Dissertations / Theses on the topic 'Thin tungsten films'

En aquesta tesis doctoral s’han investigat capes primes i nanostructures de WO3 per sensat òptic de gasos. S’han realitzats els estudis de la síntesis dels materials nanoestructurats, la possible fabricació del dispositiu i les propietats per la detecció dels gasos. Han estat investigades les capes primes de WO3, amb uns grossors al voltant de les 550 nm, crescudes mitjançant RF sputtering. Aquestes capes varen ser dopades amb nanopartícules de Pt i es varen estudiar les seves propietats de sensat òptic de gas sota la influencia de H2, CO i NOx. Aquestes capes mostraren una reposta i recuperacions ràpides sota la influencia dels gasos anteriorment esmentats. Les capes no dopades de WO3 mostren una resposta òptica detectable al gas NOx, mentre que les capes dopades amb nanopartícules de Pt mostres una resposta al H2 a temperatura ambient. De manera similar, la resposta gasocromica de les nanoagulles al gas NH3 tambe va ser investigada. Les nanoagulles de WO3 decorades amb nanopartícules de Pt i Au mostren una resposta òptica quan estan exposades a NH3 gas a temperatura ambient. És la primera vegada que es reporta la resposta òptica del WO3 a temperatura ambienti es descriu en aquesta tesis. Finalment, de manera semblant a les capes primes, el temps de detecció i recuperació de les nanoagulles als gasos; és ràpid i de l’ordre de segons. En resum, la recerca realitzada en el si d’aquesta tesis, ha complert els objectius d’investigar i desenvolupar uns sensors òptics de gasos fets de WO3 i en forma de nanoestructures i capes primers. De manera exitosa, aquest material s’ha implementat per la detecció òptica de NH3, CO, NOx i H2. Basant-nos en aquests resultats, l’avaluació final és que el WO3 és un bon material com a candidat de futurs dispositius òptics per la detecció de gasos.
En esta tesis doctoral se han investigados capas delgadas i nanoestructuras de WO3 para el sensado óptico de gases. Se han relaizado estudios de las síntesis de materiales nanoestructurados, la posible fabricación del dispositivo y las propiedades para la detección de gases. Se han investigado capas delgadas de WO3 con unos grosores cercanos a 550 nm, crecidas mediante pulverización catódica de radiofrecuencia. Dichas capas fueron dopadas con nanopartículas de Pt y se estudiaron sus propiedades para el sensado óptico de gases como el H2, Co y NOx. Estas capas mostraron un respuesta y recupèración rápidas bajo la influencia de los gases mencionados anteriormente. Las capas no dopadas de WO3 mustran una respuesta óptica mediable al NOx mientras que las dopadas con Pt muestran repsuesta al H2 a temperatura ambiente. De manera similar, la respuesta gasocrómica de nanoagujas de WO3 decoardas con nanopartículas de Pt y Au muestran una respuesta óptica a temperatura ambiente cuando se exponen a NH3. Por primera vez y en esta tesis se reporta la respuesta óptica del WO3 a temperatura ambiente. Finalmente y de manera similar a las capas delgadas, los tiempos de respuesta y recuperación de las nanoagujas de WO3 es rápido y del orden de segundos. En resumen, la investigtación que se ha desarrollado en esta tesis ha cumplido los objetivos de desarrollar sensores ópticos basados en nanomateriales de WO3. Se ha implementado la detección de NH3, CO, NOx y H2. de forma exitosa. Basandonos en estos resultados podemos concluir que el WO3 representa un buen material candiudato a ser integrado en futuros dispositivos ópticos para el sensado de gases.
n this doctoral thesis, WO3 based thin films and nanostructures have been investigated for optical gas sensing. The nano structured material synthesis, device fabrication and their gas sensing properties have been studied. WO3 thin films with thicknesses around 550 nm, grown by RF sputtering have been investigated for optical gas sensing using absorbance spectroscopy. These films were doped with Pt nanoparticles and subjected to optical gas sensing under the influence of H2, CO and NOx. These films showed fast response and recovery under the influence of mentioned gases. The response and recovery time is in the range of seconds. The bare WO3 films show a measureable optical response to NOx. The films doped with Pt nanoparticles show a response to H2 at room temperature. Similarly, the gasochromic response of WO3 nanoneedles was investigated upon the exposure to NH3. The nanoneedles decorated with Au and Pt show optical response when exposed to NH3 gas at room temperature. The optical response at room temperature of these nanoneedles is presented in this doctoral thesis for the first time. Similarly to thin films, nanoneedles have also shown a fast response and recovery time in the range of seconds. In summary, this PhD research program successfully fulfilled its objectives to investigate and develop novel WO3 optical sensors based on nanostructures and thin films. During the work the author has successfully employed this material for optically sensing the mentioned gases such as NH3, CO, NOx, and H2. The evaluation of these results indicates that WO3 is a good candidate for designing future devices for optical gas sensing.

This thesis concerns experimental studies of nanocrystalline tungsten trioxide thin films. Functional properties of WO3 have interesting applications in research areas connected to energy efficiency and green nanotechnology. The studies in this thesis are focused on characterization of fundamental electronic and optical properties in the semiconducting transition metal oxide WO3. The thesis includes also applied studies of photocatalytic and photoelectrochemical properties of the material.     All nanocrystalline WO3 thin films were prepared using DC magnetron sputtering. It was found that structures like hexagonal and triclinic phase with different properties can be produced with sputtering technique. Thin film deposition has been performed using different process parameters with emphasis on sputter pressure and films that mainly consist of monoclinic γ-phase, with small contributions of ε-phase. Changes in the pressure are shown to affect the number of oxygen vacancies in the WO3 thin film, with close to stoichiometric WO3 formed at high pressures (30 mTorr), and slightly sub-stochiometric WO3-x, x = 0.005 at lower pressures (10 mTorr). Both stoichiometric and sub-stoichiometric thin films have been characterized by several structural, optical and electronic techniques.    The electronic structure and especially band gap states have been explored and optical properties of WO3 and WO3-x have been studied in detail. The band gap has been determined to be in the range 2.7-2.9 eV. Absorption due to polaron absorption (W5+  -W6+), oxygen vacancy sites (Vo -W6+), and due to differently charged oxygen vacancy states in the band gap have been determined by spectrophotometry and photoluminescence spectroscopy, in good agreement with resonant inelastic x-ray spectroscopy and theoretical calculations. The density of electronic states in the band gap was determined from cyclic voltammetry measurements, which correlate with O vacancy concentration as compared with near infrared absorption.      By combining different experimental methods a thorough characterization of the band gap states have been possible and this opens up the opportunity to tailor the WO3 functionalities. WO3 has been shown to be visible active photocatalyst, and a promising electrode material as inferred from photo-oxidation and water splitting measurements, respectively. Links between device performance in photoelectrochemical experiments, charge transport and the electronic structure have been elucidated.

Adherent Cu films were electrodeposited onto polycrystalline W foils from purged solutions of 0.05 M CuSO4 in H2SO4 supporting electrolyte and 0.025 M CuCO3∙Cu(OH)2 in 0.32 M H3BO3 and corresponding HBF4 supporting electrolyte, both at pH = 1. Films were deposited under constant potential conditions at voltages between -0.6 V and -0.2 V vs Ag/AgCl. All films produced by pulses of 10 s duration were visible to the eye, copper colored, and survived a crude test called "the Scotch tape test", which stick the scotch tape on the sample, then peel off the tape and see if the copper film peels off or not. Characterization by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and X-ray photon spectroscopy (XPS) confirmed the presence of metallic Cu, with apparent dendritic growth. No sulfur impurity was observable by XPS or EDX. Kinetics measurements indicate that the Cu nucleation process in the sulfuric bath is slower than in the borate bath. In both baths, nucleation kinetics do not correspond to either instantaneous or progressive nucleation. Films deposited from 0.05 M CuSO4/H2SO4 solution at pH > 1 at -0.2 V exhibited poor adhesion and decreased Cu reduction current. In both borate and sulfate baths, small Cu nuclei are observable by SEM upon deposition at higher negative overpotentials, while only large nuclei (~ 1 micron or larger) are observed upon deposition at less negative potentials.

