can be widely used for storage memories, lasers and solar cells, etc.

The requirements of the consumer market on high frequency devices have been more and more demanding over the last decades. Thus, a continuing enhancement of the devices’ performance is required in order to meet these demands. In a macro view, changing the design of the device can result in an improvement of its performance. In a micro view, the physical properties of the device materials have a strong influence on its final performance. In the case of high frequency devices based on piezoelectric materials, a natural way to improve their performance is through the improvement of the properties of the piezoelectric layer. The piezoelectric material studied in this work is AlN, which is an outstanding material among other piezoelectric materials due to its unique combination of material properties. This thesis presents results from experimental studies on the synthesis of AlN thin films in view of telecom, microelectronic and sensor applications. The main objective of the thesis is to custom design the functional properties of AlN to best suit these for the specific application in mind. This is achieved through careful control of the crystallographic structure and texture as well as film composition. The piezoelectric properties of AlN films were enhanced by doping with Sc. Films with different Sc concentrations were fabricated and analyzed, and the coupling coefficient (kt2) was enhanced a factor of two by adding 15% of Sc to the AlN films. The enhancement of kt2 is of interest since it can contribute to a more relaxed design of high frequency devices. Further, in order to obtain better deposition control of c-axis tilted AlN films, a new experimental setup were proposed. When this novel setup was used, films with well-defined thicknesses and tilt uniformity were achieved. Films with such characteristics are very favorable to use in sensors based on electroacoustic devices operating in viscous media. Studies were also performed in order to obtain c-axis oriented AlN films deposited directly on Si substrates at reduced temperatures. The deposition technique used was HiPIMS, and the results indicated significant improvements in the film texture when comparing to the conventional Pulsed DC deposition process.

Θέμα της παρούσας ερευνητικής εργασίας είναι η μελέτη διατάξεων MOS σε υπόστρωμα Ge τύπου –p. Ως διηλεκτρικό πύλης χρησιμοποιήθηκε Al2O3 και ως μέταλλο πύλης Pt. Τέτοιες διατάξεις οι οποίες αποτελούνται από υπόστρωμα Ge στο οποίο εναποτίθεται διηλεκτρικό υψηλής διηλεκτρικής σταθεράς (high-k dielectric) εμφανίζουν ιδιαίτερο ερευνητικό και τεχνολογικό ενδιαφέρον για τους παρακάτω κυρίως λόγους: (i) Το Ge εμφανίζει υψηλότερη ευκινησία φορέων έναντι αυτής του Si. Eπομένως η χρήση υποστρωμάτων Ge στις διατάξεις MOS θεωρείται πλεονεκτική έναντι της χρήσης υποστρωμάτων Si, τα οποία μέχρι σήμερα έχουν μονοπωλήσει τις τεχνολογικές εφαρμογές και κατ’ επέκταση την έρευνα γύρω από αυτές. (ii) Η χρήση υλικών υψηλής διηλεκτρικής σταθεράς, όπως το Al2O3, ως διηλεκτρικά πύλης φέρεται πλέον ως ιδιαίτερα ελπιδοφόρα για την μελλοντική κατασκευή λειτουργικών διατάξεων MOS. (iii) Πρόσφατες μελέτες έχουν αποδείξει ότι, κατά την ανάπτυξη Al2O3 στα υποστρώματα Ge, στη διεπιφάνεια Ge/Al2O3, δημιουργείται ένα λεπτό στρώμα οξειδίου του γερμανίου, το οποίο αποτελεί βασική προϋπόθεση για την κατασκευή λειτουργικών CMOS δομών. Η ανάπτυξη των υμενίων Al2O3 στα υποστρώματα Ge έγινε με την τεχνική Eναπόθεσης Ατομικού Στρώματος (Atomic Layer Deposition- ALD), η οποία είναι μια από τις πιο διαδεδομένες και πολλά υποσχόμενες τεχνικές στον τομέα της Μικροηλεκτρονικής. Βασικά πλεονεκτήματα της μεθόδου αυτής έναντι άλλων μεθόδων εναπόθεσης (CVD, MBE κ.