abstract: Recently a new materials platform consisting of semiconductors grown on GaSb and InAs substrates with lattice constants close to 6.1 A was proposed by our group for various electronic and optoelectronic applications. This materials platform consists of both II-VI (MgZnCdHg)(SeTe) and III-V (InGaAl)(AsSb) compound semiconductors, which have direct bandgaps spanning the entire energy spectrum from far-IR (~0 eV) up to UV (~3.4 eV). The broad range of bandgaps and material properties make it very attractive for a wide range of applications in optoelectronics, such as solar cells, laser diodes, light emitting diodes, and photodetectors. Moreover, this novel materials system potentially offers unlimited degrees of freedom for integration of electronic and optoelectronic devices onto a single substrate while keeping the best possible materials quality with very low densities of misfit dislocations. This capability is not achievable with any other known lattice-matched semiconductors on any available substrate. In the 6.1-A materials system, the semiconductors ZnTe and GaSb are almost perfectly lattice-matched with a lattice mismatch of only 0.13%. Correspondingly, it is expected that high quality ZnTe/GaSb and GaSb/ZnTe heterostructures can be achieved with very few dislocations generated during growth. To fulfill the task, their MBE growth and material properties are carefully investigated. High quality ZnTe layers grown on various III-V substrates and GaSb grown on ZnTe are successfully achieved using MBE. It is also noticed that ZnTe and GaSb have a type-I band-edge alignment with large band offsets (delta_Ec=0.934 eV, delta_Ev=0.6 eV), which provides strong confinement for both electrons and holes. Furthermore, a large difference in refractive index is found between ZnTe and GaSb (2.7 and 3.9, respectively, at 0.7 eV), leading to excellent optical confinement of the guided optical modes in planar semiconductor lasers or distributed Bragg reflectors (DBR) for vertical-cavity surface-emitting lasers. Therefore, GaSb/ZnTe double-heterostructure and ZnTe/GaSb DBR structure are suitable for use in light emitting devices. In this thesis work, experimental demonstration of these structures with excellent structural and optical properties is reported. During the exploration on the properties of various ZnTe heterostructures, it is found that residual tensile strains exist in the thick ZnTe epilayers when they are grown on GaAs, InP, InAs and GaSb substrates. The presence of tensile strains is due to the difference in thermal expansion coefficients between the epilayers and the substrates. The defect densities in these ZnTe layers become lower as the ZnTe layer thickness increases. Growth of high quality GaSb on ZnTe can be achieved using a temperature ramp during growth. The influence of temperature ramps with different ramping rates in the optical properties of GaSb layer is studied, and the samples grown with a temperature ramp from 360 to 470 C at a rate of 33 C/min show the narrowest bound exciton emission peak with a full width at half maximum of 15 meV. ZnTe/GaSb DBR structures show excellent reflectivity properties in the mid-infrared range. A peak reflectance of 99% with a wide stopband of 480 nm centered at 2.5 um is measured from a ZnTe/GaSb DBR sample of only 7 quarter-wavelength pairs. / Dissertation/Thesis / Ph.D. Physics 2012

Amostras de Semicondutores III-V foram crescidas usando a técnica de Epitaxia por feixes Moleculares. As propriedades elétricas das estruturas de GaAs com dopagem planar com Silício foram investigadas, e também a saturação e a difusão do Silício nestas amostras. As propriedades ópticas e elétricas das estruturas dopadas planarmente com Selênio foram analisadas, usando as técnicas de Capacitância-voltagem e a de Tunelamento resonante. As propriedades elétricas dos poços quânticos a base de InGaAs/GaAs foram investigadas, em função da posição da impureza planarmente dopada com Silício. / III-V semiconductor samples were grown using the Molecular beam epitaxy technique, the electrical properties of the GaAs structures planar doped with silicon were investigated as well as the Silicon saturation and diffusion in these samles. The optcal and electrical properties of structures planar doped with Selenium were analyzed using the Capacitance Voltage and resonant Tunneling techniques. The electrical properties of InGaAs/ GaAs based quantum wells were investigated as a function of the planar doped with Silicon impurity position.