This thesis focuses on the Aerosol Assisted Chemical Vapour deposition (AACVD) of titanium dioxide (TiO2) thin films using titanum (IV) isopropoxide (TTIP) and also reports the deposition of tungsten oxide via AACVD using tungsten hexacarbonyl [W(CO)6] in different solvents including methanol and ethanol. Chapter 1 of this thesis gives an overview of TiO2, including its properties and functions and the motivation for this project. In chapter 2 brief descriptions are provided of the main characterisation techniques used throughout this thesis. The substrate and solvent effect on the phase of TiO2 obtained by AACVD is outlined in chapter 3 and 4. TiO2 was deposited via the AACVD of TTIP in different solvents including methanol, ethanol and other solvents. The films deposited showed some substrate dependent morphology and properties. In particular at 550°C the films on steel show needle and rod like particles. XRD and Raman spectra of the TiO2 films showed that on steel or titanium substrates only the rutile form could be obtained, whereas on glass either anatase, anatase-rutile mixtures or rutile could be obtained depending on substrate temperature. Using methanol as the carrier solvent produced exclusively the rutile films on steel and predominantly rutile on glass substrates while the use of the other solvents produced exclusively the anatase phase on the steel under the same conditions. TiO2 was also deposited by AACVD from a mixture of ethanol and methanol solvents. As little as 15% of methanol in ethanol produces rutile as the predominant phase. The photocatalytic properties and the hydrophilicity of the films deposited are also reported. X-ray absorption spectroscopy (XAS) was used to map across the surface of the TiO2 films deposited as described in chapter 5. The X-ray absorption near edge structure (XANES) was used to determine the phase of TiO2 present at each point on the substrate. The AACVD deposition tungsten oxide using tungsten hexacarbonyl (W(CO)6) in methanol and ethanol is reported in chapter 6. Preferred orientation was observed when using either ethanol or methanol as the carrier solvent. In chapter 7 insitu work was attempted to investigate the mechanism of the deposited titania and tungsten oxide films. A new reactor vessel was designed, constructed and tested to allow synchrotron radiation in and out using a kapton window. The XANES pattern recorded during in-situ deposition were not of high enough to resolve the mechanism. The in-situ work carried out has great potential in the growth study of thin film deposition and can in the future help control the phase and composition of deposited films to produce more desirable properties.

Tungsten oxide thin films with one-dimensional (1D) nanostructure (e.g. nanorod (NR)) show enhanced performances for gas sensing, catalysis and photocatalysis due to a large surface-to-volume ratio, high crystallinity, reduction of light reflection and relative high collection efficiency of charge carriers. This thesis details the use of aerosol assisted chemical vapour deposition (AACVD) to deposit tungsten oxide NR array thin films via optimising the deposition conditions (e.g temperature, solvent, precursor and substrate). The tungsten oxide NR array thin films were able to be grown directly on glass, quartz, silica and alumina substrates. Based on observation of the change of tungsten oxide morphologies from planar to NR on traversing from the inlet to outlet of an AACVD reactor, where the actual substrate temperature changed from 339 to 358 °C, a ‘kinetic competition’ mechanism was proposed to describe the relation between deposition parameters and the morphology formed during AACVD. In this mechanism the formation of planar and wave-like morphologies is due to the competition between rperp (perpendicular growth rate) and ri (parallel growth rate contributed by nucleation rate). When rperp is around 7 times faster than ri, the formation of tungsten oxide NR is favoured. The difference between rperp and ri is attributed to planar defects which appear in the direction perpendicular to the NR growth suppressing ri. These planar defects induced by oxygen vacancy may also be responsible for the observed dislocation loops with size (~0.4 to 1.5 nm) providing with the associated strain field generated leading to a quantum-spatial-confinement effect which modifies the band structure of WO3 NR array thin films. During photodegradation of stearic acid (SA) WO3 NR with length around 1200 nm (deposited for 5 mins) gave the highest photocatalytic activity, and the WO3 NR were more than 2 μm in length reduced tungsten states (W4+) were observed via NIR and in XPS spectra which lead to lower photocatalytic activity. In order to improve photocatalytic activity of plain WO3 NR arrays, AACVD was used to grow noble metal (Au, Pt, Pd and Ru) and metal oxide (PdO, RuO2, Co2O3, CuOx and TiO2) 4 NPs supported on 1D WO3 nanorod arrays with size of the NPs (1.9 to 7.3 nm) is directly controlled by the deposition time (0.5 to 36 minutes). Hybrid nanostructures of Au/WO3 (1 min, with particle mean size 3.0 nm), Pt/WO3 (10 min, 3.0 nm) and PdO/WO3 (5 min, 5.6 nm) increased photocatalytic activity by 40 to 50% compared to undecorated plain WO3 NR array thin films.

There is a considerable interest in the use of tungsten oxide in the research and development of new materials and devices, such as gas sensors and as photocatalysts. In order to improve the photocatalytic properties of WO3, its combination with metals which allows the preparation of WMxOy materials are believed to be promising photocatalysts under visible light. The present work deals with the synthesis of homo- and hetero-metallic tungsten alkoxide and amide compounds using the single source precursor approach for potential chemical vapour deposition precursors of mixed-metal oxide films.

Hoy en día la habilidad de producir capas de óxidos metálicos compuestos por nanogranos es muy importante, no sólo como conocimiento fundamental, sino también desde un punto de vista industrial debido a las numerosas aplicaciones de los óxidos metálicos nanoesctructurados en varios dispositivos electrónicos. Por ejemplo, en el campo de los sensores de gas, la relación superficie-volumen de las capas basadas en nanogranos de óxidos metálicos, ofrece la posibilidad de mejorar las propiedades de detección de estos dispositivos. Por esta razón, una gran fracción del total de la investigación y desarrollo en el campo de los sensores de gas basados en óxidos metálicos está dirigida a obtener capas activas compuestas por nanogranos. En la actualidad el estudio de nuevas técnicas para el depósito de capas activas compuestas por nanogranos y además compatibles con la fabricación de microsistemas se ha convertido en una necesidad imperiosa.
La presente tesis resume el trabajo del autor llevado a cabo en los últimos cuatro años y está relacionado con el desarrollo de dos regimenes especiales para depositar capas finas de óxido metálico por el método de pulverización catódica asistida por radio frecuencia para aplicaciones de sensores de gas. El primer régimen, nombrado régimen de interrupciones consiste en depositar la capa óxido metálico con una o varias interrupciones durante el proceso. El segundo régimen, nombrado régimen flotante consiste en introducir "extra" interfases dentro del volumen de la capa del óxido metálico por medio de interrupciones y empleando dos densidades de potencia durante el depósito (la primera para depositar el volumen de la capa y la segunda para depositar la capa superficial). El trabajo realizado en esta tesis fue de carácter experimental; además fue complementado por varios tipos de técnicas de caracterización que permitieron estudiar las propiedades físicas y las de detección de las capas depositadas.
Los resultados mostraron que la introducción de "extra" interfases en el volumen de las capas de trióxido de tungsteno (WO3) influye en las propiedades morfológicas y estructurales de la capa obtenida. Se determinó que la transformación de fase del WO3, de amorfo a cristalino, tiene diferente tipo de actividad en las capas depositadas con interrupciones en comparación con las depositadas sin interrupciones. Así se observó que el proceso de cristalización es más lento cuando se depositan las capas de óxido metálico mediante el régimen de interrupciones. Por otro lado, se observó una reducción del tamaño de grano en las capas de WO3 depositadas tanto a través del régimen de interrupciones como del régimen flotante. También se determinó que los microsensores de gas fabricados empleando los dos regimenes estudiados tienen prometedoras características de detección, puesto que estos dispositivos mostraron mejor sensibilidad y selectividad a bajas concentraciones de gases oxidantes, tales como NO2 y O3, en comparación con los sensores de gas fabricados a través del régimen convencional de depósito por pulverización catódica. En conclusión, los sensores desarrollados en esta tesis podrían ser usados para monitorizar los principales contaminantes del aire.

La tecnología de sensores se muestra como una de las tecnologías más importantes del futuro con una gran variedad de aplicaciones las cuales van desde el sector industrial hasta el sector privado. En la actualidad los sensores de gases son empleados para detectar y monitorizar una variedad de gases incluyendo gases tóxicos y explosivos. Las aplicaciones mas importantes de los sensores de gas están relacionados con el sector de la automoción, el sector industrial y el sector aeroespacial (donde los sensores son empleados para detectar gases tales como NOx, O2, NH3, SO2, O3, CO2 y gases de combustión para la protección del medio ambiente), el sector de la industria alimenticia (donde los sensores de gas son utilizados para controlar los procesos de fermentación), en el sector domestico (donde el CO2, humedad y gases de combustión necesitan ser detectados), el sector médico (donde los sensores de gas son aplicados para el diagnóstico y la monitorización de pacientes), y el sector de la seguridad (donde los sensores de gas son requeridos para detectar trazas de explosivos). Aunque algunas técnicas convencionales como la espectroscopia de masas o la cromatografía de gases pueden ser usadas en las aplicaciones mencionadas anteriormente con alta selectividad y sensibilidad, resulta obvio que su uso esta limitado por el coste, la instrumentación, la complejidad y el volumen de los equipos. Al contrario, los sensores de gas de estado sólido, en particular aquellos basados en capas de óxidos metálicos, representan una buena alternativa debido a su bajo costo, posibilidad de movilidad y compatibilidad con la tecnología microelectrónica. Desafortunadamente la falta de selectividad y estabilidad de largo plazo son parte de la problemática de este tipo de dispositivos. Como resultado, el desarrollo de sensores de gas basados en óxidos metálicos de alta sensibilidad, selectividad y buena estabilidad de largo plazo es el tema de muchas investigaciones.

