京都大学 / 新制・課程博士 / 博士(理学) / 甲第23452号 / 理博第4746号 / 新制||理||1680(附属図書館) / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)教授 松田 祐司, 教授 石田 憲二, 教授 柳瀬 陽一 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

Thermoelectric phenomena couple thermal and electric currents, allowing for solid-state conversion of heat into electricity. For decades Radioisotope Thermoelectric Generators have supplied power to NASA satellites and deep space probes. A more accessible application to consumers is the automotive industry's aspiration to incorporate thermoelectrics into active waste heat recovery systems. Higher power demands require these new thermoelectric devices to operate at higher temperatures and higher efficiencies, justifying new materials research. Recently, clathrates have gained interest for thermoelectric applications due to the unique properties they possess.These properties are directly related to their crystal structure. Therefore, clathrates are not only of interest from the standpoint of potential thermoelectric applications but are also of scientific interest as they presents an opportunity to investigate fundamental properties of group-IV elements in novel crystal structures. Clathrates are a class of novel open-structured materials in which molecules or atoms of one species are completely enclosed within a framework comprised of another species. This work presents a systematic investigation of the electrical properties of type I clathrate alloys, specifically Si-Ge alloys, for the first time. A series of Ba8Ga16-ySixGe30-x+y clathrates with varying Si content were synthesized and their structural and transport properties were studied. Two additional series of type I clathrates were also synthesized and characterized and their properties compared to those of the Si-Ge alloys in order to develop an understanding of their structure-property relationships. The increasing Si content correlates to a dramatic increase in Seebeck coefficient even as the resistivity decreases, suggesting the complex interaction between the Ba and the Si substitution within the Ga16Ge30 framework significantly modifies the band structure.

This master thesis is focused on characterization of electrical transport properties of one-dimensional nanostructures. First section of this work deals with theoretical description of the experimental approaches to realization of such measurements. This section involves also a detail discussion of preparation of contacts using e-beam lithography. Next, theoretical description of characterization of nanostructures using photoluminescence measurements is given. Second section describes practical application of the aforementioned electrical transport measurements. Presented results include transport and photoluminescence measurements of WS2 nanotubes, InAs and WO2.72 nanowires. The last section of this thesis deals with nanowire quantum well heterostructures. The section provides both a deeper theoretical view of the problem and results of the photoluminescence measurements are shown.

Graphene is a semimetal with zero band gap. Position of Fermi level can be changed by applied gate voltage, which results in a change of free carier concentration. This work focuses on a simultaneous measurement of surface potential by Kelvin probe force microscopy (KPFM) and transport response of graphene Hall bars in different relative humidities and with applying gate voltage. The transport response was also observed in case of graphene Hall bar structure modified by local anodic oxidation (LAO).

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20166号 / 理博第4251号 / 新制||理||1611(附属図書館) / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)教授 松田 祐司, 教授 川上 則雄, 教授 前野 悦輝 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

No description available.

