No description available.

Nanocrystal has non-negligible ratio of the surface atoms. The photophysics of the nanocrystal is strongly influenced by the surface states.There are two surface-related phenomena: the on-off blinking and the red-emission. On-off blinking is a phenomenon commonly observed in thesingle emitters, such as dye molecules and semiconductor quantum dots (QD).In the QD, the charged state caused by the charge transferring from the core to the surface states explains the off-state. Another surface-related phenomenon is the red-emission, which is the emission from the low-lying surface trapped states. This thesis investigates the correlation between the on-off blinking and the red-emissions of the semiconductor nanocrystals. CdSe/ZnS core/shell colloidal nanocrystals with 2.1nm in diameter and emission peak at 515nm were examined. PL spectrum in the solution indicates that besides the band-edge emission, there is a broadband emission spanning the wavelength range of 590 ¡V 800 nm, which is called the red-emission. The lifetime of the band-edge emission is about 20ns, and that of the red-emission is about 200ns. Since they are with different fluorescence lifetime, the band-edge emission and the red-emission are from distinct emission species. Emission intensity from individual QDs of the band-edge emission and the red-emission are recorded by an imaging CCD. Most QDs exhibit band-edge emission. Only few QDs show the red-emission. Both emissions exhibit clear on-off blinking, indicating the two phenomena are with different mechanism.Moreover, the band-edge emission and the red-emission are mutual exclusive.None QDs exhibit both emissions. This indicates the tiny structure difference from one QD particle to another QD particle resulting in a dramatic different of the excitation energy relaxation pathway.

No description available.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20630号 / 工博第4368号 / 新制||工||1679(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 阿部 竜, 教授 作花 哲夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Within the "forbidden" range of electron energies between the valence and conduction bands of titanium dioxide, crystal lattice irregularities lead to the formation of electron trapping sites. These sites are known as shallow trap states, where "shallow" refers to the close energy proximity of those features to the bottom of the semiconductor conduction band. For wide bandgap semiconductors like titanium dioxide, shallow electron traps are the principle route for thermal excitation of electrons into the conduction band. The studies described here employ a novel infrared spectroscopic approach to determine the energy of shallow electron traps in titanium dioxide nanoparticles. Mobile electrons within the conduction band of semiconductors are known to absorb infrared radiation. As those electrons absorb the infrared photons, transitions within the continuum of the conduction band produce a broad spectral signal across the entire mid-infrared range. A Mathematical expression based upon Fermi–Dirac statistics was derived to correlate the temperature of the particles to the population of charge carriers, as measured through the infrared absorbance. The primary variable of interest in the Fermi – Dirac expression is the energy difference between the shallow trap states and the conduction band. Fitting data sets consisting of titanium dioxide nanoparticle temperatures and their associated infrared spectra, over a defined frequency range, to the Fermi–Dirac expression is used to determine the shallow electron trap state energy. / Master of Science

Les aciers inoxydables martensitiques sont utilisés dans l'industrie aéronautique où de hautes propriétés mécaniques sont requises. Cependant, dû à leur faible teneur en chrome, ils sont relativement sensibles à la corrosion localisée et particulièrement à la corrosion caverneuse qui se développe en milieu confiné. Tout d'abord, le comportement électrochimique de l'acier inoxydable martensitique X12CrNiMoV12-3 a été étudié dans une solution neutre et chlorurée (NaCl 0,1 M + Na2SO4 0,04 M) en plein bain. Des mesures électrochimiques (courbes de polarisation et mesures d'impédance) couplées à des analyses de surface par XPS ont permis de caractériser les films passifs formés pour différentes conditions. Les résultats obtenus ont permis de montrer le rôle important joué par l'oxygène dissous sur la formation et/ou la modification du film passif pendant l'immersion dans l'électrolyte. Les diagrammes d'impédance obtenus au potentiel de corrosion et en milieu aéré sont caractérisés par deux constantes de temps qui ont été attribuées au film passif (hautes fréquences) et au transfert de charges (basses fréquences). L'analyse de la partie hautes fréquences des diagrammes d'impédance électrochimique à l'aide du modèle en loi de puissance a permis de montrer de faibles variations de l'épaisseur des films pendant l'immersion. Des mesures électrochimiques ont ensuite été réalisées à l'aide du montage de la cellule à couche mince qui permet de travailler avec des épaisseurs d'électrolyte rigoureusement contrôlées. Les essais réalisés ont montré l'aptitude à la repassivation de l'acier inoxydable martensitique dès qu'il est en contact avec l'oxygène dissous en particulier pour des faibles épaisseurs d'électrolyte (inférieur à 100 µm). Lorsque le milieu est confiné entre deux parois en acier afin de reproduire une situation de corrosion caverneuse, il a été montré la corrosion est fortement accélérée lorsque l'épaisseur d'électrolyte est faible (inférieur à 500 µm). / Martensitic stainless steels are mainly used for applications where high mechanical performance is required. However, due to the low chromium content, they are relatively sensitive to localised corrosion, and particularly, to crevice corrosion encountered in confined environments. First, the electrochemical behavior of X12CrNiMoV12-3 martensitic stainless steel has been studied in a bulk neutral chloride solution (0.1 M NaCl + 0.04 M Na2SO4). Electrochemical measurements (polarisation curves and impedance measures) and XPS surface analysis were performed in order to characterise the passive films formed under different experimental conditions. The results showed the important role of dissolved oxygen to form and/or modify the passive film during immersion in electrolyte. The impedance diagrams are characterised by two time constants wich are attributed to passive film response (high frequency range) and to charge transfert resistance (low frequency range). The analyse of the high frequencies part of the diagrams by using the "power law model" showed low evolution of passive films thickness during immersion. Then, electrochemical measurements were perfomed in confined environments by using a thin layer cell where the electrolyte thickness were rigourosly adjusted. The measurements showed that the martensitic stainless steel is in passive state even for low electrolyte thickness (inferior in 100 µm). When the electrolyte is confined between two stainless electrodes in order to reproduce the same conditions find during crevice corrosion, the corrosion is sharply accelerated when the electrolyte thickness is above 500 µm