Hasta ahora, varias estrategias basadas principalmente en el uso de aditivos específicos en la superficie, catalizadores y promotores, controladores de temperatura y filtros han sido estudiadas con el objetivo de resolver parcialmente la problemática de los sensores de gas basados en óxidos metálicos. Sin embargo el autor cree que el paso fundamental para mejorar las funciones de este tipo de sensores esta relacionado con las recientes estrategias que tienen por objetivo el desarrollo de métodos para incremental el área superficial de la capa activa. Es bien sabido que la eficiencia de los sensores basados en óxidos metálicos está relacionada directamente con relación superficie-volumen de las capas activas.

En esencia, las líneas de investigación estudiadas para conseguir altas áreas superficiales en las capas activas, pueden ser clasificadas en dos grupos. El primero consiste en la obtención de nanoparticulas basadas en óxidos metálicos a través de procesos químicos o físicos. El segundo consiste en la aplicación métodos especiales de preparación para el modelado de la superficie activa (por ejemplo, plantillas de estructura de alúmina porosa). Esta última opción representa una buena alternativa, pero sin métodos que permitan depositar capas activas basadas en nanopartículas no es factible. Por esta razón, es importante desarrollar métodos que permitan obtener capas de óxido metálico compuestos por nanopartículas.

En este contexto, la presente tesis tiene como objetivo desarrollar técnicas de deposito basadas en el método de pulverización catódica para depositar capas de oxido metálico compuestas por nanogranos. Este manuscrito resume el trabajo del autor llevado a cabo en los últimos cuatro años y está relacionado con el desarrollo de nuevas tecnologías para depositar capas de óxidos metálicos con el fin de ser aplicadas en sensores de gases. El trabajo realizado en esta tesis fue de carácter experimental; además fue complementado por varios tipos de técnicas de caracterización que permitieron estudiar las propiedades físicas y las de detección de las capas depositadas.

La novedad del trabajo radica en la aplicación de dos regimenes de depósito a través de la técnica de pulverización catódica asistida por radio frecuencia para la creación de capas de oxido metálico aplicadas a sensores de gas. El primer régimen, nombrado régimen de interrupciones consiste en depositar una capa óxido metálico con una o varias interrupciones durante el proceso. En este caso se introducen "extra" interfases en el volumen de la capa, donde se forma una superficie en equilibrio debido a la saturación de los enlaces libres en la superficie producida por los átomos residuales de la atmósfera y/o la relajación de la estructura en la interfase durante la interrupción. El segundo régimen, nombrado régimen flotante consiste en introducir "extra" interfases dentro del volumen de la capa del óxido metálico por medio de interrupciones y empleando dos densidades de potencia durante el depósito (la primera para depositar el volumen de la capa y la segunda para depositar la capa superficial).

Los resultados mostraron que la aplicación interrupciones durante el crecimiento de capas finas de WO3 permite la creación de capas compuestas por nanogranos. La caracterización morfológica de las muestras depositadas con este régimen dio evidencia de la reducción del tamaño de grano en el WO3 en comparación con las muestras depositadas a través del régimen convencional. Se determinó una reducción en el tamaño de grano desde 24 nm a 17 nm mediante microscopia de fuerza atómica. Por otro lado, las capas de WO3 depositadas por interrupciones revelaron una estructura monoclínica con simetría Pc. Se determinó que la transformación de fase del WO3, de amorfo a cristalino, tiene diferente tipo de actividad en las capas depositadas con interrupciones en comparación con las depositadas sin interrupciones. Así se observó que el proceso de cristalización es más lento cuando se depositan las capas de óxido metálico mediante el régimen de interrupciones. La caracterización de las propiedades de detección de los microsensores de gas fabricados empleando el régimen de interrupciones reveló una mejora de la sensibilidad y selectividad a bajas concentraciones de gases oxidantes, tales como NO2 y O3, con respecto a los sensores fabricados convencionalmente. La mejora de la sensibilidad de los sensores fabricados con el régimen de interrupciones esta relacionada con la disminución del tamaño de grano en la capa activa.

Los sensores de WO3 fabricados mediante el régimen flotante no mostraron diferencias ni en el tamaño de grano ni en la composición cristalina con respecto a las capas depositadas por interrupciones. La caracterización de las propiedades de detección de los sensores de gas fabricados con el régimen flotante dio como resultado altas sensibilidades para bajas concentraciones de NO2. La mejora de la sensibilidad observada en los sensores de gas fabricados por el régimen flotante parece estar relacionada no solo con la reducción en el tamaño de grano de la capa activa (comparando con los sensores de gas convencionales), si no también podría tener relación con el grado de limpieza de la superficie de la capa, la cual es mejor debido a que la capa superficial es depositada a una densidad de potencia más alta. En base a estos resultados se cree que los sensores desarrollados en esta tesis podrían ser usados para monitorizar los principales contaminantes del aire

Palabras clave:
Trióxido de tungsteno, RF sputtering, Nanogranos, Sensor de Gas

In this project I have studied the optical properties of electrochromic crystalline tungsten oxide, WO3. The practical application could be for a window for desalination of sea water which requires a high absorption coefficient A(λ) for near infrared radiation (NIR), while at the same time a high transmittance T(λ) in the visible spectral range.   An electrochromic (EC) material is a material that changes its optical properties when inserting or extracting ions by applying a voltage. The WO3 was prepared on a glass substrate coated by a transparent electrical conductor. The conductor used is tin doped indium oxide. In2O3:Sn, indium-tin-oxide (ITO). The preparation of the thin films has been carried out using DC magnetron reactive sputtering. The structure of unheated tungsten oxide is amorphous and once heated it is crystalline. Li+ ions were inserted into the tungsten oxide material with electrochemical methods to create the coloring effect. The optical properties were recorded in the 330 < λ < 2500 nm wavelength range by use of a Perkin-Elmer Lambda 9 spectrophotometer.   The highest reflectance R(λ), approximately 50% in NIR and absorption coefficient A(λ) = 1,5 x 105 [cm-1], were measured for the sample that had been post annealed at 500 deg C. The crystalline tungsten oxide films provides for a good switching capability in the NIR spectral range wile at the same time maintaining a high transmittance T(λ) in the visible spectrum.

Recently, refractory materials have been proposed as a strong alternative to poly-silicon and aluminum alloys as metallization systems for Very Large Scale Integrated (VLSI) circuits because of their improved performance at smaller Integrated Circuit (IC) feature size and higher interconnect current densities. However, processing and reliability problems associated with the use of refractory materials have limited their widespread acceptance. The hot-wall low pressure chemical vapor deposition (LPCVD) of Molybdenum and Tungsten from their respective hexacarbonyl sources has been studied as a potential remedy to such problems, in addition to providing the potential for higher throughput and better step coverage. Using deposition chemistries based on carbonyl sources, Mo and W deposits have been characterized with respect to their electrical, mechanical, structural, and chemical properties as well as their compatibility with conventional IC processing. Excellent film step coverage and uniformity were obtained by low temperature (300-350 C) deposition at pressures of 400-600 mTorr. As-deposited films were observed to be amorphous, with a resistivity of 250 and 350 microohm-cm for Mo and W respectively. On annealing at high temperatures in a reducing or inert atmosphere, the films crystallize with attendant reduction in resistivity to 9.3 and 12 microohm-cm for Mo and W, respectively. The average grain size also increases as a function of time and temperature to a maximum of 2500-3000 A. The metals and their silicides that are deposited, using silane as silicon source, are integratable to form desired metal-silicide gate contact structures. Thus, use of the low resistivity of the elemental metal coupled with the oxidation resistance of its silicide manifests the quality and economy of the process. MOS capacitors with Mo and W as the gate material have been fabricated on n-type (100) silicon. A work function of 4.7 +/- 0.1 eV was measured by means of MOS capacitance-voltage techniques. The experimental results further indicate that the characteristics of W-gate MOS devices related to the charges in SiO₂ are comparable to those of poly-silicon; while, the resistivity is about two orders of magnitude lower than poly-silicon. It is therefore concluded that hot-wall low pressure chemical vapor deposition of Mo and W from their respective carbonyl sources is a viable technique for the deposition of reliable, high performance refractory metal/silicide contact and interconnect structures on very large scale integrated circuits.