Si le graphène est un candidat prometteur pour de nombreuses applications, il reste des questions fondamentales à résoudre. Les objectifs de cette thèse visent à obtenir une crois- sance de graphène de haute qualité, à développer de nouveaux concepts de transfert pour réaliser de nouveaux dispositifs tout en contrôlant la formation de défauts dans sa struc- ture. Nous avons été en mesure d'augmenter la surface d'une monocouche polycristalline de graphène d'une échelle de quelques centimètres à celle d'une plaquette de silicium sans changer de chambre CVD. D'autre part, nous avons démontré une méthode permettant de diminuer la densité de nucléation et ainsi d'obtenir du graphène monocristallin de quelques centaines de microns. Concernant la réalisation de nouveaux dispositifs, nous avons obtenu des circuits à base de graphène polycristallin empilés par transferts successifs où la région de bicouche artificielle se comporte comme un bicouche intrinsèque. Nous avons également développé une nouvelle méthode pour suspendre le graphène à l'échelle macroscopique sur des supports en piliers. Dans un tel système, les contraintes dans le graphène restent in- férieures à 0,2%. Par la suite une méthode de dépôt d'électrodes par voie sèche a été développée pour éviter toute dégradation du graphène. Ce processus de transfert a été amélioré pour atteindre des tailles de substrats allant jusqu'à 4 pouces pour le silicium et le saphir. Il a été enfin utilisé comme électrode transparente d'une LED à puits quantiques pour remplacer des électrodes Ni / Au . Nous avons mis au point des procédés de création sélective de défauts sur le graphène. Tout d'abord des défauts ont été induits chimiquement de façon contrôlable et ont été analysés par spectroscopie Raman et microscopie électronique en transmission qui ont révélé un mécanisme en deux étapes de formation de défauts dans la structure de graphène. Nous avons également étudié l'effet des défauts chargés adsorbés sur la surface du graphène sans former de liaisons avec lui. Contrairement à la littérature où les particules chargées sont déposées a posteriori, les nanoparticules chargées étaient présentes pendant la croissance sur cuivre. Nous interprétons l'existence d'une bande de phonons D' très intense devant celle de la D, et encore jamais signalée avec la présence de ces nanoparticules / Though graphene is strong candidate to make various applications, still there are issues that need to be resolved. The purpose of this thesis is to grow high quality graphene and transfer it to make new graphene based devices and to engineer defects into graphene structure. We have been able to increase the growth polycrystalline monolayer graphene from few centimeter scale to wafer scale without changing the CVD chamber. At the same time, we have demonstrated a method to decrease the nucleation density which allows us to grow large single crystal graphene from few to hundreds of micrometer. Concerning new design of graphene based devices, the polycrystalline graphene was trans- ferred to create artificial bilayer crossbars where the bilayer region behaved like naturally grown bilayer graphene. We have also developed a novel method of suspending graphene in macroscopic scale in pillared surface. In such a system, the strain in graphene is found to be less than 0.2%. Thereafter a completely dry method of depositing electrodes was developed which prevents damaging of graphene. The scale and process of transferring graphene was improved to different substrates such as 4 inch Si and sapphire substrates. It was used as transparent electrode to in a quantum well LED to replace the Ni/Au electrodes. We have been able to engineer defects into graphene. Firstly defects were induced in a controllable way using chemical method and were analyzed using Raman spectroscopy and Transmission Electron Microscopy which revealed a two step mechanism of defect formation in the graphene structure. We have also studied the effect of charged defects which adsorb onto the graphene surface without forming bonds with it. Unlike in literature where charged particles were deposited onto graphene, here the charged nano particles were present dur- ing the growth process in the copper foil. We believe that due to these nano particles, the intensity of D' phonon is greatly enhanced. Such anomalously higher intensity of D' band compared to D band has not been reported before

Les matériaux conducteurs de basse dimensionnalité électronique peuvent présenter des transitions vers des états électroniques complexes tels que la supraconduction, les Ondes de Densité de Spins (ODS) et les Ondes de Densité de Charges (ODC). La coexistence de plusieurs de ces instabilités au sein d’un même matériau a donné lieu à une recherche active de nouveaux systèmes conducteurs quasi-bidimensionnels. Dans cette thèse nous avons choisi de nous intéresser à la famille des Bronzes MonoPhosphate de Tungstène à tunnels pentagonaux (MPTBp), de formule chimique (PO2)4(WO3)2m ; l’un des principaux intérêts réside dans la possibilité de contrôler directement la dimensionnalité du matériau et sa densité de porteurs en faisant varier la valeur de m (2 ≤ m ≤ 14). Dans la littérature il a été montré que certains termes de cette famille (m=4, 5, 6) admettent des états ODC successifs alors que d’autres (m=10) présentent des ordres de type ferro électrique ; l’objectif de cette thèse est alors de montrer l’effet de la dimensionnalité du matériau sur l’apparition et la stabilité de ces états électroniques dans les MPTBp. Pour cela, des mesures de transport électronique, des études des structures modulées incommensurables et commensurables par diffraction des rayons X avant et après chaque transition et des mesures de diffusion inélastique ont été effectuées sur plusieurs termes à valeur de m pair. Dans ce travail nous avons pu montrer l’existence d’un état ODC pour les termes m=2, 4, 6, 8 et 10, caractérisé par la formation d’amas de tungstène dans certaines régions du matériau, accompagné, pour les m=8 et 10, de l’installation progressive d’une mise en ordre de type anti-ferroélectrique des déplacements des atomes de tungstène. Un phénomène de dépiégeage d’ODC a été observé pour le terme quasi-unidimensionnel m=2, ce qui n’avait encore jamais été reporté chez les MPTBp. Un couplage électron-phonon fort a pu être mis en évidence pour les hauts termes (m ≥ 8) à la fois via les analyses structurales, l’observation de transitions résistives du premier ordre mais également par des mesures de diffusion inélastique des rayons X. Pour ces hauts termes, une transition de type ordre-désordre est alors à envisager. / Conductive materials with low electronic dimensionality can present some transitions toward complex electronic states as superconductivity, Spin Density Waves (SDW) and Charge Density Waves (CDW). The coexistence of several of these instabilities in the same material leads to bustling investigations on new quasi-bidimensional conductors. In this thesis, we chose to study the MonoPhosphate Tungsten Bronzes with pentagonal channels family (MPTBp), of chemical formula (PO2)4(WO3)2m ; one of the main interests of this family is the possibility to directly control the compound’s dimensionality and its carriers density by varying m value (2 ≤ m ≤ 14). In the literature, it’s been shown that some MPTBp members (m=4, 5, 6) present successive CDW states whereas others (m=10) show ferroelectric-type orders. The aim of this thesis is thus to bring into light the effect of the material’s dimensionality on the appearance and the stability of these electronic states in the MPTBp family. In this way, transport measurements, X-Rays diffraction studies of the commensurate and incommensurate modulated structures below and above each transition and inelastic scattering measurements were done on several members with even value of m. In this work we reveal the existence of a CDW state for the m=2, 4, 6, 8 and 10 members, characterized by the formation of tungsten clusters in some areas of the crystal. For the m=8 and 10 members, the CDW is accompanied by a gradual installation of an anti-ferroelectric-like ordering of the tungsten atoms displacements. A CDW depinning phenomenon was observed for the quasi-unidimensional m=2 member, which has never been reported before in the MPTBp family. A strong electron-phonon coupling was evidenced for the high terms of the family (m ≥ 8) by structural analysis, first order resistive transitions observation and by X-Rays inelastic scattering measurements. For these high terms, an order-disorder transition must be considered.

