Controlling the morphology of nanocrystals provides provides a possible pathway to tune properties and hence has been explored in depth. However, to obtain a wider spectrum of properties or for multi-functionality. Other strategies need to be devised. Combining different functional nanostructures to obtain a functional hybrid is one such strategy that holds promise for a wide range of applications. While this is simple in principle, there are no simple and general protocols for synthesis of such functional heterostructure. The challenge lies in producing a hybrid with good control over the structure and chemistry of the interfaces in the system. The use of molecular linkers or physical forces to form the hybrid has several drawbacks in terms of interface quality and stability. In this dissertation, a rational basis is developed for the evolution of symmetry forbidden FCC nanocrystals via wet chemical route which relies on appropriate choice of reagents and the reaction conditions for nucleation and growth. The concept is extended to devise general synthetic strategies for functional nanoheterostrcutres in solution via economic, facile and environment friendly routes. Electron microscopy and X-ray photoelectron spectroscopy has been used as the major tools for structural characterization of the materials and to investigates the reaction/formation mechanism. The properties of the synthesized materials are investigated primarily targeting the nanoelectronic and catalytic applications. The entire study reported in the thesis is organized as follow: chapter I leads to a general introduction of nanocrystals and role in different fields of application. It describes the motivation behind controlling the shape of nanocrystals and combining two or more nanostructures to obtain a functional heterostructure. The existing methodologies to achieve shape control and nanoscale hybrid/heterostructure with active interfaces are elaborated while indicating the role of morphology, interfaces and composition for enhanced activity/performance. The information on the chemical used for synthesis, routers adopted for synthesizing and the basic techniques utilized to characterize the materials in study are detailed in the respective chapters. Chapter 2 provides a study by which one can easily select an appropriate reductant for a metal couple to achieve the desired morphology. Moreover, the role of kinetics and the factors driving the kinetics in obtaining the symmetry breaking shapes like 2-D and I-D for Ag and Au nanocrystals is discussed in detail and validated by experiments. Chapter 3 describes the methodology to attach ultrafine Au nanowires to different nanosubstrates ranging from oxides to carbon (CNT/graphene) where the key step is heteronucleation of the Au (I) precursor on the substrate. Chapter 4 deals with the growth of ultrafine Au nanowires on various substrates and between pre-defined contacts to fabricate nanodevices. The mechanistic investigation directs to the controlled heterogeneous nucleation of the building units (Au nanoparticles) on substrate as the key step followed by its subsequent growth into wires in presence of Au nanoparticles in the medium. Kinetic control of the nucleation and growth step enabled precise control over the population and length of the wires. This is of immense importance for application like catalysis, sensors and nanoelectronics. Moreover, the method enabled the first time electrical transport studies on these wires which revealed an insulating behavior in such metallic wires on progressive lowering of temperature down to few kelvins. The concept of heterogeneous nucleation is extended to design nanoscale heterogeneous in the following three chapters where primarily a precursor coating is formed on a nanosubstrate, viz. ZnO nanorods and graphene, and converted to the phase of interest in a controlled manner to obtain the desired morphology. In each of the chapters the mechanisms of formation of the heterostructure are discussed in detail. Chapter 5 deals with formation of semiconductor based heterostructure like ZnO/CdS in solution by aqueous route. The material has been demonstrated as a potential visible light catalyst for dye degradation with enhanced activity. The interfacial chemistry could be tuned appropriately to achieve high activity in the catalyst by simple wet chemical route. In chapter 6, an ultrafast, facile, green route to obtain oxide supported metal catalyst has been demonstrated. ZnO/Au heterostructures were designed with well defined morphology and studied for low temperature CO oxidation reaction. Detail investigation reveals the surface doping of ZnO with Au the nucleation process leading to active ionic sites for CO oxidation. Chapter 7 demonstrate a rapid and economically viable route to graphene based pt catalysts where a synergistic co-reduction mechanism operates between the metal precursor and the graphic oxide to from the heterostructure. The obtained G-Pt heterostructure exhibits high catalytic activity for methanol oxidation reaction and hydrogen convention at ambient conditions. Finally a conclusion is drawn, highlighting the possibilities and prospects that the study leads to.