In this work a new wet-chemical method of preparing tungsten oxide thin films is described. This involves the dissolution of tungsten metal in aqueous hydrogen peroxide and reaction with acetic acid to form an alcohol-soluble precursor. All synthesis stages of this new precursor, termed peroxotungstic ethoxide, are characterized to determine possible reactions. The chemical and microstructural evolution of films is described as a function of firing temperature, utilizing infrared spectroscopy, diffraction and other optical data. A novel method of increasing the crack-free thickness of the films is given: a combination of oxalic acid dihydrate as a solution additive and film firing under controlled humidity. With this combination, fired crack-free films up to one micron in thickness were prepared. Oxalic acid dihydrate roughened and also caused crystallization of these films at lower temperatures (250°C) than expected. These rougher films exhibited an improved electrochromic response, as measured by optical and electrochemical characterizations.

This thesis investigates the electrochromic NixW1-x oxide thin film system, where 0 < x < 1. The thin films were deposited by reactive DC magnetron co-sputtering from one Ni and one W metal target. In addition, Ni oxide was deposited with water vapor added to the sputtering gas. The different compositions were structurally characterized by X-ray diffraction, X-ray photoelectron-, Rutherford backscattering- and Raman spectroscopy. Possible nanostructures were studied by ellipsometry together with effective medium theory. Optical and electrochemical properties were investigated by spectrophotometry and cyclic voltammetry in 1 M lithium perchlorate in propylene carbonate (Li-PC). Li-PC electrolyte was used as it is being compatible with both W and Ni oxides. Few studies have previously been made on Ni oxides in Li-PC. Films with high Ni content, 0.85 < x < 1, were polycrystalline and all other films were amorphous. W-rich films, x < 0.5, consisted of a mixture of W oxide and NiWO4 -phases, and the Ni-rich samples, x > 0.5, probably consisted of hydrated Ni oxide and NiWO4 -phases. Films with 0 < x < 0.3 showed electrochromic properties similar to W oxide, and films with 0.7 < x < 1 behaved as Ni oxide. For 0.4 < x < 0.7 no optical change was seen. At the border of cathodic electrochromic and non-electrochromic behavior, i.e. x ~ 0.4, the sample behaved as an optically passive intercalation material. The transmittance change was 0.45 and 0.15 for the W-rich and Ni-rich films, respectively. Ni addition to W oxide improved the coloration efficiency. For the Ni-rich films the charge insertion/extraction and optical modulation was low and an aging effect resulted in strong bleaching of the samples. The advantage of W addition to Ni oxide was that the transparency at the bleached state was enhanced. Moreover, it was found that the hydrous character of the Ni oxide had a large impact on the electrochromic performance, both when electrochemically cycled in KOH and in the non-aqueous Li-PC.

Orientador: Mario Antonio Bica de Moraes
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin
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Resumo: Este trabalho descreve uma nova técnica de deposição de filmes finos de óxido de tungstênio e apresenta uma investigação sobre o processo de deposição e propriedades dos filmes. Os filmes foram obtidos em uma câmara de deposição a vácuo contendo um filamento de tungstênio aquecido por uma fonte de corrente alternada. O oxigênio era admitido na câmara usando um fluxômetro de massa. Os filmes eram formados em um substrato posicionado próximo ao filamento pelos precursores voláteis WxOy, formados na superfície aquecida do tungstênio pela reação entre o oxigênio e o tungstênio. A espessura dos filmes era medida com um perfilômetro e a taxa de deposição, R, foi determinada em função da temperatura do filamento, TF, da pressão de oxigênio na câmara, PO2 e da distância substrato-filamento, D. Um aumento no valor de R foi observado com o aumento de TF de 1500 a 1950 K, mantendo-se PO2fixo. A taxa de deposição também mostrou um aumento quando PO2 era aumentada de 0,8 para 2,1 Pa, para TF fixo. Foi alcançada uma taxa de deposição de 93 nm/min para TF= 1950 K e PO2 = 2.1 Pa. Através do espectro de transmissão ultravioleta-visível dos filmes, o coeficiente de absorção e o gap óptico, EG, foram determinados. Foi encontrado um valor médio de EG de 3,56 ± 0,08 eV. As ligações químicas nos filmes foram investigadas usando-se espectroscopia infravermelha por transformada de Fourier, tanto com luz não polarizada como polarizada, e espectroscopia de fotoelétrons por raios-X. Os dados de espectroscopia infravermelha revelaram a presença de água nos filmes. A análise do pico de XPS W4f mostrou que os átomos de W estão no estado de valência W +6 , típica do tungstênio na estequiometria WO3. Através da análise dos filmes por espectroscopia de espalhamento Rutherford, foi determinada uma razão atômica média entre o oxigênio e tungstênio igual a 3,5 ± 0,3. A difração de raio-X mostrou que os filmes são amorfos. A análise por microscopia de varredura por elétrons mostrou que a superfície dos filmes era uniforme, enquanto as micrografias da seção retas dos mesmos revelaram um material sem estrutura e compacto. As propriedades eletrocrômicas dos filmes foram estudas pela intercalação de Li + em uma cela eletrolítica. Foram encontradas eficiências ópticas de 78 e 125 cm 2 C -1 para 623,8 e 950 nm, respectivamente
Abstract: This work describes a novel technique for the deposition of tungsten oxide thin films and reports an investigation on their deposition process and properties. The films were obtained in a vacuum deposition chamber fitted with a tungsten filament heated by an ac power supply. Oxygen was admitted into the chamber using mass flow meters. The films were formed on a substrate positioned near the filament from the volatile Wx Oy precursors generated on the heated filament surface from the reactions between oxygen and tungsten. Film thicknesses were measured using a perfilometer and the deposition rate, R, was determined as a function of the filament temperature, TF, pressure of oxygen in the chamber, PO2, and substrate-filament distance, D. An increase in the R-value was observed for TF increasing from 1500 to 1950 K, for a fixed PO2. The deposition rate also increased for a PO2 increase from 0.8 to 2.1 Pa, for a fixed TF. Deposition rates as high as 93 nm/min was observed for TF= 1950 K and PO2= 2.1 Pa. From the transmission ultraviolet-visible spectra of the films, the absorption coefficient and the optical gap, EG, were determined. An average EG-value of 3.56 ± 0.08 eV was found. The chemical bonds in the films were investigated using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. In the former, unpolarized and polarized infrared beams were employed. The infrared spectroscopy data revealed the presence of water in the films. Lineshape analyses of the W4f XPS peak showed that the W-atoms were in the W+6 valence state, typical of tungsten in the WO3 stoichiometry. From Rutherford backscattering spectroscopy analysis of the films, an average O/W atomic ratio of 3.5 ± 0.3 was determined. X-ray diffraction revealed that the films were amorphous. Scanning electron microscopy analysis showed that the film surface was smooth and uniform, while the fracture micrographs of the film cross-section revealed a structureless and compact material. The electrochromic properties of the films were studied for Li + intercalation using an electrochemical cell. Coloration efficiencies of 78 and 125 cm 2C -1 at wavelengths of 632,8 and 950 nm, respectively, were measured.
Mestrado
Física da Matéria Condensada
Mestre em Física