The development and characterization of experimental setups for angle-resolved photoelectron spectroscopy (ARPES) and spin- and angle-resolved photoelectron spectroscopy (SARPES) is described. Subsequently, the two techniques are applied to studies of the electronic band structure in topologically non-trivial materials. The laser-based ARPES setup works at a photon energy of 10.5 eV and a typical repetition rate in the range 200 kHz to 800 kHz. By using a time-of-flight electron energy analyzer electrons emitted from the sample within a solid angle of up to ±15 degrees can be collected and analyzed simultaneously. The SARPES setup is equipped with a traditional hemispherical electron energy analyzer in combination with a mini-Mott electron polarimeter. The system enables software-controlled switching between angle-resolved spin-integrated and spin-resolved measurements, thus providing the possibility to orient the sample by mapping out the electronic band structure using ARPES before performing spin-resolved measurements at selected points in the Brillouin zone. Thin films of the topological insulators (TIs) Bi2Se3, Bi2Te3 and Sb2Te3 are grown using e-beam evaporation and their surface states are observed by means of ARPES. By using a combination of low photon energies and cryogenic sample temperatures the topological states originating from both the vacuum interface (surface) and the substrate interface are observed in Bi2Se3 films and Bi2Se3/Bi2Te3 heterostructures, with total thicknesses in the ultra-thin limit (six to eight quintuple layers), grown on Bi-terminated Si(111) substrates. Band alignment between Si and Bi2Se3 at the interface creates a band bending through the films. The band bending is found to be independent of the Fermi level (EF) position in the bulk of the substrate, suggesting that the surface pinning of EF in the Si(111) substrate remains unaltered after deposition of the TI films. Therefore, the type and level of doping of the substrate does not show any large influence on the size of the band bending. Further, we provide experimental evidence for the realization of a topological crystalline insulator (TCI) phase in the narrow-band semiconductor Pb1−xSnxSe. The TCI phase exists for temperatures below the transition temperature Tc and is characterized by an inverted bulk band gap accompanied by the existence of non-gapped surface states crossing the band gap. Above Tc the material is in a topologically trivial phase where the surface states are gapped. Thus, when lowering the sample temperature across Tc a topological phase transition from a trivial insulator to a TCI is observed. SARPES studies indicate a helical spin structure of the surface states both in the topologically trivial and the TCI phase. / <p>QC 20130507</p>