The present work focuses on the growth and characterizations of GaN and InN layers and nanostructures on p-Si(100) and p-Si(111) substrates by plasma-assisted molecular beam epitaxy and the studies of GaN/p-Si and InN/p-Si heterojunctions properties. The thesis is divided in to seven different chapters. Chapter 1 gives a brief introduction on III-nitride materials, growth systems, substrates, possible device applications and technical background. Chapter 2 deals with experimental techniques including the details of PAMBE system used in the present work and characterization tools for III-nitride epitaxial layers as well as nanostructures. Chapter 3 involves the growth of GaN films on p-Si(100) and p-Si(111) substrates. Phase pure wurtzite GaN films are grown on Si (100) substrates by introducing a silicon nitride layer followed by low temperature GaN growth as buffer layers. GaN films grown directly on Si (100) are found to be phase mixtured, containing both cubic and hexagonal modifications. The x-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy studies reveal that the significant enhancement in the structural and optical properties of GaN films grown with silicon nitride buffer layer grown at 800 oC, when compared to the samples grown in the absence of silicon nitride buffer layer and with silicon nitride buffer layer grown at 600 oC. Core-level photoelectron spectroscopy of SixNy layers reveals the sources for superior qualities of GaN epilayers grown with the high temperature substrate nitridation process. The discussion has been carried out on the typical inverted rectification behavior exhibited by n-GaN/p-Si heterojunctions. Considerable modulation in the transport mechanism is observed with the nitridation conditions. The heterojunction fabricated with the sample of substrate nitridation at high temperature exhibites superior rectifying nature with reduced trap concentrations. Lowest ideality factors (~1.5) are observed in the heterojunctions grown with high temperature substrate nitridation which is attributed to the recombination tunneling at the space charge region transport mechanism at lower voltages and at higher voltages space charge limited current conduction is the dominating transport mechanism. Whereas, thermally generated carrier tunneling and recombination tunneling are the dominating transport mechanisms in the heterojunctions grown without substrate nitridation and low temperature substrate nitridation, respectively. A brief comparison of the structural, optical and heterojunction properties of GaN grown on Si(100) and Si(111) has been carried out. Chapter 4 involves the growth and characterizations of InN nanostructures and thinfilms on p-Si(100) and p-Si(111) substrates. InN QDs are grown on Si(100) at different densities. The PL characteristics of InN QDs are studied. A deterioration process of InN QDs, caused by the oxygen incorporation into the InN lattice and formation of In2O3/InN composite structures was established from the results of TEM, XPS and PL studies. The results confirm the partial oxidation of the outer shell of the InN QDs, while the inner core of the QDs remains unoxidized. InN nanorods are grown on p-Si(100), structural characterizations are carried out by SEM, and TEM. InN nanodots are grown on p-Si(100), structural characterizations are performed. InN films were grown on Si(100) and Si(111) substrates and structural characterizations are carried out. Chapter 5 deals with the the heterojunction properties of InN/p-Si(100) and InN/p-Si(111).The transport behavior of the InN NDs/p-Si(100) diodes is studied at various bias voltages and temperatures. The temperature dependent ZB BH and ideality factors of the forward I-V data are observed, while it is governed through the modified Richardson’s plot. The difference in FB BH and C-V BH and the deviation of ideality factor from unity indicate the presence of inhomogeneities at the interface. The band offsets derived from C-V measurements are found to be Δ EC=1.8 eV and Δ EV =1.3 eV, which are in close agreement with Anderson’s model. The band offsets of InN/p-Si heterojunctions are estimated using XPS data. A type-III band alignment with a valence band offset of Δ EV =1.39 eV and conduction band offset of ΔEC=1.81 eV is identified. The charge neutrality level model provides a reasonable description of the band alignment of the InN/p-Si interface. The interface dipole deduced by comparison with the electron affinity model is 0.06 eV. The transport studies of InN NR/p-Si(100) heterojunctions have been carried out by conductive atomic force microscopy (CAFM) as well as conventional large area contacts. Discussion of the electrical properties has been carried out based on local current-voltage (I-V) curves, as well as on the 2D conductance maps. The comparative studies on transport properties of diodes fabricated with InN NRs and NDs grown on p-Si(100) substrates and InN thin films grown on p-Si(111) substrates have also been carried out. Chapter 6 deals with the growth and characterizations of InN/GaN heterostructures on p-Si(100) and p-Si(111) substarets and also on the InN/GaN/p-Si heterojunction properties. The X-ray diffraction (XRD), scanning electron microscopy (SEM) studies reveal a considerable variation in crystalline quality of InN with grown parameters. Deterioration in the rectifying nature is observed in the case of InN/GaN/p-Si(100) heterojunction substrate when compared to InN/GaN/p-Si (111) due to the defect mediated tunneling effect, caused by the high defect concentration in the GaN and InN films grown on Si(100) and also due to the trap centers exist in the interfaces. Reduction in ideality factor is also observed in the case of n-InN/n-GaN/p–Si(111) when compared to n-InN/n-GaN/p–Si(100) heterojunction. The sum of the ideality factors of individual diodes is consistent with experimentally observed high ideality factors of n-InN/n-GaN/p–Si double heterojunctions due to double rectifying heterojunctions and metal semiconductor junctions. Variation of effective barrier heights and ideality factors with temperature are confirmed, which indicate the inhomogeneity in barrier height, might be due to various types of defects present at the GaN/Si and InN/GaN interfaces. The dependence of forward currents on both the voltage and temperatures are explained by multi step tunneling model and the activation energis were estimated to be 25meV and 100meV for n-InN/n-GaN/p–Si(100) and n-InN/n-GaN/p–Si(111) heterojunctions, respectively. Chapter 7 gives the summary of the present study and also discusses about future research directions in this area.