λπ.), είναι η άριστη ποιότητα και ομοιογένεια των αναπτυσσόμενων υμενίων, καθώς και ο απόλυτος έλεγχος του πάχους τους. Στόχος της εργασίας αυτής, είναι η μελέτη των ηλεκτρικών ιδιοτήτων δομών p-Ge/Al2O3/Pt, καθώς και της διεπιφάνειας Ge/Al2O3. Παρασκευάστηκαν δομές με πάχος διηλεκτρικού (Al2O3) 5nm, 10nm,15nm και 25nm σε θερμοκρασία εναπόθεσης 300oC. Ο δομικός χαρακτηρισμός των δειγμάτων έγινε με φασματοσκοπία XPS (X-ray Photoelectron Spectroscopy), ενώ ο ηλεκτρικός τους χαρακτηρισμός έγινε με τη μέθοδο της Διηλεκτρικής Φασματοσκοπίας Ευρέως Φάσματος (Broadband Dielectric Spectroscopy-BDS) στην περιοχή συχνοτήτων από 100Ηz έως 1ΜΗz. Τα αποτελέσματα της μελέτης του δομικού χαρακτηρισμού έδειξαν, ότι αυξανομένου του πάχους του υμενίου Al2O3, το πάχος του αναπτυσσόμενου Οξειδίου του Γερμανίου (GeOx) αυξάνεται. Παράλληλα υπάρχει ένδειξη πιθανής αλλαγής της στοιχειομετρίας του GeOx. Ο ηλεκτρικός χαρακτηρισμός των δομών αυτών, πραγματοποιήθηκε με παράμετρο αφενός μεν το πάχος του Al2O3 σε θερμοκρασία περιβάλλοντος, αφετέρου δε με παράμετρο τη θερμοκρασία, στην περιοχή θερμοκρασιών από 78Κ - 200Κ. Ελήφθησαν οι χαρακτηριστικές C-V και C-f, από τις οποίες προκύπτουν τα συμπεράσματα που αφορούν στην ηλεκτρική συμπεριφορά των δομών αλλά και στην ποιότητα της διεπιφάνειας Ge / Al2O3. Σε όλες τις δομές, ανεξαρτήτως του πάχους του Al2O3, οι χαρακτηριστικές C-V παρουσιάζουν την τυπική συμπεριφορά της δομής MOS, με διάκριτες τις τρεις περιοχές συσσώρευσης, απογύμνωσης και αναστροφής φορέων. Οι χαρακτηριστικές C-V σε θερμοκρασία περιβάλλοντος παρουσίασαν, σε όλα τα πάχη, φαινόμενα γένεσης – επανασύνδεσης φορέων, τα οποία εμφανίζονται υπό τη μορφή “γονάτων” στην περιοχή απογύμνωσης/ασθενούς αναστροφής. Τα φαινόμενα αυτά συνδέονται άμεσα με το μικρό ενεργειακό χάσμα του Ge και το μεγάλο πλήθος ενδογενών φορέων αγωγιμότητας που χαρακτηρίζει το Ge στη θερμοκρασία περιβάλλοντος. Αυτά τα φαινόμενα δεν παρατηρούνται στις χαμηλές θερμοκρασίες. Επιπλέον, από τις μετρήσεις C-f και εφαρμόζοντας τη μεθόδου αγωγιμότητας (conductance method), η οποία εφαρμόστηκε σε όλες τις θερμοκρασίες, προέκυψαν οι τιμές της πυκνότητας των διεπιφανειακών καταστάσεων, Dit’s, των δομών αυτών. Από τα αποτελέσματα αυτά, προκύπτει το συμπέρασμα ότι οι τιμές των Dit’s στη θερμοκρασία περιβάλλοντος εμφανίζονται αυξημένες σε σχέση με τις αντίστοιχες στις χαμηλές θερμοκρασίες. Η υπερεκτίμηση αυτή, η οποία μπορεί να φτάσει και τις 2 τάξεις μεγέθους, οφείλεται στην εμφάνιση των “γονάτων” στη χαρακτηριστική C-V. Επομένως το πραγματικό πλήθος των διεπιφανειακών καταστάσεων υπολογίζεται από την ανάλυση των πειραματικών μετρήσεων στις χαμηλές θερμοκρασίες. Επιπλέον, προκύπτει το συμπέρασμα ότι, η πυκνότητα διεπιφανειακών καταστάσεων, Dit’s στις δομές με το μικρότερο πάχος είναι μικρότερη από την αντίστοιχη σε παχύτερες δομές. Η συμπεριφορά αυτή έρχεται σε αντίθεση με την αναμενόμενη και η ερμηνεία της, πιθανώς να συνδέεται με τα αποτελέσματα της φασματοσκοπίας XPS σύμφωνα με τα οποία, αυξανομένου του πάχους του Al2O3, υπάρχουν ενδείξεις μεταβολής της στοιχειομετρίας του Οξειδίου του Γερμανίου. / The subject of the present research work is the study of MOS structures on p- type Ge substrates. Al2O3 was used as gate dielectric and Pt as metal gate. Such devices, which are comprised by Ge substrate on which a high -k dielectric material is deposited, are of high scientific and technological interest for the following reasons: (i) Ge shows higher carrier mobility compared to that of Si. Therefore, the use of Ge substrates in MOS devices is considered advantageous compared to Si substrates, which up to date have been used exclusively for technological applications. (ii) The use of high -k materials seems to be more promising for the construction of functional MOS structures. (iii) Recent results have shown that a thin layer of Ge oxide builds up at the Ge/Al2O3 interface during the deposition of Al2O3 on Ge. This is a basic requirement for the operation of CMOS devises. In the current work, Al2O3 films were deposited on Ge substrates by Atomic Layer Deposition (ALD). ALD is one of the most widespread and very promising techniques in microelectronics. Basic advantages of this method, compared to other deposition techniques (e.g. CVD, MBE and others), are the quality and homogeneity of the films as well as the absolute control of their thickness. The purpose of the present work is the study of the electrical properties of Ge/ Al2O3 /Pt structures as well as of the quality of the Ge/ Al2O3 interface. Structures with Al2O3 thickness of 5 nm, 10 nm, 15 nm and 25 nm were prepared, at deposition temperature of 3000C. The structural characterization of the samples was performed by means