The monolithic integration of III-V semiconductors on Si substrates is a part of a long-term technological roadmap for the semiconductor industry towards More-than-Moore technologies. Despite of the different lattice constants and thermal expansion coefficients, research efforts over the last two decades have shown that III-V crystals with a high structural quality can be grown epitaxially in the form of nanowires directly on Si using CMOS-compatible (Au-free) methods. Among other III-V compounds, InxGa1-xAs is of the special interest for the use in infrared photonics and high-speed electronics due to its tunable direct bandgap and low electron effective mass, respectively. For comparison, InxGa1-xAs thin films are typically grown on lattice-matched InP substrates with a limited range of compositions at around x=0.52. The realization of InxGa1-xAs nanowires on Si, though, has been proved challenging owing to the limited In-content when the nanowires are grown Ga-catalyzed or the high density of stacking faults when the nanowires are grown catalyst-free. In this work, the use of highly lattice-mismatched GaAs/InxGa1-xAs and GaAs/InxAl1-xAs core/shell nanowires on Si(111) substrates have been studied as an alternative to InxGa1-xAs nanowires. The core/shell mismatch strain and its accommodation within the nanowires plays an important role in the growth, the structural, and the electronic properties of the nanowires. A key parameter in this work was the unusually small diameter of 20 – 25 nm of the GaAs core. First, the strain-induced bending of the nanowires during the growth of the shell by molecular beam epitaxy was investigated. It was apparent that the nanowires bend as a result of a preferential incorporation of In adatoms on one side of the nanowires. To obtain straight nanowires with symmetric shell composition and thickness around the core, it was necessary to choose relatively low growth temperatures and high growth rates that limited the surface diffusivity of In adatoms. Second, the strain accommodation in straight nanowires was investigated as a function of the shell thickness and composition using a combination of Raman scattering spectroscopy and X-ray diffraction. For a fixed shell composition of x=0.20 and small enough shell thicknesses, the strain in the shell is compressive and decreases progressively as the shell grows thicker. On the other hand, the strain in the core is tensile with hydrostatic character and increases with shell thickness. Finally, for shell thicknesses larger than 40 nm, the shell becomes strain-free, whereas the strain in the core saturates at 3.2% without any dislocations. For a fixed shell thickness of 80 nm, the strain in the core was further increased by increasing the In-content in the shell, reaching values as high as 7% for x=0.54. A plastic relaxation via misfit dislocations was observed only for the next highest In-content of x=0.70. In agreement to theoretical predictions, the tensile strain in the core resulted in a large reduction of the GaAs bandgap (as measured by photoluminescence spectroscopy), up to approximately 40% of the strain-free value. A similar reduction in electron effective mass is also expected. The transport properties of electrons inside the strained GaAs core were assessed by optical-pump terahertz-probe spectroscopy. Quite high mobility values of approximately 6100 cm2/Vs at 300 K for a carrier concentration of 9×1017 cm−3 were measured, which are the highest reported in the literature for GaAs nanowires, but also higher than the values for unstrained bulk GaAs. The importance of the results in this work is two-fold. On the one hand, strain-free InxGa1-xAs nanowire shells were grown on Si substrates with x up to 0.54 and thicknesses well beyond the critical thickness of their thin film counterparts. Such shells could potentially be employed as conduction channels in high electron mobility transistors (HEMTs) integrated in Si platforms. On the other hand, highly tensile-strained GaAs cores with electronic properties like those of InxGa1-xAs thin films were obtained. In this case, the results demonstrate, that GaAs nanowires can be suitable for photonic devices across the near-infrared range, including telecom photonics at 1.3 and potentially 1.55 μm, as well as for high-speed electronics. GaAs as a binary material is expected to be advantageous compared to InxGa1-xAs due to the absence of structural imperfections typically present in ternary alloys. Finally, to explore the potential of the core/shell nanowires as HEMTs, self-consistent Schrödinger-Poisson calculations of two different modulation-doped heterostructures were performed. In the case of a strained GaAs core overgrown by an unstrained InxGa1-xAs shell and an additional unstrained Si-doped InxAl1-xAs shell, the possibility