The limitations of the conventional Cu/low-k interconnect technology for use in future ultra-scaled integrated circuits down to 7 nm in the year 2020 are investigated from the power/performance point of view. Compact models are used to demonstrate the impacts of various interconnect process parameters, for instance, the interconnect barrier/liner bilayer thickness and aspect ratio, on the design and optimization of a multilevel interconnect network. A framework to perform a sensitivity analysis for the circuit behavior to interconnect process parameters is created for future FinFET CMOS technology nodes. Multiple predictive cell libraries down to the 7‒nm technology node are constructed to enable early investigation of the electronic chip performance using commercial electronic design automation (EDA) tools with real chip information. Findings indicated new opportunities that arise for emerging novel interconnect technologies from the materials and process perspectives. These opportunities are evaluated based on potential benefits that are quantified with rigorous circuit-level simulations and requirements for key parameters are underlined. The impacts of various emerging interconnect technologies on the performances of emerging devices are analyzed to quantify the realistic circuit- and system-level benefits that these new switches can offer.

ABSTRACT PRODUCTION OF CARBON NANOTUBES BY CHEMICAL VAPOR DEPOSITION Ayhan, Umut BariS M.S., Department of Chemical Engineering Supervisor: Prof. Dr. G&uuml / ng&ouml / r G&uuml / nd&uuml / z Co-Supervisor: Assoc. Prof. Dr. Burhanettin &Ccedil / i&ccedil / ek July 2004, 75 pages Carbon nanotubes, which is one of the most attractive research subject for scientists, was synthesized by two different methods: Chemical vapor deposition (CVD), a known method for nanotube growth, and electron beam (e-beam), a new method which was used for the first time for the catalytic growth of carbon nanotubes. In both of the methods, iron catalyst coated silica substrates were used for the carbon nanotube growth, that were prepared by the Sol-Gel technique using aqueous solution of Iron (III) nitrate and tetraethoxysilane. The catalytic substrates were then calcined at 450 &deg / C under vacuum and iron was reduced at 500&deg / C under a flow of nitrogen and hydrogen. In CVD method the decomposition of acetylene gas was achieved at 600 &deg / C and 750 &deg / C and the carbon was deposited on the iron catalysts for nanotube growth. However, in e-beam method the decomposition of acetylene was achieved by applying pulsed high voltage on the gas and the carbon deposition on the silica substrate were done. The samples from both of the methods were characterized using transmission electron microscopy (TEM) and Raman spectroscopy techniques. TEM images and Raman spectra of the samples show that carbon nanotube growth has been achieved in both of the method. In TEM characterization, all nanotubes were found to be multi-walled carbon nanotubes (MWNT) and no single-walled carbon nanotubes (SWNT) were pictured. However, the Raman spectra show that there are also SWNTs in some of the samples.

The objective of this thesis is to study the effect of process conditions on structure and electrochemical properties of polyacrylonitrile (PAN)/carbon nanotube (CNT) composite film based electrodes developed for electrochemical capacitors. The process parameters like activation temperature, CNT loading in the composite films are varied to determine optimum process conditions for physical (CO2) and chemical (KOH) activation methods. The PAN/CNT precursors are stabilized in air, carbonized in inert atmosphere (argon), and activated by physical (CO2) and chemical (KOH) methods. The physical activation process is carried out by heat treating the carbon precursors in CO2 atmosphere at activation temperatures. In the chemical activation process, stabilized carbon precursors are immersed in aqueous solutions of activating media (KOH), dried, and subsequently heat treated in an inert atmosphere at the activation temperature. The structure and morphology are probed using scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy. The specific capacitance, power and energy density of the activated electrodes are evaluated with aqueous electrolytes (KOH) as well as organic electrolyte (ionic liquid in acetonitrile) in Cell Test. The surface area and pore size distribution of the activated composite electrodes are evaluated using nitrogen absorption. Specific capacitance dependence on factors such as surface area and pore size distribution are studied. A maximum specific capacitance of 300 F/g in KOH electrolyte and maximum energy density of 22 wh/kg in ionic liquid has been achieved. BET surface areas in excess of 2500 m2/g with controlled pore sizes in 1 - 5 nm range has been attained in this work.

