My dissertation research focuses on the investigation of the transport and magnetic properties of transition metal and rare earth doped oxides, particularly SnO2 and HfO2 thin films. Cr- and Fe-doped SnO2 films were deposited on Al2O3 substrates by pulsed-laser deposition. Xray- diffraction patterns (XRD) show that the films have rutile structure and grow epitaxially along the (101) plane. The diffraction peaks of Cr-doped samples exhibit a systematic shift toward higher angles with increasing Cr concentration. This indicates that Cr dissolves in SnO2. On the other hand, there is no obvious shift of the diffraction peaks of the Fe-doped samples. The magnetization curves indicate that the Cr-doped SnO2 films are paramagnetic at 300 and 5 K. The Fe-doped SnO2 samples exhibit ferromagnetic behaviour at 300 and 5 K. Zero-field-cooled and field-cooled curves indicate super paramagnetic behavior above the blocking temperature of 100 K, suggesting that it is possible that there are ferromagnetic particles in the Fe-doped films. It was found that a Sn0.98Cr0.02O2 film became ferromagnetic at room temperature after annealing in H2. We have calculated the activation energy and found it decreasing with the annealing, which is explained by the increased oxygen vacancies/defects due to the H2 treatment of the films. The ferromagnetism may be associated with the presence of oxygen vacancies although AMR was not observed in the samples. Pure HfO2 and Gd-doped HfO2 thin films have been grown on different single crystal substrates by pulsed laser deposition. XRD patterns show that the pure HfO2 thin films are of single monoclinic phase. Gd-doped HfO2 films have the same XRD patterns except that their diffraction peaks have a shift toward lower angles, which indicates that Gd dissolves in HfO2. Transmission electron microscopy images show a columnar growth of the films. Very weak ferromagnetism is observed in pure and Gd-doped HfO2 films on different substrates at 300 and 5 K, which is attributed to either impure target materials or signals from the substrates. The magnetic properties do not change significantly with post deposition annealing of the HfO2 films.

The emergence of semiconducting nanowires as the new building blocks for photovoltaic (PV) devices has drawn considerable attention because of the great potential of achieving high efficiency and low cost. In special, nanowires with a coaxial structure, namely, core-shell structures have demonstrated significant advantages over other device configurations in terms of radial charge collection and cost reduction. In this dissertation, several core-shell nanowire structures, including ZnO/ZnSe, ZnO/ZnS, and CdSe/ZnTe, have been synthesized and the photovoltaic devices processed from a ZnO/ZnS core-shell nanowire array and a single CdSe/ZnTe core-shell nanowire have been demonstrated. By combining the chemical vapor deposition and pulsed laser deposition (PLD) techniques, type-II heterojunction ZnO/ZnSe and ZnO/ZnS core-shell nanowire array were synthesized on indium-tin-oxide substrates. Their structures and optical properties have been investigated in detail, which revealed that, despite highly mismatched interfaces between the core and shell, both systems exhibited an epitaxial growth relationship. The quenching in photoluminescence but enhancement in photocurrent with faster response upon coating the core with the shell provides the evidence that the charge separation and collection in the type II core-shell nanowire is greatly improved. This demonstration brings much greater flexibility in designing next generation PV devices in terms of material selection and device operation mechanisms for achieving their maximum energy conversion efficiencies at a low cost and in an environmentally friendly manner. In order to achieve a high quality interface in the core-shell nanowire, CdSe and ZnTe, which have close lattice parameters and thermal expansion coefficients, were chosen to fabricate nanowire solar cells. ZnTe and CdSe nanowires were first synthesized by thermal evaporation and the shells were subsequently deposited by PLD. ZnTe/CdSe nanowires represented an inhomogeneous coating while the CdSe/ZnTe core-shell exhibited a conformal coating with obvious ZnTe eptilayer. The final PV device based on an individual CdSe/ZnTe nanowire demonstrated an efficiency of ~1.7%. In addition, a controllable synthesis of CdSe nanowire array on muscovite mica substrate was presented, providing the possibility to harvest hybrid energies in an all-inorganic nanowire array.

