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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
31

Understanding the first formation stages of (Y,Ti) nano-oxides in Oxide Dispersion Strengthened (ODS) steels / Compréhension des premiers stades de formation des nano-précipités (Y, Ti, O) dans les aciers ODS (Oxide Dispersion Strengthened)

Owusu-Mensah, Martin 26 September 2019 (has links)
Les aciers appelés ODS (pour Oxide Dispersion Strengthened), renforcés par une dispersion homogène de nano-oxydes, sont des matériaux de structure avancés pour les futurs réacteurs nucléaires de fusion et de fission. En effet ces nano-oxydes, à base d’Y et Ti, servent comme centres de recombinaison de défauts ponctuels et d'obstacles aux mouvements des dislocations, améliorant de ce fait leur résistance aux radiations et aux températures élevées. La fabrication conventionnelle des aciers ODS est réalisée par broyage mécanique suivi de traitements thermo-mécaniques, et ne permet pas facilement de comprendre les mécanismes physiques conduisant à la précipitation des nano-oxydes, ce qui serait potentiellement utile pour optimiser leur production. La cinétique de formation de ces nano-oxydes peut être étudiée en utilisant une technique alternative, à savoir la synthèse par faisceaux d’ions, qui présente de nombreux avantages, notamment le contrôle précis des paramètres expérimentaux et la possibilité de décorréler divers facteurs contribuant à la cinétique de précipitation. Au cours de cette thèse, cette technique a été utilisée pour étudier la coprécipitation d'ions métalliques (Y et/ou Ti) et d'oxygène implantés dans un alliage modèle Fe-Cr de composition proche de celle typique des aciers ODS commerciaux. Des ions de Y, Ti et O à basse énergie ont été implantés dans des échantillons d'alliage Fe10wt%Cr de haute pureté à température ambiante. Les échantillons implantés ont ensuite été recuits à diverses températures entre 600 à 1100°C pour favoriser la précipitation de nano-oxydes, conformément au principe de cette technique. La microscopie électronique à transmission a été utilisée pour caractériser la structure cristallographique et la composition chimique des nano-oxydes formés lors de trois séries d'expériences. Tout d'abord, l'implantation séquentielle d'ions Ti et O a été mise en œuvre. Un recuit ultérieur a révélé qu’il n’y avait pas de précipitation d'oxyde de titane jusqu’à des températures inférieures à 1000°C, mais la présence de nano-oxydes riches en chrome avec une structure hexagonale de type corundum, qui contiennent une certaine quantité de Ti à des températures suffisamment élevées. Ce n’est qu’après le recuit à 1100°C que des nano-oxydes d’un autre type à cœur enrichi en Ti et coquille enrichie en Cr ont également été observés. Deuxièmement, l'implantation séquentielle d’ions Y et O a entraîné la formation à 800°C de nano-oxydes probablement riches en yttrium. Le recuit à 1100°C a favorisé la croissance des particules identifiées comme étant des nano-oxydes d’yttrium avec une coquille enrichie en Cr. Enfin, une implantation ionique séquentielle de deux ions métalliques (Y et Ti) a été réalisée, suivie d'une implantation d’O. L'ordre d'implantation des ions métalliques s'est révélé crucial pour la précipitation de nano-oxydes lors du recuit ultérieur. Lors de la séquence avec une implantation de Ti en premier, une précipitation d'oxyde riche en chrome de structure corundum hexagonale a été observée, très similaire au cas de l'implantation d’ions Ti et O. En revanche, la séquence avec une implantation d’ions Y en premier a produit des nano-oxydes d'yttrium-titane qui possèdent une structure non identifiable. En résumé, l’étude a démontré la faisabilité de la formation de nano-oxydes de Y, Ti et (Y, Ti) par implantation ionique. La thèse présente la caractérisation détaillée de ces nano-oxydes, ainsi que certaines de leurs caractéristiques spécifiques, telles que la présence de relations d'orientation entre les nano-oxydes et la matrice FeCr, qui ont été observées même dans le cas de nano-oxydes de type corundum riches en Cr. Enfin, les résultats obtenus, combinées avec