La nanotechnologie a pris un rôle clé dans le développement technologique actuel de façon extrêmement grande et interdisciplinaire. L'utilisation de nanofils dans la construction de structures/dispositifs plus complexe peut être entrevue en raison de sa polyvalence. Comprendre la fabrication de nanofils et être capable de les caractériser est extrêmement important pour ce développement. Des dispositifs à base de nanofils semi-conducteurs et ferromagnétiques ont été étudiés dans cette thèse, abordant les techniques de croissance et d'adressage pour des caractérisations électroniques et structurelles, et pour des développements à grande échelle pour des applications industrielles. Les nanofils de cobalt ont été électro déposés à différents pH permettant d'associer le pH de la solution à la caractérisation de la structure cristalline. Les nanofils de semiconducteurs ont été crus par CVD. L'adressage et l'alignement des nanofils ont été faits par diélectrophorèse couplé avec l'assemblage capillaire. Pour caractériser les nanofils, des techniques de lithographie optique et électronique ont été utilisés pour la fabrication des contacts. Une étude d'interface matériaux semiconducteurs/siliciure a été réalisée démontrant que les valeurs de barrière Schottky sont différentes entre des nanofils de silicium et des matériaux massifs. Dans le cas de nanofils InAs la barrière est imperceptible et il a été constaté que le fil de ZnO était de type p. Les applications ont démontrées différents dispositifs, tels que les transistors, les vannes de spin, capteurs de gaz, de l'humidité et de la lumière. Dans le cadre de vannes de spin, la caractérisation de l'interface semiconducteur/ferromagnétique a permis d'associer la valeur de la hauteur de barrière de Schottky à l'épaisseur de SiO2, qui agit comme une barrière à effet tunnel. Grâce aux mesures de transistors à effet de champ (FET) , nous avons pu identifier le type de porteurs de charge pour chaque matériau, extraire leur mobilité, la tension de seuil... Les capteurs ont été fabriqués à base de nanofils en Si, InAs, et ZnO, afin d'être utilisés comme capteurs de lumière, l'humidité et les gaz. Cette thèse propose une amélioration des technologiques actuelles d'adressage de nanostructures et l'utilisation des propriétés à l'échelle nanométrique pour des dispositifs plus efficaces et une large applicabilité, fournissant la base pour de futures études et les réalisations pratiques des nanosciences et des nanotechnologies. / Nanotechnology is at the center of nowadays technologies in an increasing and very interdisciplinary manner. Sticking together the manufacturing and characterization of the nano-devices and their constituent nanostructures are keys for the development of the field. This thesis covered studies of ferromagnetic (Co) and semiconductors nanowires (Si, InAs and ZnO) based nanodevices. Nanowires growing and correct addressing techniques were studied for measurements and characterizations set ups and for large-scale industrial applications possibilities. The growing techniques were electrodeposition and CVD. Different pHs were used for the solutions in the case of the Co nanowires growing that were, than, connected by means of electronic lithography. The resulting measurements enabled us to associate the pH to the crystalline structure characterization. The nanowires addressing was made using the dieletrophoresis technique coupled to capillary assembly and also by contacting the isolated nanowire by means of electronic lithography. The contact made in the nanowire was favored by the silicidation technique. For this two different materials, Pt and Ni, compatible with the CMOS technology. A deep study of the interface semiconductor/silicidation was performed and the Schottky Barrier of Si nanowires was verified to be smaller than the barrier in the bulk form of Si. In the InAs nanowires case an imperceptible barrier was found. The ZnO nanowires were found to be of p-type. The following devices were manufactured: top/back-gate transistors, lateral spin valves (local and non-local valves) and multilayer-nanowires based spin valves (local valves). The semiconductor nanowires sensors (gas, humidity and luminosity) were also manufactured and tested. In the spin valves context the interface semiconductor/ferromagnetic material was studied in order to associate the Schottky Barrier height to the SiO2 width that acts as a tunnel barrier. From the semiconductors nanowires based field effect transistors (FETs) measurements it was possible to verify the charge carriers type for each different material, to extract its mobility, threshold voltage and others. The manufactured sensors were made of Si, InAs and ZnO nanowires and the main aim was to use them as gas, humidity and luminosity sensors. The ZnO nanowires have been seen to be light sensitive whereas the Si and InAs nanowires responded to the presence of humidity and of pollutant gases, e.g. the NO2.

