The next generation of optoelectronic applications like stimuli-responsive sensors, functional displays or nanophotonic circuits demands a basic understanding of lightmatter interactions on the nanoscale. Top-down fabrication has been employed in the past to demonstrate coherent energy transfer in functional nanostructures, yet these fabrication methods are problematic due to their limited scalability and high costs as well as the high optical losses. This work adapted physical principles like radiation properties of metallic nanoantennas and Bragg diffraction in periodic nanostructures and realized these concepts using bottom-up self-assembly methods based on colloidal chemistry. With this approach, single plasmonic nanoparticles and semiconductor quantum emitters were co-assembled into complex structures. This work took the colloidal concept from plasmonics and introduced quantum dots in order to characterize the radiative and non-radiative decay processes as well as the arising light-matter interactions. Due to electromagnetic coupling between the components, hybridized modes were detected instead of the single particle resonances observed in the isolated case. It was furthermore shown that these colloidal building blocks can be assembled into functional optical grids on a large scale using template-assisted self-assembly. Thus, this work established spectroscopic principles for self-assembled colloidal building blocks that can be integrated in parallelized processes in the future.

No description available.

Three-dimensional nanocomposite networks consisting of percolated Si nanowires in a SiOx matrix, Si:SiO2, were studied. The structures were obtained by reactive ion beam sputter deposition of SiOx (x~0.6) thin films at 450 °C and subsequent crystallization using conventional oven as well as millisecond line focus laser annealing. Rutherford backscattering spectrometry, Raman spectroscopy, X-ray diffraction, cross-sectional and energy-filtered transmission electron microscopy were applied for sample characterization. While oven annealing resulted in a mean Si wire diameter of 10 nm and a crystallinity of 72 % within the Si volume, almost single-domain Si structures with 30 nm in diameter and almost free of amorphous Si were obtained by millisecond laser application. The structural differences are attributed to the different crystallization processes: Conventional oven tempering proceeds via solid state, millisecond laser application via liquid phase crystallization of Si. The 5 orders of magnitude larger diffusion constant in the liquid phase is responsible for the three times larger Si nanostructure diameter. In conclusion, laser annealing offers not only significantly shorter process times but moreover a superior structural order of nano-Si compared to conventional heating.

Polyhedral Oligomeric Silsesquioxane (POSS) cages are investigated in terms of their potential to enclose small metal hydrides, with the objective of defining conditions that maximize the number of encapsulated hydrogen atoms. Systems of the form MH2n@Tm, where n = 1-3, m = 8, 10, and M comprises metal atom species of the groups IV, VI, VIII, X, and XII, are studied by methods of ab initio and density functional theory (DFT). The resulting composites are categorized with respect to their structural and energetic features. For MH2@T8, it is found in all cases considered that including MH2 into the POSS cage is an endothermic process. For MH2@T10 and M = Ti, Ru, Os, Pt, inclusion of the MH2 guest into the cage turns out to be exothermic, and also leaves the cage intact. For MH4@Tm, this behavior is only observed for one system, OsH4@T10.

Polyhedral Oligomeric Silsesquioxane (POSS) cages are investigated in terms of their potential to enclose small metal hydrides, with the objective of defining conditions that maximize the number of encapsulated hydrogen atoms. Systems of the form MH2n@Tm, where n = 1-3, m = 8, 10, and M comprises metal atom species of the groups IV, VI, VIII, X, and XII, are studied by methods of ab initio and density functional theory (DFT). The resulting composites are categorized with respect to their structural and energetic features. For MH2@T8, it is found in all cases considered that including MH2 into the POSS cage is an endothermic process. For MH2@T10 and M = Ti, Ru, Os, Pt, inclusion of the MH2 guest into the cage turns out to be exothermic, and also leaves the cage intact. For MH4@Tm, this behavior is only observed for one system, OsH4@T10.

The spin-dependent transmission properties of (0,8) graphene nanoribbons (GNRs) with two substitutional Fe atom impurities (2Fe-aGNRs) have been studied by the non-equilibrium Green's function (NEGF) method in conjunction with density functional theory (DFT). Emphasis is placed on the spin-filtering activity of current transmission elements derived from these structures. In particular, it is shown that devices based on 2Fe-aGNR approach the limit of half-metallicity, where the magnitude and the sign of the current spin polarization is controlled by the bias across the device as well as the spin state of the 2Fe subsystem. This effect is rationalized by electronic structure and partial-density-of-states (PDOS) analysis of the transmission element. An occupied spin minority state, induced by the Fe-atom moiety and close to the Fermi energy of 2Fe-aGNR, accounts for the predominance of minority spin polarization. Comparison with nanosystems obtained from 2Fe-aGNR, involving vacancies rather than impurities, or both types of defects, reveals that substantial degrees of current spin polarization prevail across a wide variety of device types.

