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Dans le manuscrit, nous étudions l'impact des défauts sur le transport électronique dépendant du spin dans les jonctions tunnel magnétiques (JTM). Ces études ont été effectuées sur des hétérostructures possédant des barrières tunnel composé de SrTiO3, TiO2 et de MgO. Dans le cas des deux premières structures, nous montrons comment l'oxydation à l'interface induit réduction très prononcée de la magnétorésistance tunnel (TMR). Dans le cas du MgO, des études optiques sur les états induits par les défauts dans la barrière isolante ont été effectué. Nous avons montré qu'il est possible de contrôler la densité de certain type de défaut (lacune d'oxygène) en altérant les conditions de dépôts du MgO. Les études électriques et optiques effectué sur ces échantillons permettent de remonter à l'énergie des défauts au sein de la barrière. Les méthodes d'analyses des mesures électrique Î (I chapeau), qui représente la variation relative ou absolue du courant électrique en fonction de la température, permet de définir différents régime de transport à travers les jonctions CoFeB/MgO/CoFeB. Le régime intrinsèque observé à basse température s'explique par les effets de structure de bande du CoFeB et du MgO (filtrages des électrons de différente symétrie par la barrière de MgO), tandis que le régime " extrinsèque " observé aux températures intermédiaires résulte d'une activation thermique progressive des lacunes d'oxygène et est accompagné d'une réduction de la résistance ainsi que du signal TMR. Nous avons également montré dans des études préliminaires qu'une excitation optique des défauts a un impact sut le magnéto-transport.

Colloidal semiconductor quantum dots (QDs) have gained substantial interest as adjustable, bright and spectrally tunable fluorophores in the past decades. Besides their in-depth analyses in the scientific community, first industrial applications as color conversion and color enrichment materials were implemented. However, stability and processability are essential for their successful use in these and further applications. Methods to embed QDs into oxides or polymers can only partially solve this challenge. Recently, our group introduced the embedding of QDs into ionic salts, which holds several advantages in comparison to polymer or oxide-based counterparts. Both gas permeability and environmental-related degradation processes are negligible, making these composites an almost perfect choice of material. To evaluate this new class of QD-salt mixed crystals, a thorough understanding of the formation procedure and the final composites is needed. The present work is focused on embedding both aqueous-based and oil-based metal-chalcogenide QDs into several ionic salts and the investigations of their optical and chemical properties upon incorporation into the mixed crystals. QDs with well-known, reproducible and high-quality synthetic protocols are chosen as emissive species. CdTe QDs were incorporated into NaCl as host matrix by using the straightforward "classical" method. The resulting mixed crystals of various shapes and beautiful colors preserve the strong luminescence of the incorporated QDs. Besides NaCl, also borax and other salts are used as host matrices. Mercaptopropionic acid stabilized CdTe QDs can easily be co-crystallized with NaCl, while thioglycolic acid as stabilizing agent results in only weakly emitting powder-like mixed crystals. This challenge was overcome by adjusting the pH, the amount of free stabilizer and the type of salt used, demonstrating the reproducible incorporation of highest-quality CdTe QDs capped with thioglycolic acid into NaCl and KCl salt crystals. A disadvantage of the "classical" mixed crystallization procedure was its long duration which prevents a straightforward transfer of the protocol to less stable QD colloids, e.g., initially oil-based, ligand exchanged QDs. To address this challenge, the "Liquid-liquid-diffusion-assisted-crystallization" (LLDC) method is introduced. By applying the LLDC, a substantially accelerated ionic crystallization of the QDs is shown, reducing the crystallization time needed by one order of magnitude. This fast process opens the field of incorporating ligand-exchanged Cd-free QDs into NaCl matrices. To overcome the need for a ligand exchange, the LLDC can also be extended towards a two-step approach. In this modified version, the seed-mediated LLDC provides for the first time the ability to incorporate oil-based QDs directly into ionic matrices without a prior phase transfer. The ionic salts appear to be very tight matrices, ensuring the protection of the QDs from the environment. As one of the main results, these matrices provide extraordinary high photo- and chemical stability. It is further demonstrated with absolute measurements of photoluminescence quantum yields (PL-QYs), that the PL-QYs of aqueous CdTe QDs can be considerably increased upon incorporation into a salt matrix by applying the "classical" crystallization procedure. The achievable PL enhancement factors depend strongly on the PL-QYs of the parent QDs and can be described by the change of the dielectric surrounding as well as the passivation of the QD surface. Studies on CdSe/ZnS in NaCl and CdTe in borax showed a crystal-induced PL-QY increase below the values expected for the respective change of the refractive index, supporting the derived hypothesis of surface defect curing by a CdClx formation as one main factor for PL-QY enhancement. The mixed crystals developed in this work show a high suitability as color conversion materials regarding both their stability and spectral tunability. First proof-of-concept devices provide promising results. However, a combination of the highest figures of merit at the same time is intended. This ambitious goal is reached by implementing a model-experimental feedback approach which ensures the desired high optical performance of the used emitters throughout all intermediate steps. Based on the approach, a white LED combining an incandescent-like warm white with an exceptional high color rendering index and a luminous efficacy of radiation is prepared. It is the first time that a combination of this highly related figures of merit could be reached using QD-based color converters. Furthermore, the idea of embedding QDs into ionic matrices gained considerable interest in the scientific community, resulting in various publications of other research groups based on the results presented here. In summary, the present work provides a profound understanding how this new class of QD-salt mixed crystal composites can be efficiently prepared. Applying the different crystallization methods and by changing the matrix material, mixed crystals emitting from blue to the near infrared region of the electromagnetic spectrum can be fabricated using both Cd-containing and Cd-free QDs. The resulting composites show extraordinary optical properties, combining the QDs spectral tunability with the rigid and tight ionic matrix of the salt. Finally, their utilization as a color conversion material resulted in a high-quality white LED that, for the first time, combines an incandescent-like hue with outstanding optical efficacy and color rendering properties. Besides that, the mixed crystals offer huge potential in other high-quality applications which apply photonic and optoelectronic components.