Indiana University-Purdue University Indianapolis (IUPUI) / Preparation and characterization of multiferroic materials in which ferroelectricity and ferromagnetism coexist would be a milestone for functionalized materials and devices. First, electric properties of polyvinylidene (PVDF) films fabricated using the Langmuir-Schaefer method have been studied. Films of different thickness were deposited on silicon substrates and analyzed using several techniques. X-ray diffraction (XRD) data showed that PVDF films crystallize at an annealing temperature above 130 °C. Polarization versus electric field (PE) ferroelectric measurements were done for samples prepared with electrodes. PE measurements show that the coercivity of the films increases as the maximum applied electric field increases. The coercivity dependence on the frequency of the applied electric field can be fitted as . The results also show that the coercivity decreases with increasing the thickness of PVDF film due to the pinning effect. Next, we have demonstrated that those PVDF properties can be controlled by applying an external magnetic field. Samples were created in a layered heterostructure, starting with a Fe thin film, PVDF above that, and followed by another thin film of Fe. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to study the interface between PVDF polymer films and ferromagnetic iron thin films. Conventional EXAFS was applied to identify the structure of a Fe film sandwiched between two PVDF layers. An electric signal was then applied to the polymer to study the effects polarizing the polymer has on the Fe atoms at the interface. This shows that the Fe atoms diffuse into the PVDF layer at the interface between the two layers. Polarizing the film causes further diffusion of Fe atoms into the polymer. We also found that as the applied magnetic field is changed, the switching of electric polarization for the PVDF displayed a dependence on the external magnetic field. We also noticed that both the coercivity and polarization for the PVDF polymer display hysteretic features as the applied magnetic field is changed. We also found that the thickness of both the iron layers and the PVDF layer has an effect on the magnetoelectric coupling in our samples. The same strain applied to a thicker PVDF layer becomes tougher to flip the polarization compared to a thinner PVDF layer. As the iron film thickness increases, the strain also increases, and the polarization of the PVDF polymer is more easily flipped. We also found that the magnetoelectric sensitivity increases as both the PVDF and iron layers increase in thickness. We have shown that it is possible to control the ferroelectric properties of a PVDF film by tuning the magnetic field in a heterostructure. Our experiments show a coupling between the electric polarization and applied magnetic field in multiferroic heterostructures much larger than any previously reported values. Previous reports have used inorganic materials for the ferroelectric layer. Organic polymers have an electric dipole originating at the molecular level due to atoms with different electronegativity that are free to rotate. To flip the polarization, the chains must rotate and the position of the atoms must change. This increases the force felt locally by those chains. Using this polymer, we are able to increase the magnetoelectric coupling.