of X-Ray Photoelectron Spectroscopy –XPS whereas the electrical characterization was performed with the Broadband Dielectric Spectroscopy- BDS in the frequency range from 100 Hz to 1 MHz. The XPS results suggest that the thickness of the Ge oxide (GeOx), grown during deposition, increases by increasing the thickness of the deposited Al2O3 films. Furthermore, there is evidence of possible change in the stoichiometry of GeOx. The electrical behaviour of these structures was determined using as parameters either the thickness of Al2O3 at room temperature or the temperature at constant thickness. Measurements were performed in the range of 78 oC to 200 oC. C-V and C-f characteristics were constructed, from which conclusions are drawn regarding the electrical behaviour of the structures and the quality of the interface Ge/ Al2O3. The C-V characteristics of all samples, show the typical behaviour of a MOS structure with the three distinct regions of accumulation, depletion and inversion, regardless the thickness of Al2O3. The C-V characteristics at room temperature show generation-recombination phenomena, which are demonstrated through “humps” in depletion / weak inversion regime. These phenomena are intimately connected with the small energy gap and the large density of intrinsic conductivity carriers of Ge. These “humps” do not appear at low temperatures, below 170K, indicating that “generation-recombination” phenomena have been suppressed by reducing temperatures. Furthermore, from C-f measurements the values of the interfacial trap density (Dit) were determined through the conductance method, in all temperatures. The Dit values at room temperature seem to be overestimated compared to those at low temperatures due to the “generation- recombination” phenomena. Therefore, the actual density of interfacial traps is determined from the analysis at low temperatures. Furthermore, the Dit values of the Al2O3 -10nm structure are lower compared to those of the Al2O3 -25nm structure. This behavior, which is in contradiction to the expected one, is connected with the XPS results, according to which there is evidence of change in the stoichiometry of Ge oxide as the thickness of Al2O3 is increased.

Les mémoires flash sont intégrées dans presque tous les aspects de la vie moderne car leurs uns et zéros représentent les données stockées sur les cartes à puce et dans les capteurs qui nous entourent. Dans les mémoires flash à grille flottante ces données sont représentées par la quantité de charge stockée sur une grille en poly-Si, isolée par un oxyde tunnel et un diélectrique entre grilles (IGD). Au fur et à mesure que les chercheurs et les ingénieurs de l'industrie microélectronique poussent continuellement les limites de mise à l'échelle, la capacité des dispositifs à contenir leurs informations risque de devenir compromise. Même la perte d'un électron par jour est trop élevée et entraînerait l'absence de conservation des données pendant dix ans. Étant trop faibles, les courants de fuite sont impossible à mesurer directement. Cette thèse présente une nouvelle méthode, la séparation du stress aux oxydes (OSS), pour mesurer ces courants en suivant les changements de la tension de seuil de la cellule flash. La nouveauté de la technique est que les conditions de polarisation sont sélectionnées afin que le stress se produise entièrement dans l'IGD, permettant la reconstruction d'une courbe IV de l'IGD à des tensions faibles. Cette thèse décrit également les changements de processus nécessaires pour intégrer la première mémoire flash embarquée de 40 nm basée sur un IGD d'alumine, en remplacement du SiO2/ Si3N4/SiO2 standard. L'intérêt pour les matériaux high-k vient de la motivation de créer un IGD qui est électriquement mince pour augmenter le couplage tout en étant physiquement épais pour bloquer le transport de charge. Comme la flash intégrée au noeud de 40 nm se rapproche de la production, l'approche à prendre dans les nœuds futurs doit également être discutée. Cela fournit la motivation pour le chapitre final de la thèse qui traite de la co-intégration des différents IGD avec des dispositifs logiques ayant les gilles « high-k metal » nécessaires à 28 nm et au-delà. / Flash