In this thesis, gas sensors based on on-chip hydrothermally grown 1-D zinc oxide (ZnO) nanostructures are presented, to improve the sensitivity, selectivity, and stability of the gas sensors. Metal-oxide-semiconductor (MOS) gas sensors are well-established tools for the monitoring of air quality indoors and outdoors. In recent years, the use of 1-D metal oxide nanostructures for sensing toxic gases, such as nitrogen dioxide, ammonia, and hydrogen, has gained significant attention. However, low-dimensional nanorod (NR) gas sensors can be enhanced further. Most works synthesize the NRs first and then transfer them onto electrodes to produce gas sensors, thereby resulting in large batch-to-batch difference. Therefore, in this thesis six studies on 1-D ZnO NR gas sensors were carried out. First, ultrathin secondary ZnO nanowires (NWs) were successfully grown on a silicon substrate. Second, an on-chip hydrothermally grown ZnO NR gas sensor was developed on a glass substrate. Its performance with regard to sensing nitrogen dioxide and three reductive gases, namely, ethanol, hydrogen, and ammonia, was tested. Third, three 1-D ZnO nanostructures, namely, ZnO NRs, dense ZnO NWs, and sparse ZnO NWs, were synthesized and tested toward nitrogen dioxide. Fourth, hydrothermally grown ZnO NRs, chemical vapor deposited ZnO NWs, and thermal deposited ZnO nanoparticles (NPs) were tested toward ethanol. Fifth, the effect of annealing on the sensitivity and stability of ZnO NR gas sensors was examined. Sixth, ZnO NRs were decorated with palladium oxide NPs and tested toward hydrogen at high temperature. The following conclusions can be drawn from the work in this thesis: 1) ZnO NWs can be obtained by using a precursor at low concentration, temperature of 90 °C, and long reaction time. 2) ZnO NR gas sensors have better selectivity to nitrogen dioxide compared with ethanol, ammonia, and hydrogen. 3) Sparse ZnO NWs are highly sensitive to nitrogen dioxide compared with dense ZnO NWs and ZnO NRs. 4) ZnO NPs have the highest sensitivity to ethanol compared with dense ZnO NWs and ZnO NRs. The sensitivity of the NPs is due to their small grain sizes and large surface areas. 5) ZnO NRs annealed at 600 °C have lower sensitivity toward nitrogen dioxide but higher long-term stability compared with those annealed at 400 °C. 6) When decorated with palladium oxide, both materials form alloy at a temperature higher than 350 °C and decrease the amount of ZnO, which is the sensing material toward hydrogen. Thus, controlling the amount of palladium oxide on ZnO NRs is necessary.