Ce travail examine des nanofils III-V synthétisés en mode vapeur-liquide-solide, une goutte liquide catalysant la croissance unidimensionnelle. En conjuguant expériences d’épitaxie par jets moléculaires, caractérisations structurales et analyses théoriques, j'étudie et clarifie plusieurs questions cruciales. L’une d'elles est le contrôle de la phase cristalline, qui s’avère souvent un mélange de segments cubiques et hexagonaux. Au moyen d’une analyse probabiliste de la séquence d'empilement de nanofils d’InP, je montre que la sélection de phase est déterminée non seulement par les conditions de croissance mais aussi par des interactions entre monocouches. Je souligne et discute le rôle de l'énergie de bord du germe qui médie la formation de chaque monocouche. On sait par ailleurs que le caractère abrupt des interfaces dans les hétérostructures axiales est limité par l’accumulation de matière dans la goutte (effet réservoir). J'étudie la formation de telles hétérostructures dans des nanofils de GaAs auto-catalysés en utilisant un second élément des groupes V (P) ou III (Al). Les profils compositionnels des insertions ternaires sont analysés à la résolution atomique. Les interfaces se révèlent soit plus larges (GaAsP) soit plus étroites (AlGaAs) qu’attendu et la morphologie du front de croissance dépend de la supersaturation. Je montre que, dans les deux cas, la largeur d’interface peut être réduite à quelques monocouches et je suggère d’autres améliorations. Enfin, je présente mes tentatives pour réaliser des nanofils ultraminces de GaAs et GaP et je discute du contrôle de la croissance à l’échelle d’une monocouche par réduction du caractère stochastique de la nucléation. / This work investigates III-V nanowires synthesized via the vapor-liquid-solid method, whereby a catalyst droplet promotes one-dimensional growth. By combining molecular beam epitaxy experiments, structural characterization and theoretical analyses, I study and clarify several critical issues. One of them is the control of the crystal phase, which is frequently found to be a mix of cubic and hexagonal segments. By performing a probabilistic analysis of the stacking sequence of InP nanowires, I show that phase selection is determined not only by growth conditions but also by interactions between layers. I highlight and discuss the role of the edge energy of the nucleus that mediates the formation of each monolayer. Another important problem is the formation of axial heterostructures, which interface sharpness is severely limited by material accumulation in the droplet (‘reservoir effect’). To this end, I study the formation of such heterostructures in Ga-catalyzed GaAs nanowires using either a second group V element (P) or a second group III element (Al). The composition profiles of the ternary insertions are analyzed with monolayer resolution. The interface widths are found to be larger (GaAsP) or narrower (AlGaAs) than expected, and the morphology of the growth front depends on supersaturation. In both cases, I demonstrate that the interface width can be reduced to a few monolayers and suggest further improvements. Attempts to achieve ultrathin GaAs and GaP nanowires that would permit lateral quantum confinement are presented. Finally, I consider the possibility of minimizing the stochastic character of nucleation ultimately to control the growth of single monolayers.

This diploma thesis deals with the preparation of the graphene membranes for depo-sition of gallium atoms by the molecular beam epitaxy. In the first part properties ofgraphene and methods of its production are described. Second part focuses on the gra-phene membranes, their specific properties, applications and methods of production. Thirdpart describes growth theory of the thin films. Practical part is focused on preparationof graphene membranes, which consists of covering the holes in the silicon substrate bygraphene layer. For that mechanical exfoliated and chemical vapor deposited graphenewere used. Subsequently, gallium atoms were deposited on these membranes by molecularbeam epitaxy and in situ observed by scanning electron microscopy.