Ce travail est consacré à l’étude de la diffraction d’atomes rapides (d’énergie cinétiquede l’ordre du keV) en incidence rasante (angles d’incidence ~ 1°) le long ou proche d’unedirection principale d’une surface cristalline. Cette géométrie en incidence rasante permet de(i) récolter, en quelques secondes, la totalité du cliché de diffraction sur un détecteur sensible enposition ; (ii) préserver la cohérence de l’onde de matière en réduisant les sources de décohérencecomme l’excitation électronique et l’agitation thermique. La grande sensibilité des atomes àla forme de la densité électronique de surface (partie répulsive) et au puits attractif de Vander Waals révèle les résonances de Fano et démontre que l’atome voyage, piégé au-dessus de lasurface, de façon cohérente, sur une distance de 0.2μm. Il est également montré que la diffractiond’atomes rapides est une technique robuste pour suivre la dynamique de croissance de semiconducteurs(GaAs) par épitaxie (reconstructions, transitions de phase). Enfin, l’observationde la diffraction sur une feuille de graphène déposé sur 6H-SiC(0001) suggère l’utilisation desatomes rapides comme outil de diagnostic pour le suivi et la caractérisation en temps réel dela croissance du graphène dont les propriétés exceptionnelles dépendent beaucoup des défautsde surface. / This work was devoted to the study of fast atom diffraction (energies in the keV range)at grazing incidence angles (~ 1°) along or close to a low indexed direction of crystalline surfaces.This specific scattering geometry bears two advantages : (i) the diffraction pattern as a wholeis collected within seconds on a position sensitive detector ; (ii) the low energy associated to themotion normal to the surface quenches decoherence due to electronic excitations and stronglyreduces decoherence due to thermal vibrations. The high sensitivity of probe atoms to thesurface electron density (repulsive part) and to the Van der Waals attractive well reveals Fanoresonances where the trapped atoms preserve their coherence over distances as long as 0.2μm.As a complement to these fundamental studies, fast atom diffraction has been proved to be arobust mean to probe the dynamics of epitaxial growth of semiconductors (GaAs). Finally, workperformed on monolayer graphene grown on 6H-SiC(0001) suggest the possibility to use fastatoms to monitor graphene growth in real time, a key process to measure the level of alterationof the intrinsic graphene electronic structure.

L’objectif de cette thèse était d’étudier les mécanismes responsables de la luminescence des ions lanthanides dans des polymères de coordination. Pour cela, des séries d’alliages moléculaires à base d’acide 4 carboxyphénylboronique ont été synthétisées, en faisant varier les proportions relatives des ions lanthanides. Les produits synthétisés ont été étudiés dans la perspective de leur application dans les domaines de la lutte anti-contrefaçon et des thermomètres moléculaires. D’autre part, de nouveaux systèmes utilisant d’autres dérivés d’acide boronique ont été synthétisés. Une nouvelle structure cristalline a été obtenue à base de l’acide 2-carboxyphénylboronique. La seconde partie de cette thèse a porté sur la synthèse et la caractérisation de poudres microcristallines de type coeur-coquille. Il s’agit de la première micro-structuration de polymères de coordination réalisée à l’échelle micrométrique. Les poudres synthétisées ont été caractérisées par microscopies électroniques à balayage, à transmission et par analyses EDS. Leurs propriétés optiques ont été comparées avec celles des alliages moléculaires. Les résultats obtenus ont mis en évidence l'intérêt de la micro-structuration de ces poudres concernant les transferts d'énergie intermétalliques. Cette technique de synthèse basée sur la croissance épitaxiale, est rendue possible par les propriétés chimiques similaires des terres rares. Nos travaux ont montré que lorsque les constantes thermodynamiques et\ou cinétiques le permettent, la phase cristalline de la coquille présente la structure cristalline du cœur même lorsque le composé constituant la coquille cristallise dans une autre phase lorsqu'il est synthétisé seul. / The aim of this thesis was to study the luminescence mechanisms of lanthanide ions in coordination polymers. Series of molecular alloys (hetero-lanthanide compounds in which lanthanide ions are randomly distributed) based on 4-carboxyphenylboronic acid were synthesized, by varying the relative contents of the lanthanide ions. The