Semiconductor nanowire synthesis provides a promising route to engineer novel nanoscale materials for applications in energy conversion, electronics, and photonics. The addition of methylgermane (GeH₃CH₃) to standard GeH₄/H₂ chemistry is demonstrated to induce a transition from <111> to <110> oriented growth during the vapor-liquid-solid synthesis of Ge nanowires. This hydride-based chemistry is subsequently leveraged to rationally fabricate kinking superstructures based on combinations of <111> and <110> segments with user defined angles and segment lengths. The addition of GeH₃CH₃ also eliminates sidewall tapering and enables Ge nanowire growth at temperatures exceeding 475 °C, which greatly expands the process window. User-programmable diameter modulation is demonstrated without kinking using tetramethyltin (Sn(CH₃)₄) or trimethylsilane (SiH(CH₃)₃) reacting directly on the sidewalls of growing nanowires to either block or allow conformal deposition. Catalyst modification with tetramethyltin is demonstrated to tune growth kinetics and provides further control over nanowire design. Morphological markers, generated via user-defined changes to diameter along the nanowire axial direction, enable a new approach to rapid, accurate, and facile extraction of growth rate information from electron microscopy images. The ability to engineer nanowire structure by tuning chemistry either at the nucleation point or on the sidewall is demonstrated in this work, thus enabling the rational fabrication of complex superstructures.

Die vorliegende Arbeit behandelt die Züchtung von mikrokristallinem Silicium auf Glas bei niedrigen Temperaturen. Da Glas ein amorphes Material ist, können konventionelle Epitaxietechniken nicht angewendet werden. Im untersuchten Wachstumsprozess werden zunächst Silicium-Saatkristallite durch Anwendung des Vapor-Liquid-Solid Verfahrens abgeschieden. Als Lösungsmittel kommt Indium zum Einsatz. Die so erzeugten Kristallite werden anschließend mittels stationärer Lösungszüchtung vergrößert. Bei der Apparatur handelt es sich um einen Prototypen im Labormaßstab, welcher aus einer vertikalen Anordnung eines Sättigungssubstrates und des Lösungsmittels (Indium) besteht. Ein Temperaturgradient bewirkt gleichzeitig eine ausreichende Übersättigung der Nährlösung sowie konvektiven Stofftransport zum oben befindlichen Züchtungssubstrat. Die chemische Stabilität verschiedener Zwischenschichten wurde durch Berechnungen im ternären Stoffsystem Molybdän, Silicium und Indium betrachtet. Darauf basierend erfolgte die Präparation von MoSi2 auf Glas durch Temperung alternierender Molybdän-Silicium Schichtpakete. Die Stabilität dieser Schichten im Kontakt mit Silicium gesättigter Züchtungslösung konnte experimentell nachgewiesen werden. Die anschließende Untersuchung des Vapor-Liquid-Solid Prozesses auf MoSi2-Schichten zeigte eine signifikante Anhängigkeit von den Parametern der Schichtpräparation sowie der Substrattemperatur während der Lösungsmittelverdampfung. Saatkristallite wurden mittels stationärer Lösungszüchtung ausgewachsen und das gezüchtete Material bezüglich Kristallinität, Orientierung und Reinheit charakterisiert. Zusätzlich standen Untersuchungen zur Morphologie im Vordergrund. Die prinzipielle Anwendbarkeit des Prozesses zur Abscheidung von mikrokristallinem Silicium auf Glas konnte nachgewiesen werden. Allerdings verbleiben Limitierungen bezüglich des erreichbaren Bedeckungsgrades sowie der Größe unter stabilen Bedingungen gewachsener Silicium Kristallite. / This work deals with low-temperature solution growth of micro-crystalline silicon on glass. As glass is an amorphous material, conventional epitaxy is not applicable. Therefore, growth is conducted in a two-step process. The first step aims at the spatial arrangement of silicon seed crystals, which is realized by means of vapor-liquid-solid processing using indium as solvent. Seed crystals are afterwards enlarged by applying a specially developed steady-state solution growth apparatus. This laboratory prototype consists of a vertical stack of a silicon feeding source and the solvent (indium). A temperature gradient between feeding source and growth substrate at the top promotes both, supersaturation and material transport by solvent convection. To ensure thermodynamic stability of all materials involved during steady-state solution growth, the ternary phase equilibrium between molybdenum, indium and silicon at 600°C was considered. Based on the obtained results, the use of molybdenum disilicide as conductive coating material