les données de la littérature, sont discutées pour une meilleure compréhension des mécanismes impliqués dans la formation des nano-oxydes dans les aciers ODS. / Oxide Dispersion Strengthened (ODS) steels, that is steels reinforced with a homogeneous distribution of (Y,Ti) oxide nano-particles, are advanced structural materials for nuclear applications. The oxide particles serve as point defect recombination centres and obstacles to dislocation motion thereby improving radiation resistance and high-temperature strength of these steels making them perfect candidate materials for future fusion and fission nuclear reactors. The conventional fabrication of ODS steels is achieved by mechanical alloying followed by thermomechanical heat treatments. This way of ODS steel production seems complicated to understand the physical mechanisms leading to the precipitation of nano-oxide particles. The kinetics of nanoparticle formation can be much better studied using an alternative technique of nanoparticle growth, namely Ion Beam Synthesis (IBS). This approach has many advantages including the precise control of experimental parameters and the ability to de-correlate various factors contributing to precipitation kinetics. A better knowledge gained in this way would be potentially helpful for optimization of ODS steel production routines. In the course of this PhD study, the IBS approach was applied to investigate the co-precipitation of metal (Y and/or Ti) and oxygen ions implanted into a model Fe-Cr alloy with the composition close to those typical for commercial ODS steels. Following the standard IBS schedule, consisting of ion implantation followed by high-temperature heat treatment, ions of Y, Ti and O at low energies were implanted into high-purity Fe10wt%Cr alloy samples at room temperature. The implanted samples were then annealed at various temperatures ranging from 600 to 1100°C to promote the precipitation of nano-oxide particles. A range of Transmission Electron Microscopy techniques were used to characterize the crystallographic structure and chemical composition of the nanoparticles. The study has been performed following three sets of experiments. First of all, the sequential implantation of Ti and O ions was implemented. Subsequent annealing at temperatures below 1000°C revealed that precipitation of titanium oxide was suppressed. Instead, chromium-rich nano-oxide particles with corundum hexagonal structure were found to precipitate. At sufficiently high temperatures these corundum particles were found to contain certain amount of Ti. Only after annealing at the highest temperature of 1100°C, particles of another type with Ti enriched core and Cr enriched shell were additionally fixed. Secondly, sequential Y and O ion implantation resulted in the formation of probable yttrium-rich oxides at 800°C. Annealing at 1100°C promoted their growth to larger sized yttria (Y₂O₃) particles with a Cr enriched shell. Finally, sequential ion implantation of both metal ions (Y and Ti) was performed, followed by O implantation. The order of metal ion implantation has been found to be crucial for subsequent oxide precipitation at the annealing stage. With the Ti implantation first in the sequence, the precipitation of corundum hexagonal chromium-rich oxide was observed, very similar to the case of Ti and O implantation. In contrast, implantation starting with Y produced yttrium-titanium oxide particles with unidentifiable structure. Summing up, the study has demonstrated the feasibility of the formation of Y, Ti and (Y,Ti) oxides by ion implantation. The thesis presents the detailed characterization of the nanoparticles, as well as the discovered specific features of precipitated particles, such as the presence of orientation relationships between the particles and the FeCr matrix, which was observed even for the case of Cr-rich corundum particles. Finally, the implications of the obtained results, in conjunction with the already known data from the existing literature, for the better understanding of the mechanisms involved in the formation of nano-oxide particles in ODS steels are discussed.
32