synthesized products have been studied from the perspective of their application in the fields of anti-counterfeiting and molecular thermometers. On the other hand, new systems using other boronic acid derivatives have been synthesized. A new crystal structure was obtained based on 2-carboxyphenylboronic acid. The second part of this thesis focused on the synthesis and characterization of core-shell microcrystalline powders. This is the first time that micro-structuration of a coordination polymer is achieved at the micrometric scale. The synthesized powders were characterized by scanning electron microscopy, transmission electron microscopy and EDS analyses. Their optical properties have been compared with those of the corresponding molecular alloys. The obtained results highlighted the interest of the micro-structuration concerning intermetallic energy transfers. This strategy of synthesis based on epitaxial growth, is possible because of lanthanide similar chemical properties. This work demonstrates that in the case where the thermodynamic and\or kinetic constants allow it, the shell crystallizes according to the same crystal structure than the core even if its crystal structure is different when it is synthesized alone.

A wide variety of group III-Nitride-based photonic and electronic devices have opened a new era in the field of semiconductor research in the past ten years. The direct and large bandgap nature, intrinsic high carrier mobility, and the capability of forming heterostructures allow them to dominate photonic and electronic device market such as light emitters, photodiodes, or high-speed/high-power electronic devices. Avalanche photodiodes (APDs) based on group III-Nitrides materials are of interest due to potential capabilities for low dark current densities, high sensitivities and high optical gains in the ultraviolet (UV) spectral region. Wide-bandgap GaN-based APDs are excellent candidates for short-wavelength photodetectors because they have the capability for cut-off wavelengths in the UV spectral region (λ < 290 nm). These intrinsically solar-blind UV APDs will not require filters to operate in the solar-blind spectral regime of λ < 290 nm. For the growth of GaN-based heteroepitaxial layers on lattice-mismatched substrates, a high density of defects is usually introduced during the growth; thereby, causing a device failure by premature microplasma, which has been a major issue for GaN-based APDs. The extensive research on epitaxial growth and optimization of Al_x Ga _1-x N (0 ≤ x ≤ 1) grown on low dislocation density native bulk III-N substrates have brought UV APDs into realization. GaN and AlGaN UV <i> p-i-n </i> APDs demonstrated first and record-high true avalanche gain of > 10,000 and 50, respectively. The large stable optical gains are attributed to the improved crystalline quality of epitaxial layers grown on low dislocation density bulk substrates. GaN <i>p-i-n </i> rectifiers have brought much research interest due to its superior physical properties. The AIN-free full-vertical GaN<i> p-i-n </i> rectifiers on<i> n </i>- type 6H-SiC substrates by employing a conducting AIGaN:Si buffer layer provides the advantages of the reduction of sidewall damage from plasma etching and lower forward resistance due to the reduction of current crowding at the bottom<i> n </i> -type layer. The AlGaN:Si nucleation layer was proven to provide excellent electrical properties while also acting as a good buffer role for subsequent GaN growth. The reverse breakdown voltage for a relatively thin 2.5 μm-thick<i> i </i>-region was found to be over -400V.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第18982号 / 工博第4024号 / 新制||工||1620 / 31933 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 酒井 明, 教授 邑瀬 邦明 / 学位規則第4条第1項該当

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Optoelectronics in the deep-ultraviolet (DUV) regime is still a growing research field that requires significant effort to understand the material properties and optimize the device structures to realize efficient DUV devices. Aluminum gallium nitride (AlGaN) is perhaps the most studied semiconductor to replace the environmentally hazardous mercury lamps; however, the external quantum efficiency of AlGaN based DUV devices is insufficient to replace the existing old-fashioned mercury UV lamps. Despite the tunability in the bandgap of AlGaN, the excessive strain accumulation associated with increased alloying of Al in AlGaN and the poor dopant activation due to the