Ce travail porte sur la croissance par épitaxie sous jets moléculaires (EJM) et sur les propriétés structurales et optiques de boîtes quantiques (BQs) AlyGa1-yN insérées dans une matrice AlxGa1-xN (0001). L’objectif principal est d’étudier le potentiel des BQs en tant que nouvelle voie pour la réalisation d’émetteurs ultraviolets (UV) efficaces.Tout d'abord, nous avons étudié la croissance des BQs GaN en utilisant soit une source plasma (N2, appelée PAMBE) soit une source ammoniac (NH3, appelée NH3-MBE) afin de choisir la meilleure approche pour former les BQs les plus efficaces. Il a été montré que le procédé de croissance est mieux contrôlé en utilisant l’approche PAMBE, conduisant à la croissance de BQs GaN avec des densités plus élevées, une meilleure uniformité en taille et des intensités de photoluminescence (PL) jusqu’à trois fois plus élevées. En outre, l'influence de la contrainte épitaxiale sur le processus d'auto-assemblage des BQs a été étudiée en fabriquant des BQs GaN sur différentes couche tremplins d’AlxGa1-xN (avec 0,5 ≤ x ≤ 0,7). Nous avons montré que des BQs avec des densités plus élevées et des hauteurs plus faibles sont formées en augmentant le désaccord de paramètre de maille (c.à.d en utilisant des tremplins avec xAl plus élevé). Cependant, les mesures de photoluminescence (PL) indiquent un fort décalage de l'énergie d'émission vers le rouge lorsque xAl augmente, en raison de l'augmentation de la discontinuité du champ électrique interne de 3 à 5,3 MV/cm.Ensuite, des études approfondies sur les conditions de croissance et les propriétés optiques des BQs Al0,1Ga0,9N / Al0,5Ga0,5N ont été présentées, montrant les différents défis pour fabriquer des BQs efficaces. L’optimisation de la procédure de croissance, notamment l’étape de recuit post-croissance, a montré une modification de la forme des BQs. Plus précisément, un changement d’une forme allongée (pour un recuit à 740 °C), à une forme symétrique (pour un recuit à une température proche de ou supérieure à 800°C) a été observé. En plus, une bande d’émission supplémentaire vers les plus grandes longueurs d’onde a également été observée pour les BQs formées avec un recuit à 740°C. Cette bande a été attribuée à une fluctuation de composition des BQs, induisant la formation d’une famille additionnelle de BQs avec des hauteurs plus grandes et une compostions en Al inférieure à 10 %, estimée proche de l’alliage binaire GaN. Enfin, il a été démontré qu’en faisant un recuit à plus haute température (≥ 800°C), l’émission de PL de cette famille supplémentaire de BQs (BQs riche en Ga ou (Al)GaN) diminue très fortement. De plus, cette étape de recuit impacte fortement la forme des BQs et a conduit à une amélioration de leur efficacité radiative d’un facteur 3. Ensuite, la variation de la composition en Al des BQs AlyGa1-yN (0,1 ≤ y ≤ 0,4), ainsi que la quantité de matière déposée ont permis d’évaluer la gamme de longueurs d’onde d’émission accessibles. En ajustant les conditions de croissance, l’émission des BQs a été déplacée de l’UVA vers l’UVC, atteignant une émission autour de 270 - 275 nm (pour les applications de purification de l’eau et de l’air) avec des rendements radiatifs élevés. Les mesures de photoluminescence résolue en temps (TRPL), combinées avec les mesures de PL en fonction de la température, nous ont permis de déterminer les efficacités quantiques internes (IQE) des BQs GaN / AlxGa1-xN (0001). Des valeurs d’IQE comprises entre 50 % et 66 % ont été obtenues à basse température, avec la possibilité d’atteindre un rapport d’intensité intégré de PL, entre 300 K et 9 K, allant jusqu’à 75 % pour les BQs GaN et 46 % pour les BQs AlyGa1-yN (contre 0,5 % pour des structures équivalents