memory circuits are embedded in almost every aspect of modern life as their ones and zeros represent the data that is stored on smart cards and in the sensors around us. In floating gate flash memories this data is represented by the amount of charge stored on a poly-Si gate, isolated by a tunneling oxide and an Inter Gate Dielectric (IGD). As the microelectronics industry’s researchers and engineering continuously push the scaling limits, the ability of the devices to hold their information may become compromised. Even the loss of one electron per day is too much and would result in the failure to retain the data for ten years. At such low current densities, the direct measurement of the leakage current is impossible. This thesis presents a new way, Oxide Stress Separation, to measure these currents by following the changes in the threshold voltage of the flash cell. The novelty of the technique is that the biasing conditions are selected such that the stress occurs entirely in the IGD, allowing for the reconstruction of an IV curve of the IGD at low biases. This thesis also describes the process changes necessary to integrate the world’s first 40 nm embedded flash based on an alumina IGD, in replacement of the standard SiO2/Si3N4/SiO2. The interest in high-k materials comes from the motivation to make an IGD that is electrically thin to increase coupling while being physically thick to block charge transport. As embedded flash at the 40 nm node nears production, the approach to be taken in future nodes must also be discussed. This provides the motivation for the final chapter of the thesis which discusses the co-integration of the different IGDs with logic devices having the high-k metal gates necessary at 28 nm and beyond.

O estágio pós-colisional Neoproterozoico no sul do Brasil é marcado por intenso magmatismo granítico controlado por zonas de cisalhamento transcorrentes, relacionadas ao Cinturão de Cisalhamento Sul-brasileiro (CCSb). O CCSb controlou a ascensão e o posicionamento de magmas crustais e mantélicos. Neste contexto, O Granito Corre-mar (GCM) representa uma pequena intrusão posicionado em uma zona de baixa deformação localizada entre dois importantes segmentos do CCSb: as Zonas de Cisalhamento Major Gercino e Itajaí- Perimbó. O GCM possui um diagnóstico par de foliações subevetical que forma um par S-C sinistral, presente em todas as intrusões, independentemente do tamanho, e foi posicionado em um sistema conjugado, onde um cisalhamento sinistral de direção NNE, e uma extensão na direção NW-SE, gerando espaço ao longo da direção NE. Deformação de estado sólido associada ao cisalhamento NNE é atestado por microestruturas como recristalização de feldspatos e caudas de recristalização assimétricas. A abertura é atribuída à dinâmica regional destral transcorrente das zonas de cisalhamento Major Gercino e Itajaí-Perimbó, sendo que o posicionamento foi controlado essencialmente pela componente de estensão NW-SE. A idade de cristalização em zircão U-Pb LAMC- ICP-MS do GCM de 615 ± 4 Ma, muito próxima a outros granitos regionais, como as idades de 611 Ma do Granito Serra dos Macacos (GSM) e de 620 Ma do Granito Rio Pequeno (GRP) sugere que esses três corpos graníticos são sincrônicos. As fortes feições de deformação presents no GCM, diferentemente dos granitos Neoproterozoicos próximos, demonstra que o espaço, mais do que o tempo, pode explicar a diferença dos padrões estruturais identificados no GCM. Assinaturas geoquímicas e de isótopos de Sr-Nd, como caráter levemente peraluminoso, altos conteúdos de K, altas razões de ETRL/ETRP, moderados conteúdos de Rb, Nb, Zr e ETR em relação à SiO2, juntamente com baixas razões de 86Sr/87Sri e valores de εNdt fortemente negativos, indicam que o GCM é derivado de fontes crustais antigas, possivelmente relacionadas à rochas quartzofeldspáticas ortognáissicas Paleoproterozoicas do Complexo Camboriú. A relaçãodas das idades das heranças Arqueanas a Paleoproterozoicas do GCM com as idades dos eventos de migmatização identificados no Complexo Camboriú, além da relação das idades de cristalização de ~615-611 Ma dos granitos crustais da área com o último evento de migmatização em 640-610, reforça a