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The investigation of novel structure-to-property relations of many transition metal trihalides MX₃ by downscaling to promising monolayer is still pending. However, the production of two-dimensional MX₃ sheets that are both high crystalline and thin is an experimental challenge. This thesis is focused on the rational synthesis planning and the derived targeted preparation of thin MX₃ nanosheets (≤ 100 nm) on suitable substrates by chemical vapor transport (CVT) as well as their characterization by complementary analytical methods. CVT of nanosheets directly on substrates benefits of low timescales, less material consumption and only few structural distortions. For the determination of optimal growth conditions, the CVT processes of investigated compounds were initially simulated by using the Calphad method (program package TRAGMIN). Thus, the occurring transport efficient gas species and temperature dependent, dominating vapor transport equilibria were calculated to optimize the growth process in a direct and straightforward way. Based on prior simulation results single crystalline sheets of MCl₃ (M = Ru, Mo, Ti, Cr) and CrX₃ (X = I, Br, Cl) were successfully prepared at temperatures between 573 – 1023 K on YSZ (yttrium stabilized zirconia) or sapphire substrates. The adjustable CVT parameters (transport duration, temperatures or weighed starting material) were optimized with respect to the targeted synthesis of either bulk or nanosheets at substrates. Microsheets with thicknesses of less than 4 μm (α-TiCl₃) and about 20 nm thin nanosheets (α-RuCl₃, CrCl₃ and CrI₃) down to ultrathin flakes (≈ 3 nm, α-MoCl₃ and CrBr₃) were obtained by CVT. As a highlight, monolayers of α-RuCl₃ and CrCl₃ were isolated successfully by means of a subsequent delamination. The MX₃ sheets morphology and dimension was described by optical and electron microscopy, highlighting their two-dimensional nature. By several X-ray spectroscopy and diffraction techniques the desired composition (M:X = 1:3), high crystallinity and phase-purity of thick and thin MX₃ platelets was confirmed subsequently. With respect to MX₃ nanosheets a slight increase (α-RuCl₃, α-MoCl₃ and CrBr₃) or decrease (CrCl₃) in phonon energies was observed in comparison to their bulk counterparts. The magnetic properties of CrCl₃ micro- and nanosheets were determined to be solely ferromagnetic and thus different than those of the bulk samples. Finally, the structure-to-property relations were investigated at a first example. The catalytic properties of α-TiCl₃ microsheets were investigated by gas-phase polymerization of ethylene. By downscaling the catalysts thickness by CVT, we obtained an activity improvement of 24 % in comparison to bulk α-TiCl₃.
Gallium nitride (GaN) is a III-V semiconductor, characterized by direct, wide band gap of 3.4 eV at RT. As a material of particular interest for opto- and power electronics applications, it has been thoroughly studied in recent years. Utilization of GaN homoepitaxy in manufacturing of laser diodes (LDs), light-emitting diodes (LEDs), power devices, etc. would be beneficial in terms of reducing defect density, thus improving their lifetime and performance. Yet cost-effective process for providing native GaN substrates has not been established so far.
The focus of this work is put on development of a new method to grow single crystalline GaN layers from Ga vapour. Our approach exploits microwave (MW) plasma as a source of excited nitrogen species, in contrast to classical physical vapour transport (PVT)-based technique, in which ammonia (NH3) serves as a source of reactive nitrogen. Novelty of MW plasma enhanced growth of GaN from vapour lies in MW nitrogen plasma formation in the vicinity of the seed, at moderate pressure (200 – 800 mbar range), and concurrent physical vapour transport of Ga to the growth zone. Simulations of the growth setup (HEpiGaN software) and of the MW plasma source (CST Microwave software) have followed the extensive investigations of material properties. The growth setup and the MW plasma source, with the resonance cavity being its crucial part, have been constructed and implemented into the existing growth reactor.
The stability of MW plasma in function of temperature and pressure has been studied along with its influence on the seed temperature, and thus on the growth conditions. Furthermore, optical emission spectroscopy (OES) has been utilized for in-situ characterization of the growth atmosphere. Studies on the interaction of Ga vapour with the nitrogen discharge were interpreted on the basis of the level structure of lower excited states of Ga.