Fabrication of polymeric composite nanofiber materials and their antibacterial activity for effective wound healing

More, Dikeledi Selinah January 2023 (has links)
D. Tech. (Department of Biotechnology and Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / The synthesis of Ag and Cu nanoparticles was carried out using the thermal decomposition method in the presence of oleylamine as a capping agent. This method was used because it can produce uniform and monodisperse nanoparticles with controlled size distribution. The nanoparticles synthesized under various conditions were characterized by transmission electron microscopy (TEM), UV/Vis spectroscopy, photoluminescence spectroscopy (PL), and X-ray diffraction (XRD). The effect of precursor concentration on the morphology and size of the nanoparticles was investigated. It was observed that an increase in the precursor concentration resulted in an increase in particle sizes with different morphologies for both Ag and Cu nanoparticles. The increase in particle sizes for Ag nanoparticles was due to Ostwald ripening, while for Cu nanoparticles it was due to agglomeration, as Cu tends to oxidize in the atmosphere, leading to a change in particle size and shape. However, the ability to control and manipulate their physical and chemical properties depends on tuning their size and shape. Therefore, varying the precursor concentration helped in selecting the optimal concentration for this study. The nanoparticles produced were used in another study as fillers or additives for the production of nanofiber composites. The development of nanofibers by electrospinning process has led to potential applications in filtration, tissue engineering scaffolds, drug delivery, wound dressing and etc. The current study is an attempt to fabricate composite nanofibers that can be used as wound dressing material for effective wound healing. The approach involves the blending of two different polymers both being biocompatible and biodegradable were one is a natural polymer and the other is a synthetic polymer. In this study, different weight ratios of CS/PVA blends, Ag/Cu/CS/PVA, Ag/CS/PVA and Cu/CS/PVA composite fibers have been successfully prepared by the electrospinning process. The tip-to-collector distance was kept at 15 cm and the applied voltage was varied from 15 to 25 kV. The effects of the weight ratios applied voltage and the nanoparticles loading on the morphology and diameter of the fibers were investigated. The resultant fibers were characterized using scanning electron microscopy (SEM), XRD, Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetric analysis (TGA) and UV-Vis spectroscopy. The SEM results showed that an increase the amount of chitosan in the CS/PVA blend resulted in a decrease in the fiber diameters while an increase in the voltage from 15 to 25 kV led to a decrease in the fiber diameters. Furthermore, an increase in fiber diameters was observed with irregular morphologies upon addition of Ag/Cu nanoparticles into the blend. The latter changes are perceived to be as a result of an increased conductivity and a higher charge density. The XRD results showed peaks which correspond to Ag in the face centred cubic. Ag peaks are more dominant than Cu peaks in the XRD of the mixed nanoparticles. The FTIR spectra of the Ag/Cu/CS/PVA composite fibers gave almost identical features as the blend. This proves that there was an interaction between CS and PVA polymer due to intermolecular hydrogen bonding. The TGA curves showed no significant effect on the thermal stability of the composite fibers upon addition of different nanoparticles loadings. The absorption spectra of the composite fibers showed an improved optical properties compared to the blend. For Ag and Cu nanoparticles composite fibers it was observed that addition of Ag nanoparticles in the blend resulted in an increase in fiber diameters with uniform morphology whereas for Cu resulted in a decrease in fiber diameters. Both Ag and Cu composite fibers showed an improved optical properties. The effect of CS/PVA, Ag/Cu, Ag, and Cu nanofibers on the selected microorganism (K.pneumoniae, S. aureus, P. aeruginosa, and E.coli) was evaluated using the disk diffusion method. It was observed that Ag/Cu/CS/PVA composite fibers showed greater activity against all microorganisms compared to Ag and Cu composite fibers. The alamar blue and Pierce Lactase dehydrogenase (LDH) assay were used to assess the effect of the blend and the composite fibers on cell viability and cytotoxicity, respectively. The results show that the prepared blend and the composite fibers did not have any toxic effect on human adipose derived stem cells (hADSC). The results also showed that as the concentration of Ag/Cu nanoparticles was increased the viability of the cells also increased after 24 hour incubation. More proliferation was observed in day 1 compared to day 3. The 30/70 blend showed more viable cell compared to the negative control. For Ag and Cu composite fibers the 30/70 CS/PVA blend increased cell proliferation after 3 days with 17% more viable cells compared to the negative control. These results show that the prepared blend with its composite fibers are biocompatible with human (ADSC) and may be suitable for use in biomedical application such as wound dressing.
33

Copper Oxide Films Grown by Atomic Layer Deposition from Bis(tri-n-butylphosphane)copper(I)acetylacetonate on Ta, TaN, Ru, and SiO2