Orientador: Abner de Siervo
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin
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Resumo: Algumas evidências na literatura apontam para um possível ordenamento ferromagnético do Paládio. Na natureza, o Paládio é um metal de transição não ferromagnético. Filmes ultrafinos podem induzir ordenamento ferromagnético devido a diferenças nos parâmetros de rede entre o filme(Pd) e o substrato que o suporta. Neste trabalho, cresceram-se filmes ultrafinos de Paládio sobre o substrato de W(100). Para tanto, o substrato foi limpo por meio de tratamento térmico e bom- bardeamento de íons. Filmes de Paládio foram crescidos usando epitaxia por feixe atômico e obteve-se um filme com espessura de cinco monocamadas de Paládio. Esse filme foi caracterizado pelas técnicas de espectroscopia de fotoemissão e espalhamento de elétrons de baixa energia. Determinou-se a estrutura de superfície por meio da técnica de difração de fotoelétrons usando radiação síncroton (LNLS), oriunda da linha SXS, com energia do fóton de 1810 eV. Realizou-se o mesmo estudo para filmes de Paládio sobre substrato de Nb(100). Neste sistema, depositou-se Paládio sobre uma superfície reconstruída de NbO(3 x 1) - 2D. Caracterizou-se este filme e o arranjo estrutural foi obtido por meio da técnica de difração de fotoelétrons com fótons de raio-X AI Ka de energia 1486.6 eV. Em seguida calculamos, por meio da teoria do funcional da densidade, propriedades estruturais e eletrônicas do Páladio. A partir destes cálculos, os resultados encontrados na determinação estrutural foram analisados. Calculou-se a densidade de estados para alguns modelos de empacotamento e discutiu-se sobre a existência ou não de ordenamento ferromagnético nesses sistemas
Abstract: Some evidence in the literature suggest a possible ferromagnetic ordering of the Palladium. In nature, the Palladium is a non-ferromagnetic metal transition. Ultra- thin films can induce ferromagnetic ordering due to differences in lattice parameters between the film(Palladium) and the substrate that supports it. In this work, it has been grown Palladium ultrathin films on the substrate W(100). First, The substrate was cleaned by heat treatment and ion bombardment. Palladium films were grown using atomic beam epitaxy and it was obtained a film with a thickness of tive monolayers of Palladium. This film was characterized by X- ray photoelectron spectroscopy and by low energy electron diffraction. The surface structure has been determined by X-ray photoelectron diffraction technique using synchrotron radiation (LNLS), from SXS line with the photon energy of 1810 eV. We performed the same study for Palladium films over Nb(100). In this system, Palladium monolayers were deposited on a reconstructed surface of NbO(3 x 1)- 2D. These films has been characterized and the structural arrangement was achieved through the technique of photoelectron diffraction with photons from a AI Ka source with energy of 1486.6 eV. Then, it was calculated by density functional theory, the electronic and structural properties of Palladium. From these calculations, the results found in structural determination were analyzed. It has been calculated the density of states for some models of packaging and it was argued about the existence of ferromagnetic ordering in these systems
Mestrado
Física da Matéria Condensada
Mestre em Física

Orientador: Younès Messaddeq
Banca: Maria Aparecida Zaghete Bertochi
Banca: Máximo Siu Li
Resumo: Filmes finos de óxido de tungstênio apresentam várias propriedades ópticas interessantes. As propriedades eletrocrômicas, fotocrômicas e termocrômicas são conhecidas como uma mudança de cor pela ação de um campo elétrico, radiação eletromagnética e calor, respectivamente e têm sido amplamente estudadas. Muitos sistemas foram investigados e suas propriedades são largamente influenciadas por muitos parâmetros experimentais. Este comportamento é devido à facilidade dos átomos de tungstênio adotar vários estados de oxidação. Amostras vítreas foram preparadas nos sistemas ternário (NaPO3)n - BaF2 - WO3 e binário (NaPO3)n - WO3. Esses vidros apresentam grande estabilidade térmica frente à cristalização. Amostras contendo altas concentrações de WO3 (acima de 40% em mol) foram usadas como precursores na preparação dos filmes finos. Os filmes foram depositados pela técnica de evaporação por canhão de elétrons. Substratos de vidro borosilicato foram utilizados devido a melhor aderência. Os filmes foram caracterizados pela difração de raios X, perfilometria, espectroscopia de dispersão de raios X (EDX), espectroscopia de absorção eletrônica na região do UV-visível, espectroscopia de absorção vibracional na região do infravermelho, espectroscopia de espalhamento Raman, espectroscopia de absorção de raios X (XANES), m-lines e microscopia eletrônica de varredura (MEV). Filmes finos estáveis contendo altas concentrações de WO3 foram obtidos e parâmetros experimentais foram estabelecidos. Propriedades termocrômicas foram estudadas em função do tempo e da temperatura. A umidade atmosférica foi o parâmetro fundamental no estudo do termocromismo. Propriedades ópticas e estruturais foram estudadas em função da concentração de WO3. Tratamentos térmicos controlados foram realizados nos filmes e somente a fase WO3 pode ser cristalizada a partir de filmes contendo altas concentrações de tungstênio.
Abstract: Tungsten oxide thin films present several interesting optical properties. Electrochromic, photochromic and thermochromic properties are known as a colour change by the action of an electric field, electromagnetic radiation and heat respectively and have been widely studied. Many systems were investigated and their properties are largely influenced by many experimental parameters. This behavior is due to the facility of tungsten atoms to adopt various oxidation states. Vitreous samples were prepared in the (NaPO3)n - BaF2 - WO3 ternary and (NaPO3)n - WO3 binary systems. These glasses present high thermal stability against crystallization. Samples containing high concentrations of WO3 (above 40% molar) have been used as target to prepare thin films. Such films were deposited by electron beam evaporation method. Borosilicate glasses substrates were used due to better adherence. The films were characterized by X-ray diffraction, perfilometry, X-ray dispersion spectroscopy (XDS), UV-visible transmittance, infrared reflectance spectroscopy, Raman spectroscopy, X-ray absorption near edge structure (XANES), m-lines and Scanning Electronic Microscopy (SEM). Stable thin films containing high concentration of WO3 were obtained and experimental parameters were established. Thermochromic properties were studied in function of time and temperature. Humidity of the atmosphere was a fundamental parameter in the study of the thermochromism. Optical and structural properties were studied in function of concentration WO3. Controlled thermal treatments were accomplished in the films and only the phase WO3 was crystallized starting from films containing high tungsten concentrations.
Mestre

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
Filmes finos de óxido de tungstênio apresentam várias propriedades ópticas interessantes. As propriedades eletrocrômicas, fotocrômicas e termocrômicas são conhecidas como uma mudança de cor pela ação de um campo elétrico, radiação eletromagnética e calor, respectivamente e têm sido amplamente estudadas. Muitos sistemas foram investigados e suas propriedades são largamente influenciadas por muitos parâmetros experimentais. Este comportamento é devido à facilidade dos átomos de tungstênio adotar vários estados de oxidação. Amostras vítreas foram preparadas nos sistemas ternário (NaPO3)n - BaF2 - WO3 e binário (NaPO3)n - WO3. Esses vidros apresentam grande estabilidade térmica frente à cristalização. Amostras contendo altas concentrações de WO3 (acima de 40% em mol) foram usadas como precursores na preparação dos filmes finos. Os filmes foram depositados pela técnica de evaporação por canhão de elétrons. Substratos de vidro borosilicato foram utilizados devido a melhor aderência. Os filmes foram caracterizados pela difração de raios X, perfilometria, espectroscopia de dispersão de raios X (EDX), espectroscopia de absorção eletrônica na região do UV-visível, espectroscopia de absorção vibracional na região do infravermelho, espectroscopia de espalhamento Raman, espectroscopia de absorção de raios X (XANES), m-lines e microscopia eletrônica de varredura (MEV). Filmes finos estáveis contendo altas concentrações de WO3 foram obtidos e parâmetros experimentais foram estabelecidos. Propriedades termocrômicas foram estudadas em função do tempo e da temperatura. A umidade atmosférica foi o parâmetro fundamental no estudo do termocromismo. Propriedades ópticas e estruturais foram estudadas em função da concentração de WO3. Tratamentos térmicos controlados foram realizados nos filmes e somente a fase WO3 pode ser cristalizada a partir de filmes contendo altas concentrações de tungstênio.
Tungsten oxide thin films present several interesting optical properties. Electrochromic, photochromic and thermochromic properties are known as a colour change by the action of an electric field, electromagnetic radiation and heat respectively and have been widely studied. Many systems were investigated and their properties are largely influenced by many experimental parameters. This behavior is due to the facility of tungsten atoms to adopt various oxidation states. Vitreous samples were prepared in the (NaPO3)n - BaF2 - WO3 ternary and (NaPO3)n - WO3 binary systems. These glasses present high thermal stability against crystallization. Samples containing high concentrations of WO3 (above 40% molar) have been used as target to prepare thin films. Such films were deposited by electron beam evaporation method. Borosilicate glasses substrates were used due to better adherence. The films were characterized by X-ray diffraction, perfilometry, X-ray dispersion spectroscopy (XDS), UV-visible transmittance, infrared reflectance spectroscopy, Raman spectroscopy, X-ray absorption near edge structure (XANES), m-lines and Scanning Electronic Microscopy (SEM). Stable thin films containing high concentration of WO3 were obtained and experimental parameters were established. Thermochromic properties were studied in function of time and temperature. Humidity of the atmosphere was a fundamental parameter in the study of the thermochromism. Optical and structural properties were studied in function of concentration WO3. Controlled thermal treatments were accomplished in the films and only the phase WO3 was crystallized starting from films containing high tungsten concentrations.