Dye-sensitized solar cells (DSSCs) and perovskite solar cells are emerging as promising potential low-cost alternatives to established crystalline silicon photovoltaics. Of the employed functional materials, however, many fundamental optoelectronic properties governing photovoltaic device operation are not sufficiently well understood. This thesis reports on a series of studies using ultrafast THz and photoluminescence spectroscopy on two classes of such materials, providing insight into the dynamics of charge-transport and recombination processes following photoexcitation. For TiO₂-nanotubes, which have been proposed as easy-to-fabricate electron transporters for DSSCs, fast, shallow electron trapping is identified as a limiting factor for efficient charge collection. Trapping lifetimes are found to be about an order of magnitude shorter than in the prevalently employed sintered nanoparticles under similar excitation conditions and trap saturation effects are not observed, even at very high excitation densities. In organo-lead halide perovskites - specifically CH₃NH₃PbI₃ and CH₃NH₃PbI_3-xCl_x, which have only recently emerged as highly efficient absorbers and charge transporters for thin-film solar cells, carrier mobilities and fundamental recombination dynamics are revealed. Extremely low bi-molecular recombination rates at least four orders of magnitude below the prediction of Langevin's model are found as well as relatively high charge-carrier mobilities in comparison to other solution-processable materials. Furthermore a very low influence of trap-mediated recombination channels was observed. Due to a combination of these factors, diffusion lengths reach hundreds of nanometres for CH₃NH₃PbI₃ and several microns for CH₃NH₃PbI_3-xCl_x. These results are shown to hold for both, solution processed and vapour-deposited CH₃NH₃PbI_3-xCl_x and underline the superb suitability of the materials as absorbers in solar cells, even in planar heterojunction architectures. The THz-frequency spectrum of the conductivity of the investigated perovskites is consistent with Drude-like charge transport additionally exhibiting weak signatures of phonon coupling. These coupling effects are also reflected in the luminescence of CH₃NH₃PbI_3-xCl_x, where they are believed to be the cause of the observed homogeneous spectral broadening. Further photoluminescence measurements were performed at temperatures between 4 K and room temperature to study the nature of recombination pathways in the material.

Experimental investigations of the optical properties of GaN nanostructured light emitting diode (LED) arrays are presented. Microphotoluminescence spectroscopy with pulsed and continuous wave lasers was used to probe the carrier dynamics and emission mechanisms of nanorod LED arrays fabricated by a top down etching method. Results show a possible reduction in internal electric field as nanorod diameter decreases. Localisation effects were also observed, affecting the spectral shape of the nanorod emission. Under two-photon excitation, quantum dot-like sharp spectral peaks in the PL spectra are found to exist in abundance amongst all the nanorod samples. The optical properties of these localised states, which are shown to be associated with the nanorod free-surfaces, are characterised using non-linear and time resolved spectroscopy. An investigation into spatially resolved single nanorods was also carried out. Single nanorods were isolated, and characterised using pulsed lasers. The etching is shown to increase the carrier decay life-time at extended intervals over several hundred ns. The temporal evolution and excitation power density dependence of the quantum dot-like states are also presented for the first time. The long lived localised states are thought to arise from surface effects, in particular Fermi-surface pinning, causing localisation and spatial separation of carriers. Additional work on nano-pyramid array LEDs, with quantum wells on semi-polar surfaces is also presented. Optical properties using micro-photoluminescence are compared to cathodoluminescence studies. An uneven distribution of emission wavelengths across the pyramid facet is thought to lead to an emission mechanism involving carriers transferring between multiple spatially localised states. Finally, experimental techniques and fabrication methods for future work are documented in detail.

This dissertation is a theoretical treatment of the electric field dependence of optical properties such as Quantum Confined Stark (QCS) shifts, Photoluminescence Quenching (PLQ), and Excitonic Mixing in quantum well heterostructures. The reduced spatial dimensionality in heterostructures greatly enhances these optical properties, more than in three dimensional semiconductors. Charge presence in the quantum well from doping causes the potential to bend and deviate from the ideal square well potential. A potential bending that varies as the square of distance measured from the heterostructure interfaces is derived self-consistently. This potential is used to solve the time-independent Schrodinger equation for bound state energies and wave functions within the framework of the Wentzel, Kramers, and Brillouin (WKB) approximation. The theoretical results obtained from the WKB approximation are limited to wide gap semiconductors with large split off bands such as gallium arsenide-gallium aluminum arsenide and indium gallium arsenide—indium phosphide. Quantum wells with finite confinement heights give rise to an energy dependent WKB phase. External electric and magnetic fields are incorporated into the theory for two different geometries. For electric fields applied perpendicular to the heterostructure multilayers, QCS shifts and PLQ are found to be in excellent agreement with the WKB calculations. Orthogonality between electrons and holes gives rise to interband mixing in the presence of an external electric field. On the contrary, intraband mixing between light and heavy holes is not sufficiently accounted for in the WKB approximation.