Waechtler, Thomas, Oswald, Steffen, Roth, Nina, Jakob, Alexander, Lang, Heinrich, Ecke, Ramona, Schulz, Stefan E., Gessner, Thomas, Moskvinova, Anastasia, Schulze, Steffen, Hietschold, Michael 02 May 2009 (has links) (PDF)
The thermal atomic layer deposition (ALD) of copper oxide films from the non-fluorinated yet liquid precursor bis(tri-<it>n</it>-butylphosphane)copper(I)acetylacetonate, [(<sup><it>n</it></sup>Bu<sub>3</sub>P)<sub>2</sub>Cu(acac)], and wet O<sub>2</sub> on Ta, TaN, Ru and SiO<sub>2</sub> substrates at temperatures of < 160&deg;C is reported. Typical temperature-independent growth was observed at least up to 125&deg;C with a growth-per-cycle of ~ 0.1 &Aring; for the metallic substrates and an ALD window extending down to 100&deg;C for Ru. On SiO<sub>2</sub> and TaN the ALD window was observed between 110 and 125&deg;C, with saturated growth shown on TaN still at 135&deg;C. Precursor self-decomposition in a chemical vapor deposition mode led to bi-modal growth on Ta, resulting in the parallel formation of continuous films and isolated clusters. This effect was not observed on TaN up to about 130&deg;C and neither on Ru or SiO<sub>2</sub> for any processing temperature. The degree of nitridation of the tantalum nitride underlayers considerably influenced the film growth. With excellent adhesion of the ALD films on all substrates studied, the results are a promising basis for Cu seed layer ALD applicable to electrochemical Cu metallization in interconnects of ultralarge-scale integrated circuits.<br> &copy; 2009 The Electrochemical Society. All rights reserved. <br> / Es wird die thermische Atomlagenabscheidung (ALD) von Kupferoxidschichten, ausgehend von der unfluorierten, fl&uuml;ssigen Vorstufenverbindung Bis(tri-<it>n</it>-butylphosphan)kupfer(I)acetylacetonat, [(<sup><it>n</it></sup>Bu<sub>3</sub>P)<sub>2</sub>Cu(acac)], sowie feuchtem Sauerstoff, auf Ta-, TaN-, Ru- und SiO<sub>2</sub>-Substraten bei Temperaturen < 160&deg;C berichtet. Typisches temperaturunabh&auml;ngiges Wachstum wurde zumindest bis 125&deg;C beobachtet. Damit verbunden wurde f&uuml;r die metallischen Substrate ein Zyklenwachstum von ca. 0.1 &Aring; erzielt sowie ein ALD-Fenster, das f&uuml;r Ru bis zu einer Temperatur von 100&deg;C reicht. Auf SiO<sub>2</sub> und TaN wurde das ALD-Fenster zwischen 110 und 125&deg;C beobachtet, wobei auch bei 135&deg;C noch ges&auml;ttigtes Wachstum auf TaN gezeigt werden konnte. Die selbst&auml;ndige Zersetzung des Precursors &auml;hnlich der chemischen Gasphasenabscheidung f&uuml;hrte zu einem bimodalen Schichtwachstum auf Ta, wodurch gleichzeitig geschlossene Schichten und voneinander isolierte Cluster gebildet wurden. Dieser Effekt wurde auf TaN bis zu einer Temperatur von 130&deg;C nicht beobachtet. Ebensowenig trat er im untersuchten Temperaturbereich auf Ru oder SiO<sub>2</sub> auf. Der Nitrierungsgrad der TaN-Schichten beeinflusste hierbei das Schichtwachstum stark. Mit einer sehr guten Haftung der ALD-Schichten auf allen untersuchten Substratmaterialien erscheinen die Ergebnisse vielversprechend f&uuml;r die ALD von Kupferstartschichten, die f&uuml;r die elektrochemische Kupfermetallisierung in Leitbahnsystemen ultrahochintegrierter Schaltkreise anwendbar sind.
34

Preparation and characterization of Carbon Nanotube based vertical interconnections for integrated circuits: Preparation and characterization of Carbon Nanotube based verticalinterconnections for integrated circuits