conexão genética entre eles. As idades TDM paleoproterozoicas, as assinaturas geoquímicas e isotópicas, a cristalização e as idades de heranças do GCM e do GSM atestam que eles representam pulsos graníticos contemporâneos e comagmáticos, com uma conexão genética com o evento de migmatização Neoproterozoico do Complexo Camboriú. / The Neoproterozoic post-collisional stage in south Brazil is marked by intense granitic magmatism controlled by transcurrent shear zones all related to the Southern Brazilian Shear Belt (SBSB). The SBSB controls the ascent and emplacement of crustal and mantle magmas. In such scenario, the Corre-mar Granite (CMG), represent a small intrusion emplaced in a low strain zone located between two important segments of the SBSB: the Major Gercino and Itajaí-Perimbó Shear Zones. The CMG have a diagnostic subvertical foliation pair that form a sinistral S-C pair, present in all intrusions regardless of their size, and was emplaced within a conjugate system, where sinistral NNE shearing and NW-SE extension were both active, generating space along the NE direction. Solid state deformation associated to the NNE shearing is attested by microstructures as feldspar recrystallization and asymmetric recrystallization tails. The opening is attributed to the regional dextral transcurrent dynamics of the Major Gercino and Itajaí-Perimbó shear zones and magma emplacement was essentially conditioned by the NW extension component. The zircon U-Pb LA-MC-ICP-MS crystallization age of CMG at 615 ± 4 Ma, very close to other regional granites, as the 611 Ma Serra dos Macacos (SMG) and 620 Ma Rio Pequeno Granite (RPG) points these three granitic bodies as quite synchronous. The strong deformation features present in the CMG, as opposed to the other nearby Neoproterozoic granites (RPG and SMG) demonstrate that space, rather than time, must be called upon to explain the difference in the structural patterns identified in the CMG. Geochemical and Sr-Nd isotopic signatures, as slight peraluminous character, high-K contents, high LREE/HREE ratios, moderate Rb, Nb, Zr, and REE contents to regular SiO2, together with low 86Sr/87Sri and the strongly negative εNdt values indicate that the CMG is derived from old crustal sources possibly related to the Paleoproterozoic Camboriú Complex quartz-feldspatic orto-gneissic rocks. The match of the Archean to Paleoproterozoic inheritance ages of the CMG with the migmatization event ages identified in the Camboriú Complex and moreover the match of the crystallization ages of ~615-611 Ma of the crustalderived granites with the last migmatization event at 640-610 Ma reinforces the genetic link between them. The Paleoproterozoic TDM ages, the geochemical and isotopic signatures, the crystallization and inheritance ages resemblance of the CMG and the SMG attest that they represent comagmatic and contemporaneous granitic pulses with a genetic connection with the Neoproterozoic migmatization event in the Camboriu Complex.

O estágio pós-colisional Neoproterozoico no sul do Brasil é marcado por intenso magmatismo granítico controlado por zonas de cisalhamento transcorrentes, relacionadas ao Cinturão de Cisalhamento Sul-brasileiro (CCSb). O CCSb controlou a ascensão e o posicionamento de magmas crustais e mantélicos. Neste contexto, O Granito Corre-mar (GCM) representa uma pequena intrusão posicionado em uma zona de baixa deformação localizada entre dois importantes segmentos do CCSb: as Zonas de Cisalhamento Major Gercino e Itajaí- Perimbó. O GCM possui um diagnóstico par de foliações subevetical que forma um par S-C sinistral, presente em todas as intrusões, independentemente do tamanho, e foi posicionado em um sistema conjugado, onde um cisalhamento sinistral de direção NNE, e uma extensão na direção NW-SE, gerando espaço ao longo da direção NE. Deformação de estado sólido associada ao cisalhamento NNE é atestado por microestruturas como recristalização de feldspatos e caudas de recristalização assimétricas. A abertura é atribuída à dinâmica regional destral transcorrente das zonas de cisalhamento Major Gercino e Itajaí-Perimbó, sendo que o posicionamento foi controlado essencialmente pela componente de estensão NW-SE. A idade de