Étude de l'absorption qui apparait dans ce matériau au cours de sa coloration et des possibilités d'utilisation pour la réalisation des systèmes d'affichage. On montre que les couches formées par oxydation anodique présentent une cristallisation progressive en fonction de la tension anodique. Pour de faibles tensions, ces couches sont amorphes. Calcul des indices de réfraction et d'absorption à partir des données spectroreflectrométriques. Au cours de l'électrocoloration avec des ions H**(+), Li**(+), Na**(+), une diminution des pics Raman des vibrations des liaisons W-O et une apparition des pics des vibrations des liaisons W=O sont observées. .

Dans ce travail, nous étudions la stabilité thermique et les effets des irradiations par un plasma d'hélium ou de deutérium de films minces de WO3 d’intérêt pour la fusion magnétique (projet ITER). L’objectif est de comprendre comment une oxydation du divertor modifie les interactions plasma paroi. Pour cela, nous avons synthétisé des films de WO3 par oxydation thermique de substrats de W à 400°C et caractérisé les effets du type de substrat, de la pression d’oxygène et du temps d’oxydation sur la structure et sur l’épaisseur des oxydes formés. La structure (monoclinique nanocristalline), la morphologie et les défauts des échantillons ont été analysés avant et après traitement, à différentes échelles, en utilisant la microscopie électronique, la microscopie Raman, la diffraction de rayons X, et la microscopie à force atomique.Le chauffage sous vide (400 - 800°C) a conduit à la formation de WO2. Le bombardement aux ions D+ (11 eV) a mené à une diffusion profonde du deutérium à travers le film d’oxyde, engendrant un effet électrochimique, observé ici pour la première fois sous irradiation plasma. Cet effet, réversible, est associé à la formation de bronzes de tungstène (DxWO3) et à une transition de phase vers une structure hexagonale. Des bombardements aux ions He+ (20 eV) ont été réalisés afin de dissocier les effets physiques et chimiques. A température ambiante, le bombardement a causé peu de changements morphologiques et structuraux. Par contre, le autre bombardement à 400°C a causé une érosion du film d’oxyde accompagnée d’un changement de couleur, une amorphisation en surface et la formation de bulles à l’interface W / WO3
As part of laboratory studies devoted to magnetic fusion we have investigated the thermal stability and the effects of helium and deuterium plasma irradiation on tungsten oxide thin films. The objective is to predict the consequences of the oxidation of the W plasma facing component (divertor) for plasma wall interactions.To this aim, we have synthesized WO3 films by thermal oxidation of W substrates at 400°C and we have characterized the effects of the W substrate, the oxygen pressure and the oxidation duration on the structure and the thickness of the oxide films. The sample crystalline structure (monoclinic nanocrystalline), defects and morphologies were characterized before and after treatment using scanning and transmission electron microscopies, Raman microscopy, X-Ray diffraction and atomic force microscopy. Heating under vacuum up to 800°C leads to changes in the film structure and composition which results in the formation of WO2. D+ bombardment (11 eV) leads to D+ diffusion throughout the oxide film and to an electrochromic effect, here observed for the first time under plasma irradiation. This effect - which turned out to be reversible - is related to the formation of W bronzes (DxWO3) and to a phase transition of the oxide toward a hexagonal structure. Helium bombardments (20 eV) have then been performed to unravel physical and chemical processes at play. He+ bombardment at room temperature causes slight structural and morphological changes. On the contrary, He+ bombardment at 400°C leads to a significant erosion of the oxide film, accompanied by a colour change, the surface amorphisation and the formation of bubbles at the W / WO3 interface

For sustainable development, it is highly important to limit the loss of energy and materials in machines used for transportation, manufacturing, and other purposes. Large improvements can be achieved by reducing friction and wear in machine elements, for example by the application of coatings. This work is focused on triboactive coatings, for which the outermost layer changes in tribological contacts to form so-called tribofilms. The coatings are deposited by magnetron sputtering (a physical vapor deposition method) and thoroughly chemically and structurally characterized, often theoretically modelled, and tribologically evaluated, to study the connection between the composition, structure and tribological performance of the coatings. Tungsten disulfide, WS2, is a layered material with the possibility of ultra-low friction. This work presents a number of nanocomposite or amorphous coatings based on WS2, which combine the low friction with improved mechanical properties. Addition of N can give amorphous coatings consisting of a network of W, S and N with N2 molecules in nanometer-sized pockets, or lead to the formation of a metastable cubic tungsten nitride. Co-deposition with C can also give amorphous coatings, or nanocomposites with WSx grains in an amorphous C-based matrix. Further increase in coating hardness is achieved by adding both C and Ti, forming titanium carbide. All the WS2-based materials can provide very low friction (down to µ<0.02) by the formation of WS2 tribofilms, but the performance is dependent on the atmosphere as O2 and H2O can be detrimental to the tribofilm functionality. Another possibility is to form low-friction tribofilms by tribochemical reactions between the two surfaces in contact. Addition of S to TiC/a-C nanocomposite coatings leads to the formation of a metastable S-doped carbide phase, TiCxSy, from which S can be released. This enables the formation of low-friction WS2 tribofilms when a Ti-C-S coating is run against a W counter-surface. Reduced friction, at a moderate level, also occurs for steel counter-surfaces, likely due to formation of beneficial iron sulfide tribofilms. The studied coatings, whether based on WS2 or TiC, are thus triboactive, with the ability to form low-friction tribofilms in a sliding contact.

Dans les cellules photovoltaïques organiques, le matériau utilisé pour le transport de trous entre la couche active et l'électrode, est généralement un polymère dopé, dont la stabilité peut être problématique. L'objectif de cette thèse a été de développer des matériaux inorganiques, a priori plus stables, pour remplacer les couches de polymères de transport de trous, tout en restant compatible avec les méthodes de dépôts par voie liquide. L'utilisation de nanoparticules dispersées en solution a été choisie car cela permet le dépôt à basse température, sans nécessité de conversion vers une couche fonctionnelle, contrairement aux voies sol-gel. Le premier objectif de ce travail a donc été l'obtention de nanoparticules d'oxyde de tungstène, hydraté ou non, et de thiocyanate de cuivre. Une synthèse de chauffage assisté par micro-ondes a été utilisée pour l'oxyde de tungstène, permettant d'obtenir des nanoparticules de 30 nm et monodisperses. Pour le thiocyanate de cuivre, il a été choisi de travailler par broyage. Les paramètres du broyage ont été optimisés pour obtenir des particules avec la plus faible distribution en taille possible. Le dépôt de ces dispersions de nanoparticules a permis l'obtention de couches minces et la caractérisation de leurs propriétés optoélectroniques, et notamment du travail de sortie, qui s'est révélé adapté pour une utilisation en dispositif. Des cellules solaires organiques de structures standard et inverse incorporant ces matériaux ont ensuite été réalisées. De bonnes performances ont été obtenues avec une couche active à base de P3HT, notamment en structure inverse où la possibilité d'utiliser le thiocyanate de cuivre a été démontrée pour la première fois. Le suivi des performances sous éclairement et atmosphère contrôlée a également été effectué et a montré un vieillissement rapide pour ces cellules comparées aux cellules de référence à couche de transport de trous polymère
In organic solar cells, a doped polymer is the most used material for hole transport between the active layer and the electrode, but his stability can be an important issue. The goal of this PhD thesis was to develop inorganic materials, expected to be more stable, in order to replace polymer based hole transporting layers. Another requirement was to keep the compatibility with solution-based deposition methods. The target was to develop nanoparticle dispersions, deposited at low temperature and giving directly a functional layer, without the need of further treatments which are usually required via sol-gel processes. A first objective of the present work was thus the elaboration of nanoparticles of tungsten oxide, hydrated or non-hydrated, and copper thiocyanate. A microwave-assisted heating synthesis has been used for tungsten oxide, leading to mono-dispersed particles around 30 nm. Concerning copper thiocyanate, a ball milling technique has been chosen. The process parameters have been optimized to obtain nanoparticles to narrow the size distribution as much as possible. The deposition of the nanoparticles has allowed the formation of thin layers and the characterization of their optoelectronic properties, such as work function, which was shown to be a relevant parameter for a use in devices. Organic solar cells with standard or inverted structures have been fabricated using these materials as a hole transporting layer. Good photovoltaic performances have been obtained, especially in the inverted structure, in which the possibility to use copper thiocyanate has been demonstrated for the first time. Ageing experiments under light in a controlled atmosphere have also been carried out and have shown a rapid drop in performances for these cells compared to cells incorporating polymer based hole transport layers

Le but de cette these est d'etudier les proprietes structurales et magnetiques des couches epitaxiees de w/fe/w et gd/fe elaborees par depot laser pulse. La technique de depot laser pulse est presentee dans le premier chapitre. La croissance des couches minces est discutee dans le deuxieme chapitre puis l'analyse des proprietes structurales des couches elaborees est presentee dans le troisieme chapitre. Une revue des proprietes magnetiques des couches ultra-minces, telle que le moment magnetique, l'anisotropie et les excitations thermiques est presentee dans le quatrieme chapitre. La determination experimentale de ces proprietes magnetiques dans les couches de w/fe/w est discutee dans le cinquieme chapitre. Le couplage interfacial dans les couches de gd/fe est analyse dans le dernier chapitre

Cette thèse participe à l'étude générale et à la compréhension des relations structure- propriétés optiques de couches minces d'oxyde de tungstène, nanostructurées lors de leur dépôt par la technique Glancing Angle Déposition. Cette technique repose sur le contrôle de l'orientation relative du substrat vis à vis de la source de vapeur.[...]