to form a cylindrical-like two-dimensional electron gas inside the InxGa1-xAs shell was found. In the alternative case of a strained GaAs core overgrown by an unstrained Si-doped InxAl1-xAs shell, it was found that it is possible to form a quasi-one-dimensional electron gas at the center of the core. Both structures are the subject of ongoing research.:1 Introduction 1 2 Fundamentals and state-of-the-art 7 2.1 Electronic and structural properties of III-V semiconductors 7 2.2 Growth of III-V nanowires on Si 20 2.3 Core/shell heterostructure nanowires 29 2.4 Strain in epilayers and core/shell nanowires 36 2.5 Strain engineering in core/shell nanowires and its effect on band parameters 46 2.6 Modulation-doped III-V semiconductor heterostructures 56 3 Methods 61 3.1 Optical and electron microscopes 61 3.2 X-ray diffraction 64 3.3 Raman scattering spectroscopy 65 3.4 Photoluminescence spectroscopy 75 3.5 Optical-pump terahertz-probe spectroscopy and photoconductivity in semiconductors 77 3.6 Device processing 82 3.7 Semiconductor nanodevice software “nextnano” 85 3.8 MBE for crystal growth and core/shell nanowire growth 86 4 Results and discussions 91 4.1 Structural, compositional analyses of straight nanowires and coherent growth limit 91 4.2 Bent nanowires 95 4.3 Strain analyses in core/shell nanowires 97 4.3.1 Dependence of strain on shell thickness 97 4.3.2 Dependence of strain on the shell chemical composition 102 4.3.3 Dependence of strain on the core diameter 105 4.4 Strain-induced modification of electronic properties 106 4.5 Strain-enhanced electron mobility of GaAs nanowires higher than the bulk limit 114 4.6 Towards high electron mobility transistors 123 5 Conclusion and outlook 129 Bibliography 131 List of abbreviations I List of Symbols III List of publications VII List of conference contributions VIII Acknowledgements X

Ausgangspunkt dieser Arbeit war die Frage, inwieweit die zur Herstellung von Compositmaterialien aus leitfähigen Polymerfilmen (Polythiophen, Polypyrrol) und Metalloxidschichten (anodisch oxidiertes Titan, chemisch oxidiertes Silicium bzw. Aluminium) entwickelte Präparationsmethode auf die Herstellung hybrider Core - Shell - Partikel (Core: Metalloxidpartikel; Shell: leitfähiges Polymer) übertragbar ist. Die erfolgreiche Beschichtung dispergierter Oxidpartikel mit leitfähigen Poly- meren zeigte, dass nicht nur eine analoge Verfahrensweise (Adsorption des Monomers auf der Substratoberfläche und anschließende Zugabe des Oxidationsmittels) verwendet werden konnte, sondern dass bei der Pulverbeschichtung infolge der großen spezifischen Oberfläche der Materialien auch ohne Einsatz spezieller Haftvermittler, hervorragende Schichtqualitäten (hohe Haftfestigkeit, hoher Be- deckungsgrad) erreicht wurden, und die auf diesem Wege hergestellten Verbundmaterialien in Pulverform in beliebiger Menge, Partikelgröße und Zusam-mensetzung verfügbar waren. Der durch die Verkapselung der Oxidteilchen mit intrinsich leitfähigen Polymeren bewirkte enge Kontakt zwischen Polymer- und Oxidphase und die auf diesem Wege realisierte Oberflächenmodifizierung führte zu einem im Vergleich zu den reinen Komponenten wesentlich veränderten Eigenschaftsspektrum. Durch die Herstellung von Compositen waren die leitfähigen Polymere leichter dispergierbar, und konnten kathaphoretisch in guter Qualität, auch auf großen Substratflächen abgeschieden werden. / Starting with the question about the possibility of producing composites based on conducting polymer films (polythiophene, polypyrrole) and metal oxide layers (anodically oxidized titanium, chemical oxidized silicon or aluminium) it was the goal of this work to transfer and modify this method for the preparation of hybrid core - shell - particles (core: metal oxide particle; shell: conducting polymer). By the successfully covering of dispersed oxide particles it was shown, that not only an analogous procedure (adsorption of the monomer on the substrate surface and the following addition of an oxidant) can be used, but that in the case of powder covering because of the high specific surface area of the oxide powders, outstanding layer qualities without using adhesion promotors can be produced. Following this way, powder-like compound materials can be ordered and designed in any quantity, particle size and composition. Through the encapsulation of the oxide particles with intrinsic conducting polymers a narrow contact between the polymer and the oxide phase and a surface modification were made by a very simple way. By this surface modification a totally different behaviour of the composites, compared to their components was realized. The producing of composites allowes a better dispersibility of conducting polymers and their cathaphoretically deposition with a good quality, also on larger substrate surfaces.

