Techn. Universiẗat, Diss., 2002--Berlin.

Nürnberg, Universiẗat, Diss., 2004--Erlangen.

Techn. Universiẗat, Diss., 2005--Berlin.

abstract: The goal of this research was to reduce dislocations and strain in high indium content bulk InGaN to improve quality for optical devices. In an attempt to achieve this goal, InGaN pillars were grown with compositions that matched the composition of the bulk InGaN grown on top. Pillar height and density were optimized to facilitate coalescence on top of the pillars. It was expected that dislocations within the pillars would bend to side facets, thereby reducing the dislocation density in the bulk overgrowth, however this was not observed. It was also expected that pillars would be completely relaxed at the interface with the substrate. It was shown that pillars are mostly relaxed, but not completely. Mechanisms are proposed to explain why threading dislocations did not bend and how complete relaxation may have been achieved by mechanisms outside of interfacial misfit dislocation formation. Phase separation was not observed by TEM but may be related to the limitations of the sample or measurements. High indium observed at facets and stacking faults could be related to the extra photoluminescence peaks measured. This research focused on the InGaN pillars and first stages of coalescence on top of the pillars, saving bulk growth and device optimization for future research. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2011

Feinfokussierte Ionenstrahlen dienen in den Gebieten der Halbleiterindustrie und Materialforschung der Mikro- und Nanostrukturierung. Die vorliegende Arbeit beschäftigt sich mit den beiden Hauptanwendungen von fokussierten Ionenstrahlen, dem Materialabtrag und der ionenstrahlinduzierten Materialabscheidung. Dabei wird die hochauflösende Ionensäule CANION 31Z der Firma Orsay Physics mit Stromdichten von bis zu 10 A/cm2 und mit integriertem Gassystem eingesetzt. Es wird ausführlich auf Anwendungsbeispiele von Fokussierten Ionenstrahlsystemen im Bereich der Industrie und Forschung eingegangen. Schwerpunktmäßig wird die Abscheidung von Wolfram aus dem Precursorgas W(CO)6 (Wolframhexacarbonyl) auf Si und SiO2 als Substrat untersucht, mit dem Ziel, gut leitfähige Drähte (hier im Sinne von Leiterbahnen) mit minimalem Querschnitt herzustellen. Die Optimierung der Ionenstrahl-Parameter dieser Feinfokussierten Ionenstrahlanlage bezüglich der Abscheidung steht im Vordergrund. Dabei wird ein kurzer Einblick in die Theorie der Schichtentstehung beim Abscheidevorgang gegeben. Untersuchungen der erzeugten Strukturen entsprechend der Schichtqualität und der Strukturabmessungen werden erläutert und die Ergebnisse diskutiert. Es konnten Wolframdrähte mit einer Länge von 20 ... 100 µm, einer Breite von minimal 150 nm und einer Höhe von maximal 600 nm angefertigt werden. Die Zusammensetzung der Drähte in Abhängigkeit der Prozessparameter wurde mittels AES bestimmt. Im optimalen Fall wurden die Schichtanteile zu 80% W, 5% O, 6% C und 9% Ga ermittelt (Angaben in Atomprozent). Der spezifische Widerstand der Wolframdrähte ist im Bereich 150 ... 320 µWcm gemessen worden.