The work presented in this thesis was broadly focussed on the investigation of the magnetic behaviour of different superconducting materials in the form of bulk (singe crystals and pellets) and thin films (nanomagnetic devices like superconducting spin valves etc). Neutrons and muons were extensively used to probe the structural and magnetic behaviour of these systems at the nanoscale along with bulk characterisation techniques like high-sensitive magnetic property measurements, scanning probe microscopy and magneto-transport measurements etc. The nanoscale interplay of Superconductivity and Ferromagnetism was studied in the thin film structures using a combination of Polarised Neutron Reflectivity (PNR) and Low Energy Muon Spin Rotation (LE-µSR) techniques while bulk Muon Spin Rotation (µSR) technique was used for microscopic magnetic investigation in the bulk materials. In the Fe/Pb heterostructure, evidence of the Proximity Effect was observed in the form of an enhancement of the superconducting penetration depth (λs) with an increase in the ferromagnetic layer thickness (dF) in both the bilayered and the trilayered structures. The existence of an Inverted Magnetic Region was also detected at the Ferromagnet-Superconductor (F/S) interface in the normal state possibly originating from the induced spin polarisation within the Pb layer in the presence of the neighbouring Fe layer(s). The spatial size (height and width) of the Inverted Magnetic Region did not change much while cooling the sample below the superconducting transition temperature(Tc)and it also stayed unaffected by an increase in the Fe layer thickness and by a change of the applied magnetic field. In the superconducting spin valve structure containing Permalloy (Py) as ferromagnetic layer and Nb as the superconducting layer, LE-µSR measurements revealed the evidence of the decay of magnetic flux density (as a function of thickness) within the Nb layer symmetrically from the Py/Nb interfaces towards the centre of the Nb layer in the normal state. The thickness dependent magnetisation decay occurred over two characteristic length scales in the normal state that stayed of similar values in the superconducting state also. In the superconducting state, an additional contribution towards the magnetisation was found in the vicinity of the Py/Nb interfaces possibly originating from the spin polarisation of the singlet Cooper pairs in these areas. The nanoscale magnetic investigation on a highly engineered F/S/F structure (where each of the F blocks made of multiple Co/Pd layers with magnetic moments aligned perpendicular to the plane of these layers and neighbouring magnetic blocks separated by Ru layers giving rise to antiferromagnetic alignment) using LE-µSR showed an antisymmetric thickness dependent magnetic flux density profile with two characteristic length scales. In the superconducting state, the magnetic flux density profile got modified within the superconducting Nb₆₇Ti₃₃ layer near the F/S interfaces in a way similar to that of observed in the case of Py/Nb system, most likely because of the spin polarisation of the superconducting electron pairs. The vortex magnetic phase diagram of Bi₂Sr₂Ca₂Cu₃O10-δ was studied using the Muon Spin Rotation (µSR) technique to explore the effects of vortex lattice melting and rearrangements for vortex transitions and crossover as a function of magnetic field and temperatures. At low magnetic fields, the flux vortices undergo a first order melting transition from a vortex lattice to a vortex liquid state with increasing temperature while another transition also occurred with increasing field at fixed temperature to a vortex glass phase at the lowest temperatures. Evidence of a frozen liquid phase was found in the intermediate field region at low temperature in the form of a lagoon in the superconducting vortex state which is in agreement with earlier observations made in BiSCCO-2212. The magnetic behaviour of the unconventional superconductor Sr₂RuO₄ was investigated using µSR to find the evidence of normal state magnetism and the nature of the vortex state. In the normal state, a weak hysteretic magnetic signal was detected over a wide temperature and field range believed to be supporting the evidence of a chiral order parameter. The nature of the vortex lattice structure was obtained in different parts of the magnetic phase diagram and the evidence of magnetic field driven transition in the lattice structure was detected from a Triangular→Square structure while the vortex lattice stayed Triangular over the entire temperature region below Tc at low fields with a disappearance of pinning at higher temperatures.