relatively large ionization energy of the donors and acceptors are not favorable for realizing efficient DUV emitters. In addition, the crossover among the light hole, heavy hole and split-off bands in the valance band for Al-rich AlGaN suppresses the transverse-electric polarization, which further worsens the external quantum efficiency. Furthermore, for DUV photodetection, commercially available Si-photodetectors suffer from poor responsivity for wavelengths shorter than 400 nm in contrast to the visible spectrum. Hence, the-state-of-art photodetectors in the DUV regime also need a significant upgrade, particularly for high-speed applications. Firstly, we utilized the high quantum confinement in plasma-assisted MBE grown ultrathin GaN QDisks to realize DUV (λ ≈ 260 nm) emission using a binary compound (GaN) in contrast to conventionally used ternary compound (AlGaN). More importantly, we experimentally demonstrated TE-dominant DUV emission, unlike Al-rich AlGaN, illustrating a unique pathway for realizing efficient DUV vertical emitters. Secondly, inspired by the light manipulation technique practiced in nature, we presented iridocytes on giant clams (Tridacna maxima), known for their symbiotic relationship with algae as a color downconverting material for DUV photodetection. Investigating the structural and optical properties of iridocytes found in Tridacna maxima, we established a robust UV communication allowing the data transfer rate of 100 Mbit/s within the forward error correction limit for modulated 375 nm-laser diode. Using a similar matrix implemented to 375 nm-laser, with high-power UV-C LED (λ ≈ 278 nm), we could establish an optical wireless communication that could allow a data-transmission rate of tens of Mbit/s within the forward error correction limit.

Micro-electro-mechanical systems (MEMS) have become an essential component of a wide range ofelectronic devices over the last decades such as accelerometers, microphones, gas sensors, and filters.During this new millennium, a new radio frequency (RF) technology has been developed to satisfy thetough demands that arose due to the implementation of 5G wireless communication: bulk acoustic wave(BAW) filters.BAW devices use the piezoelectric effect, converting mechanical vibrations to electrical signals, topower wireless devices. BAW filters can operate between 3.5 GHz and 6 GHz, therefore, within therange of the new 5G. BAW technology offers lower insertion loss, higher heat dissipation, andperformances at higher power and frequency which increases the data speed considerably.This thesis will be focused on the study of the materials used in BAW devices. A common BAW filteris made from different layers distributed in a stack, from the bottom to the upper part, the BAW filteris composed of a substrate, a transducer layer made of a piezoelectric layer in between of two electrodes,and intermediate layers that can enhance the addition of the deposited layers on top called buffer layers,or the crystal quality of the films on top called seed layers.The main characteristic that a buffer layer must possess is an intermediate lattice parameter betweenthat of the substrate and the top layer. When these two layers present a high lattice mismatch, theinterface quality is rather poor. By using a buffer layer, and therefore, by adding two different interfaces,the crystal quality is improved by decreasing the internal stress and the crystal distortion. Buffer layermaterials depend on the type of materials that will be in contact with them.A seed layer is usually used to improve the crystal quality of a layer that requires extreme sputteringparameters to be used to be deposited possessing a high crystal quality and a preferred orientation. Seedlayers used in BAW devices, whose piezoelectric layer is made of AlScN or AlN, are usually made ofhighly c-axis oriented and highly crystalline AlN.The objective of this study is to analyze the deposition of AlN and HfN by means of reactive radiofrequency magnetron sputtering and reactive pulsed-direct current magnetron sputtering, respectively.AlN is largely used as a buffer layer and as a seed layer, however, the new approach of this report is tostudy the sputtering of HfN and compare it as a possible candidate to replace AlN as a seed layer.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18982号 / 工博第4024号 / 新制||工||1620(附属図書館) / 31933 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 酒井 明, 教授 邑瀬 邦明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM