Production and characterization of Tm3+/Yb3+ codoped waveguides based on PbO-GeO2 thin films

Fabrication and optical characterization of Tm3+/Yb3+ codoped PbO-GeO2 (PGO) pedestal-type waveguides are investigated in this work. It is important to mention that, to the best of authors' knowledge, the use of PGO pedestal-type waveguide has not been studied before. PGO thin films codoped with Tm3+ and Yb3+ were obtained through RF magnetron sputtering technique. The pedestal profile was obtained using conventional optical lithography procedures, followed by plasma etching and sputtering deposition. The profile of Tm3+/Yb3+ codoped PGO waveguides was observed by means of Scanning Electron Microscopy (SEM) measurements. Also the infrared and infrared-to-visible frequency upconversion luminescences of Tm3+ ions were measured exciting the samples with a cw 980 nm diode laser. Propagation losses around 11 dB/cm and 9 dB/cm were obtained at 630 and 1050 nm, respectively, for waveguides in the 20-100 μm width range. Single-mode propagation was observed for waveguides width up to 12 μm and 7 μm, at 1050 nm and 630 nm, respectively; larger waveguides width provided multi-mode propagation. The present results corroborate the possibility of using Tm3+/Yb3+ codoped PGO thin films as active waveguide for photonic applications. © 2013 Elsevier B.V. All rights reserved.

Fabrication of Yb3+/Er3+ codoped Bi2O3-WO3-TeO2 pedestal type waveguide for optical amplifiers

We report, for the first time to our knowledge, experimental results on pedestal waveguides produced with Yb3+/Er3+ codoped Bi2O3-WO3-TeO2 thin films deposited by RF Sputtering for photonic applications. Thin films were deposited using Ar/O-2 plasma at 5 mTorr pressure and RF power of 40 W on substrates of silicon wafers. The definition of the pedestal waveguide structure was made using conventional optical lithography followed by plasma etching. Propagation losses around 2.0 dB/cm and 2.5 dB/cm were obtained at 633 and 1050 nm, respectively, for waveguides in the 20-100 mu m width range. Single-mode propagation was measured for waveguides width up to 10 mu m and 12 mu m, at 633 nm and 1050 nm, respectively; for larger waveguides widths multi-mode propagation was obtained. Internal gain of 5.6 dB at 1530 nm, under 980 nm excitation, was measured for 1.5 cm waveguide length (similar to 3.7 dB/cm). The present results show the possibility of using Yb3+/Er3+ codoped Bi2O3-WO3-TeO2 pedestal waveguide for optical amplifiers. (C) 2014 Elsevier B.V. All rights reserved.

Production and characterization of Tm3+/Yb3+ codoped pedestal-type PbO-GeO2 waveguides

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Noble-metal nanoparticles produced with colloidal lithography: fabrication, optical properties and applications

In this work, metal nanoparticles produced by nanosphere lithography were studied in terms of their optical properties (in connection to their plasmon resonances), their potential application in sensing platforms - for thin layer sensing and bio-recognition events -, and for a particular case (the nanocrescents), for enhanced spectroscopy studies. The general preparation procedures introduced early in 2005 by Shumaker-Parry et al. to produce metallic nanocrescents were extended to give rise to more complex (isolated) structures, and also, by combining colloidal monolayer fabrication and plasma etching techniques, to arrays of them. The fabrication methods presented in this work were extended not only to new shapes or arrangements of particles, but included also a targeted surface tailoring of the substrates and the structures, using different thiol and silane compounds as linkers for further attachment of, i.e. polyelectrolyte layers, which allow for a controlled tailoring of their nanoenvironment. The optical properties of the nanocrescents were studied with conventional transmission spectroscopy; a simple multipole model was adapted to explain their behaviour qualitatively. In terms of applications, the results on thin film sensing using these particles show that the crescents present an interesting mode-dependent sensitivity and spatial extension. Parallel to this, the penetrations depths were modeled with two simplified schemes, obtaining good agreement with theory. The multiple modes of the particles with their characteristic decay lengths and sensitivities represent a major improvement for particle-sensing platforms compared to previous single resonance systems. The nanocrescents were also used to alter the emission properties of fluorophores placed close to them. In this work, green emitting dyes were placed at controlled distances from the structures and excited using a pulsed laser emitting in the near infrared. The fluorescence signal obtained in this manner should be connected to a two-photon processes triggered by these structures; obtaining first insight into plasmon-mediated enhancement phenomena. An even simpler and faster approach to produce plasmonic structures than that for the crescents was tested. Metallic nanodiscs and nanoellipses were produced by means of nanosphere lithography, extending a procedure reported in the literature to new shapes and optical properties. The optical properties of these particles were characterized by extinction spectroscopy and compared to results from the literature. Their major advantage is that they present a polarization-dependent response, like the nanocrescents, but are much simpler to fabricate, and the resonances can be tailored in the visible with relative ease. The sensing capabilities of the metallic nanodiscs were explored in the same manner as for the nanocrescents, meaning their response to thin layers and to bio-recognition events on their surface. The sensitivity of these nanostructures to thin films proved to be lower than that of the crescents, though in the same order of magnitude. Experimental information about the near field extension for the Au nanodiscs of different sizes was also extracted from these measurements. Further resonance-tailoring approaches based on electrochemical deposition of metals on the nanodiscs were explored, as a means of modifying plasmon resonances by changing surface properties of the nanoparticles. First results on these experiments would indicate that the deposition of Ag on Au on a submonolayer coverage level can lead to important blue-shifts in the resonances, which would open a simple way to tailor resonances by changing material properties in a local manner.

Surface InGaAs nanostructures for sensing applications

El desarrollo de sensores está ganando cada vez mayor importancia debido a la concienciación ciudadana sobre el medio ambiente haciendo que su desarrollo sea muy elevado en todas las disciplinas, entre las que cabe destacar, la medicina, la biología y la química. A pesar de la existencia de estos dispositivos, este área está aún por mejorar, ya que muchos de los materiales propuestos hasta el momento e incluso los ya comercializados muestran importantes carencias de funcionamiento, eficiencia e integrabilidad entre otros. Para la mejora de estos dispositivos, se han propuesto diversas aproximaciones basadas en nanosistemas. Quizá, uno de las más prometedoras son las nanoestructuras de punto cuántico, y en particular los semiconductores III-V basados en la consolidada tecnología de los arseniuros, las cuáles ofrecen excelentes propiedades para su uso como sensores. Además, estudios recientes demuestran su gran carácter sensitivo al medio ambiente, la posibilidad de funcionalizar la superficie para la fabricación de sensores interdisciplinares y posibilididad de mejorar notablemente su eficiencia. A lo largo de esta tesis, nos centramos en la investigación de SQD de In0.5Ga0.5As sobre substratos de GaAs(001) para el desarrollo de sensores de humedad. La tesis abarca desde el diseño, crecimiento y caracterización de las muestras hasta la el posterior procesado y caracterización de los dispositivos finales. La optimización de los parámetros de crecimiento es fundamental para conseguir una nanoestructura con las propiedades operacionales idóneas para un fin determinado. Como es bien sabido en la literatura, los parámetros de crecimiento (temperatura de crecimiento, relación de flujos del elemento del grupo V y del grupo I II (V/III), velocidad de crecimiento y tratamiento térmico después de la formación de la capa activa) afectan directamente a las propiedades estructurales, y por tanto, operacionales de los puntos cuánticos (QD). En esta tesis, se realiza un estudio de las condiciones de crecimiento para el uso de In0.5Ga0.5As SQDs como sensores. Para los parámetros relacionados con la temperatura de crecimiento de los QDs y la relación de flujos V / I I I se utilizan los estudios previamente realizados por el grupo. Mientras que este estudio se centrará en la importancia de la velocidad de crecimiento y en el tratamiento térmico justo después de la nucleación de los QDs. Para ello, se establece la temperatura de creciemiento de los QDs en 430°C y la relación de flujos V/III en 20. Como resultado, los valores más adecuados que se obtienen para la velocidad de crecimiento y el tratamiento térmico posterior a la formación de los puntos son, respectivamente, 0.07ML/s y la realización de una bajada y subida brusca de la temperatura del substrato de 100°C con respecto a la temperatura de crecimiento de los QDs. El crecimiento a una velocidad lo suficientemente alta que permita la migración de los átomos por la superficie, pero a su vez lo suficientemente baja para que se lleve a cabo la nucleación de los QDs; en combinación con el tratamiento brusco de temperatura que hace que se conserve la forma y composición de los QDs, da lugar a unos SQDs con un alto grado de homogeneidad y alta densidad superficial. Además, la caracterización posterior indica que estas nanoestructuras de gran calidad cristalina presentan unas propiedades ópticas excelentes incluso a temperatura ambiente. Una de las características por la cual los SQD de Ino.5Gao.5As se consideran candidatos prometedores para el desarrollo de sensores es el papel decisivo que juega la superficie por el mero hecho de estar en contacto directo con las partículas del ambiente y, por tanto, por ser capaces de interactuar con sus moléculas. Así pues, con el fin de demostrar la idoneidad de este sistema para dicha finalidad, se evalúa el impacto ambiental en las propiedades ópticas y eléctricas de las muestras. En un primer lugar, se analiza el efecto que tiene el medio en las propiedades ópticas. Para dicha evaluación se compara la variación de las propiedades de emisión de una capa de puntos enterrada y una superficial en distintas condiciones externas. El resultado que se obtiene es muy claro, los puntos enterrados no experimentan un cambio óptico apreciable cuando se varían las condiciones del entorno; mientras que, la emisión de los SQDs se modifica significativamente con las condiciones del medio. Por una parte, la intensidad de emisión de los puntos superficiales desaparece en condiciones de vacío y decrece notablemente en atmósferas secas de gases puros (N2, O2). Por otra parte, la fotoluminiscencia se conserva en ambientes húmedos. Adicionalmente, se observa que la anchura a media altura y la longitud de onda de emisión no se ven afectadas por los cambios en el medio, lo que indica, que las propiedades estructurales de los puntos se conservan al variar la atmósfera. Estos resultados apuntan directamente a los procesos que tienen lugar en la superficie entre estados confinados y superficiales como responsables principales de este comportamiento. Así mismo, se ha llevado a cabo un análisis más detallado de la influencia de la calidad y composición de la atmósfera en las propiedades ópticas de los puntos cuánticos superficiales. Para ello, se utilizan distintas sustancias con diferente polaridad, composición atómica y masa molecular. Como resultado se observa que las moléculas de menor polaridad y más pesadas causan una mayor variación en la intensidad de emisión. Además, se demuestra que el oxígeno juega un papel decisivo en las propiedades ópticas. En presencia de moléculas que contienen oxígeno, la intensidad de fotoluminiscencia disminuye menos que en atmósferas constituidas por especies que no contienen oxígeno. Las emisión que se observa respecto a la señal en aire es del 90% y del 77%, respectivamente, en atmósferas con presencia o ausencia de moléculas de oxígeno. El deterioro de la señal de emisión se atribuye a la presencia de defectos, enlaces insaturados y, en general, estados localizados en la superficie. Estos estados actúan como centros de recombinación no radiativa y, consecuentemente, se produce un empeoramiento de las propiedades ópticas de los SQDs. Por tanto, la eliminación o reducción de la densidad de estos estados superficiales haría posible una mejora de la intensidad de emisión. De estos experimentos de fotoluminiscencia, se deduce que las interacciones entre las moléculas presentes en la atmósfera y la superficie de la muestra modifican la superficie. Esta alteración superficial se traduce en un cambio significativo en las propiedades de emisión. Este comportamiento se atribuye a la posible adsorción de moléculas sobre la superficie pasivando los centros no radiativos, y como consecuencia, mejorando las propiedades ópticas. Además, los resultados demuestran que las moléculas que contienen oxígeno con mayor polaridad y más ligeras son adsorbidas con mayor facilidad, lo que hace que la intensidad óptica sufra variaciones despreciables con respecto a la emisión en aire. Con el fin de desarrollar sensores, las muestras se procesan y los dispositivos se caracterizan eléctricamente. El procesado consiste en dos contactos cuadrados de una aleación de Ti/Au. Durante el procesado, lo más importante a tener en cuenta es no realizar ningún ataque o limpieza que pueda dañar la superficie y deteriorar las propiedades de las nanostructuras. En este apartado, se realiza un análisis completo de una serie de tres muestras: GaAs (bulk), un pozo cuántico superficial (SQW) de Ino.5Gao.5As y SQDs de Ino.5Gao.5As. Para ello, a cada una de las muestras se le realizan medidas de I-V en distintas condiciones ambientales. En primer lugar, siguiendo los resultados obtenidos ópticamente, se lleva a cabo una comparación de la respuesta eléctrica en vacío y aire. A pesar de que todas las muestras presentan un carácter más resistivo en vacío que en aire, se observa una mayor influencia sobre la muestra de SQD. En vacío, la resistencia de los SQDs decrece un 99% respecto de su valor en aire, mientras que la variación de la muestras de GaAs e Ino.5Gao.5As SQW muestran una reducción, respectivamente, del 31% y del 20%. En segundo lugar, se realiza una evaluación aproximada del posible efecto de la humedad en la resistencia superficial de las muestras mediante la exhalación humana. Como resultado se obtiene, que tras la exhalación, la resistencia disminuye bruscamente y recupera su valor inicial cuando dicho proceso concluye. Este resultado preliminar indica que la humedad es un factor crítico en las propiedades eléctricas de los puntos cuánticos superficiales. Para la determinación del papel de la humedad en la respuesta eléctrica, se somete a las muestras de SQD y SQW a ambientes con humedad relativa (RH, de la siglas del inglés) controlada y se analiza el efecto sobre la conductividad superficial. Tras la variación de la RH desde 0% hasta el 70%, se observa que la muestra SQW no cambia su comportamiento eléctrico al variar la humedad del ambiente. Sin embargo, la respuesta de la muestra SQD define dos regiones bien diferenciadas, una de alta sensibilidad para valores por debajo del 50% de RH, en la que la resistencia disminuye hasta en un orden de magnitud y otra, de baja sensibilidad (>50%), donde el cambio de la resistencia es menor. Este resultado resalta la especial relevancia no sólo de la composición sino también de la morfología de la nanostructura superficial en el carácter sensitivo de la muestra. Por último, se analiza la influencia de la iluminación en la sensibilidad de la muestra. Nuevamente, se somete a las muestras SQD y SQW a una irradiación de luz de distinta energía y potencia a la vez que se varía controladamente la humedad ambiental. Una vez más, se observa que la muestra SQW no presenta ninguna variación apreciable con las alteraciones del entorno. Su resistencia superficial permanece prácticamente inalterable tanto al modificar la potencia de la luz incidente como al variar la energía de la irradiación. Por el contrario, en la muestra de SQD se obtiene una reducción la resistencia superficial de un orden de magnitud al pasar de condiciones de oscuridad a iluminación. Con