<p>The demand for the faster information transport and better computational abilities is ever increasing. In the last few decades, the electronic industry has met this requirement by increasing the number of transistors per square inch. This lead to the scaling of devices to tens of nm. However, the speed of the electronics is limited to few GHz. Using light, the operating speed of photonic devices can be much larger than GHz. But the photonic devices are diffraction limited and hence the size of photonic device is much larger than the electronic components. Plasmonics is an emerging field with light-induced surface excitations, and can manipulate the light at nanoscale. It can bridge the gap between electronics and photonics. </p> <p>With the present scaling of devices to few nm, the scientific community is looking for alternatives for continued progress. This has opened up several promising routes recently, including two-dimensional materials, quantum computing, topological computing, spintronics and valleytronics. The discovery of graphene has led to the immense interest in the field of two-dimensional materials. Two dimensional-materials have extraordinary properties compared to its bulk. This work discusses the applications of plasmonics in this emerging field of two-dimensional materials and for heat assisted magnetic recording.</p> <p>Black phosphorus is an emerging low-direct bandgap two-dimensional semiconductor, with anisotropic optical and electronic properties. It has high mobility and is promising for photo detection at infrared wavelengths due to its low band gap. We demonstrate two different plasmonic designs to enhance the photo responsivity of black phosphours by localized surface plasmons. We use bowtie antenna and bowtie apertures to increase the absorption and polarization selectivity respectively. Plasmonic structures are designed by numerical electromagnetic simulations, and are fabricated to experimentally demonstrate the enhanced photo responsivity of black phosphorus. </p> <p>Next, we look at another emerging two-dimensional material, bismuth telluride selenide (Bi₂Te₂Se). It is a topological insulator with an insulating bulk but conducting electronic surface states. These surface states are Dirac like, similar to graphene and can lead to exotic plasmonic phenomena. We investigated the optical properties of Bi₂Te₂Se and found that the bulk is plasmonic below 650 nm wavelength. We study the distinct surface plasmons arising from the bulk and surface state of the topological insulator, Bi₂Te₂Se. The propagating surface plasmons at a nanoscale slit in Bi₂Te₂Se are imaged using near-field scanning optical microscopy. The surface state plasmons are studied with a below band gap excitation of 10.6 µm wavelength and the surface plasmons of the bulk are studied with a visible wavelength of 633 nm. The surface state plasmon wavelength is 100 times shorter than the incident wavelength in sharp contrast to the plasmon wavelength of the bulk. </p> <p>Next, we look at the application of plasmonics in heat assisted magnetic recording (HAMR). HAMR is one of the next generation data storage technology that can increase the areal density to beyond 1 Tb/in². Near-field transducer (NFT) is a key component of the HAMR system that locally heats the recording medium by concentrating light below the diffraction limit using surface plasmons. In this work, we use density-based topology optimization for inverse design of NFT for a desired temperature profile in the recording medium. We first perform an inverse thermal calculation to obtain the required volumetric heat generation (electric field) for a desired temperature profile. Then an inverse electromagnetic design of NFT is performed for achieving the desired electric field. NFT designs for both generating a small heated spot size and a heated spot with desired aspect ratio in recording medium are demonstrated. The effect of waveguide, write pole and moving recording medium on the heated spot size is also investigated. </p>