Fiedler, Holger 12 June 2014 (has links)
(ULSI) causes an increase of the resistance of the wiring system by increased scattering of electrons at side walls and grain boundaries in the state of the art Cu technology, which increases the RC delay of the interconnect system and thus degrades the performance of the device. The outstanding properties of carbon nanotubes (CNT) such as a large mean free path, a high thermal conductance and a large resistance against electromigration make them an ideal candidate to replace Cu in future feature nodes. The present thesis contributes to the preparation and properties of CNT based vertical interconnections (vias). In addition, all processes applied during the fabrication are compatible to ULSI and an interface between CNT based vias and a Cu metallization is studied. The methodology for the evaluation of CNT based vias is improved; it is highlighted that by measuring the resistance of one multiwall CNT and taking into account the CNT density, the performance of the CNT based vias can be predicted accurately. This provides the means for a systematic evaluation of different integration procedures and materials. The lowest contact resistance is obtained for carbide forming metals, as long as oxidation during the integration is avoided. Even though metal-nitrides exhibit an enhanced contact resistance, they are recommended to be used at the bottom metallization in order to minimize the oxidation of the metal-CNT contact during subsequent processing steps. Overall a ranking for the materials from the lowest to the highest contact resistance is obtained: Ta < Ti < TaN < TiN « TiO2 « Ta2O5 Furthermore the impact of post CNT growth procedures as chemical mechanical planarization, HF treatment and annealing procedures after the CNT based via fabrication are evaluated. The conductance of the incorporated CNTs and the applicable electrical transport regime relative to the CNT quality and the CNT length is discussed. In addition, a strong correlation between the temperature coefficient of resistance and the initial resistance of the CNT based vias at room temperature has been observed. / Die kontinuierliche Miniaturisierung der charakteristischen Abmessungen in hochintegrierten Schaltungen (ULSI) verursacht einen Anstieg des Widerstandes im Zuleitungssystem aufgrund der erhöhten Streuung von Elektronen an Seitenwänden und Korngrenzen in der Cu-Technologie, wodurch die Verzögerungszeit des Zuleitungssystems ansteigt. Die herausragenden Eigenschaften von Kohlenstoffnanoröhren (CNT), wie eine große mittlere freie Weglänge, hohe thermische Leitfähigkeit und eine starke Resistenz gegenüber Elektromigration machen diese zu einem idealen Kandidaten, um Cu in zukünftigen Technologiegenerationen zu ersetzen. Die vorliegende Arbeit beschreibt die Herstellung und daraus resultierenden Eigenschaften von Zwischenebenenkontakten (Vias) basierend auf CNTs. Alle verwendeten Prozessierungsschritte sind kompatibel mit der Herstellung von hochintegrierten Schaltkreisen und eine Schnittstelle zwischen den CNT Vias und einer Cu-Metallisierung ist vorhanden. Insbesondere das Verfahren zur Evaluierung von CNT Vias wurde durch den Einsatz verschiedener Methoden verbessert. Insbesondere soll hervorgehoben werden, dass durch die Messung des Widerstandes eines einzelnen CNTs, bei bekannter CNT Dichte, der Via Widerstand sehr genau vorausgesagt werden kann. Dies ermöglicht eine systematische Untersuchung des Einflusses der verschiedenen Prozessschritte und der darin verwendeten Materialien auf den Via Widerstand. Der niedrigste Kontaktwiderstand wird für Karbidformierende Metalle erreicht, solange Oxidationsprozesse ausgeschlossen werden können. Obwohl Metallnitride einen höheren Kontaktwiderstand aufweisen, sind diese für die Unterseitenmetallisierung zu empfehlen, da dadurch die Oxidation der leitfähigen Schicht minimiert wird. Insgesamt kann eine Reihenfolge beginnend mit dem niedrigsten zum höchsten Kontaktwiderstand aufgestellt werden: Ta < Ti < TaN < TiN « TiO2 « Ta2O5 Desweiteren wurde der Einfluss von Verfahren nach dem CNTWachstum wie die chemischmechanische Planarisierung, eine HF Behandlung und einer Temperaturbehandlung evaluiert, sowie deren Einfluss auf die elektrischen Parameter des Vias untersucht. Die Leitfähigkeit der integrierten CNTs und die daraus resultierenden elektrischen Transporteigenschaften in Abhängigkeit der CNT Qualität und Länge werden besprochen. Ebenso wird die starke Korrelation zwischen dem Temperaturkoeffizienten des elektrischen Widerstandes und des Ausgangswiderstandes der CNT basierten Vias bei Raumtemperatur diskutiert.
35

Performance characterisation of duplex stainless steel in nuclear waste storage environment