respecto a la potencia y energía de la luz incidente, se observa que a pesar de que la muestra no experimenta variaciones notables con la potencia de la irradiación, esta sufre cambios significativos con la energía de la luz incidente. Cuando se ilumina con energías por encima de la energía de la banda prohibida (gap) del GaAs (Eg ~1.42 eV ) se produce una reducción de la resistencia de un orden de magnitud en atmósferas húmedas, mientras que en atmósferas secas la conductividad superficial permanece prácticamente constante. Sin embargo, al inicidir con luz de energía menor que Eg, el efecto que se produce en la respuesta eléctrica es despreciable. Esto se atribuye principalmente a la densidad de portadores fotoactivados durante la irradiación. El volumen de portadores excita dos depende de la energía de la luz incidente. De este modo, cuando la luz que incide tiene energía menor que el gap, el volumen de portadores generados es pequeño y no contribuye a la conductividad superficial. Por el contrario, cuando la energía de la luz incidente es alta (Eg), el volumen de portadores activados es elevado y éstos contribuyen significantemente a la conductividad superficial. La combinación de ambos agentes, luz y humedad, favorece el proceso de adsorción de moléculas y, por tanto, contribuye a la reducción de la densidad de estados superficiales, dando lugar a una modificación de la estructura electrónica y consecuentemente favoreciendo o dificultando el transporte de portadores. ABSTRACT Uncapped three-dimensional (3D) nanostructures have been generally grown to assess their structural quality. However, the tremendous growing importance of the impact of the environment on life has become such nanosystems in very promising candidates for the development of sensing devices. Their direct exposure to changes in the local surrounding may influence their physical properties being a perfect sign of the atmosphere quality. The goal of this thesis is the research of Ino.5Gao.5As surface quantum dots (SQDs) on GaAs(001), covering from their growth to device fabrication, for sensing applications. The achievement of this goal relies on the design, growth and sample characterization, along with device fabrication and characterization. The first issue of the thesis is devoted to analyze the main growth parameters affecting the physical properties of the Ino.5Gao.5As SQDs. It is well known that the growing conditions (growth temperature , deposition rate, V/III flux ratio and treatment after active layer growth) directly affect the physical properties of the epilayer. In this part, taking advantage of the previous results in the group regarding Ino.5Gao.5As QD growth temperature and V/III ratio, the effect of the growth rate and the temperature treatment after QDs growth nucleation is evaluated. Setting the QDs growth temperature at 430°C and the V/III flux ratio to ~20, it is found that the most appropriate conditions rely on growing the QDs at 0.07ML/s and just after QD nucleation, rapidly dropping and again raising 100°C the substrate temperature with respect to the temperature of QD growth. The combination of growing at a fast enough growth rate to promote molecule migration but sufficiently slow to allow QD nucleation, together with the sharp variation of the temperature preserving their shape and composition yield to high density, homogeneous Ino.5Gao.5As SQDs. Besides, it is also demonstrated that this high quality SQDs show excellent optical properties even at room temperature (RT). One of the characteristics by which In0.5Ga0.5As/GaAs SQDs are considered promising candidates for sensing applications is the crucial role that surface plays when interacting with the gases constituting the atmosphere. Therefore, in an attempt to develop sensing devices, the influence of the environment on the physical properties of the samples is evaluated. By comparing the resulting photoluminescence (PL) of SQDs with buried QDs (BQDs), it is found that BQDs do not exhibit any significant variation when changing the environmental conditions whereas, the external conditions greatly act on the SQDs optical properties. On one hand, it is evidenced that PL intensity of SQDs sharply quenches under vacuum and clearly decreases under dry-pure gases atmospheres (N2, O2). On the other hand, it is shown that, in water containing atmospheres, the SQDs PL intensity is maintained with respect to that in air. Moreover, it is found that neither the full width at half maximun nor the emission wavelength manifest any noticeable change indicating that the QDs are not structurally altered by the external atmosphere. These results decisively point to the processes taking place at the surface such as coupling between confined and surface states, to be responsible of this extraordinary behavior. A further analysis of the impact of the atmosphere composition on the optical characteristics is conducted. A sample containing one uncapped In0.5Ga0.5As QDs layer is exposed to different environments. Several solvents presenting different polarity, atomic composition and molecular mass, are used to change the