L'objectif de ce travail était l'élaboration par ablation laser pulsé (PLD) et la caractérisation de couches minces d'oxydes dans le système K-Nb-O, et plus précisément d'une phase de structure bronze de tungstène quadratique (TTB) sous forme de nanorods, potentiellement intéressante dans le contexte de la recherche de nouveaux piézoélectriques sans plomb. Malgré une forte compétition de croissance entre les différentes phases, l'étude approfondie des conditions de dépôt a montré la possibilité d'obtenir les phases KNb3O8, K4Nb6O17, K6Nb10,88O30 (TTB) et KNbO3, en films minces après une phase d’optimisation essentielle. Nous avons déterminé l'influence des conditions de dépôt sur la formation et la nanostructuration de ces composés en couches minces. En particulier, il a été démontré que la température et la composition de la cible PLD avaient une forte influence sur la croissance de la phase de structure TTB. Une étude plus approfondie de ces phases a révélé que toutes avaient une morphologie spécifique liée à leur structure anisotrope, que nous avons pu contrôler par la croissance épitaxiale sur les substrats SrTiO3 orienté (100) et (110). L'existence d'une activité piézoélectrique dans des couches minces de la phase TTB, mise en évidence par PFM, lui confère un intérêt certain. Cette phase TTB a également été obtenue dans le système Na-K-Nb-O, très connu pour ses propriétés piézoélectriques et ferroélectriques, ouvrant la voie sur de nouvelles recherches
The purpose of this work was the elaboration by pulsed laser deposition (PLD) and the characterization of thin films of oxides in the K-Nb-O system, and more precisely that of a tetragonal tungsten bronze phase (TTB) as nanorods, of potential interest as a new lead free piezoelectric. In spite of a strong growth competition between the different phases, the detailed study of the deposition conditions showed that it is possible to obtain KNb3O8, K4Nb6O17, K6Nb10,88O30 (TTB ) and KNbO3 in thin films form after an important optimization step. We have determined the influence of these deposition conditions on the formation and the nanostructuration of these compounds as thin films. In particular, it was shown that the temperature and the PLD target’s composition has a strong influence on the growth of the TTB structure. A further study of these phases revealed that all have a specific morphology related to their anisotropic structure, that we have controlled by the epitaxial growth on the (100) and (110) SrTiO3 substrates. The existence of a piezoelectric activity in the TTB thin films, evidenced by PFM, gives a great interest to this phase. This TTB phase was also obtained in the Na-K-Nb-O system, well known for its piezoelectric and ferroelectric properties, opening the way to new research

L’oxydation des échantillons de tungstène chauffés par effet Joule, est réalisée dans un spectrophotomètre infrarouge sous atmosphère contrôlée (10^-2 torr d'oxygène) et à des températures T ≥ 1100 K pour créer des surfaces rugueuses. La morphologie de la couche d'oxyde est caractérisée par analyseur d'images à partir du cliché d'une coupe réalisée par microscopie électronique à balayage. On assimile l'oxyde à une superposition de films minces, dont l'un hétérogène, contenant la rugosité, est étudié par la théorie de BRUGGMAN en vue de déterminer sa constante diélectrique. Les propriétés optiques d'un corps hétérogène sont interprétées généralement à partir de la théorie des milieux dispersés qui ne tient compte que très partiellement de la rugosité des surfaces. Ce travail expose la conception et l'élaboration d'outils destinés à caractériser l'influence de la complexité et de la forme de la rugosité sur l'émissivité d'une surface, selon une approche originale qui tient compte de la morphologie réelle des surfaces (profils fractals). Le calcul de l'émissivité d'une surface rugueuse est mené de la manière suivante: numérisation des profils expérimentaux calcul de la constante diélectrique d'une couche homogène optiquement équivalente contenant la rugosité du profil considéré calcul du facteur moyen de dépolarisation gm par une méthode originale de remplissage du profil par des ellipsoïdes utilisation de la théorie des films minces, pour calculer l'émissivité monochromatique et directionnelle de cette surface. Une étude analogue a été réalisée sur des profils théoriques crées par interpolation fractale, pour la validation théorique du modèle. Nous mettons en évidence une relation entre la dimension fractale, l'émissivité et le facteur de dépolarisation

Advances in microlithography, dry etching, scaling of devices, ion-implantation, process control, and computer aid design brought the integrated circuit technology into the era of VLSI circuits. Those circuits are characterized by high packing density, improved performance, complex circuits, and large chip sizes. Interconnects and their spacing dominate the chip area of VLSI circuits and they degrade the circuit performance through the unacceptable high time delays. Multilayer metallization enables shorter interconnects, ease of design and yet higher packing density for VLSI circuits. It was shown in this dissertation that, tungsten films deposited in a cold-wall LPCVD reactor offer viable solution to the problems of VLSI multilayer interconnects. Experiments showed that LPCVD tungsten films have good uniformity, high purity, low resistivity, low stress-good adherence and are readily patterned into high resolution lines. Moreover, a multilayer interconnect system consisting of three layers of tungsten metallization followed by a fourth layer of aluminum metallization has been designed, fabricated and tested. The interlevel dielectric used to separate the metal layers was CVD phosphorus doped silicon dioxide. Low ohmic contacts were achieved for heavily doped silicon. Also, low resistance tungsten-tungsten intermetallic contacts were obtained. In addition to excellent step coverage, high electromigration resistance of interconnects was realized. Finally, CMOS devices and logic gates were successfully fabricated and tested using tungsten multilayer metallization schemes.

Tungsten disulfide is a proven material as a low friction solid coating. The material is well characterized and has proven its capabilities the last century. Graphene is this centurys most promising material with electrical and mechanical properties. With it the 2D material revolution have started. In this thesis I present a feasible way to sputter tungsten disulfide on graphene as a substrate with little damage to the graphene from energetic particles and a straight forward method to quantize the damage before and after deposition. Further I investigate compositional changes in the sputtered films depending on processing pressure and how tungsten disulfide film thickness and the amount of graphene damage affects the materials low friction capabilities. It is shown that graphene is not a viable substrate for a low friction tungsten disulfide film and that tungsten disulfide is an excellent material for low friction coatings even down too a few nanometers and that the films behavior during load in the friction testing significantly depends on the processing pressure during sputtering.

The thin film technology is of great importance in modern society and is a key technology in wide spread applications from electronics and solar cells to hard protective coatings on cutting tools and diffusion barriers in food packaging. This thesis deals with various aspects of thin film processing and the aim of the work is twofold; firstly, to obtain a fundamental understanding of the sputter deposition and the reactive sputter deposition processes, and secondly, to evaluate sputter deposition of specific material systems with low friction properties and to improve their performance.From studies of the reactive sputtering process, two new methods of eliminating the problematic and undesirable hysteresis effect were found. In the first method it was demonstrated that an increased process pressure caused a reduction and, in some cases, even elimination of the hysteresis. In the second method it was shown that sufficiently high oxide content in the target will eliminate the hysteresis. Further studies of non-reactive magnetron sputtering of multi-element targets at different pressures resulted in huge pressure dependent compositional gradients over the chamber due to different gas phase scattering of the elements. This has been qualitatively known for a long time but the results presented here now enable a quantitative estimation of such effects. For example, by taking gas phase scattering into consideration during sputtering from a WS2 target it was possible to deposit WSx films with a sulphur content going from sub-stoichiometric to over-stoichiometric composition depending on the substrate position relative the target. By alloying tungsten disulphide (WS2) with carbon and titanium (W-S-C-Ti) its hardness was significantly increased due to the formation of a new titanium carbide phase (TiCxSy). The best sample increased its hardness to 18 GPa (compared to 4 GPa for the corresponding W-S-C coating) while still maintaining a low friction (µ=0.02) due to the formation of easily sheared WS2 planes in the wear track.