à base de puits quantiques).Enfin, nous avons montré la possibilité de fabriquer des DELs à base de BQs (Al,Ga)N couvrant une grande gamme de longueurs d’onde allant du bleu-violet jusqu’à l’UVB (de 415 nm à 305 nm). / This PhD deals with the epitaxial growth, structural and optical properties of AlyGa1-yN quantum dots (QDs) grown on AlxGa1-xN (0001) by molecular beam epitaxy (MBE), with the aim to study their potential as a novel route for efficient ultraviolet (UV) emitters.First, we have studied the growth of GaN QDs using either plasma MBE (PAMBE) or ammonia MBE (NH3-MBE) to find the most adapted nitrogen source for the fabrication of UV emitting QDs. It was shown that the growth process is better controlled using PAMBE, leading to the growth of GaN QDs with higher densities, better size uniformity and up to three times higher photoluminescence (PL) intensities. Also, the influence of the epitaxial strain on the QD self-assembling process was studied by fabricating GaN QDs on different AlxGa1-xN surfaces (with 0.5 ≤ x ≤ 0.7). We showed that QDs with higher densities and smaller sizes (heights) are formed by using a larger lattice-mismatch (i.e. a higher xAl composition). However, photoluminescence (PL) measurements indicated a strong redshift in the emission energy as the Al content of the AlxGa1-xN template increases due to the increase of the internal electric field discontinuity from 3 to 5.3 MV/cm.Next, in-depth investigations of the growth conditions and optical properties of Al0.1Ga0.9N QDs / Al0.5Ga0.5N were done presenting the different challenges to be solved to grow efficient QDs. Changing the growth procedure, especially the post-growth annealing step, has shown a modification of the QD shape from elongated QDs, formed with an annealing at 740°C, to symmetric QDs, formed with an annealing at a temperature around or above 800°C. An additional band emission at lower energies was also observed for QDs grown with a lower annealing temperature (740°C). This additional band emission was attributed to the formation of QDs with higher heights and a reduced Al composition less than the nominal one of 10 % (i.e. forming Ga-rich QDs). The influence of the annealing step performed at higher temperature has been shown to strongly decrease the PL emission from this additional QD family. In addition, this annealing step strongly impacted the QD shape and led to an improvement of the QD radiative efficiency by a factor 3. Then, the AlxGa1-xN barrier composition (0.5 ≤ x ≤ 0.7), the AlyGa1-yN QD composition (0.1 ≤ y ≤ 0.4) as well as the deposited amount were varied in order to assess the range of accessible emission energies. Also, the influence of varying the AlxGa1-xN barrier composition on the QD formation was studied. By varying these growth conditions, the QD wavelength emission was shifted from the UVA down to the UVC range, reaching a minimum wavelength emission of 270 - 275 nm (for water and air purification applications) with a high radiative efficiency. Time resolved photoluminescence (TRPL) combined with temperature dependent PL measurements enabled us to determine the internal quantum efficiencies (IQE) of AlyGa1-yN QDs / AlxGa1-xN (0001). IQE values between 50 % and 66 % were found at low temperature, combined with the ability to reach a PL integrated intensity ratio, between 300 K and 9 K, up to 75 % for GaN QDs and 46 % for AlyGa1-yN QDs (versus 0.5 % in a similar quantum well structure emitting in the UVC range).Finally, the demonstration of AlyGa1-yN QD-based light emitting diode prototypes, emitting in the whole UVA range, using GaN and Al0.1Ga0.9N QDs, and in the UVB range down to 305 nm with Al0.2Ga0.8N QDs active regions, was shown.