La pollution des eaux par des composés organiques constitue un problème mondial majeur. Parmi cescomposés, les molécules aromatiques de faibles masses molaires constituent une famille largementrependue dont la toxicité et la cancérogénicité est avérée et bien documentée. La Directive-CadreEuropéenne sur l’eau (2000/60/EC, 2006/118/EC and 2006/11/EC) établit des normes de qualitéenvironnementales ayant pour objectif d’améliorer la qualité des eaux. Dans ce contexte, ledéveloppement d’outils analytiques robustes, permettant de détecter et de quantifier précisément et insitula présence de polluants dans les eaux est d’une importante primordiale. L’objectif principal de cetteétude est l’élaboration de nanocapteurs sensibles, robustes et réutilisables, permettant l’analyse depolluants organiques dans les eaux grâce à la Spectroscopie Raman Exaltée de Surface (SERS).Tout d’abord, une attention particulière a été portée à la sélection des récepteurs et des différentesstratégies de fonctionnalisation permettant d’élaborer un nanocapteur SERS capable de pré-concentrerles polluants visés. L’utilisation d’antigènes et de fragments d’antigènes (F(ab)2) a montré des résultatsprometteurs pour l’élaboration de nanocapteurs très sélectifs. Une seconde approche basée surl’utilisation de cavitants ou molécules hôtes, telles que les cyclodextrines (CDs), a été développée. Lapré-concentration sélective des polluants grâce à leur taille a été démontrée par spectroscopie Raman etSERS. Enfin, grâce à la possibilité d’identification moléculaire en milieu complexe offerte par laspectroscopie SERS, une approche permettant une pré-concentration non spécifique des polluants a étédéveloppée. Pour ce faire, différents sels de diazoniums (DSs) ont été synthétisés et greffés à la surfacedes nanocapteurs afin de créer une couche hydrophobe permettant la pré-concentration et la détection decomposés apolaires. Les performances de ces nano-capteurs ont été démontrées pour la détection de plusieurs PAHs apolaires. / Environmental water pollution by organic compounds is in continues worldwide concern. Low molecular mass aromatic molecules consisting in benzene rings have received considerable attention due to a documented significant toxicity and carcinogenicity. Within the objectives of the European Water Framework Directives (2000/60/EC, 2006/118/EC and 2006/11/EC) aiming in water quality improvement, the development of analytical tools allowing in-situ accurate and sensitive detection is of primary importance and would be a meaningful innovation. With this regard, the main scope of this study was to design sensitive, reproducible, specific and reusable nanosensor for the detection of organic pollutants in environmental waters using Surface Enhanced Raman Spectroscopy (SERS).During this study the main attention was paid to the selection of suitable receptors and strategies for SERS nanosensor surface functionalisation in order to preconcentrate targeted pollutants. The application of antibodies and antigen binding fragments (F(ab)2) for surface decoration was found to be promising approach for highly selective nanosensor design. Another strategy exploited during this study was related with an application of cyclodextrins (CDs). Using Raman and SERS spectroscopies the size selective encapsulation of analytes was demonstrated. Finally, taking advantage of molecular identification in the complex environments offered by SERS technique, nanosensors providing non-specific molecular pre-concentration was considered. For this purpose several diazonium salts (DSs) were studied and applied to the surface functionalisation to create highly hydrophobic coating layer. The performance of such nanosensor was evaluated by detection of aromatic pollutants.

No description available.