Deposition experiments have been conducted, using sapphire seeds, GaN, AlN and AlGaN templates, while GaN single crystalline layers have been grown on sapphire and GaN templates. Characterization of GaN layers have been done by various methods, i.e. structure of layers by scanning electron microscopy (SEM), their composition by energy dispersive X-ray spectroscopy (EDX) and secondary ion mass spectrometry (SIMS), and crystal quality by high resolution X-ray diffraction (HRXRD). Results of the characterization together with outcome of OES measurements revealed importance of carbon for the sub-atmospheric MW plasma enhanced growth of GaN from vapour. In addition, this fact was confirmed by experiments in the setup with reduced carbon content. Possible routes for GaN synthesis have been discussed, with the most probable being CN-assisted GaN formation. While CN was detected in the plasma spectra, there was no evidence for the existence of GaN molecules in vapour phase.
In der Promotionsarbeit wurde ein Züchtungsverfahren zur Herstellung strukturell hochqualitativer AlN-Volumenkristalle mittels PVT-Methode entwickelt. Wesentliche Grundvoraussetzungen dafür sind ein thermisch und chemisch stabiles Tiegelmaterial, ein AlN-Quellmaterial mit Sauerstoffverunreinigungen <300 ppm und AlN-Keime mit hoher kristalliner Perfektion. Unter den getesteten potenziellen Tiegelmaterialien (BN, TaC, TaN, NbC, NbN, TaB2, W) zeigten sich TaC und mit Abstrichen W unter AlN-Züchtungsbedingungen ausreichend stabil und wurden für die Wachstumsversuche verwendet. Zur effektiven Reduzierung der Sauerstoffverunreinigungen im AlN-Quellmaterial wurde ein karbothermischer Reduktionsprozess entwickelt, welcher eine Restsauerstoffkonzentration im Quellmaterial von <300 ppm gewährleistet. AlN-Keime für die Homoepitaxie von AlN-Volumenkristallen wurden durch heteroepitaktisches Wachstum auf SiC-Substraten und über spontane Nukleation freistehender AlN-Kristalle hergestellt. Beim heteroepitaktischen Wachstum auf SiC zeigte sich eine starke Abhängigkeit von der Substratpolarität. Wachstum auf C-polarem SiC ist mit geringeren Ätzgrubendichten von 5*10^4 - 10^6 cm^(-2) gegenüber Si-polarem Wachstum mit Ätzgrubensdichten von 5*10^6 - 10^7 cm^(-2) gekennzeichnet. Für beide Substratpolaritäten wurden Modelle des Anwachsstadiums entwickelt. AlN-Kristalle mit bis zu 35 mm im Durchmesser wurden gezüchtet. Die hohe Rissneigung aufgrund von Abkühlspannungen und Si-Konzentrationen von mehreren Prozent im gewachsenen AlN-Kristall vermindern aber die Kristallqualität erheblich. Eine sehr hohe kristalline Perfektion kann hingegen durch spontane Nukleation freistehender AlN-Kristalle auf einer Zwischenebene in der Tiegelmitte gewährleistet werden. Bei Nukleationstemperaturen von 2200 °C wurden isometrische Kristalle mit 12*12*14 mm^3 gezüchtet. Die Kristalle weisen eine zonare Struktur auf, welche durch einen in [000-1]-Richtung gewachsenen Kernbereich mit Versetzungsdichten <10^2 cm^(-2) und einem senkrecht um den Kernbereich gewachsenen Randbereich mit Versetzungsdichten von 10^2 - 10^4 cm^(-2) gekennzeichnet ist. Strukturell hochqualitative (000-1)-Keime wurden aus spontan nukleierten isometrisch gewachsenen AlN-Kristallen präpariert und für die homoepitaktische Volumenkristallzüchtung verwendet. Unter Zuhilfenahme numerischer Temperaturfeldsimulationen wurde ein angepasster Keimhalter entwickelt, welcher ein leicht konvexes Temperaturfeld am Keim gewährleistet und Parasitärwachstum unterdrückt. Somit konnten AlN-Volumenkristalle homoepitaktisch gezüchtet werden, welche eine Durchmesservergrößerung unter Beibehaltung der hohen strukturellen Qualität der Keimkristalle zeigen. Dieses Verfahren bietet die Grundlage, durch die Züchtung mehrerer Kristallgenerationen eine Durchmesseraufweitung auf industriell relevante Größen von 1-2" zu erreichen.