Group III-nitride semiconductors have received much research attention and witnessed a significant development due to their ample applications in solid-state lighting and high-power/high-frequency electronics. Numerous growth methods were explored to achieve device quality epitaxial III-nitride semiconductors. Among the growth methods for III-nitride semiconductors, molecular beam epitaxy provides advantages such as formation of abrupt interfaces and in-situ monitoring of growth. The present research work focuses on the growth and characterizations of III-nitride based epitaxial films, nanostructures and heterostructures on c-sapphire substrate using plasma-assisted molecular beam epitaxy system. The correlation between structural, optical and electrical properties of III-nitride semiconductors would be extremely useful. The interfaces of the metal/semiconductor and semiconductor heterostructures are very important in the performance of semiconductor devices. In this regard, the electrical transport studies of metal/semiconductor and semiconductor heterostructures have been carried out. Besides, studies involved with the defect induced room temperature ferromagnetism of GaN films and InN nano-structures have also been carried out. The thesis is organized in eight different chapters and a brief overview of each chapter is given below. Chapter 1 provides a brief introduction on physical properties of group III-nitride semiconductors. It also describes the importance of III-nitride heterostructures in the operation of optoelectronic devices. In addition, it also includes the current strategy of the emergence of room temperature ferromagnetism in III-nitride semiconductors. Chapter 2 deals with the basic working principles of molecular beam epitaxy system and different characterization tools employed in the present work. Chapter 3 describes the growth of GaN films on c-sapphire by plasma-assisted molecular beam epitaxy. The effects of N/Ga flux ratio on structural, morphological and optical properties have been studied. The flux ratio plays a major role in controlling crystal quality, morphology and emission properties of GaN films. The dislocation density is found to increase with increase in N/Ga flux ratio. The surface morphologies of the films as seen by scanning electron microscopy show pits on the surface and found that the pit density on the surface increases with flux ratio. The room temperature photoluminescence study reveals the shift in band-edge emission towards the lower energy with increase in N/Ga flux ratio. This is believed to arise from the reduction in compressive stress in the GaN films as it is evidenced by room temperature Raman study. The transport studies on the Pt/GaN Schottky diodes showed a significant increase in leakage current with an increase in N/Ga ratio and is found to be caused by the increase in dislocation density in the GaN films. Chapter 4 deals with the fabrication and characterization of Au/GaN Schottky diodes. The temperature dependent current–voltage measurements have been used to determine the current transport mechanism in Schottky diodes. The barrier height (φb) and the ideality factor (η) are estimated from the thermionic emission model and are found to be temperature dependent in nature, indicating the existence of barrier height inhomogeneities at the Au/GaN interface. The conventional Richardson plot of ln(Is/T2) versus 1/kT gives Richardson constant value of 3.23×10-5 Acm-2 K-2, which is much lower than the known value of 26.4 Acm-2 K-2 for GaN. Such discrepancy of Richardson constant value was attributed to the existence of barrier height inhomogeneities at the Au/GaN interface. The modified Richardson plot of ln(Is/T2)-q2σs2/2k2T2 versus q/kT, by assuming a Gaussian distribution of barrier heights at the Au/GaN interface, provides the Schottky barrier height of 1.47 eV and Richardson constant value of 38.8 Acm-2 K-2 which is very close to the theatrical value of Richardson constant. The temperature dependence of barrier height is interpreted on the basis of existence of the Gaussian distribution of the barrier heights due to the barrier height inhomogeneities at the Au/GaN interface. Chapter 5 addresses on the influence of GaN underlayer thickness on structural, electrical and optical properties of InN thin films grown using plasma-assisted molecular beam epitaxy. The high resolution X-ray diffraction study reveals superior crystalline quality for the InN film grown on thicker GaN film. The electronic and optical properties seem to be greatly influenced by the structural quality of the films, as can be evidenced from Hall measurement and optical absorption spectroscopy. Also, we present the studies involving the dependence of structural, electrical and optical properties of InN films, grown on thicker GaN films, on growth temperature. The optical absorption edge of InN film is found to be strongly dependent on carrier concentration. Kane’s k.p model is used to describe the dependence of optical absorption edge on carrier concentration by considering the non-parabolic dispersion relation for carrier in the conduction band. Chapter 6 deals with the analysis of the temperature dependent current transport mechanisms in InN/GaN heterostructure based Schottky junctions. The barrier height (φb) and the ideality factor (η) of the InN/GaN Schottky junctions are found to be temperature dependent. The temperature dependence of the barrier height indicates that the Schottky barrier height is inhomogeneous in nature at the heterostructure interface. The higher value of the ideality factor and its temperature dependence suggest that the current transport is primarily dominated by thermionic field emission (TFE) other than thermionic emission (TE). The room temperature barrier height and the ideality factor obtained by TFE model are 1.43 eV and 1.21, respectively. Chapter 7 focuses on the defect induced room temperature ferromagnetism in Ga deficient GaN epitaxial films and InN nano-structures grown on c-sapphire substrate by using plasma-assisted molecular beam epitaxy. The observed yellow emission peak in room temperature photoluminescence spectra and the peak positioning at 300 cm-1 in Raman spectra confirms the existence of Ga vacancies in GaN films. The ferromagnetism in Ga deficient GaN films is believed to originate from the polarization of the unpaired 2p electrons of nitrogen surrounding the Ga vacancy. The InN nano-structures of different size are grown on sapphire substrate, the structural and magnetic properties are studied. The room temperature magnetization measurement of InN nano-structures exhibits the ferromagnetic behavior. The saturation magnetization is found to be strongly dependent on the size of the nano-structures. Finally, Chapter 8 gives the summary of the present work and the scope for future work in this area of research.