Magnetic nanoparticles and molecules, in particular ferromagnetic noble metal nanoparticles, molecular magnet and single-molecule magnets (SMM), are perfect examples to investigate the role of quantum mechanics at the nanoscale. For example, SMMs are known to reverse their magnetization by quantum tunneling in the absence of thermal excitation and show a number of fundamental quantum mechanical manifestations, such as quantum interference effects. On the other hand, noble metal nanoparticles are found to behave ferromagnetically for diameters below a few nanometers. Some of these manifestations are still intriguing, and novel research approaches are necessary to advance towards a more complete understanding of these exciting nanoscale systems. In particular, the ability to study an isolated individual nanoscale system (i.e just one molecule or nanoparticle) is both challenging technologically and fundamentally essential. It is expected that accessing to the energy landscape of an isolated molecule/nanoparticle will allow unprecedented knowledge of the basic properties that are usually masked by collective phenomena when the systems are found in large ensembles or in their crystal form. Several approaches to this problem are currently under development by a number of research groups. For instance, some groups are developing deposition techniques to create patterned thin films of isolated magnetic nanoparticles and molecular magnets by means of optical lithography, low-energy laser ablation, or pulsed-laser evaporation or specific chemical functionalization of metallic surfaces with special molecular ligands. However, it is still a challenge to access the properties of an individual molecule or nanoparticle within a film or substrate. iv I have studied molecular nanomagnets and ferromagnetic noble metal nanoparticles by means of a novel experimental approach that mixes the chemical functionalization of nano-systems with the use of single-electron transistors (SETs). I have observed the Coulomb-blockade single-electron transport response through magnetic gold nanoparticles and single-molecule magnet. In particular, Coulomb-blockade response of a Mn4-based SET device recorded at 240 mK revealed the appearance of two diamonds (two charge states) with a clear switch between one and the other is indicative of a conformational switching of the molecule between two different states. The excitations inside the diamonds move with magnetic field. The curvature of the excitations and the fact of having them not going down to zero energy for zero magnetic field, indicated the presence of magnetic anisotropy (zero-field splitting) in the molecule. In addition, the high magnetic field slope of the excitations indicates that transitions between charge states differ by a net spin value equal to 9 (|∆S| = 9), as expected from the behavior of Mn4 molecules in their crystalline form. Anticrossings between different excitations are indicative of quantum superpositions of the molecular states, which are observed for the first time in transport measurements through and individual SMM.

Detection of explosive gas leaks such as hydrogen (H2) becomes key element in the wake of counter-terrorism threats, introduction of hydrogen powered vehicles and use of hydrogen as a fuel for space explorations. In recent years, a significant interest has developed on metal oxide nanostructured sensors for the detection of hydrogen gas. Gas sensors properties such as sensitivity, selectivity and response time can be enhanced by tailoring the size, the shape, the structure and the surface of the nanostructures. Sensor properties (sensitivity, selectivity and response time) are largely modulated by operating temperature of the device. Issues like instability of nanostructures at high temperature, risk of hydrogen explosion and high energy consumption are driving the research towards detection of hydrogen at low temperatures. At low temperatures adsorption of O2- species on the sensor surface instead of O- (since O- species reacts easily with hydrogen) result in need of higher activation energy for hydrogen and adsorbed species interaction. This makes hydrogen detection at room temperature a challenging task. Higher surface area to volume ratio (resulting higher reaction sites), enhanced electronic properties by varying size, shape and doping foreign impurities (by modulating space charge region) makes nanocrystalline materials ideal candidate for room temperature gas sensing applications. In the present work various morphologies of nanostructured tin oxide (SnO2) and indium (In) doped SnO2 and titanium oxide (titania, TiO2) were synthesized using sol-gel, hydrothermal, thermal evaporation techniques and successfully integrated with the micro-electromechanical devices H2 at ppm-level (as low as 100ppm) has been successfully detected at room temperature using the SnO2 nanoparticles, SnO2 (nanowires) and TiO2 (nanotubes) based MEMS sensors. While sensor based on indium doped tin oxide showed the highest sensitivity (S =Ra/Rg= 80000) and minimal response time (10sec.). Highly porous SnO2 nanoparticles thin film (synthesized using template assisted) showed response time of about 25 seconds and sensitivity 4. The one dimensional tin oxide nanostructures (nanowires) based sensor showed a sensitivity of 4 and response time of 20 sec. Effect of aspect ratio of the nanowires on diffusion of hydrogen molecules in the tin oxide nanowires, effect of catalyst adsorption on nanowire surface and corresponding effect on sensor properties has been studied in detail. Nanotubes of TiO2 prepared using hydrothermal synthesis showed a sensitivity 30 with response time as low as 20 seconds where as, TiO2 nanotubes synthesized using anodization showed poor sensitivity. The difference is mainly attributed to the issues related to integration of the anodized nanotubes with the MEMS devices. The effect of MEMS device architecture modulation, such as, finger spacing, number and length of fingers and electrode materials were studied. It has been found that faster sensor response (~ 10 sec) was observed for smaller finger spacing. A diffusion model is proposed for elucidating the effect of inter-electrode distance variation on conductance change of a nano-micro integrated hydrogen sensor for room temperature operation. Both theoretical and experimental results showed a faster response upon exposure to hydrogen when sensor electrode gap was smaller. Also, a linear increase in the sensor sensitivity from 500 to 80000 was observed on increasing the electrode spacing from 2 to 20 μm. The improvement in sensitivity is attributed to the higher reactive sites available for the gaseous species to react on the sensor surface. This phenomenon also correlated to surface adsorbed oxygen vacancies (O-) and the rate of change of surface adsorbed oxygen vacancies. This dissertation studied in detail dimensionality aspects of materials as well as device in detecting hydrogen at room temperature.