Rotationally averaged polarizabilities and intrinsic electric dipole moments of sodium clusters are measured and reported. The experimental method is a molecular beam deflection. Our precision is the highest (<5%) and the range of the cluster sizes is the broadest to date (Na₁₀ ∼ Na₃₀₀). Compared to the earlier measurements, our data covers all sizes with no gaps up to the largest cluster. The fine structure in the polarizability curve is previously unobserved. We have carefully ruled out several possible explanations. And we find an earlier existing theory could explain the facts but will lead to magic numbers which were not seen in some previous experiments. A detailed theory is needed to understand the behaviors we see. Intrinsic electric dipole moments (EDM) of sodium clusters are probed to answer the intriguing question: Do metal clusters develop electric dipole moments like molecules? Some theories have predicted the existence of EDM in ground state sodium clusters and gave their magnitudes. We put upper bounds on the EDM of sodium clusters and find that they are orders of magnitude smaller than the predictions. This provokes an interesting question: how can one define metallicity in metal clusters? Our measurements are performed at cryogenic temperature 20 Kelvin. At this temperature the clusters are believed to be in their vibronic ground states.

The memristor is a two-terminal semiconductor device that is able to mimic the conductance response of synapses and can be utilized in next-generation computing platforms that will compute similarly to the mammalian brain. The initial memristor implementation is operated by the digital formation and dissolution of a highly conductive filament. However, an analog memristor is necessary to mimic analog synapses in the mammalian brain. To understand the mechanisms of operation and impact of different device designs, analog memristors were fabricated, modeled, and characterized. To realize analog memristors, lithiated transition metal oxides were grown by molecular beam epitaxy, RF sputtering, and liquid phase electro-epitaxy. Analog memristors were modeled using a finite element model simulation and characterized with X-ray absorption spectroscopy, impedance spectroscopy, and other electrical methods. It was shown that lithium movement facilitates analog memristance and nanoscopic ionic-electronic memristors with ion-soluble electrodes can be key enabling devices for brain-inspired computing.

Heterostructures of materials with dramatically different properties are exciting for a variety of devices. In particular, the epitaxial integration of metals with semiconductors is promising for low-loss tunnel junctions, embedded Ohmic contacts, high-conductivity spreading layers, as well as optical devices based on the surface plasmons at metal/semiconductor interfaces. This thesis investigates the structural, electrical, and optical properties of compound (III-V) semiconductors employing rare-earth monopnictide (RE-V) nanostructures. Tunnel junctions employing RE-V nanoparticles are developed to enhance current optical devices, and the epitaxial incorporation of RE-V films is discussed for embedded electrical and plasmonic devices. Leveraging the favorable band alignments of RE-V materials in GaAs and GaSb semiconductors, nanoparticle-enhanced tunnel junctions are investigated for applications of wide-bandgap tunnel junctions and lightly-doped tunnel junctions in optical devices. Through optimization of the growth space, ErAs nanoparticle-enhanced GaAs tunnel junctions exhibit conductivity similar to the best reports on the material system. Additionally, GaSb-based tunnel junctions are developed with low p-type doping that could reduce optical loss in the cladding of a 4 μm laser by ~75%. These tunnel junctions have several advantages over competing approaches, including improved thermal stability, precise control over nanoparticle location, and incorporation of a manifold of states at the tunnel junction interface. Investigating the integration of RE-V nanostructures into optical devices revealed important details of the RE-V growth, allowing for quantum wells to be grown within 15nm of an ErAs nanoparticle layer with minimal degradation (i.e. 95% of the peak photoluminescence intensity). This investigation into the MBE growth of ErAs provides the foundation for enhancing optical devices with RE-V nanostructures. Additionally, the improved understanding of ErAs growth leads to development of a method to grow full films of RE-V embedded in III-V materials. The growth method overcomes the mismatch in rotational symmetry of RE-V and III-V materials by seeding film growth with epitaxial nanoparticles, and growing the film through a thin III-V spacer. The growth of RE-V films is promising for both embedded electrical devices as well as a potential path towards realization of plasmonic devices with epitaxially integrated metallic films. / text