Semiconductor nanowires are nanostructures with lengths up to few microns and small cross sections (10ths of nanometers). In the recent years the development in the field of III-N nanowire technology has been spectacular. In particular they are consider as promising building in nanoscale electronics and optoelectronics devices; such as photodetectors, transistors, biosensors, light source, solar cells, etc. In this work, we present fabrication and the characterization of photodetector and light emitter based devices on III-N nanowires. First we present a study of a visible blind photodetector based on p-i-n GaN nanowires ensembles grown on Si (111). We show that these devices exhibit a high responsivity exceeding that of thin film counterparts. We also demonstrate UV photodetectors based on single nanowires containing GaN/AlN multi-axial quantum discs in the intrinsic region of the nanowires. Photoluminescence and cathodoluminescence spectroscopy show spectral contributions above and below the GaN bandgap according to the variation of the discs thickness. The photocurrent spectra show a sub-band-gap peak related to the interband absorption between the confined states in the large Qdiscs. Finally we present a study of photodetectors and light emitters based on radial InGaN/GaN MQW embedded in GaN wires. The wires used as photodetectors showed a contribution below the GaN bandgap. OBIC measurements demonstrate that, this signal is exclusively generated in the InGaN MQW region. We showed that LEDs based on this structure show a electroluminescence emission and a red shift when the In content present in the QWs increases which is in good agreement with photoluminescence and cathodoluminescence results.

Les phénomènes de diffusion cohérente non-linéaire ont été récemment proposés en alternatives à la fluorescence comme processus de marquage en microscopie multiphotonique. Les matériaux couramment appliqués dans ce contexte buttent toutefois sur une limite inférieure en taille déterminée par le seuil de détection de signaux faibles en optique non-linéaire. Aucun des efforts récents en détection en génération de second-harmonique (GSH), qui est le processus non-linéaire d’ordre le plus bas, n’a permis de descendre à ce jour au-dessous d’une barrière en taille de 40nm même en ayant recours aux techniques de détection les plus sensibles telles que le comptage de photons uniques. Les nanoparticules (NPs) restent ainsi dans la famille des nano-diffuseurs de “grande“ taille. Il apparaît toutefois possible de déplacer de façon significative cette limite inférieure vers les plus petites tailles en substituant aux isolants diélectriques ou aux semi-conducteurs à grands gaps des particules quantiques (PQs) à base de semi-conducteurs à gaps directs.Dans ce travail, un nouveau type de nanosondes hautement non-linéaires a été conçu et développé de façon à franchir cette barrière de taille minimale pour atteindre l’échelle de nanoparticules uniques. Nous considérons ainsi l’excitation résonnante à deux photons de nanoparticules quantiques individuelles à base de CdTe (de la famille des “zinc-blendes”) d’un diamètre d’environ 12.5nm, qui fournissent une émission cohérente efficace par GSH jusqu’à hauteur de 105 comptages de photons par seconde. Elles présentent de plus l’avantage d’une remarquable sensibilité à l’orientation de leur réseau cristallin octupolaire.De plus, il a été démontré que les effets de confinement quantique déterminent fortement les caractéristiques de la susceptibilité non-linéaire du second-ordre χ(2). La caractérisation quantitative du χ(2) des PQs, en particulier leur dispersion spectrale et leur dépendance en taille est menée par spectroscopie de particules uniques ainsi qu’en moyenne d’ensemble par diffusion Hyper-Rayleigh (HRS). Nous fournissons en particulier la preuve que sous certaines conditions, le χ(2) de structures à base de semi-conducteurs en mode de confinement quantique peut très largement dépasser sa valeur en milieu massif. De plus, un nouveau type de PQs hybridant des semi-conducteurs en géométries de type “bâtonnet sur sphère” (BS) a été développé sur la base de composantes cristallines de symétries différentes, afin d’augmenter leur non-linéarité quadratique effective, tout en maintenant leur taille dans un régime proche d’un fort confinement quantique. Le nouveau tenseur hybride complexe χ(2) est analysé en terme d’interférence des susceptibilités constitutives, en prenant en compte les différentes formes et symétries associées aux composantes octupolaires et dipolaires.Il en résulte pour de telles structures une