is proposed. MoSi2 thin films on glass are shown to resist solution contact. Subsequent investigation of feasibility of the vapor-liquid-solid mechanism revealed the success of indium microdroplet formation to be determined by both, the multilayer deposition parameters and the substrate temperature during indium deposition. Steady-state solution growth at 610°C was utilized to enlarge silicon seed crystals to diameters of up to 200 micrometer. The grown material has been subject of characterization regarding the crystallinity, orientation and purity. Additionally, morphological anomalies are considered. The feasibility of the process for growth of microcrystalline silicon on glass has been shown in principle. Nevertheless, limitations exist regarding the achievable crystalline solidity ratio and the size of crystallites grown under stable conditions.

ZnO nanowires are a promising material with great semiconductor properties. ZnO nanowires were prepared by carbothermal reduction and vapor-liquid-solid growth mechanism. Altering a variety of parameters ranging from mole to mole ratio of ZnO to C all the way to gas flow rate was examined. The nanowires were then characterized and their morphology examined under a SEM to observe what effect the parameter had on the morphology of the nanowires. From the experiments and the parameters tested it was observed that in order to produce the highest quality straight nanowires one should use a mole to mole ratio of ZnO to C graphite of 1 to 3. With a dwell temperature and time of 900 °C for 3 hours. A gold seed catalyst of 4nm and a gas flow rate of 50 to 100sccm of Ar provides the straightest nanowires. Understanding the effect of each parameter on the morphology of ZnO nanowires is vital for the current research. This will only lead to further the research and provide a better understanding of the growth mechanism of these wires and how the production of specific wires with certain morphologic features and characteristics can be achieved.

In this research, selective and bottom-up manufacturing of silica nanowires on silicon (Si) and its applications has been investigated. Localized synthesis of these nanowires on Si was achieved by metal thin film catalysis and metal ion implantation based seeding approach. The growth mechanism of the nanowires followed a vapor-liquid-solid (VLS) mechanism. Mass manufacturing aspects such as growth rate, re-usability of the substrate and experimental growth model were also investigated. Further, silica nanowires were explored as surface enhanced Raman (SER) substrate and immunoassay templates towards optical and electrochemical detection of cancer biomarkers respectively. Investigating their use in photonic applications, optically active silica nanowires were synthesized by erbium implantation after nanowire growth and implantation of erbium as a metal catalyst in Si to seed the nanowires. Ion implantation of Pd in Si and subsequent annealing in Ar at 1100° C for 60 mins in an open tube furnace resulted in silica nanowires of diameters ranging from 15 to 90 nm. Similarly, Pt was sputtered on to Si and further annealed to obtain silica nanowires of diameters ranging from 50 to 500 nm. Transmission electron microscopy studies revealed the amorphous nature of the wires. In addition, nano-sized Pd catalyst was found along the body of the nanowires seeded by Pd implantation into Si. After functionalization of the wires with 3-AminoPropylTriMethoxySilane (APTMS), the Pd decorated silica nanowires served as an SER substrate exhibiting a sensitivity of 107 towards the detection of interleukin-10 (IL-10, a cancer biomarker) with higher spatial resolution. Voltammetric detection of IL-10 involved silica nanowires synthesized by Pd thin film catalysis on Si as an immunoassay template. Using the electrochemical scheme, the presence of IL-10 was detected down to 1fg/mL in ideal pure solution and 1 pg/mL in clinically relevant samples. Time resolved photoluminescence (PL) results from the Er doped silica nanowires indicate a sharp emission around 1.54 µm representative of the I13/2 to I15/2 transition in Erbium. Also, a five-fold increase in the PL intensity and 30% augment in luminescence life time have been observed in nanowires when compared to fused silica sample prepared under similar conditions. The experimental results indicate the potential of silica nanowires in a wide variety of applications such as the development of orthogonal biosensors, fabrication of metallic nanowires, and environmental sensing probes.