Ornek, Cem January 2016 (has links)
The majority of UK’s intermediate level radioactive waste is currently stored in 316L and 304L austenitic stainless steel containers in interim storage facilities for permanent disposal until a geological disposal facility has become available. The structural integrity of stainless steel canisters is required to persevere against environmental degradation for up to 500 years to assure a safe storage and disposal scheme. Hitherto existing severe localised corrosion observances on real waste storage containers after 10 years of exposure to an ambient atmosphere in an in-land warehouse in Culham at Oxfordshire, however, questioned the likelihood occurrence of stress corrosion cracking that may harm the canister’s functionality during long-term storage. The more corrosion resistant duplex stainless steel grade 2205, therefore, has been started to be manufactured as a replacement for the austenitic grades. Over decades, the threshold stress corrosion cracking temperature of austenitic stainless steels has been believed to be 50-60°C, but lab- and field-based research has shown that 304L and 316L may suffer from atmospheric stress corrosion cracking at ambient temperatures. Such an issue has not been reported to occur for the 2205 duplex steel, and its atmospheric stress corrosion cracking behaviour at low temperatures (40-50°C) has been sparsely studied which requires detailed investigations in this respect. Low temperature atmospheric stress corrosion cracking investigations on 2205 duplex stainless steel formed the framework of this PhD thesis with respect to the waste storage context. Long-term surface magnesium chloride deposition exposures at 50°C and 30% relative humidity for up to 15 months exhibited the occurrence of stress corrosion cracks, showing stress corrosion susceptibility of 2205 duplex stainless steel at 50°C.The amount of cold work increased the cracking susceptibility, with bending deformation being the most critical type of deformation mode among tensile and rolling type of cold work. The orientation of the microstructure deformation direction, i.e. whether the deformation occurred in transverse or rolling direction, played vital role in corrosion and cracking behaviour, as such that bending in transverse direction showed almost 3-times larger corrosion and stress corrosion cracking propensity. Welding simulation treatments by ageing processes at 750°C and 475°C exhibited substantial influences on the corrosion properties. It was shown that sensitisation ageing at 750°C can render the material enhanced susceptible to stress corrosion cracking at even low chloride deposition densities of ≤145 µm/cm². However, it could be shown that short-term heat treatments at 475°C can decrease corrosion and stress corrosion cracking susceptibility which may be used to improve the materials performance. Mechanistic understanding of stress corrosion cracking phenomena in light of a comprehensive microstructure characterisation was the main focus of this thesis.
36

Efekt submikrometrických rysů na reologii polymerních nanokompozitů / Effect of sub-micrometer structural features on rheology of polymer nanocomposites

Lepcio, Petr January 2018 (has links)
Polymerní nanokompozity (PNCs) mají slibnou budoucnost jako lehké funkční materiály zpracovatelné aditivními výrobními technologiemi. Jejich rychlému rozšíření však brání silná závislost jejich užitných vlastností na prostorovém uspořádání nanočástic (NP). Schopnost řídit disperzi nanočástic je tak klíčovým předpokladem pro jejich uplatnění ve funkčních kompozitech. Tato práce zkoumá přípravu polymerních nanokompozitů v modelové sklotvorné polymerní matrici roztokovou metodou, technikou schopnou vytvářet prostorové uspořádání nanočástic řízené strukturními a kinetickými parametry přípravného procesu. Prezentované výsledky popisují rozdíly mezi změnami rheologického chování roztoku polystyrenu při oscilačním smyku s vysokou amplitudou (LAOS) vyvolanými nanočásticemi. Výsledky vedou k závěru, že vysoce-afinní OP-POSS nanočástice při nízkých koncentracích dobře interagují s PS a tvoří tuhé agregáty, zatímco nízko-afinní OM-POSS nanočástice za těchto podmínek neovlivňují deformační chování polymerních řetězců. Dále byla pozornost zaměřena na vliv použitého rozpouštědla na uspořádání nanočástic v SiO2/PMMA a SiO2/PS nanokompozitech, který je v literatuře prezentován jako parametr řídící prostorové uspořádání nanočástic v pevném stavu. Důraz byl kladen na kvalitativní rozdíly mezi „špatně dispergovanými“ shluky nanočástic, které byly na základě rheologie a strukturální analýzy (TEM, USAXS) identifikovány jako polymerními řetězci vázané nanočásticové klastry a dva typy agregátů, jeden termodynamického a druhý kinetického původu. Jednotlivé druhy agregátů se vyznačují odlišnými kinetikami vzniku a rozdílnými vlastnostmi jak mezi sebou, tak v porovnání s dispergovanými nanočásticemi. Pozorované typy disperze nanočástic byly kvantitativně posouzeny podle svých rheologických vlastností během roztokové přípravy, podle kterých byla vyhodnocena míra adsorpce polymeru na povrch nanočástic a atrakce ve vypuzeném objemu. Výsledky byly porovnány s teorií PRISM. Důležitost uspořádání nanočástic byla demonstrována na porovnání teplot skelných přechodů různých struktur při stejném chemickém složení.
37