cristalização em zircão U-Pb LAMC- ICP-MS do GCM de 615 ± 4 Ma, muito próxima a outros granitos regionais, como as idades de 611 Ma do Granito Serra dos Macacos (GSM) e de 620 Ma do Granito Rio Pequeno (GRP) sugere que esses três corpos graníticos são sincrônicos. As fortes feições de deformação presents no GCM, diferentemente dos granitos Neoproterozoicos próximos, demonstra que o espaço, mais do que o tempo, pode explicar a diferença dos padrões estruturais identificados no GCM. Assinaturas geoquímicas e de isótopos de Sr-Nd, como caráter levemente peraluminoso, altos conteúdos de K, altas razões de ETRL/ETRP, moderados conteúdos de Rb, Nb, Zr e ETR em relação à SiO2, juntamente com baixas razões de 86Sr/87Sri e valores de εNdt fortemente negativos, indicam que o GCM é derivado de fontes crustais antigas, possivelmente relacionadas à rochas quartzofeldspáticas ortognáissicas Paleoproterozoicas do Complexo Camboriú. A relaçãodas das idades das heranças Arqueanas a Paleoproterozoicas do GCM com as idades dos eventos de migmatização identificados no Complexo Camboriú, além da relação das idades de cristalização de ~615-611 Ma dos granitos crustais da área com o último evento de migmatização em 640-610, reforça a conexão genética entre eles. As idades TDM paleoproterozoicas, as assinaturas geoquímicas e isotópicas, a cristalização e as idades de heranças do GCM e do GSM atestam que eles representam pulsos graníticos contemporâneos e comagmáticos, com uma conexão genética com o evento de migmatização Neoproterozoico do Complexo Camboriú. / The Neoproterozoic post-collisional stage in south Brazil is marked by intense granitic magmatism controlled by transcurrent shear zones all related to the Southern Brazilian Shear Belt (SBSB). The SBSB controls the ascent and emplacement of crustal and mantle magmas. In such scenario, the Corre-mar Granite (CMG), represent a small intrusion emplaced in a low strain zone located between two important segments of the SBSB: the Major Gercino and Itajaí-Perimbó Shear Zones. The CMG have a diagnostic subvertical foliation pair that form a sinistral S-C pair, present in all intrusions regardless of their size, and was emplaced within a conjugate system, where sinistral NNE shearing and NW-SE extension were both active, generating space along the NE direction. Solid state deformation associated to the NNE shearing is attested by microstructures as feldspar recrystallization and asymmetric recrystallization tails. The opening is attributed to the regional dextral transcurrent dynamics of the Major Gercino and Itajaí-Perimbó shear zones and magma emplacement was essentially conditioned by the NW extension component. The zircon U-Pb LA-MC-ICP-MS crystallization age of CMG at 615 ± 4 Ma, very close to other regional granites, as the 611 Ma Serra dos Macacos (SMG) and 620 Ma Rio Pequeno Granite (RPG) points these three granitic bodies as quite synchronous. The strong deformation features present in the CMG, as opposed to the other nearby Neoproterozoic granites (RPG and SMG) demonstrate that space, rather than time, must be called upon to explain the difference in the structural patterns identified in the CMG. Geochemical and Sr-Nd isotopic signatures, as slight peraluminous character, high-K contents, high LREE/HREE ratios, moderate Rb, Nb, Zr, and REE contents to regular SiO2, together with low 86Sr/87Sri and the strongly negative εNdt values indicate that the CMG is derived from old crustal sources possibly related to the Paleoproterozoic Camboriú Complex quartz-feldspatic orto-gneissic rocks. The match of the Archean to Paleoproterozoic inheritance ages of the CMG with the migmatization event ages identified in the Camboriú Complex and moreover the match of the crystallization ages of ~615-611 Ma of the crustalderived granites with the last migmatization event at 640-610 Ma reinforces the genetic link between them. The Paleoproterozoic TDM ages, the geochemical and isotopic signatures, the crystallization and inheritance ages resemblance of the CMG and the SMG attest that they represent comagmatic and contemporaneous granitic pulses with a genetic connection with the Neoproterozoic migmatization event in the Camboriu Complex.