The main goal of this work is design and synthesis of novel composite hydrogel-based core-shell microparticles and their application for fabrication of coatings, which provide the “inverse-switching” behaviour to the surface, namely, to become more hydrophobic in water environment. Since contact angle of heterogeneous surfaces is dependent on the nature and ratio of surface components, an increase of amount of more hydrophobic component on the surface will cause the reducing of surface wettability. It was suggested that core-shell particles having water-swellable hydrogel core and hydrophobic, but permeable for water shell when deposited on the hydrophilic substrate should increase the total amount of hydrophobic component on the surface when the cores of particles will swell in water. During the work different approaches to obtain freely dispersed and surface-immobilized core-shell particles with required structure were developed. Obtained particles were applied for preparation of coatings with ability to display “inverse-switching” behaviour. It was demonstrated that properly designed and properly prepared core-shell particles could be successfully used for creation of smart adaptive coatings having the ability to alter the surface properties upon changing of the environment.

The main goal of this work is design and synthesis of novel composite hydrogel-based core-shell microparticles and their application for fabrication of coatings, which provide the “inverse-switching” behaviour to the surface, namely, to become more hydrophobic in water environment. Since contact angle of heterogeneous surfaces is dependent on the nature and ratio of surface components, an increase of amount of more hydrophobic component on the surface will cause the reducing of surface wettability. It was suggested that core-shell particles having water-swellable hydrogel core and hydrophobic, but permeable for water shell when deposited on the hydrophilic substrate should increase the total amount of hydrophobic component on the surface when the cores of particles will swell in water. During the work different approaches to obtain freely dispersed and surface-immobilized core-shell particles with required structure were developed. Obtained particles were applied for preparation of coatings with ability to display “inverse-switching” behaviour. It was demonstrated that properly designed and properly prepared core-shell particles could be successfully used for creation of smart adaptive coatings having the ability to alter the surface properties upon changing of the environment.

Poly(3,4-ethylenedioxythiophene), PEDOT, belongs to the group of conducting polymers and is characterized by its high stability, a moderate band gap and its optical transparency in the conductive state. A large disadvantage of conducting polymers, and also PEDOT, is their poor solubility. One way to achieve processible materials is the synthesis of colloidal particles. Thus, this work focuses on the development of conductive particles by preparing composite structures. Polymeric colloids like latex particles and microgels were used as templates for the oxidative polymerization of EDOT. Depending on template structure completely different composite morphologies with variable properties were obtained. It was found that modification with PEDOT did not only cause conductive particles for application as humidity sensor materials, but also candidates for further functionalization with gold nanoparticles (Au-NPs). Due to a multi-stage synthesis route it was possible to achieve polystyrene(core)-PEDOT(shell)-particles decored with Au-NPs. Microgels acting as “micro reactors” for