Nanofios semicondutores de óxido metálico apresentam enorme potencial em aplicações de nano-sensoriamento de diferentes gases e substâncias químicas e biológicas, bem como na aplicação a detectores UV-visível. Neste trabalho, desenvolvemos e aperfeiçoamos a síntese de nanofios de ZnO em substratos de safira (001), silício (111) e silício (100) sob diferentes concentrações de oxigênio usando o processo de transporte de vapor-liquido-sólido (VLS). No presente trabalho, investigamos a influência da concentração de oxigênio no crescimento de nanofios de ZnO por Espectroscopia de Fotoluminescência a temperatura variável com a finalidade de estudo da mudança na concentração de defeitos. Apresentamos, ainda, caracterizações elétricas (IxV e Ixt) de nanoestruturas de ZnO sob diferentes pressões com o objetivo de estudar os defeitos envolvidos nos processos de transportes eletrônicos. Por último, propomos o desenvolvimento de micro-contatos através da técnica de microfeixe iônico e através de nanolitografia por feixe de elétrons com a finalidade de aplicações a sensores químicos, gasosos e fotodetectores. / Metal oxide nanowires semiconductors have enormous potential in high-sensitive, fast and selective sensing applications. It may be used to selectively detect different gases, chemical and biological substances and also in UV-visible photodetectors. The described processes involve the synthesis as well as the characterization of ZnO nanowires grown on sapphire (001), silicon (100) e silicon (111) substrates by the Vapor-liquid-solid transport method. In the present work, we describe the influence of oxygen concentration introduced in the growth step measured by photoluminescence at variable temperature to demonstrate the change in defect levels emission (DLE). Furthermore, we have shown electrical characterization (IxV and Ixt) in order to study the ambient effect for transport mechanisms in ZnO nanowires. We also report the development of crucial steps in the fabrication for an upcoming ZnO nanowire sensor device (gas, chemical and photodetector) using lithography techniques such as ion micro-beam and electron beam with the purpose of fabricating metallic micro-pads.

Nanofios semicondutores de óxido metálico apresentam enorme potencial em aplicações de nano-sensoriamento de diferentes gases e substâncias químicas e biológicas, bem como na aplicação a detectores UV-visível. Neste trabalho, desenvolvemos e aperfeiçoamos a síntese de nanofios de ZnO em substratos de safira (001), silício (111) e silício (100) sob diferentes concentrações de oxigênio usando o processo de transporte de vapor-liquido-sólido (VLS). No presente trabalho, investigamos a influência da concentração de oxigênio no crescimento de nanofios de ZnO por Espectroscopia de Fotoluminescência a temperatura variável com a finalidade de estudo da mudança na concentração de defeitos. Apresentamos, ainda, caracterizações elétricas (IxV e Ixt) de nanoestruturas de ZnO sob diferentes pressões com o objetivo de estudar os defeitos envolvidos nos processos de transportes eletrônicos. Por último, propomos o desenvolvimento de micro-contatos através da técnica de microfeixe iônico e através de nanolitografia por feixe de elétrons com a finalidade de aplicações a sensores químicos, gasosos e fotodetectores. / Metal oxide nanowires semiconductors have enormous potential in high-sensitive, fast and selective sensing applications. It may be used to selectively detect different gases, chemical and biological substances and also in UV-visible photodetectors. The described processes involve the synthesis as well as the characterization of ZnO nanowires grown on sapphire (001), silicon (100) e silicon (111) substrates by the Vapor-liquid-solid transport method. In the present work, we describe the influence of oxygen concentration introduced in the growth step measured by photoluminescence at variable temperature to demonstrate the change in defect levels emission (DLE). Furthermore, we have shown electrical characterization (IxV and Ixt) in order to study the ambient effect for transport mechanisms in ZnO nanowires. We also report the development of crucial steps in the fabrication for an upcoming ZnO nanowire sensor device (gas, chemical and photodetector) using lithography techniques such as ion micro-beam and electron beam with the purpose of fabricating metallic micro-pads.