A variety of benefits motivate the development of epitaxial metals, among which include the ability to design fully integrated layer structures where metallic films and nanostructures can be embedded into the cores of optoelectronic devices. Applications include high-performance tunnel-junctions, epitaxial transparent Ohmic contacts, photomixer material, and thermoelectrics. Additionally, the integration of metallic nanostructures and films into optoelectronic devices has shown potential for improving device performance and functionality through sub-wavelength confinement of plasmonic modes and enhancement of light/matter interactions. The rare-earth monopnictide (RE-V) material system can be integrated epitaxially with conventional zincblende III-V substrates under normal growth conditions, resulting in high-quality, thermodynamically stable interfaces. The RE-V semimetals span a range of optical, electrical, and structural properties, making them ideal for integration into III-V-based optoelectronic devices and applications. In this dissertation, high-quality epitaxial LuAs, LaAs and La(x)Lu(1-x)As films and nanostructures were grown and characterized for their structural, electrical, optical, and plasmonic properties. Through a sweep of alloy film compositions of the RE-V alloy material La(x)Lu(1-x)As, the ability to produce tunable epitaxial metals was demonstrated, with a range of peak transmission spectra from near- to mid-infrared wavelengths, plasmonic response in the mid-infrared, moderate resistivity, and lattice-matching potential to many relevant III-V substrates. Additionally, there is a great deal of interest in developing techniques to produce optoelectronic devices that are not restricted by substrate lattice constant. Many epitaxial approaches have been tried, with moderate success; however, growing low defect-density heteroepitaxial materials with differing crystal structures and highly-mismatched lattice parameters is extremely challenging, and such structures suffer from poor thermal properties and reliability issues. A general approach is needed for thin metamorphic buffer layers with minimal threading dislocations that simultaneously have low thermal resistance for effective heat-sinking and device reliability. An investigation was conducted into the use of RE-V nanostructure superlattices towards the reduction of dislocation density in highly-mismatched III-V systems. / text

This thesis discusses two ensembles, the study of which was dependent upon the controllable production of cold gas-phase samples using supersonic beams. The experiments on DNA bases and base clusters were carried out in Germany at the Max Born Institute. The experiments anticipating the construction of a molecular beam slower were carried out in the United States at the University of Texas at Austin. Femtosecond pump-probe techniques were employed to study the dynamics and electronic character of DNA bases, pairs and clusters in the gas phase. Experiments on DNA base monomers confirmed the dominance of a particular relaxation pathway, the nπ* state. Competition between this state and another proposed relaxation pathway was demonstrated through observations of the DNA base pairs and base-water clusters, settling a recent controversy. Further, it was determined that the excited state dynamics in base pairs is due to intramolecular processes rather than intermolecular processes. Finally, results from base-water clusters confirm that microsolvation permits comparison with biologically relevant liquid phase experiments and with ab initio calculations, bridging a long-standing gap. A purely mechanical technique that does not rely upon quantum or electronic properties to produce very cold, very slow atoms and molecules would be more generally applicable than current approaches. The approach described here uses supersonic beam methods to produce a very cold beam of particles and a rotating paddle-wheel, or rotor, to slow the cold beam. Initial experiments testing the possibility of elastic scattering from a single crystal surface were conducted and the implications of these experiments are discussed. / text

We have studied fundamental aspects of photo-induced dissociation kinetics and dynamics in several phenyl halides. By combining femtosecond pump-probe measurements with ab initio calculations we are able to account for several observations. In mixed phenyl halides, the dissociation kinetics is found to be dependent on the nature, the number, and the position of the substituents, and also on the excitation wavelength. A surprisingly large reduction in the dissociation time constant, compared to that of bromobenzene (~30 ps), is observed when having two or more fluorine atoms. For example, in bromopentafluorobenzene a subpicosecond time constant is obtained. This can be explained by a significant lowering of the repulsive potential energy curves (PEC) along the C-Br bond. However, several of the experimental results cannot be accounted for by one-dimensional PECs. Therefore, we suggest a refined model for the dissociation, in which the excited states of the same spin multiplicity are coupled by employing multidimensional potential energy surfaces. This model has been explicitly evaluated by quantum dynamics simulations in the case of 3-BrFPh, and it seems to be capable of capturing the main features in the measured kinetics. Thereby we are also able to clarify the role of spin-orbit coupling in these molecules.

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