Cette thèse est dédiée à l’élaboration de couches minces d'oxydes de tungstène par pulvérisation cathodique réactive. Afin de jouer sur la composition des films, le procédé de pulsation du gaz réactif (RGPP) est mis en œuvre pour changer les concentrations en oxygène et en tungstène. En parallèle, la technique de dépôt sous incidence oblique (GLAD) est développée pour produire différentes architectures, à savoir des colonnes inclinées, des zigzags ou encore des spirales, et augmenter le rapport surface-volume dans les films. La co-pulvérisation GLAD est également étudiée en utilisant deux cibles inclinées et séparées de W et WO3. Les relations entre la microstructure, la composition, les propriétés électroniques et optiques des films d'oxydes de tungstène sont systématiquement étudiées. Ils sont finalement appliqués comme couches actives pour des capteurs résistifs afin d'améliorer la détection de vapeur de dodécane et d'ozone gazeux. La microstructure poreuse élevée des colonnes inclinées produite par GLAD combinée à une composition ajustée par RGPP conduit à définir une gamme de films d'oxydes de tungstène attractifs pour améliorer les performances capteurs
This thesis is focused on the reactive sputter deposition of W-O thin films. In order to play with their composition, the Reactive Gas Pulsing Process (RGPP) is implemented and allows tunable oxygen and tungsten concentrations. Similarly, the GLancing Angle Deposition (GLAD) technique is developed to produce various architectures, namely inclined columns, zigzags and spirals, and increases the surface-to-volume ratio of the films. The GLAD co-sputtering approach is also investigated by means of two inclined and separated W and WO3 targets. Relationships between microstructure, composition, electronic and optical properties of W-O films are systematically studied. They are finally applied as active layers for resistive sensors in order to improve detection of dodecane vapor and ozone gas. The high porous microstructure of inclined columns produced by GLAD combined to the suitable composition adjusted by RGPP leads to define a range of W-O films attractive for sensing performances

碩士
國立交通大學
應用化學研究所
86
The new complexes W(NtBu)2(NEt)2 and W(NtBu)2(NEtMe)2 were successfully synthesized by reacting W(NtBu)2(NHtBu)2 with excess NHEt2 and NHEtMe. 　　They were used as single-source precursors to deposit thin films by low pressure chemical vapor deposition (LPCVD). Deposition of thin films on silicon was carried out at temperatures 723-823K in a cold-wall reator while the precursors were vaporized at 323K. 　　The thin films were studied by WDS, ESCA, AES, XRD and SEM. Volatile products were identified by nuclear magnetic resonance (NMR), gas chromatography-mass (GC-MS) and residual gas analysis (RGA). Rrom these observations, decomposition of the tBuN- and Et2N- groups by β-hydrogen elimination and γ-methy1 elimination pathways are proposed.

The ability to detect and quantify presence and concentration of unknown gasses is sought for applications ranging from environmental monitoring to medical analysis. Metal oxide based chemical sensing technology currently exists but the ability to provide a compositional gas breakdown reliably within a short time frame is not readily available. A very small sensor that can differentially identify the type and concentration of a gas is required. Novel methods of creating low cost and easily tuned one and two-dimensional gas sensing elements are explored. Tungsten trioxide has been thoroughly documented as an electrochromic coating, but highly sensitive WO3 elements with beam and nanowire structures have yet to be explored. Research of WO3 as a gas sensor encompasses three major components: A suitable sensing chamber with accurate analyte gas flow control and temperature control, a reliable method for WO3 deposition, and a high yield fabrication process. This thesis explores all three of these technologies. Chapter two starts with a summary of existing tungsten trioxide fabrication methods. An overview of WO3 processing follows. A comprehensive setup was designed and created to test the gas sensing response of a series of metal oxide based resistive elements through conductimetric analysis. Chapter three provides an in depth account of gas sensor test chamber design and testing. Critical test chamber aspects such as temperature control, precise gas flow control, highly efficient analyte gas switching and ease of use are presented. Chapter four outlines WO3 electrodeposition and the fabrication of beam structures for testing, while chapter five explores the templated electrodeposition of WO3 segments intercalated between gold nanowire segments. Finally, chapter six provides a summary of the research presented in this thesis as well as future directions and options available for further exploration of WO3 gas sensing elements.
Micro-Electro-Mechanical Systems (MEMS) and Nanosystems

碩士
正修科技大學
化工與材料工程研究所
94
The multilayer titanium oxide/tungsten films were prepared by radio frequency magnetron sputtering. The effect of RF power and substrate temperature on structures, morphology observation transmittance, and photo luminescence of TiO2 film were investigated. The effect of annealing temperature on morphology observation transmittance, and photo luminescence were also studied. Results showed that the rutile phase is fund in TiO2 film when deposited at both lower temperature and lower RF power. Subsequently, both the rutile and anatase phase appeared in TiO2 films at higher temperature and RF power. Because of tungsten deposition, the ratio of rutile in the film increased. Increasing RF power, both the grain size and growth rate of TiO2 films linearly increased, at the same time, the energy gap of TiO2 films decreased from 3.25 to 3.08 eV. Increasing deposition temperature, maximum value was found in both the grain size and growth rate of TiO2 films. However, the similar phenomena was found in energy gap calculation, which changed from 3.05 to 3.21 and then 3.01 eV. For annealing no obvious chug was found in the energy gap of TiO2, however, the energy gap of W/TiO2 and TiO2/W/TiO2 decreased from 3.15, and 3.03 eV, to 3.10, and 2.96 eV, respectively.

β-W is an A15 structured phase commonly found in tungsten thin films together with the bcc structured W, and it has been found that β-W has the strongest spin Hall effect among all metal thin films. Therefore, it is promising for application in spintronics as the source of spin-polarized current that can be easily manipulated by electric field. However, the deposition conditions and the formation mechanism of β-W in thin films are not fully understood. The existing deposition conditions for β-W make use of low deposition rate, high inert gas pressure, substrate bias, or oxygen impurity to stabilize the β-W over α-W, and these parameters are unfavorable for producing β-W films with high quality at reasonable yield. In order to optimize the deposition process and gain insight into the formation mechanism of β-W, a novel technique using nitrogen impurity in the pressure range of 10-5 to 10-6 torr in the deposition chamber is introduced. This techniques allows the deposition of pure β-W thin films with only incorporation of 0.4 at% nitrogen and 3.2 at% oxygen, and β-W films as thick as 1μm have been obtained. The dependence of the volume fraction of β-W on the deposition parameters, including nitrogen pressure, substrate temperature, and deposition rate, has been investigated. The relationship can be modeled by the Langmuir-Freundlich isotherm, which indicates that the formation of β-W requires the adsorption of strongly interacting nitrogen molecules on the substrate. The dependence of β-W formation on the choice of underlayer materials has also been investigated. The β-W phase can only be obtained on the underlayer materials containing non-metallic elements. The dependence is explained by the existence of strong covalent bonds in β-W compared with that in α-W. The nickel and permalloy underlayers are the only exception to the above rule, and β-W has been successfully deposited on permalloy underlayer using very low deposition rate for spin-diffusion length measurement of β-W. The permalloy thin films usually take the (111) texture, since its (111) planes have the lowest surface energy. However, permalloy thin films deposited on β-W underlayer can achieve (002) texture using amorphous glass substrates. Therefore, the permalloy/β-W bilayer system can work as a seed layer for the formation of (002) textured films with fcc or bcc structure. The mechanism of the (002) texture formation cannot be explained by the existing models. The β-W to α-W phase transition was characterized by differential scanning calorimetry. The enthalpy of transformation is measured to be 8.3±0.4 kJ/mol, consistent with the value calculated using density functional theory. The activation energy for the β-W to α-W phase transformation kinetics is 2.2 eV, which is extremely low compared with that of lattice and grain boundary diffusion in tungsten. The low activation energy might be attributed to a diffusionless shuffle transformation process.

碩士
長庚大學
化工與材料工程研究所
97
Tungsten (W) thin films has many applications in industry, including the organic material urges nearly pharmaceutical, only such functions as refracting material and wire are mended. This paper thesis utilize LCVD system photolytic by laser beam W(CO)6 deposit W mental line. By changing the laser power , response temperature and flow of gas on the glass substrate is covered with ITO thin film, to discussion about thin films growth and electricity change. Which is measured by XRD , SEM and C-AFM . Confirms the tungsten metal line structure and vary thin film growth and measures the tungsten thin films with EDX with XRD , SEM, learn implicit C , O atoms of tungsten thin films, examine average electric current of the tungsten line, and resistivity of calculate thin films of Sheet Resistance method with C-AFM amount.