III-nitride semiconductors have garnered significant attention due to their diverse applications in the fields of optics and electronics. As GaN-based visible light-emitting diodes (LEDs) and laser technologies continue to advance, there has been a surge of interest in the development of ultraviolet (UV) devices. In order to explore the UV range, extensive research has been conducted on BN-based materials and their alloys with conventional III-nitrides, driven by the quest for materials exhibiting larger bandgaps and enhanced refractive index contrast. Additionally, the incorporation of boron into III-nitrides through alloying provides a promising avenue for effectively modulating lattice parameters and manipulating the crystalline structure. This offers a novel approach for strain engineering, lattice matching, and structural manipulation, facilitating the optimization of device performance and expanding the capabilities of III-nitride semiconductors in the realm of UV device development. In this work, we optimize and investigate the epitaxial growth of BGaN using metalorganic chemical vapor deposition, and characterize the physical and electronic properties of the grown films using several techniques such as X-ray diffraction, atomic force microscopy, UV-Visible spectroscopy, X-ray Photoelectron Spectroscopy (XPS), electron energy loss spectroscopy (EELS) and more. We have explored different metalorganic chemical vapor deposition techniques —such as continuous growth and pulsed-flow modulation, high temperature and low temperature growths, hydrogen-containing and hydrogen-free growths, trimethylgallium (TMG) and triethylgallium (TEG) sourced growths, Triethylborane (TEB) and borazine (BRZN) sourced growths— to grow BGaN alloys. Samples grown using continuous-flow method, low temperatures, TEG source and hydrogen-free carrier gas show higher boron content and better crystalline quality when having TEB as a boron source. BRZN is used to reduce carbon impurities for the purpose of film doping. With BRZN, TMG was found as a preferred gallium source. Additionally, we have characterized the electronic properties of the grown films in details using XPS, EELS and other related techniques. We have studied the band offset of BGaN with AlN using traditional methods. Furthermore, we have developed a statistical technique to find small offsets at interfaces at the precision of the measuring instrument.

This work has analyzed the complex interfaces of GaN and InGaN grown by sputter deposition and GaN grown by metal-organic chemical vapor deposition (MOCVD) with CdTe and CdS. First, the GaN and InGaN films were characterized by AFM and XRD, and it has been shown that the MOCVD samples have a very smooth surface and are single crystalline with growth in the (002) direction. On the other hand, the sputter deposited samples have rougher surfaces and are polycrystalline. Furthermore, complete interface studies have been performed using in-situ XPS and deposition between GaN grown by sputter deposition and MOCVD and CdTe and CdS to determine the band alignments, conduction and valence band offsets, and Fermi level positions. These interface studies will help determine basic properties to see if these GaN films can be incorporated in a CdTe solar cell to improve its efficiency. It was determined that all the interfaces between the sputtered GaN/InGaN and CdTe/CdS have small conduction band offsets of less than 0.1 eV that do not significantly prevent electron flow across the interface. However, the valence band offsets were much more significant, as they ranged from 0.43 eV to over 1.8 eV. For purposes of the desired positions of the GaN in the CdTe solar cell, the conduction band offsets are much more crucial, and very small conduction band offsets are desired. An interesting effect was that the interfaces between InGaN/CdTe and InGaN/CdS showed In migration into the CdTe and CdS, causing a rise in the Fermi level for the CdTe and CdS, which has been known to worsen the performance of the CdTe solar cell. The MOCVD GaN/CdTe and CdS interfaces showed a slightly higher conduction band offset of about 0.15 eV, but this barrier still should not significantly prevent current flow. / Master of Science