atmosphere composition. It is revealed that low polarity and heavy molecules cause a greater variation on the PL intensity. Besides, oxygen is demonstrated to play a decisive role on the PL response. Results indicate that in presence of oxygen-containing molecules, the PL intensity experiments a less reduction than that suffered in presence of nonoxygen-containing molecules, 90% compared to 77% signal respect to the emission in air. In agreement with these results, it is demonstrated that high polarity and lighter molecules containing oxygen are more easily adsorbed, and consequently, PL intensity is less affected. The presence of defects, unsaturated bonds and in general localized states in the surface are proposed to act as nonradiative recombination centers deteriorating the PL emission of the sample. Therefore, suppression or reduction of the density of such states may lead to an increase or, at least, conservation of the PL signal. This research denotes that the interaction between sample surface and molecules in the atmosphere modifies the surface characteristics altering thus the optical properties. This is attributed to the likely adsoption of some molecules onto the surface passivating the nonradiative recombination centers, and consequently, not deteriorating the PL emission. Aiming for sensors development, samples are processed and electrically characterized under different external conditions. Samples are processed with two square (Ti/Au) contacts. During the processing, especial attention must be paid to the surface treatment. Any process that may damage the surface such as plasma etching or annealing must be avoided to preserve the features of the surface nanostructures. A set of three samples: a GaAs (bulk), In0.5Ga0.5As SQDs and In0.5Ga0.5As surface quantum well (SQW) are subjected to a throughout evaluation. I-V characteristics are measured following the results from the optical characterization. Firstly, the three samples are exposed to vacuum and air. Despite the three samples exhibit a more resistive character in vacuum than in air, it is revealed a much more clear influence of the pressure atmosphere in the SQDs sample. The sheet resistance (Rsh) of SQDs decreases a 99% from its response value under vacuum to its value in air, whereas Rsh of GaAs and In0.5Ga0.5As SQW reduces its value a 31% and a 20%, respectively. Secondly, a rough analysis of the effect of the human breath on the electrical response evidences the enormous influence of moisture (human breath is composed by several components but the one that overwhelms all the rest is the high concentration of water vapor) on the I-V characteristics. Following this result, In0.5Ga0.5As SQDs and In0.5Ga0.5As SQW are subjected to different controlled relative humidity (RH) environments (from 0% to 70%) and electrically characterized. It is found that SQW shows a nearly negligible Rsh variation when increasing the RH in the surroundings. However, the response of SQDs to changes in the RH defines two regions. Below 50%, high sensitive zone, Rsh of SQD decreases by more than one order of magnitude, while above 50% the dependence of Rsh on the RH becomes weaker. These results remark the role of the surface and denote the existence of a finite number of surface states. Nevertheless, most significantly, they highlight the importance not only of the material but also of the morphology. Finally, the impact of the illumination is determined by means of irradiating the In0.5Ga0.5As SQDs and In0.5Ga0.5As SQW samples with different energy and power sources. Once again, SQW does not exhibit any correlation between the surface conductivity and the external conditions. Rsh remains nearly unalterable independently of the energy and power of the incident light. Conversely, Rsh of SQD experiences a decay of one order of magnitude from dark-to-photo conditions. This is attributed to the less density of surface states of SQW compared to that of SQDs. Additionally, a different response of Rsh of SQD with the energy of the impinging light is found. Illuminating with high energy light results in a Rsh reduction of one order of mag nitude under humid atmospheres, whereas it remains nearly unchanged under dry environments. On the contrary, light with energy below the bulk energy bandgap (Eg), shows a negligible effect on the electrical properties regardless the local moisture. This is related to the density of photocarriers generated while lighting up. Illuminating with excitation energy below Eg affects a small absorption volume and thus, a low density of photocarriers may be activated leading to an insignificant contribution to the conductivity. Nonetheless, irradiating with energy above the Eg can excite a high density of photocarriers and greatly improve the surface conductivity. These results demonstrate that both illumination and humidity are therefore needed for sensing. The combination of these two agents improves the surface passivation by means of molecule adsorption reducing the density of surface states, thus modifying the electronic structures, and consequently, promoting the carrier motion.