exaltation significative du χ(2), qui excède celle des PQs à constituant unique compte tenu du couplage entre matériaux non-linéaires et d’un temps de décohérence plus long, que nous attribuons à un effet de separation de charge photo-induit. / Nonlinear coherent scattering phenomena from single nanoparticles have been recently proposed as alternative processes for fluorescence in multiphoton microscopy staining. Commonly applied nanoscale materials, however, have reached a certain limit in size dependent detection efficiency of weak nonlinear optical signals. None of the recent efforts in detection of second-harmonic generation (SHG), the lowest order nonlinear process, have been able to cross a ~40 nm size barrier for nanoparticles (NPs), thus remaining at the level of “large” nanoscatterers, even when resorting to the most sensitive detection techniques such as single-photon counting technology. As we realize now, this size limitation can be significantly lowered when replacing dielectric insulators or wide gap semiconductors by direct-gap semiconducting quantum dots (QDs). Herein, a new type of highly nonlinear nanoprobes is engineered in order to surpass above mentioned size barrier at the single nanoparticle scale. We consider two-photon resonant excitation in individual zinc-blende CdTe QDs of about 12.5 nm diameter, which provide efficient coherent SHG radiation, as high as 105 Hz, furthermore exhibiting remarkable sensitivity to spatial orientation of their octupolar crystalline lattice. Moreover, quantum confinement effects have been found to strongly contribute to the second-order nonlinear optical susceptibility χ(2) features. Quantitative characterization of the χ(2) of QDs by way of their spectral dispersion and size dependence is therefore undertaken by single particle spectroscopy and ensemble Hyper-Rayleigh Scattering (HRS) studies. We prove that under appropriate conditions, χ(2) of quantum confined semiconducting structures can significantly exceed that of bulk. Furthermore, a novel type of semiconducting hybrid rod-on-dot (RD) QDs is developed by building up on crystalline moieties of different symmetries, in order to increase their effective quadratic nonlinearity while maintaining their size close to a strong quantum confinement regime. The new complex hybrid χ(2) tensor is analyzed by interfering the susceptibilities from each component, considering different shape and point group symmetries associated to octupolar and dipolar crystalline structures. Significant SHG enhancement is consequently observed, exceeding that of mono-compound QDs, due to a coupling between two nonlinear materials and slower decoherence, which we attribute to the induced spatial charge separation upon photoexcitation.

Grâce au récent développement des synthèses chimiques en suspension colloïdale, de nouveaux photosensibilisateurs possédant une grande surface spécifique ont été envisagés dans cette thèse pour supporter des réactions d'oxydoréduction induite par la lumière. Ce travail s'inscrit donc dans la recherche de nouvelles sources d'énergie pour répondre aux problèmes inhérents à l'appauvrissement des énergies fossiles. Ainsi des nanobâtonnets quantiques de composition cœur@coquille et des nanobâtonnets d'or ont été synthétisés. Leur anisotropie de forme permet également de les assembler dans des phases cristal liquides. Grâce à une méthode de séchage originale, des assemblages hiérarchiques ont été obtenus, ce qui est prometteur pour réaliser des réactions de photocatalyses sur ces assemblages par la suite. Par ailleurs, un catalyseur naturel, une hydrogénase, a été greffée avec succès sur les nanocristaux et étudié en électrochimie. Ces systèmes permettraient d'améliorer les performances des biopiles à combustibles. / With the recent development of chemical synthesis in colloidal suspension, new photosensitizers with high surface area have been considered in this thesis to support redox reactions induced by light. This work is therefore in the scope of finding new energy sources to meet the problems posed by the depletion of fossil fuels. Quantum nanorods with a core@shell composition and gold nanorods were synthesized. Their shape anisotropy permits to assemble them in liquid crystal phases. Thanks to an original method of drying, hierarchical assemblies were obtained, which is promising to perform photoredox reactions on these assemblies thereafter. Furthermore, a natural catalyst, a hydrogenase was successfully grafted onto the nanocrystals and studied in electrochemistry. These systems would improve the performance of biofuel cells.