O presente trabalho teve como objetivos o estudo das propriedades nanoestruturais, características morfológicas e avaliação do comportamento fotocatalítico de filmes de dióxido de titânio dopados com enxofre. Os filmes de TiO2 foram crescidos sobre borossilicato, por meio da técnica de MOCVD, na temperatura de 400 °C. O processo de dopagem com enxofre deu-se a partir do tratamento termoquímico de sulfetação, realizado sob atmosfera de H2 / 2%v. H2S, nas temperaturas de 50 °C, 100 °C e 150 °C, o que resultou em teores de S de 8 at.%, 3 at.% e 0,2 at.%, respectivamente. A degradação do corante alaranjado de metila foi utilizada para avaliar a atividade fotocatalítica dos filmes sob radiação ultravioleta e visível. Todos os filmes exibiram a formação da fase anatase, compostos por grãos bem definidos, e estrutura colunar densificada. Foi observada a formação de grupos SO42- na superfície dos filmes dopados, indicando a substituição dos íons Ti4+ pelo cátion S6+, e a formação da ligação Ti-O-S nos filmes. Os testes de degradação indicaram que os filmes de S-TiO2 apresentam atividade fotocatalítica tanto sob radiação UV, quanto em luz visível. O filme de 8 at.% S-TiO2, dopado a 50 °C, exibiu o melhor comportamento fotocatalítico, com 72,1 % de degradação do corante sob luz visível. Os resultados sugerem que a dopagem com S, além de formar uma morfologia favorável ao processo de fotocatálise, promoveu um deslocamento da absorção do TiO2 para a região do espectro visível, o que consequentemente permite a sua aplicação prática sob luz solar ou lâmpadas de luz visível. / The present work aims the study of the nanostructural properties, morphological characteristics and photocatalytic behavior evaluation of sulfur-doped titanium dioxide films. TiO2 films were grown on borosilicate by MOCVD at 400 °C. Sulfur doping process was carried out by the thermochemical treatment under H2 / 2%v. H2S atmosphere at 50 °C, 100 °C and 150 °C, which resulted in S contents of 8 at%, 3 at% and 0.2 at%, respectively. Methyl orange dye degradation was used to evaluate the photocatalytic activity of the films under UV-Vis radiation. All films exhibited the formation of the anatase phase, composed to well-defined grains, and dense columnar structure. SO42- groups were observed on the surface of all S-doped films, indicating the substitution of the Ti4+ ions by the S6+ cation, and the formation of Ti-O-S bond in the films. Degradation tests indicated that the S:TiO2 films present photocatalytic activity both under UV radiation and visible light. 8 at.% S:TiO2 film, doped at 50 °C, presented a higher photocatalytic performance, with 72.1 % of dye degradation under visible light. The results suggest that the sulfur doping, besides forming a morphology favorable to the photocatalysis process, caused a shift of the TiO2 films absorption to the visible spectrum region, which allows their practical application under sunlight or visible light bulbs.

O presente trabalho teve como objetivos o estudo das propriedades nanoestruturais, características morfológicas e avaliação do comportamento fotocatalítico de filmes de dióxido de titânio dopados com enxofre. Os filmes de TiO2 foram crescidos sobre borossilicato, por meio da técnica de MOCVD, na temperatura de 400 °C. O processo de dopagem com enxofre deu-se a partir do tratamento termoquímico de sulfetação, realizado sob atmosfera de H2 / 2%v. H2S, nas temperaturas de 50 °C, 100 °C e 150 °C, o que resultou em teores de S de 8 at.%, 3 at.% e 0,2 at.%, respectivamente. A degradação do corante alaranjado de metila foi utilizada para avaliar a atividade fotocatalítica dos filmes sob radiação ultravioleta e visível. Todos os filmes exibiram a formação da fase anatase, compostos por grãos bem definidos, e estrutura colunar densificada. Foi observada a formação de grupos SO42- na superfície dos filmes dopados, indicando a substituição dos íons Ti4+ pelo cátion S6+, e a formação da ligação Ti-O-S nos filmes. Os testes de degradação indicaram que os filmes de S-TiO2 apresentam atividade fotocatalítica tanto sob radiação UV, quanto em luz visível. O filme de 8 at.% S-TiO2, dopado a 50 °C, exibiu o melhor comportamento fotocatalítico, com 72,1 % de degradação do corante sob luz visível. Os resultados sugerem que a dopagem com S, além de formar uma morfologia favorável ao processo de fotocatálise, promoveu um deslocamento da absorção do TiO2 para a região do espectro visível, o que consequentemente permite a sua aplicação prática sob luz solar ou lâmpadas de luz visível. / The present work aims the study of the nanostructural properties, morphological characteristics and photocatalytic behavior evaluation of sulfur-doped titanium dioxide films. TiO2 films were grown on borosilicate by MOCVD at 400 °C. Sulfur doping process was carried out by the thermochemical treatment under H2 / 2%v. H2S atmosphere at 50 °C, 100 °C and 150 °C, which resulted in S contents of 8 at%, 3 at% and 0.2 at%, respectively. Methyl orange dye degradation was used to evaluate the photocatalytic activity of the films under UV-Vis radiation. All films exhibited the formation of the anatase phase, composed to well-defined grains, and dense columnar structure. SO42- groups were observed on the surface of all S-doped films, indicating the substitution of the Ti4+ ions by the S6+ cation, and the formation of Ti-O-S bond in the films. Degradation tests indicated that the S:TiO2 films present photocatalytic activity both under UV radiation and visible light. 8 at.% S:TiO2 film, doped at 50 °C, presented a higher photocatalytic performance, with 72.1 % of dye degradation under visible light. The results suggest that the sulfur doping, besides forming a morphology favorable to the photocatalysis process, caused a shift of the TiO2 films absorption to the visible spectrum region, which allows their practical application under sunlight or visible light bulbs.