Fabrication and Characterization of Efficient Optical Filter Arrays Implemented by 3D Nanoimprint

In dieser Arbeit werden optische Filterarrays für hochqualitative spektroskopische Anwendungen im sichtbaren (VIS) Wellenlängenbereich untersucht. Die optischen Filter, bestehend aus Fabry-Pérot (FP)-Filtern für hochauflösende miniaturisierte optische Nanospektrometer, basieren auf zwei hochreflektierenden dielektrischen Spiegeln und einer zwischenliegenden Resonanzkavität aus Polymer. Jeder Filter erlaubt einem schmalbandigem spektralen Band (in dieser Arbeit Filterlinie genannt) ,abhängig von der Höhe der Resonanzkavität, zu passieren. Die Effizienz eines solchen optischen Filters hängt von der präzisen Herstellung der hochselektiven multispektralen Filterfelder von FP-Filtern mittels kostengünstigen und hochdurchsatz Methoden ab. Die Herstellung der multiplen Spektralfilter über den gesamten sichtbaren Bereich wird durch einen einzelnen Prägeschritt durch die 3D Nanoimprint-Technologie mit sehr hoher vertikaler Auflösung auf einem Substrat erreicht. Der Schlüssel für diese Prozessintegration ist die Herstellung von 3D Nanoimprint-Stempeln mit den gewünschten Feldern von Filterkavitäten. Die spektrale Sensitivität von diesen effizienten optischen Filtern hängt von der Genauigkeit der vertikalen variierenden Kavitäten ab, die durch eine großflächige ‚weiche„ Nanoimprint-Technologie, UV oberflächenkonforme Imprint Lithographie (UV-SCIL), ab. Die Hauptprobleme von UV-basierten SCIL-Prozessen, wie eine nichtuniforme Restschichtdicke und Schrumpfung des Polymers ergeben Grenzen in der potenziellen Anwendung dieser Technologie. Es ist sehr wichtig, dass die Restschichtdicke gering und uniform ist, damit die kritischen Dimensionen des funktionellen 3D Musters während des Plasmaätzens zur Entfernung der Restschichtdicke kontrolliert werden kann. Im Fall des Nanospektrometers variieren die Kavitäten zwischen den benachbarten FP-Filtern vertikal sodass sich das Volumen von jedem einzelnen Filter verändert , was zu einer Höhenänderung der Restschichtdicke unter jedem Filter führt. Das volumetrische Schrumpfen, das durch den Polymerisationsprozess hervorgerufen wird, beeinträchtigt die Größe und Dimension der gestempelten Polymerkavitäten. Das Verhalten des großflächigen UV-SCIL Prozesses wird durch die Verwendung von einem Design mit ausgeglichenen Volumen verbessert und die Prozessbedingungen werden optimiert. Das Stempeldesign mit ausgeglichen Volumen verteilt 64 vertikal variierenden Filterkavitäten in Einheiten von 4 Kavitäten, die ein gemeinsames Durchschnittsvolumen haben. Durch die Benutzung der ausgeglichenen Volumen werden einheitliche Restschichtdicken (110 nm) über alle Filterhöhen erhalten. Die quantitative Analyse der Polymerschrumpfung wird in iii lateraler und vertikaler Richtung der FP-Filter untersucht. Das Schrumpfen in vertikaler Richtung hat den größten Einfluss auf die spektrale Antwort der Filter und wird durch die Änderung der Belichtungszeit von 12% auf 4% reduziert. FP Filter die mittels des Volumengemittelten Stempels und des optimierten Imprintprozesses hergestellt wurden, zeigen eine hohe Qualität der spektralen Antwort mit linearer Abhängigkeit zwischen den Kavitätshöhen und der spektralen Position der zugehörigen Filterlinien.