abstract: Semiconductor nanowires are important candidates for highly scaled three dimensional electronic devices. It is very advantageous to combine their scaling capability with the high yield of planar CMOS technology by integrating nanowire devices into planar circuits. The purpose of this research is to identify the challenges associated with the fabrication of vertically oriented Si and Ge nanowire diodes and modeling their electrical behavior so that they can be utilized to create unique three dimensional architectures that can boost the scaling of electronic devices into the next generation. In this study, vertical Ge and Si nanowire Schottky diodes have been fabricated using bottom-up vapor-liquid-solid (VLS) and top-down reactive ion etching (RIE) approaches respectively. VLS growth yields nanowires with atomically smooth sidewalls at sub-50 nm diameters but suffers from the problem that the doping increases radially outwards from the core of the devices. RIE is much faster than VLS and does not suffer from the problem of non-uniform doping. However, it yields nanowires with rougher sidewalls and gets exceedingly inefficient in yielding vertical nanowires for diameters below 50 nm. The I-V characteristics of both Ge and Si nanowire diodes cannot be adequately fit by the thermionic emission model. Annealing in forming gas which passivates dangling bonds on the nanowire surface is shown to have a considerable impact on the current through the Si nanowire diodes indicating that fixed charges and traps on the surface of the devices play a major role in determining their electrical behavior. Also, due to the vertical geometry of the nanowire diodes, electric field lines originating from the metal and terminating on their sidewalls can directly modulate their conductivity. Both these effects have to be included in the model aimed at predicting the current through vertical nanowire diodes. This study shows that the current through vertical nanowire diodes cannot be predicted accurately using the thermionic emission model which is suitable for planar devices and identifies the factors needed to build a comprehensive analytical model for predicting the current through vertically oriented nanowire diodes. / Dissertation/Thesis / Ph.D. Electrical Engineering 2014

Nanofios semicondutores de óxido metálico apresentam enorme potencial em aplicações de nano-sensoriamento de diferentes gases e substâncias químicas e biológicas, bem como na aplicação a detectores UV-visível. Neste trabalho, desenvolvemos e aperfeiçoamos a síntese de nanofios de ZnO em substratos de safira (001), silício (111) e silício (100) sob diferentes concentrações de oxigênio usando o processo de transporte de vapor-liquido-sólido (VLS). No presente trabalho, investigamos a influência da concentração de oxigênio no crescimento de nanofios de ZnO por Espectroscopia de Fotoluminescência a temperatura variável com a finalidade de estudo da mudança na concentração de defeitos. Apresentamos, ainda, caracterizações elétricas (IxV e Ixt) de nanoestruturas de ZnO sob diferentes pressões com o objetivo de estudar os defeitos envolvidos nos processos de transportes eletrônicos. Por último, propomos o desenvolvimento de micro-contatos através da técnica de microfeixe iônico e através de nanolitografia por feixe de elétrons com a finalidade de aplicações a sensores químicos, gasosos e fotodetectores. / Metal oxide nanowires semiconductors have enormous potential in high-sensitive, fast and selective sensing applications. It may be used to selectively detect different gases, chemical and biological substances and also in UV-visible photodetectors. The described processes involve the synthesis as well as the characterization of ZnO nanowires grown on sapphire (001), silicon (100) e silicon (111) substrates by the Vapor-liquid-solid transport method. In the present work, we describe the influence of oxygen concentration introduced in the growth step measured by photoluminescence at variable temperature to demonstrate the change in defect levels emission (DLE). Furthermore, we have shown electrical characterization (IxV and Ixt) in order to study the ambient effect for transport mechanisms in ZnO nanowires. We also report the development of crucial steps in the fabrication for an upcoming ZnO nanowire sensor device (gas, chemical and photodetector) using lithography techniques such as ion micro-beam and electron beam with the purpose of fabricating metallic micro-pads.