O estágio pós-colisional Neoproterozoico no sul do Brasil é marcado por intenso magmatismo granítico controlado por zonas de cisalhamento transcorrentes, relacionadas ao Cinturão de Cisalhamento Sul-brasileiro (CCSb). O CCSb controlou a ascensão e o posicionamento de magmas crustais e mantélicos. Neste contexto, O Granito Corre-mar (GCM) representa uma pequena intrusão posicionado em uma zona de baixa deformação localizada entre dois importantes segmentos do CCSb: as Zonas de Cisalhamento Major Gercino e Itajaí- Perimbó. O GCM possui um diagnóstico par de foliações subevetical que forma um par S-C sinistral, presente em todas as intrusões, independentemente do tamanho, e foi posicionado em um sistema conjugado, onde um cisalhamento sinistral de direção NNE, e uma extensão na direção NW-SE, gerando espaço ao longo da direção NE. Deformação de estado sólido associada ao cisalhamento NNE é atestado por microestruturas como recristalização de feldspatos e caudas de recristalização assimétricas. A abertura é atribuída à dinâmica regional destral transcorrente das zonas de cisalhamento Major Gercino e Itajaí-Perimbó, sendo que o posicionamento foi controlado essencialmente pela componente de estensão NW-SE. A idade de cristalização em zircão U-Pb LAMC- ICP-MS do GCM de 615 ± 4 Ma, muito próxima a outros granitos regionais, como as idades de 611 Ma do Granito Serra dos Macacos (GSM) e de 620 Ma do Granito Rio Pequeno (GRP) sugere que esses três corpos graníticos são sincrônicos. As fortes feições de deformação presents no GCM, diferentemente dos granitos Neoproterozoicos próximos, demonstra que o espaço, mais do que o tempo, pode explicar a diferença dos padrões estruturais identificados no GCM. Assinaturas geoquímicas e de isótopos de Sr-Nd, como caráter levemente peraluminoso, altos conteúdos de K, altas razões de ETRL/ETRP, moderados conteúdos de Rb, Nb, Zr e ETR em relação à SiO2, juntamente com baixas razões de 86Sr/87Sri e valores de εNdt fortemente negativos, indicam que o GCM é derivado de fontes crustais antigas, possivelmente relacionadas à rochas quartzofeldspáticas ortognáissicas Paleoproterozoicas do Complexo Camboriú. A relaçãodas das idades das heranças Arqueanas a Paleoproterozoicas do GCM com as idades dos eventos de migmatização identificados no Complexo Camboriú, além da relação das idades de cristalização de ~615-611 Ma dos granitos crustais da área com o último evento de migmatização em 640-610, reforça a conexão genética entre eles. As idades TDM paleoproterozoicas, as assinaturas geoquímicas e isotópicas, a cristalização e as idades de heranças do GCM e do GSM atestam que eles representam pulsos graníticos contemporâneos e comagmáticos, com uma conexão genética com o evento de migmatização Neoproterozoico do Complexo Camboriú. / The Neoproterozoic post-collisional stage in south Brazil is marked by intense granitic magmatism controlled by transcurrent shear zones all related to the Southern Brazilian Shear Belt (SBSB). The SBSB controls the ascent and emplacement of crustal and mantle magmas. In such scenario, the Corre-mar Granite (CMG), represent a small intrusion emplaced in a low strain zone located between two important segments of the SBSB: the Major Gercino and Itajaí-Perimbó Shear Zones. The CMG have a diagnostic subvertical foliation pair that form a sinistral S-C pair, present in all intrusions regardless of their size, and was emplaced within a conjugate system, where sinistral NNE shearing and NW-SE extension were both active, generating space along the NE direction. Solid state deformation associated to the NNE shearing is attested by microstructures as feldspar recrystallization and asymmetric recrystallization tails. The opening is attributed to the regional dextral transcurrent dynamics of the Major Gercino and Itajaí-Perimbó shear zones and magma emplacement was essentially conditioned by the NW extension component. The zircon U-Pb LA-MC-ICP-MS crystallization age of CMG at 615 ± 4 Ma, very close to other regional granites, as the 611 Ma Serra dos Macacos (SMG) and 620 Ma Rio Pequeno Granite (RPG) points these three granitic bodies as quite synchronous. The strong deformation features present in the CMG, as opposed to the other nearby Neoproterozoic granites (RPG and SMG) demonstrate that space, rather than time, must be called upon to explain the difference in the structural patterns identified in the CMG. Geochemical and Sr-Nd isotopic signatures, as slight peraluminous character, high-K contents, high LREE/HREE ratios, moderate Rb, Nb, Zr, and REE contents to regular SiO2, together with low 86Sr/87Sri and the strongly negative εNdt values indicate that the CMG is derived from old crustal sources possibly related to the Paleoproterozoic Camboriú Complex quartz-feldspatic orto-gneissic rocks. The match of the Archean to Paleoproterozoic inheritance ages of the CMG with the migmatization event ages identified in the Camboriú Complex and moreover the match of the crystallization ages of ~615-611 Ma of the crustalderived granites with the last migmatization event at 640-610 Ma reinforces the genetic link between them. The Paleoproterozoic TDM ages, the geochemical and isotopic signatures, the crystallization and inheritance ages resemblance of the CMG and the SMG attest that they represent comagmatic and contemporaneous granitic pulses with a genetic connection with the Neoproterozoic migmatization event in the Camboriu Complex.