Ce travail est consacré à l'épitaxie en phase gazeuse d'organométallique de nanostructures de nitrures en forme de fil et de pyramide, pour lesquelles nous cherchons à comprendre les mécanismes de croissance mis en jeu. Une étude paramétrique complète est présentée pour optimiser et mieux appréhender la croissance de nanofils GaN auto-assemblés non-catalysés. Nous démontrons notamment que l'injection de silane est un paramètre-clé pour la croissance des nanofils grâce à la formation d'une couche SiNx de passivation sur les facettes latérales qui joue le rôle d'un masque favorisant ainsi la croissance verticale. Un nouveau procédé de croissance de nanofils sans silane est aussi proposé dans ce travail en utilisant de très faibles flux de précurseurs qui favorise la formation de facettes verticales. De tels nanofils présentent d'excellentes propriétés structurales et optiques grâce à l'absence de silicium. Par ailleurs, nous montrons que la polarité joue un rôle crucial sur la croissance des nanostructures de GaN puisque la forme des nanostructures peut être simplement déterminée par l'orientation de la polarité: une polarité N résulte en fils alors qu'une polarité Ga en pyramides. Par conséquent, la forme fil/pyramide des nanostructures peut être directement choisie en contrôlant la polarité sur des substrats de saphir ou de GaN. Nous avons justement exploité cette méthode pour obtenir des réseaux ordonnés de fils et de pyramides de GaN en utilisant la croissance sélective à travers un masque nanostructuré par lithographie. De telles nanostructures ont été utilisées pour la croissance d'hétérostructures InGaN/GaN pour obtenir soit des puits quantiques non-polaires sur les flans des nanofils, soit des boîtes quantiques d'InGaN aux sommets des pyramides. / This work reports the metal-organic vapour phase epitaxy of III-Nitride wire- or pyramid-shaped nanostructures and focuses on the growth mechanisms related to these two types of GaN nanostrcutures. A complete parametric study is presented in order to optimize and to understand the catalyst-free self-assembled GaN nanowire growths. We demonstrate that the silane flux injection is a key-parameter for nanowire growth thanks to the formation of SiNx passivation layer along the sidewall facets that acts as a mask favoring the vertical growth. A novel silane-free nanowire growth is also proposed in this work using ultra-low precursor flux that favors the formation of vertical facets. Such nanowires exhibit excellent structural and optical properties due to the absence of silicon. In addition, the polarity is found to play a key-role for GaN nanostructure growth, since the nanostructure shape can be basically determined by the polarity orientation: N-polar nanostructure results in wire, whereas Ga-polar in pyramid. Consequently, the shape wire/pyramid of nanostructure can be chosen depending on the polarity control on sapphire or GaN substrates. This method is applied to get ordered arrays of GaN wires and pyramids using selective area growth on patterned mask. Such nanostructures can be used as template for InGaN/GaN heterostructure growth to get either non-polar multi-quantum wells along the wire sidewalls or InGaN quantum dots at the pyramid apex.