Développement de procédés technologiques pour une intégration 3D monolithique de dispositifs nanoélectroniques sur CMOS

Résumé : Le transistor monoélectronique (SET) est un dispositif nanoélectronique très attractif à cause de son ultra-basse consommation d’énergie et sa forte densité d’intégration, mais il n’a pas les capacités suffisantes pour pouvoir remplacer complètement la technologie CMOS. Cependant, la combinaison de la technologie SET avec celle du CMOS est une voie intéressante puisqu’elle permet de profiter des forces de chacune, afin d’obtenir des circuits avec des fonctionnalités additionnelles et uniques. Cette thèse porte sur l’intégration 3D monolithique de nanodispositifs dans le back-end-of-line (BEOL) d’une puce CMOS. Cette approche permet d’obtenir des circuits hybrides et de donner une valeur ajoutée aux puces CMOS actuelles sans altérer le procédé de fabrication du niveau des transistors MOS. L’étude se base sur le procédé nanodamascène classique développé à l’UdeS qui a permis la fabrication de dispositifs nanoélectroniques sur un substrat de SiO2. Ce document présente les travaux réalisés sur l’optimisation du procédé de fabrication nanodamascène, afin de le rendre compatible avec le BEOL de circuits CMOS. Des procédés de gravure plasma adaptés à la fabrication de nanostructures métalliques et diélectriques sont ainsi développés. Le nouveau procédé nanodamascène inverse a permis de fabriquer des jonctions MIM et des SET métalliques sur une couche de SiO2. Les caractérisations électriques de MIM et de SET formés avec des jonctions TiN/Al2O3 ont permis de démontrer la présence de pièges dans les jonctions et la fonctionnalité d’un SET à basse température (1,5 K). Le transfert de ce procédé sur CMOS et le procédé d’interconnexions verticales sont aussi développés par la suite. Finalement, un circuit 3D composé d’un nanofil de titane connecté verticalement à un transistor MOS est réalisé et caractérisé avec succès. Les résultats obtenus lors de cette thèse permettent de valider la possibilité de co-intégrer verticalement des dispositifs nanoélectroniques avec une technologie CMOS, en utilisant un procédé de fabrication compatible.

Applications for nanomaterials in critical technologies

This thesis is devoted to the development, synthesis, properties, and applications of nano materials for critical technologies, including three areas: (1) Microbial contamination of drinking water is a serious problem of global significance. About 51% of the waterborne disease outbreaks in the United States can be attributed to contaminated ground water. Development of metal oxide nanoparticles, as viricidal materials is of technological and fundamental scientific importance. Nanoparticles with high surface areas and ultra small particle sizes have dramatically enhanced efficiency and capacity of virus inactivation, which cannot be achieved by their bulk counterparts. A series of metal oxide nanoparticles, such as iron oxide nanoparticles, zinc oxide nanoparticles and iron oxide-silver nanoparticles, coated on fiber substrates was developed in this research for evaluation of their viricidal activity. We also carried out XRD, TEM, SEM, XPS, surface area measurements, and zeta potential of these nanoparticles. MS2 virus inactivation experiments showed that these metal oxide nanoparticle coated fibers were extremely powerful viricidal materials. Results from this research suggest that zinc oxide nanoparticles with diameter of 3.5 nm, showing an isoelectric point (IEP) at 9.0, were well dispersed on fiberglass. These fibers offer an increase in capacity by orders of magnitude over all other materials. Compared to iron oxide nanoparticles, zinc oxide nanoparticles didn’t show an improvement in inactivation kinetics but inactivation capacities did increase by two orders of magnitude to 99.99%. Furthermore, zinc oxide nanoparticles have higher affinity to viruses than the iron oxide nanoparticles in presence of competing ions. The advantages of zinc oxide depend on high surface charge density, small nanoparticle sizes and capabilities of generating reactive oxygen species. The research at its present stage of development appears to offer the best avenue to remove viruses from water. Without additional chemicals and energy input, this system can be implemented by both points of use (POU) and large-scale use water treatment technology, which will have a significant impact on the water purification industry. (2) A new family of aliphatic polyester lubricants has been developed for use in micro-electromechanical systems (MEMS), specifically for hard disk drives that operate at high spindle speeds (>15000rpm). Our program was initiated to address current problems with spin-off of the perfluoroether (PFPE) lubricants. The new polyester lubricant appears to alleviate spin-off problems and at the same time improves the chemical and thermal stability. This new system provides a low cost alternative to PFPE along with improved adhesion to the substrates. In addition, it displays a much lower viscosity, which may be of importance to stiction related problems. The synthetic route is readily scalable in case additional interest emerges in other areas including small motors. (3) The demand for increased signal transmission speed and device density for the next generation of multilevel integrated circuits has placed stringent demands on materials performance. Currently, integration of the ultra low-k materials in dual Damascene processing requires chemical mechanical polishing (CMP) to planarize the copper. Unfortunately, none of the commercially proposed dielectric candidates display the desired mechanical and thermal properties for successful CMP. A new polydiacetylene thermosetting polymer (DEB-TEB), which displays a low dielectric constant (low-k) of 2.7, was recently developed. This novel material appears to offer the only avenue for designing an ultra low k dielectric (1.85k), which can still display the desired modulus (7.7Gpa) and hardness (2.0Gpa) sufficient to withstand the process of CMP. We focused on further characterization of the thermal properties of spin-on poly (DEB-TEB) ultra-thin film. These include the coefficient of thermal expansion (CTE), biaxial thermal stress, and thermal conductivity. Thus the CTE is 2.0*10-5K-1 in the perpendicular direction and 8.0*10-6 K-1 in the planar direction. The low CTE provides a better match to the Si substrate which minimizes interfacial stress and greatly enhances the reliability of the microprocessors. Initial experiments with oxygen plasma etching suggest a high probability of success for achieving vertical profiles.