Diese Arbeit beschäftigt sich mit theoretischen Untersuchung von Oberflächenzuständen in ferromagnetischen Halbleitern. Einleitend wird ein analytisches "tight-binding"-Modell zur Beschreibung der Oberflächenzustände. Es liefert Aussagen zur Existenz von Oberflächenzuständen, zu deren spektralen Gewicht und Position bezüglich der Energie. Das Kondogitter-Modell wird verwendet, um Korrelations- und Temperatureffekte sowie Oberflächenzustände zu beschreiben. Dies erfolgt zunächst für sc-(100)-Modellfilme im Rahmen des sf-Modells. Die temperaturabhängigen der Oberflächenzustände zeigen abhängig vom Ort in der Brillouinzone sowie den "hopping"-Parametern in der Oberfläche sowohl Stoner-artiges als auch "spin-mixing"-Verhalten. Mit wachsender Temperatur werden Lebensdauereffekte in den Spektren sichtbar. Das Kondogitter-Modell (KLM) wird auf die Mehrbandsituation zum df-Modell verallgemeinert, um eine Beschreibung der Prototypen für magnetische Halbleiter EuS und EuO zu erreichen. Durch die Kombination von LDA-Bandstrukturrechnungen mit Vielteilchenrechnungen zum Multiband-KLM ist es gelungen, die ausgeprägte Temperaturabhängigkeit des unbesetzten 5d-Leitungsbandes und das Verhalten der Oberflächenzustände in EuS- und EuO-Filmen realistisch zu beschreiben. Der exakte Grenzfall des Kondogitter-Modells, das magnetischen Polaron (T=0), ermöglicht Kombination von ab-initio-Bandstrukturrechnungen und der Vielteilchentheorie ohne das Auftreten von Doppelzählungen relevanter Wechselwirkungen. Sowohl in EuO als auch in EuS temperaturabhängige Oberflächenzustände beobachtet werden, die im Fall von EuS jedoch schwerer nachzuweisen sind, da sie im Energiebereich des Volumenbandes auftreten. Die für EuS und EuO berechneten Rotverschiebungen sowie die dickenabhängige Magnetisierung von EuS stimmen hervorragend mit experimentellen Befunden überein. Eine Vielzahl von Korrelationseffekten ist mit wachsender Temperatur in den Spektren der unbesetzten Europium-5d-Bänder zu beobachten. / This work is dedicated to the theoretical investigation of surface states in ferromagnetic semiconductors. After the introduction a exact solvable analytical model is presented. It figures out for given conditions if surface states exist, which spectral weight they have, and at which position in energy they can be found. Thereafter the Kondo-Lattice-Model (KLM) is used to describe correlation and temperature effects. The description focuses initially to the sc-(100) model films in the sf-model. The resulting temperature dependent surface states both Stoner behavior and "spin-mixing" behavior dependent on the chosen hopping parameters and the position in the two dimensional Brillouin zone. With increasing temperature (up to Tc) lifetime effects arise in the spectra. In conclusion the KLM is extended to the multi-band situation (df-Model) in order to provide a description of the prototypes of magnetic semiconductor EuS and EuO. We succeed in describing the distinct temperature dependence of the unoccupied 5d-conduction band and the behavior of the surface states in EuS and EuO films realistically by a combination of a LDA band-structure calculation and the manybody theory. The exact limiting case of the KLM (T=0) -the magnetic polaron- allows a combination of a ab-initio band-structure calculation and manybody theory without double counting of any relevant interaction. The presented theory provides numerous results. In EuO and EuS can be found temperature dependent surface states. In case of EuS it''s detection is much more complicated thus the surface state energies are located inside the energy range of the bulk band. The famous redshift in EuS and EuO and the thickness dependent film magnetization of EuS agree very well with the experimental results. A lot of correlation effects are present in the calculated unoccupied Europium 5d bands. With increasing temperature these effects become stronger.

Des puits quantiques à base d'hétérostructures In0.53 Ga0.47 As/In0.52 Al0.48 As, fabriqués par épitaxie par jets moléculaires sur substrats InP(111)A, sont étudiés par microscopie et spectroscopie à effet tunnel à basse température et sous ultra-vide. La première partie est consacrée à une étude de la surface épitaxiée (111)A de In0.53 Ga0.47 As de type n. Il est découvert que le niveau de Fermi de surface est positionné dans la bande de conduction, à proximité du niveau de Fermi de volume, et peut être partiellement contrôlé en variant la concentration d'impuretés de type n dans le volume. Ce résultat est confirmé en déterminant la relation de dispersion de la bande de conduction en surface. Un tel dépiégeage partiel du niveau de Fermi de surface indique que la densité d'états de surface accepteurs est faible. Il est proposé que ces états proviennent de défauts ponctuels natifs localisés à la surface. La deuxième partie, basée sur les résultats obtenus dans la première partie, est consacrée à une étude de puits quantiques In0.53 Ga0.47 As de surface, déposés sur des barrières In0.52 Al0.48 As selon la direction (111)A. Les mesures sont conduites sur la surface épitaxiée (111)A du puits quantique In0.53 Ga0.47 As, de manière à pouvoir sonder à l'échelle du nanomètre la distribution de densité locale d'états électroniques dans le plan du puits quantique. Il est confirmé que des sous-bandes électroniques sont formées dans le puits quantique, et que la concentration d'électrons dans le puits peut être contrôlée du fait du dépiégeage partiel du niveau de Fermi de surface. Il est découvert qu'un phénomène de percolation d'états localisés survient dans la queue de chaque sous-bande, ce qui indique la présence d'un potentiel désordonné dans le puits quantique. Les seuils de percolation sont déterminés en utilisant un modèle semi-classique. L'origine du potentiel désordonné est attribuée à une distribution aléatoire des défauts ponctuels natifs à la surface du puits quantique. Il est également découvert qu'un état lié apparaît au bas de chaque sous-bande à proximité d'un défaut ponctuel natif de type donneur. L'énergie de liaison et le rayon de Bohr des états liés peuvent être directement déterminés. De plus, il est démontré que l'énergie de liaison et le rayon de Bohr sont fonctions de l'épaisseur du puits quantique, en accord quantitatif avec des calculs variationnels d'impuretés dans le modèle de l'atome d'hydrogène.