We investigated dynamic response of Cu46Zr54 metallic glass under adiabatic planar shock wave loading (one-dimensional strain) with molecular dynamics simulations, including Hugoniot (shock) states, shock-induced plasticity, and spallation. The Hugoniot states are obtained up to 60 GPa along with the von Mises shear flow strengths, and the dynamic spall strengths, at different strain rates and temperatures. For the steady shock states, a clear elastic-plastic transition is identified. The local von Mises shear strain analysis is used to characterize local deformation, and the Voronoi tessellation analysis, the corresponding local structures at various stages of shock, release, tension and spallation. The plasticity in this glass, manifested as localized shear transformation zones, is of local structure rather than thermal origin, and void nucleation occurs preferentially at the highly shear-deformed regions. The Voronoi and shear strain analyses show that the atoms with different local structures are of different shear resistances that lead to shear localization. Additionally, we performed large-scale molecular dynamics simulations to investigate plasticity in Cu/Cu46Zr54 glass nanolaminates under uniaxial compression. Partial and full dislocations are observed in the Cu layers, and screw dislocations, near the amorphous−crystalline interfaces (ACIs). Shear bands are directly induced by the dislocations in the crystalline Cu layer through ACIs, and grow from the ACIs into the glass layers and absorb ambient shear transformation zones. Plasticity in the glass layers is realized via pronounced, stable shear banding. As the last part of the dissertation, we investigated with nonreactive molecular dynamics simulations, the dynamic response of phenolic resin and its carbon-nanotube (CNT) composites to shock wave compression. For phenolic resin, our simulations yielded shock states in agreement with experiments on similar polymers, except the "phase change" observed in experiments, indicating that such phase change is chemical in nature. The elastic–plastic transition is characterized by shear stress relaxation and atomic-level slip, and phenolic resin shows strong strain hardening. Shock loading of the CNT-resin composites was applied parallel or perpendicular to the CNT axis, and the composites demonstrated anisotropy in wave propagation, yield and CNT deformation. Our simulations suggested that the bulk shock response of the composites depends on the volume fraction, length ratio, impact cross-section, and geometry of the CNT components; the short CNTs in current simulations had insignificant effect on the bulk response of resin polymer.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23715号 / 理博第4805号 / 新制||理||1688(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 北川 宏, 教授 吉村 一良, 教授 竹腰 清乃理 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

abstract: Nanofluidic devices in which one single-walled carbon nanotube (SWCNT) spans a barrier between two fluid reservoirs were constructed, enabling direct electrical measurement of the transport of ions and molecules. Ion current through these devices is about 2 orders of magnitude larger than that predicted from the bulk resistivity of the electrolyte. Electroosmosis drives excess current, carried by cations, and is found to be the origin of giant ionic current through SWCNT as shown by building an ionic field-effect transistor with a gate electrode embedded in the fluid barrier. Wetting of inside of the semi-conducting SWCNT by water showed the change of its electronic property, turning the electronic SWCNT field-effect transistor to "on" state. These findings provide a new method to investigate and control the ion and molecule behavior at nanoscale. / Dissertation/Thesis / Ph.D. Physics 2011

Title: Theoretical studies of rolled-up and wrinkled nanomembranes Author: Mgr. Peter Cendula Department: Department of Condensed Matter Physics Thesis Supervisors: Prof. Dr. Oliver G. Schmidt, Prof. RNDr. Václav Holý, CSc. Abstract : The thesis is devoted to three similar topics from the field of rolled-up and wrinkled nanomembranes. We start by recalling classical theory of thin plates, which will be used to describe deformation of nanomembranes. In the first topic, relaxation of internal strain is studied when a flat film is partially released from the substrate by etching the sacrificial layer underneath. Energetic competition of the tube and wrinkle shape is quantitatively investigated. Similar model is used to investigate the limiting maximum value of tube rotations. In the second topic, roll-up of initially wrinkled film is shown to favor tubes forming on the flat edge of rectangular wrinkled pattern, enabling precise control of tube position. Experiment is provided to justify our theoretical predictions. In the third topic, quantum well is assumed inside a wrin- kled nanomembrane. Shift of transition energy induced by lateral modulation due to bending strain is quantified, being of interest for strain-sensitive optical detectors and emitters. In addition, lateral localization of electron and hole due to...

For the past three decades, newly discovered carbon nanostructures such as fullerenes, graphene and carbon nanotubes (CNTs) have revolutionized the field of nanoscience, introducing many practical and potential applications pertaining to their exceptional structural, mechanical, thermal, and optoelectronic properties. Raman spectroscopy has been an instrumental technique for characterizing these materials due to its non-destructive nature and high sensitivity to the material responses. While Raman spectroscopy is broadly used for identifying specific material types and quality, it has also been increasingly useful as a tool for probing the electronic and excitonic properties, as well as their interplay with the vibrational properties in the aforementioned carbon nanomaterials. In this dissertation, we present our Raman-related research on carbon nanotubes and a new member of the nano-carbon family - carbon nanohoops (cycloparaphenylenes, or CPPs). We discuss our new findings on the resonance Raman spectroscopy (RRS) of various semiconducting CNTs, with the focus on the Raman excitation profiles (REPs) for the G-band. The asymmetric lineshapes observed in the G-band REPs for the second excitonic (E22) transition of these CNTs contradict a long-held approximation, the Franck-Condon principle, for the vibronic properties of the carbon nanotubes. In addition, the G-band REPs from the closely spaced E33 and E44 transitions are investigated, and we demonstrate that these excitonic levels exhibit significant quantum interference effects between each other. We also present the first comprehensive study of Raman spectroscopy of CPPs. Analogously to CNTs, we show that Raman spectroscopy can be used to identify CPPs of different sizes. A plethora of Raman modes are observed in these spectra, including modes that are comparable to those of CNTs, such as the G-band, as well as Raman peaks that are unique for CPPs. Calculated Raman spectra using density functional theory (DFT) are compared with the experimental results for the assignment of different modes. Furthermore, we refine our knowledge of the CPP Raman modes by concentrating on the even-numbered CPPs. By taking advantage of the symmetry arguments in the even [n]CPPs, we are able to utilize group theory and accurately identify the size dependences of different Raman-active modes.