Orientadores: Luiz Fernando Zagonel, Mônica Alonso Cotta / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2017-05-11T13:05:53Z (GMT). No. of bitstreams: 1 Silva, Bruno Cesar da_M.pdf: 3758085 bytes, checksum: 042d8ff5a8d495ad70b0f10c888cd418 (MD5) Previous issue date: 2016 / Made available in DSpace on 2017-06-14T17:38:47Z (GMT). No. of bitstreams: 1 Silva_BrunoCesarda_M.pdf: 3758085 bytes, checksum: 042d8ff5a8d495ad70b0f10c888cd418 (MD5) Previous issue date: 2016 / Resumo: Neste trabalho, estudamos a dinâmica de crescimento de nanofios de GaP crescidos pelo método VLS (Vapor-Líquido-Sólido) via Epitaxia por Feixe Químico (CBE), usando nanopartículas catalisadoras de ouro. Investigando o efeito da temperatura na dinâmica de crescimento de nanofios de GaP encontramos uma grande variedade de nanofios em cada amostra, caracterizadas por diferentes direções de crescimento e/ou morfologias, apresentando sempre uma população dominante. Com o aumento da temperatura (510°C) observamos uma transição drástica na morfologia da população dominante, de nanofios típicos para uma nova e inesperada morfologia assimétrica. Mostramos ainda que modificando o tamanho da nanopartícula catalisadora de 5nm para 20nm os nanofios assimétricos ainda são favorecidos a alta temperatura. Procurando compreender o mecanismo de formação dos nanofios assimétricos, mostramos que estas estruturas cristalizam-se na fase WZ, com baixa densidade de defeitos, comparadas às outras amostras. Além disso, mostramos que a assimetria destes nanofios não é oriunda de diferenças de polaridade nas facetas laterais ou formação de defeitos cristalográficos que pudessem modificar a dinâmica de crescimento de modo a levar à morfologia assimétrica. Desta forma, propomos um cenário de crescimento simplificado, no qual a estrutura assimétrica é formada pela combinação do crescimento de nanofios ordinários, via VLS, junto com estruturas que crescem livre de catalizador via mecanismo VS (Vapor-Sólido), estas duas estruturas então se juntam, transferindo material e dando lugar a facetas de menor energia, resultando na formação da estrutura assimétrica. Por fim, medidas de fotoluminescência mostram a emissão característica no verde do GaP WZ para os nanofios assimétricos, mesmo com a estrutura não estando passivada, confirmando a boa qualidade cristalina das nossas amostras / Abstract: In this work, we study the growth dynamics of GaP nanowires grown by VLS (Vapor-Liquid-Solid) method via Chemical Beam Epitaxy (CBE) using gold nanoparticles as catalyst. Investigating the effect of temperature on the growth dynamics of GaP nanowires we find a wide variety of nanowires in each sample, characterized by different growth directions and/or morphologies, always having a dominant population. With increasing temperature (510°C), we observed a dramatic transition in the morphology of the dominant population of typical nanowires to a new and unexpected asymmetric morphology. We also show that modifying the size of the catalyst nanoparticle from 5nm to 20mn the asymmetric nanowires are still favored at high temperature. Looking forward to understand the mechanism of formation of the asymmetric nanowires, we show that these structures crystallize in the WZ phase with low defect density when compared to the other samples. Furthermore, we show that the asymmetry of these nanowires is not derived from differences in polarity in side facets or the formation of crystallographic defects which might modify the growth dynamics so as to bring the asymmetric morphology. Thus, we propose a simplified growth scenario, in which the asymmetric structure is formed by growth combination of ordinary nanowires via VLS, along with structures that grow catalyst-free via VS (vapor-solid) mechanism, these two structures joined and by transferring materials facets with lower energy facets appear, resulting in the formation of asymmetrical structure. Finally, photoluminescence measurements show the characteristic emission in the green of WZ GaP for asymmetric nanowires, even with no passivation, which confirms the good crystalline quality of our samples / Mestrado / Física / Mestre em Física