Copper Oxide Films Grown by Atomic Layer Deposition from Bis(tri-n-butylphosphane)copper(I)acetylacetonate on Ta, TaN, Ru, and SiO2

Waechtler, Thomas, Oswald, Steffen, Roth, Nina, Jakob, Alexander, Lang, Heinrich, Ecke, Ramona, Schulz, Stefan E., Gessner, Thomas, Moskvinova, Anastasia, Schulze, Steffen, Hietschold, Michael 02 May 2009 (has links)
The thermal atomic layer deposition (ALD) of copper oxide films from the non-fluorinated yet liquid precursor bis(tri-<it>n</it>-butylphosphane)copper(I)acetylacetonate, [(<sup><it>n</it></sup>Bu<sub>3</sub>P)<sub>2</sub>Cu(acac)], and wet O<sub>2</sub> on Ta, TaN, Ru and SiO<sub>2</sub> substrates at temperatures of < 160&deg;C is reported. Typical temperature-independent growth was observed at least up to 125&deg;C with a growth-per-cycle of ~ 0.1 &Aring; for the metallic substrates and an ALD window extending down to 100&deg;C for Ru. On SiO<sub>2</sub> and TaN the ALD window was observed between 110 and 125&deg;C, with saturated growth shown on TaN still at 135&deg;C. Precursor self-decomposition in a chemical vapor deposition mode led to bi-modal growth on Ta, resulting in the parallel formation of continuous films and isolated clusters. This effect was not observed on TaN up to about 130&deg;C and neither on Ru or SiO<sub>2</sub> for any processing temperature. The degree of nitridation of the tantalum nitride underlayers considerably influenced the film growth. With excellent adhesion of the ALD films on all substrates studied, the results are a promising basis for Cu seed layer ALD applicable to electrochemical Cu metallization in interconnects of ultralarge-scale integrated circuits.<br> &copy; 2009 The Electrochemical Society. All rights reserved. <br> / Es wird die thermische Atomlagenabscheidung (ALD) von Kupferoxidschichten, ausgehend von der unfluorierten, fl&uuml;ssigen Vorstufenverbindung Bis(tri-<it>n</it>-butylphosphan)kupfer(I)acetylacetonat, [(<sup><it>n</it></sup>Bu<sub>3</sub>P)<sub>2</sub>Cu(acac)], sowie feuchtem Sauerstoff, auf Ta-, TaN-, Ru- und SiO<sub>2</sub>-Substraten bei Temperaturen < 160&deg;C berichtet. Typisches temperaturunabh&auml;ngiges Wachstum wurde zumindest bis 125&deg;C beobachtet. Damit verbunden wurde f&uuml;r die metallischen Substrate ein Zyklenwachstum von ca. 0.1 &Aring; erzielt sowie ein ALD-Fenster, das f&uuml;r Ru bis zu einer Temperatur von 100&deg;C reicht. Auf SiO<sub>2</sub> und TaN wurde das ALD-Fenster zwischen 110 und 125&deg;C beobachtet, wobei auch bei 135&deg;C noch ges&auml;ttigtes Wachstum auf TaN gezeigt werden konnte. Die selbst&auml;ndige Zersetzung des Precursors &auml;hnlich der chemischen Gasphasenabscheidung f&uuml;hrte zu einem bimodalen Schichtwachstum auf Ta, wodurch gleichzeitig geschlossene Schichten und voneinander isolierte Cluster gebildet wurden. Dieser Effekt wurde auf TaN bis zu einer Temperatur von 130&deg;C nicht beobachtet. Ebensowenig trat er im untersuchten Temperaturbereich auf Ru oder SiO<sub>2</sub> auf. Der Nitrierungsgrad der TaN-Schichten beeinflusste hierbei das Schichtwachstum stark. Mit einer sehr guten Haftung der ALD-Schichten auf allen untersuchten Substratmaterialien erscheinen die Ergebnisse vielversprechend f&uuml;r die ALD von Kupferstartschichten, die f&uuml;r die elektrochemische Kupfermetallisierung in Leitbahnsystemen ultrahochintegrierter Schaltkreise anwendbar sind.

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