<div>Recently, atomically thin two-dimensional (2D) layered materials such as graphene and transition metal dichalcogenides (TMDCs) have emerged as a new class of materials due to their unique electronic structures and optical properties at the nanoscale limit. 2D materials also hold great promises as building blocks for creating new heterostructures for optoelectronic applications such as atomically thin photovoltaics, light emitting diodes, and photodetectors. Understanding the fundamental photo-physics process in 2D semiconductors and heterostructures is critical for above-mentioned applications. </div><div>In Chapter 1, we briefly describe photo-generated charge carriers in two-dimensional (2D) transition metal dichalcogenides (TMDCs) semiconductors and heterostructures. Due to the reduced dielectric screening in the single-layer or few-layer of TMDCs semiconductors, Columbo interaction between electron and hole in the exciton is greatly enhanced that leads to extraordinary large exciton binding energy compared with bulk semiconductors. The environmental robust 2D excitons provide an ideal platform to study exciton properties in TMDCs semiconductors. Since layers in 2D materials are holding by weak van de Waals interaction, different 2D layers could be assembled together to make 2D heterostructures. The successful preparation of 2D heterostructures paves a new path to explore intriguing optoelectronic properties.</div><div>In Chapter 2, we introduce various optical microscopy techniques used in our work for the optical characterization of 2D semiconductors and heterostructures. These optical imaging tools with high spatial and temporal resolution allow us to directly track charge and energy flow at 2D interfaces.</div><div>Exciton recombination is a critical factor in determining the efficiency for optoelectronic applications such as semiconductor lasers and light-emitting diodes. Although exciton dynamics have been investigated in different 2D semiconductor, large variations in sample qualities due to different preparation methods have prevented obtaining intrinsic exciton lifetimes from being conclusively established. In Chapter 3, we study exciton dynamics in 2D TMDCs semiconductors using ultrafast PL and transient absorption microscopy. Here we employ 2D WS2 semiconductor as a model system to study exciton dynamics due to the low defect density and high quantum yield of WS2. We mainly focus on how the exciton population affects exciton dynamics. At low exciton density regime, we demonstrate how the interlayer between the bright and dark exciton populations influence exciton recombination. At high exciton density regime, we exhibit significant exciton-exciton annihilation in monolayer WS2. When comparing with the bilayer and trilayer WS2, the exciton-exciton annihilation rate in monolayer WS2 increases by two orders of magnitude due to enhanced many-body interactions at single layer limit. </div><div>Long-range transport of 2D excitons is desirable for optoelectronic applications based on TMDCs semiconductors. However, there still lacks a comprehensive understanding of the intrinsic limit for exciton transport in the TMDCs materials currently. In Chapter 4, we employ ultrafast transient absorption microscopy that is capable of imaging excitons transport with ~ 200 fs temporal resolution and ~ 50 nm spatial precision to track exciton motion in 2D WS2 with different thickness. Our results demonstrate that exciton mobility in single layer WS2 is largely limited by extrinsic factors such as charge impurities and surface phonons of the substrate. The intrinsic phonon-limited exciton transport is achieved in WS2 layers with a thickness greater than 20 layers.</div><div>Efficient photocarrier generation and separation at 2D interfaces remain a central challenge for many optoelectronic applications based on 2D heterostructures. The structural tunability of 2D nanostructures along with atomically thin and sharp 2D interfaces provides new opportunities for controlling charge transfer (CT) interactions at 2D interfaces. A largely unexplored question is how interlayer CT interactions contribute to interfacial photo-carrier generation and separation in 2D heterostructures. In Chapter 5, we present a joint experimental and theoretical study to address carrier generation from interlayer CT transitions in WS2-graphene heterostructures. We use spatially resolved ultrafast transient absorption microscopy to elucidate the role of interlayer coupling on charge transfer and photo-carrier generation in WS2-graphene heterostructures. These results demonstrate efficient broadband photo-carrier generation in WS2-graphene heterostructures which is highly desirable for atomically thin photovoltaic and photodetector applications based on graphene and 2D semiconductors.