This diploma thesis deals with preparation of graphene samples for depositions of ultrathin layers of gallium and gallium nitride. Graphene substrates were prepared by chemical vapour deposition in home-build high temperature reactor. After graphene transfer to silicon wafers, a series of chemical and thermal treatments were performed. Obtained samples were suitable for the study of growth of ultrathin layers of Ga and GaN. The growth of Ga and GaN was realized in ultra high vacuum conditions. Molecular beam epitaxy technique was used for gallium depositions together with ion source for nitridation. Obtained ultrathin layers were studied with X-ray photoelectron spectroscopy, atomic force microscopy and with scanning electron microscopy.

This master's thesis deals with preparation and analysis of ultrathin films of aluminum and aluminum nitride. Films were prepared by effusion cells designed in previous bachelor's thesis. Cell construction and testing is included in this thesis. Behavior of aluminum on silicon dioxide, silicon and graphene was studied. Preparation of aluminum nitride by effusion cell and nitrogen ion source is described.

Im Rahmen dieser Diplomarbeit wurden Si(001)-Oberflächen mit Selen modifiziert und anschließend charakterisiert. Die Herstellung der Selenpassivierungsschichten wurde in einer MBE-Anlage durchgeführt. Die Charakterisierung erfolgte durch RHEED-, LEED- und RBS-Untersuchungen.

Germanium-on-Insulator (GeOI) substrates combine the potential of the Silicon-on-Insulator (SOI) technology with the superior properties of Ge over Si in terms of a) charge carrier mobilities (relevant for CMOS), b) optical bandgap and absorption coefficient (of impact for infra-red photodetectors and high-bandwidth optical interconnects), and c) lattice and thermal match with GaAs (of interest for integration of III-V based optoelectronics and photovoltaics on the mainstream Si platform). Several techniques are under study for the achievement of GeOI structures, such as layer transfer, Ge condensation, and Ge epitaxial overgrowth of Si via crystalline oxide templates. Following the GeOI heteroepitaxial approach, Ge was deposited by molecular beam epitaxy (MBE) on PrO2(111) / Si(111) support systems, and the initial growth stages were studied by means of in-situ reflection high energy electron diffraction (RHEED), and x-ray and ultra-violet photoelectron spectroscopy (XPS and UPS, respectively). It was shown that in the first evaporation stages an amorphous GeO2-like layer forms as a result of the Ge adatom interaction with the PrO2 substrate, namely the diffusion of lattice oxygen from the dielectric into the growing semiconductor deposit. In consequence the PrO2(111) buffer oxide is fully reduced to an oxygen-deficient cub (cubic) Pr2O3(111) film structure. Since no oxidizing species are available in the process anymore, the Ge oxide layer converts under continuous Ge evaporation to GeO, which is volatile at the deposition temperature (~550°C). The sublimation of GeO uncovers the cub-Pr2O3(111) surface, which finally provides a thermodynamically stable template for the heteroepitaxial growth of elemental Ge. A Volmer-Weber growth mode is initially observed, which, by properly tuning the deposition parameters, results after island coalescence in the formation of a closed and flat Ge / cub-Pr2O3 / Si heterostructure. Ge epilayer thickness (in the range 20-1000 nm) and morphology were studied ex-situ by means of x-ray reflectivity (XRR) and secondary electron microscopy (SEM). Dynamic secondary ion mass spectroscopy (D-SIMS) was employed to study the chemical compositions of the Ge films, which turned out to be free from Si and Pr impurities at the sensitivity of some parts-per-billion (ppbs), even after supplying a high thermal budget. This is an important achievement, because in most applications (i.e., optoelectronics), there is the demand for ultra-pure Ge epilayers. Then, laboratory- and synchrotron-based x-ray diffraction (XRD) analyses were performed to assess the epitaxial relationship and the defect structure of the Ge epifilms. It was demonstrated that the Ge layers grow single crystalline with (111) orientation and an exclusive type-A stacking configuration on the type-B cub-Pr2O3(111) / Si(111) support system. Furthermore, the Ge epifilms are fully relaxed in the thickness range 20-1000 nm. Finally, XRD techniques combined with transmission electron microscopy (TEM) permitted the identification and the quantification of three main types of defects at work during the growth of the Ge epi-layers, namely rotation twins, stacking faults and microtwins across {11-1} net-planes. These structural flaws were studied as a function of Ge film thickness and after annealing at 825°C for 30 min in ultrahigh vacuum. It turned out that rotation twins constitute less than 1% of the Ge matrix, are located at the Ge(111) / cub-Pr2O3(111) interface and their amount can be lowered by the thermal treatment. Microtwins across {11-1} were detected only in closed Ge films, after Ge island coalescence. The fraction of Ge film volume affected by microtwinning is constant within the thickness range 20–260 nm. Beyond 260 nm, the density of microtwins is clearly reduced, resulting in thick layers with a top part of higher crystalline quality. Microtwins were found to be insensitive to the post-deposition annealing (PDA). Instead, the density of stacking faults across {11-1} planes decreased after the thermal treatment. In conclusion, the defect density was proved to diminish with increasing Ge thickness and after annealing. A defect density of 10^8-10^9 per cm^2 was estimated in case of a ~ 1000 nm-thick Ge film after PDA.