abstract: This thesis describes several experiments based on carbon nanotube nanofludic devices and field-effect transistors. The first experiment detected ion and molecule translocation through one single-walled carbon nanotube (SWCNT) that spans a barrier between two fluid reservoirs. The electrical ionic current is measured. Translocation of small single stranded DNA oligomers is marked by large transient increases in current through the tube and confirmed by a PCR (polymerase chain reaction) analysis. Carbon nanotubes simplify the construction of nanopores, permit new types of electrical measurement, and open new avenues for control of DNA translocation. The second experiment constructed devices in which the interior of a single-walled carbon nanotube field-effect transistor (CNT-FET) acts as a nanofluidic channel that connects two fluid reservoirs, permitting measurement of the electronic properties of the SWCNT as it is wetted by an analyte. Wetting of the inside of the SWCNT by water turns the transistor on, while wetting of the outside has little effect. This finding may provide a new method to investigate water behavior at nanoscale. This also opens a new avenue for building sensors in which the SWCNT functions as an electronic detector. This thesis also presents some experiments that related to nanofabrication, such as construction of FET with tin sulfide (SnS) quantum ribbon. This work demonstrates the application of solution processed IV-VI semiconductor nanostructures in nanoscale devices. / Dissertation/Thesis / Ph.D. Physics 2011

Le Lanréotide est un octapeptide amphiphile cationique et un analogue thérapeutique de la somatostatine. Cette molécule synthétique a été conçue au sein de Beaufour-Ipsen comme thérapie contre l’acromégalie. Ce peptide révèle la propriété de former des nanotubes avec un haut degré de monodispersité en diamètre des tubes (244 Å) et épaisseur de la paroi (~18 Å) lorsqu’il est mélangé avec de l’eau pure à 10% (w/w). Le peptide forme des tubes emboîtés à plus haute concentration. Cette propriété d’auto-assemblage est utilisée pour concevoir un implant sous cutané à libération prolongée d’un mois : la Somatuline Autogel. Les gels de Lanréotide deviennent de plus en plus visqueux avec la concentration en peptide et cette viscosité limite la dose maximale injectable. L’ajout d’un adjuvant dans la formulation : le polyéthylène glycol (PEG600) à permit d’augmenter le temps de libération du peptide dans l’organisme tout en diminuant la viscosité du gel. Dans le but d’étudier l’effet du PEG600 sur l’auto-assemblage du Lanréotide, une étude structurale et thermodynamique est proposée. Cette étude est réalisée grâce à une approche par diagramme de phase systématique, par la technique de diffusion des rayons X et de modèles d’analyses des clichés, croisé par différentes techniques de caractérisations moléculaires. Cette étude révèle des interactions fortes du PEG avec le Lanréotide conduisant à la formation d’un complexe en solution. Ce complexe influe sur les équilibres entre deux phases du système biphasique, tube et intermédiaire du Lanréotide (rubans et dimères), ce qui pourrait jouer un rôle important dans les propriétés rhéologiques des gels. Enfin, il est montré qu’il est possible de réaliser la transition pratiquement totale du Lanréotide vers un dimère chimique conduisant à la formation de fibre type amyloïde. La simplicité du procédé de fabrication à température ambiante de ce dimère non actif dans l’organisme par un simple changement d’ordre d’addition des composants, fait de la compréhension des paramètres physico-chimiques de formations de ce dimère, un point capital du point de vue industriel. / The Lanreotide is an cationic octapeptide and a therapeutic analogue of the somatostatin. This synthetic molecule was designed by Beaufour Ipsen as a therapy against acromegaly. This peptide has the capacity to form monodisperse nanotubes with a high degree of monodispersity in diameter (244 Å) and wall thickness (~18 Å) when the peptide is mixed with pure water at 10% (w/w); embedded tubes are found at higher concentration. The viscosity of Lanreotide gels is strongly increasing with the peptide concentration, a property that limits the maximum injectable dose. The addition of a polymer (polyethylene glycol, PEG600) as an adjuvant in the formulation allows one to increase the release time in the organism to be treated and to decrease the gel viscosity. To study the effect of PEG600 on the self-assembly of the Lanreotide, a structural and thermodynamic work is proposed. This study is performed with a systematic phase diagram approach, by X-ray scattering and modeling of the scattering pattern and different experimental techniques at the molecular scale. This study reveals strong interaction between PEG and Lanreotide that form a complex in solution. This complex impacts the equilibrium state between two phases of the biphasic system, i.e., pure tubes and an intermediate state consisting of a mixture between ribbons and dimers of the Lanreotide. This result could play an important role for the gel’s rheological properties. Then, we demonstrate that it is possible to obtain an almost complete transition to a covalent dimer which yields the formation of amyloid fibers. To sum up, we discuss a new process for the fabrication of a dimer that is not active in the organism, this process being (i) based on a simple change of the order at which the components are added in solution and (ii) easy to implement at room temperature. Our findings could impact industrial applications.