</div><div>CT exciton transport at heterointerfaces plays a critical role in light to electricity conversion using 2D heterostructures. One of the challenges is that direct measurements of CT exciton transport require quantitative information in both spatial and temporal domains. In order to address this challenge, we employ transient absorption microscopy (TAM) with high temporal and spatial resolution to image both bright and dark CT excitons in WS2-tetrance and CVD WS2-WSe2 heterostructure. In Chapter 6, we study the formation and transport of interlayer CT excitons in 2D WS2-Tetracene vdW heterostructures. TAM measurements of CT exciton transport at these 2D interfaces reveal coexistence of delocalized and localized CT excitons. The highly mobile delocalized CT excitons could be the key factor to overcome large CT exciton binding energy in achieving efficient charge separation. In Chapter 7, we study stacking orientational dependent interlayer exciton recombination and transport in CVD WS2-WSe2 heterostructures. Temperature-dependent interlayer exciton dynamics measurements suggest the existence of moiré potential that localizes interlayer excitons. TAM measurements of interlayer excitons transport reveal that CT excitons at WS2-WSe2 heterointerface are much more mobile than intralayer excitons of WS2. We attributed this to the dipole-dipole repulsion from bipolar interlayer excitons that efficiently screen the moiré potential fluctuations and facilitate interlayer exciton transport. Our results provide fundamental insights in understanding the influence of moiré potential on interlayer exciton dynamics and transport in CVD WS2-WSe2 heterostructures which has important implications in optoelectronic applications such as atomically thin photovoltaics and light harvesting devices. </div><div><br></div>

The fast progress in the exploration of 2D materials such as graphene became possible due to development of fabrication techniques that allowed these materials to be protected from e.g. undesirable doping and gave rise to new functionalities realized within van der Waals heterostructures. Attracted by van der Waals interaction the constituent layers of such heterostructures preserve their exceptional electronic quality and for example in graphene allow for high electron mobility to be achieved. However, the studies of atomically thin layers such as NbSe2 that exhibit metallic behavior have been impeded by their reactivity and hence oxidation during exposure to ambient or oxidizing agents such as solvents. In this thesis, the existing heterostructure assembly technique was improved by the introduction of exfoliation and re-stacking by a fully motorized system placed in an inert atmosphere. This approach allowed us to overcome the problem of environmental degradation and create Hall bars and planar tunnel junctions from atomically thin superconducting NbSe2. Furthermore, this versatile approach allowed us to study the thickness dependence of the normal and superconducting state transport properties of NbSe2, uncovering the reduction of the superconducting energy gap and transition temperature in the thinnest samples. On the other hand, 2D materials being just 1-3 atoms thick represent an ultimate example of a membrane - thin but laterally extended object. Consisting of such atomically thin membranes the van der Waals heterostructures can be used for purposes other than the studies of electronic transport. In this work, ubiquitous bubbles occurring during van der Waals heterostructure assembly are employed as a tool to explore 2D materials' mechanical properties and mutual adhesion. This allowed us to measure Young's modulus of graphene and other 2D materials under 1-2% strain and deduce the internal pressure that can reach up to 1 GPa in sub-nanometer size bubbles.

The motivation of this study is to investigate the size dependent properties of Gadolinium silicide nanoparticles and their potential applications in Biomedicine. We use two approaches in our investigation - size dependence and possible exchange interaction in a core-shell structure. Past results showed Gd5Si4 NPs exhibit significantly reduced echo time compared to superparamagnetic iron oxide nanoparticles (SPION) when measured in a 7 T magnetic resonance imaging (MRI) system. This indicates potential use of Gd5Si4 ferromagnetic nanoparticles as T2 contrast agents for MRI. Until recently most contrast agents (CA) that are used in Magnetic Resonance Imaging (MRI) studies have been paramagnetic. However, ferromagnetic CAs are potentially more sensitive as T2 CAs than T1 paramagnetic compounds due to their large magnetic moments. Furthermore, the need for better MRI images without the need of upgrading to the higher magnetic field strength can be achieved using better CA such as Gd5Si4 NP. The quality of the image contrast in MRI is improved by shortening T1 and T2 relaxation times at the site or close proximity to the CA. In this study, effect of Gd5Si4 NP of varying sizes and with different concentrations are investigated on T1, T2 and T2* (effective/observed T2) relaxations times. Further study was carried out on possible exchange interaction between Fe3O4 and Gd5Si4 to enhance the magnetic properties of the Gd5Si4 which could be later used to synthesize core-shell structures. Exchange interaction / bias is a phenomena associated with the exchange anisotropy created at the interface between the two magnetic materials. Therefore, thin films of varying thickness was deposited and studied for their magnetic properties.