the incorporation of PEDOT and Au-NPs were also used for preparing multifunctional composites for catalytic applications. / Poly(3,4-ethylendioxythiophen), PEDOT, gehört zur Gruppe der leitfähigen Polymere und zeichnet sich durch seine hohe Stabilität, eine moderate Bandlücke und seine optische Transparenz im dotierten Zustand aus. Ein Nachteil leitfähiger Polymere, wie auch von PEDOT, ist deren schlechte Löslichkeit. Die Synthese kolloidaler Partikel bietet jedoch eine Möglichkeit dieses Problem zu umgehen. In diesem Zusammenhang richtete sich der Fokus dieser Arbeit auf die Darstellung leitfähiger Partikel in Form von Kompositstrukturen. Polymerkolloide, wie Latex- und Mikrogelpartikel, sind als Template eingesetzt worden, in deren Gegenwart PEDOT durch eine oxidative Polymerisation synthetisiert wurde. In Abhängigkeit von der Struktur des Templats sind unterschiedliche Kompositmorphologien mit steuerbaren Eigenschaften erhalten worden. Auf diese Weise wurden neben Materialien für die Feuchtigkeitssensorik leitfähige Kompositpartikel hergestellt, die zusätzlich mit Gold-Nanopartikeln (Au-NP) funktionalisiert werden konnten. Durch ein mehrstufiges Syntheseverfahren sind somit Polystyrol(Kern)-PEDOT(Schale)-Partikel mit Au-NP-funktionalisierter Oberfläche synthetisiert worden. Mikrogelpartikel, die als „Mikroreaktoren“ für die Inkorporation von PEDOT- und Au-NP dienten, wurden ebenfalls eingesetzt, um multifunktionale Komposite mit katalytischen Eigenschaften herzustellen.

Nanopartikel aus Natriumseltenerdfluoriden (NaREF4) erlangen aufgrund ihrer besonderen optischen und magnetischen Eigenschaften zunehmend Beachtung im Bereich der Lebenswissenschaften und bei optoelektronischen Anwendungen. Einige NaREF4-Materialien wie z.B. NaYF4, NaGdF4 und NaLuF4 sind geeignete Wirtsgitter für eine Dotierung mit Seltenerdelementen wie z.B. Eu(III), Tb(III), Nd(III), Pr(III) und Er(III), die Lumineszenzübergänge im sichtbaren Bereich aufweisen. Um NaREF4-Nanopartikel mit hoher Lumineszenzquantenausbeute zu erhalten oder um multifunktionale Nanomaterialien herzustellen, können über einen Kern/Schale-Aufbau mehrere Materialien innerhalb eines Partikels vereint werden. Bislang wurde jedoch nur in wenigen Studien der Kern/Schale-Aufbau von NaREF4-Nanopartikeln detailliert untersucht und die meisten dieser Studien basierten auf elektronenmikroskopischen Analysemethoden. Vor diesem Hintergrund wurde im Rahmen dieser Arbeit der Syntheseverlauf von nahezu monodispersen NaEuF4/NaGdF4-Kern/Schale-Nanopartikeln als Modellsystem untersucht, wobei zur Herstellung der Partikel zwei verschiedene Synthesemethoden verwendet wurden. Neben Untersuchungen durch Röntgendiffraktometrie und Transmissionselektronenmikroskopie wurden zusätzlich Methoden der optischen Spektroskopie eingesetzt, mit denen eine quantitative Bestimmung der Durchmischung zwischen dem Eu(III)-haltigen Kern und der Gd(III)-haltigen Schale innerhalb des Nanopartikels möglich war. Durch den Einsatz spezieller, sensibilisierender Oberflächenliganden konnte zudem der Eu(III)-Anteil auf der Oberfläche der Kern/Schale-Nanopartikel ermittelt werden. Obwohl beide Syntheseverfahren zu NaEuF4/NaGdF4-Kern/Schale-Nanopartikeln führten, die in Form, Größe und Kristallstruktur sehr ähnlich waren, wurden deutliche Unterschiede in der Durchmischung von NaEuF4-Kern- und NaGdF4-Schalenmaterial sichtbar. Aus den quantitativen, spektroskopischen Untersuchungen zum Kern/Schale-Aufbau ging hervor, dass in Abhängigkeit zur verwendeten Synthesemethode unterschiedlich stark ausgeprägte Eu(III)-Dotierungskonzentrationen und -gradienten in der NaGdF4-Schale der synthetisierten Kern/Schale-Nanopartikel vorlagen.