The scaling down of Complementary Metal Oxide Semiconductor (CMOS) transistors to sub-100nm requires replacement of conventional Silicon dioxide layer with high dielectric constant (K) material for gate dielectric. Among the various high-K dielectrics that have been studied, HfO2 is found to be a promising candidate because of its high dielectric constant (~25), large band gap (5.68 eV), thermodynamic stability and good interface with Si. The HfO2 films have already been deposited using different growth techniques such as Atomic layer Deposition (ALD), Metalorgonic Chemical Vapor Deposition (MOCVD) and Pulsed Laser Deposition (PLD). Ion Assisted Deposition (IAD) is a novel technique that has been successfully employed to produce optical coatings of required quality. This growth technique presents many advantages over the other techniques such as formation from solid oxide sources, low growth temperatures (25-3000C) and film densification by ion bombardment. Hence this technique has been used to prepare HfO2 films in the present investigations. This thesis presents the structural, optical and electrical properties of HfO2 thin films prepared by Ion assisted deposition (IAD). The suitability of Ion assisted deposition process and the importance of investigations on the influence of process parameters on the film characteristics have been brought out in the process parameters-structure-composition and properties correlation presented in this thesis. The aim of this work is to process and characterize HfO2 films and investigate the influence of process parameters on the structure, composition and properties of the films to identify their suitability for CMOS gate applications. HfO2 films were deposited on p-type Si (100) wafers by Ion assisted deposition in an electron beam evaporation (Leybold,L-560) system. Pre-bombardment of the substrates with Argon ions has been done to remove any native oxide layer formation on Silicon by using a hallow cathode ion source (DENTON VACUUM CC103). During the film deposition a collimated oxygen ion beam, generated from the ion source is directed towards the substrate. The oxygen ion current is controlled by adjusting the voltage applied to the ion source and the oxygen flow through the ion source. The oxygen ions bombard the film as it grows and in that process improves its packing density as well as its stoichiometry. Keeping the deposition rate and thickness constant, HfO2 films have been deposited by varying Ion Current, Ion energy and substrate temperature. MOS capacitors were fabricated with Aluminum as gate electrode deposited by thermal evaporation. Ellipsometry techniques have been used to measure the optical thickness of the films. The interfacial layer (IL) formed at the HfO2/ Si interface was investigated by using Fourier transform Infrared spectroscopy (FT-IR). The structural characterization was carried out by X-ray diffraction technique. The high frequency capacitance-voltage and DC leakage current characteristics were measured to analyze the electrical characteristics of MOS capacitors. The effect of post deposition annealing (PDA) of the films at 600°C and 700ºC in Forming Gas (15%H2+85%N2) ambient and Post metallization annealing (PMA) at 400ºC in the same ambient was also investigated to observe the changes in electrical characteristics. The initial step of this work was to compare the characteristics of the films deposited by reactive evaporation and Ion assisted deposition which confirmed the superiority of the quality of IAD coatings and justified the need to proceed further with a more detailed study on the influence of various parameters on the properties of IAD coatings. HfO2 films deposited on substrates maintained at 1000C exhibited better structural, Optical and Electrical properties. The leakage current in these films were lower which has been attributed to silicate free interface as confirmed by XRD studies. Investigations on films deposited with oxygen ion beams of different currents in the range 20 to 40mA indicated that the films deposited at 20mA ion current showed better electrical properties. Better stoichiometry of these films as indicated by FT IR studies was one of the reasons for their improved performance. Annealing of these films at 6000C and 7000C in FGA medium resulted in creation of silicates and silicides at the interface thereby increasing the leakage currents and degraded the film properties. The films deposited with oxygen ion beams generated with a driving voltage 265V showed better structural and optical properties with silicate free interface compared with low and high driving voltages. Among all the films, the maximum dielectric constant of about 21.9 with a minimum EOT of 5.5 nm corresponding to a film deposited at ion current 20mA with PMA 400°C in FG ambient for 20minites is achieved. The lowest value of interface charge density achieved is 2.7 x1012 per cm-2 eV-1 corresponding to the sample deposited at substrate temperature 100°C with deposition rate of 0.5Å/sec followed by post metallization annealing at 400°C in forming gas for 20minutes. The range of Dit values that were obtained are varying from 2.7x 1012 – 16.7x1012 cm-2eV-1.It was also found that, the samples deposited at higher ion currents show lower Dit values than the samples deposited at lower ion currents. From the I−V analysis, the leakage current density is found to be comparatively less in IAD than in reactive evaporation. Leakage current increases with increase in substrate temperature and the same trend is observed with annealed films also. The lowest leakage current density of 1.05x10–8 A/cm2 at a gate bias of 1V was observed in the films deposited at substrate temperature 1000C. The present thesis focused on the suitability of the Ion Assisted deposition process for the preparation of HfO2 films for high-K gate dielectric application and the importance of investigations on the influence of process parameters on the film characteristics.

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