雑誌名: Electron device letters. In reference to IEEE copyrighted material which is used with permission in this thesis, the IEEE does not endorse any of Kyoto University's products or services. Internal or personal use of this material is permitted. If interested in reprinting/republishing IEEE copyrighted material for advertising or promotional purposes or for creating new collective works for resale or redistribution, please go to http://www.ieee.org/publications_standards/publications/rights/rights_link.html to learn how to obtain a License from RightsLink. / 京都大学 / 0048 / 新制・論文博士 / 博士(工学) / 乙第13043号 / 論工博第4144号 / 新制||工||1652(附属図書館) / 33035 / (主査)教授 藤田 静雄, 教授 川上 養一, 教授 木本 恒暢 / 学位規則第4条第2項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

In this work, a body of knowledge is presented which pertains to the growth, characterization and exploitation of high quality, novel II-IV oxide epitaxial films and structures grown by plasma-assisted molecular beam epitaxy. The two compounds of primary interest within this research are the ternary films NixMg1-xO and ZnxMg1-xO and the investigation focuses predominantly on the realization, assessment and implementation of these two oxides as optoelectronic materials. The functioning hypothesis for this largely experimental effort has been that these cubic ternary oxides can be exploited - and possibly even juxtaposed - to realize novel wide band gap optoelectronic technologies. The results of the research conducted presented herein overwhelmingly support this hypothesis in that they confirm the possibility to grow these films with sufficient quality by this technique, as conjectured. NixMg1-xO films with varying Nickel concentrations ranging from x = 0 to x = 1 have been grown on lattice matched MgO substrates (lattice mismatch ε < 0.01) and characterized structurally, morphologically, optically and electrically. Similarly, cubic ZnxMg1-xO films with Zinc concentrations ranging from x = 0 to x ≈ 0.53, as limited by phase segregation, have also been grown and characterized. Photoconductive devices have been designed and fabricated from these films and characterized. Successfully engineered films in both categories exhibit the desired deep ultraviolet photoresponse and therefore verify the hypothesis. While the culminating work of interest here focuses on the two compounds discussed above, the investigation has also involved the characterization or exploitation of related films including hexagonal phase ZnxMg1-xO, ZnO, CdxZn1-xO and hybrid structures based on these compounds used in conjunction with GaN. These works were critical precursors to the growth of cubic oxides, however, and are closely relevant. Viewed in its entirety, this document can therefore be considered a multifaceted interrogation of several novel oxide compounds and structures, both cubic and wurtzite in structure. The conclusions of the research can be stated succinctly as a quantifiably successful effort to validate the use of these compounds and structures for wide bandgap optoelectronic technologies.