Orientador: Mônica Alonso Cotta / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-19T18:21:16Z (GMT). No. of bitstreams: 1 Oliveira_DouglasSoaresde_M.pdf: 3151118 bytes, checksum: 954bfe85e80e3ae53e5e5c87d10aa961 (MD5) Previous issue date: 2012 / Resumo: O estudo em nanofios semicondutores é crescente, seja pelo grande potencial de aplicações previsto para eles, seja para entender a dinâmica de formação dessas nanoestruturas. Entretanto, estes dois elementos estão ligados, pois é necessário entender o processo de síntese dos nanofios semicondutores para utilizar todo o seu potencial para aplicações. Neste trabalho, crescemos e estudamos nanofios de fosfeto de índio. Os nanofios foram crescidos pela técnica vapor-líquido-sólido em uma câmara de crescimento epitaxial por feixe químico (CBE). Através de microscopia eletrônica de varredura e microscopia eletrônica de transmissão, obtivemos dados para análise dos nossos resultados. Os parâmetros de crescimento utilizados foram escolhidos de forma que nossos nanofios apresentassem um número bastante significativo de falhas de empilhamento. Utilizamos também nanopartículas catalisadoras muito pequenas (~5nm). Nosso resultado principal foi uma nova morfologia para nanofios. Obtivemos nanofios com variações periódicas de diâmetro sem modificar os parâmetros durante o crescimento. Sendo a distância entre essas variações de diâmetro crescente com o inverso do fluxo do precursor de índio (Trimetil-índio) fornecido durante o crescimento. Análise por microscopia eletrônica de transmissão nos mostrou que essas oscilações periódicas de diâmetro estão associadas com um aumento muito grande no número de falhas de empilhamento e mudanças na fase cristalográfica, de wurtzita para blenda de zinco. Esta morfologia foi modelada por nós como a nanopartícula englobando parcialmente a lateral do nanofio periodicamente durante o crescimento. Nosso modelo é baseado em considerações sobre a competição entre as rotas de incorporação de índio durante o crescimento, as condições termodinâmicas para a nucleação na linha de três fases e estabilidade mecânica da nanopartícula sobre o nanofio durante o crescimento / Abstract: The study of semiconductor nanowires is growing, either due to the great potential for applications or to understand the dynamics of formation of these nanostructures. However, these two elements are linked since it is necessary to understand the synthesis of semiconductor nanowires in order to use all its potential for applications. In this work, we studied and grew nanowires of indium phosphide. These nanowires were grown by the vapor-liquid-solid method on a chemical beam epitaxy (CBE) chamber. They were studied by scanning and transmission electron microscopy. The growth parameters used were chosen so that our NWs presented a significant number of stacking faults and very small (~5nm) catalyst nanoparticles (NPs). Our main result was the observation of a new NW morphology. We have obtained NWs with periodical variations in diameter without any changes in growth parameters during the run. The distance between these oscillations depends almost linearly on the inverse of the Indium precursor flow (TMI) provided during growth. Analysis by transmission electron microscopy has shown that the periodic oscillations in diameter are associated with a very large increase of SF densities and crystallographic phase changes, from Wurtzite to Zinc Blende phase. We have modeled the formation of this morphology as the NP partly wetting the NW sidewalls periodically during growth. Our model is based in considerations of competition between the routes of incorporation of indium during growth, the thermodynamic conditions for nucleation at the three-phase line and mechanical stability of the NP on the NW during growth / Mestrado / Física / Mestre em Física