Optimized condition for etching fused-silica phase gratings with inductively coupled plasma technology

Polymer deposition is a serious problem associated with the etching of fused silica by use of inductively coupled plasma (ICP) technology, and it usually prevents further etching. We report an optimized etching condition under which no polymer deposition will occur for etching fused silica with ICP technology. Under the optimized etching condition, surfaces of the fabricated fused silica gratings are smooth and clean. Etch rate of fused silica is relatively high, and it demonstrates a linear relation between etched depth and working time. Results of the diffraction of gratings fabricated under the optimized etching condition match theoretical results well. (c) 2005 Optical Society of America.

Defined etching of carbon-diamond films on silicon using an oxygen plasma with titanium masking

A technique for pattern transfer onto carbon-diamond films deposited by radio-frequency plasma-enhanced chemical vapour deposition is reported. Such a technique involves standard photolithography processes and reactive ion etching by oxygen and is compatible with present day microelectronic technology. The patterns transferred are well defined with very good resolution. © 1992.

CYTOPLASMIC AND PLASMA-MEMBRANE ULTRASTRUCTURE OF PARACOCCIDIOIDES-BRASILIENSIS YEAST-PHASE CELLS AS REVEALED BY FREEZE-ETCHING

Using a freeze-etch technique the cytoplasmic and plasma membrane ultrastructure of Paracoccidiodies brasiliensis yeast-phase cells was studied. The multinucleate yeast-phase cells which grow by simultaneous multiple budding, like those of Mucor sp. contain several nuclei, mitochondria, well-developed ER, small vacuoles and lipid droplets. Complex structures with no apparent connexion to the plasma membrane of P. brasiliensis usually lack inveginations, but invaginations which do occur are always rod-shaped which indicates P. brasiliensis to be of either ascomycetous or basidiomycetous origin.

Enhanced electron field emission from plasma-nitrogenated carbon nanotips

Nitrogenated carbon nanotips (NCNTPs) are synthesized by plasma-enhanced hot filament chemical vapor deposition from the hydrogen, methane, and nitrogen gas mixtures with different flow rate ratios of hydrogen to nitrogen. The morphological, structural, compositional, and electron field emission (EFE) properties of the NCNTPs were investigated by field emissionscanning electron microscopy, Raman spectroscopy, x ray photoelectron spectroscopy, and EFE high-vacuum system. It is shown that the NCNTPs deposited at an intermediate flow rate ratio of hydrogen to nitrogen feature the best size/shape and pattern uniformity, the highest nanotip density, the highest nitrogen concentration, as well as the best electron field emission performance. Several factors that come into play along with the nitrogen incorporation, such as the combined effect of the plasma sputtering and etching, the transition of sp 3carbon clusters to sp 2carbon clusters, the increase of the size of the sp 2 clusters, as well as the reduction of the work function, have been examined to interpret these experimental findings. Our results are highly relevant to the development of the next generation electron field emitters, flat panel displays, atomic force microscope probes, and several other advanced applications.