Les MEMS RF sont des composants clés pour le développement de nombreuses fonctions de systèmes hyperfréquences plus efficaces et plus compactes (déphaseurs, module transmission/réception, réseau d’antennes à déphasage, circuits reconfigurables, réseau d’adaptation …). Pour le développement des prochaines générations de systèmes RADAR, Thales s’intéresse notamment à l’intégration de MEMS RF capacitifs pour développer des fonctions reconfigurables pouvant supporter des puissances hyperfréquences de l’ordre de 30 W. Les travaux exposés dans ce manuscrit se sont concentrés sur l’étude de matériaux diélectriques et de techniques de dépôts pour identifier, intégrer et démontrer la viabilité de diélectriques prometteurs pour les MEMS RF capacitifs de puissance. Les aspects relatifs à la fabrication de ces composants ont également été étudiés, particulièrement l’impact de la maitrise des états de surface sur les performances, la tenue en puissance et la défaillance des dispositifs. En outre, ces travaux ont montrés qu’avec l’introduction des matériaux déposés par ALD, la tenue en puissance des MEMS RF capacitifs n’est plus limitée par le diélectrique. En intégrant ces matériaux ALD, l’architecture des dispositifs devient le facteur limitant la tenue en puissance, particulièrement l’épaisseur de la membrane et la configuration du commutateur. En perspectives, différentes architectures ont donc été développées et étudiées pour adresser ces limitations de tenue en puissance. / RF MEMS are key components to improve the efficiency and size of numerous functions of microwave systems (Phase shifter, transmission/reception module, antennas array, reconfigurable systems, impedance matching…). To develop the next generation of RADAR systems, Thales takes special interest in the integration of capacitive RF MEMS devices to demonstrate reconfigurable functions with power handling capabilities up to 30 W. The work reported in this thesis did focus on the study of dielectric materials and deposition techniques to identify, integrate and demonstrate the advantages of promising dielectrics for capacitive RF MEMS power handling. The components fabrication aspects have also been studied, especially the impact of surface state quality on performances, power handling and devices failure mechanisms. Furthermore, this work did point out that with the integration of ALD material, power handling of capacitive RF MEMS is no longer limited by the capacitance dielectric. Furthermore, with the integration of ALD material the components design become the limiting factor for power handling, particularly the membrane thickness and the switch configuration. To open new prospects, several designs have been developed and studied to address these power handling limitations.

This thesis investigates the ability of transparent surface coatings to reduce xenon diffusion into plastic scintillators. The motivation for the work is improved radioxenon monitoring equipment, used with in the framework of the verification regime of the Comprehensive Nuclear-Test-Ban Treaty. A large part of the equipment used in this context incorporates plastic scintillators which are in direct contact with the radioactive gas to be detected. One problem with such setup is that radioxenon diffuses into the plastic scintillator material during the measurement, resulting in an unwanted memory effect consisting of residual activity left in the detector. In this work coatings of Al2O3 and SiO2, with thicknesses between 20 and 400 nm have been deposited onto flat plastic scintillator samples, and tested with respect to their Xe diffusion barrier capabilities. All tested coatings were found to reduce the memory effect, and 425 nm of Al2O3 showed the most promise. This coating was deposited onto a complete detector. Compared to uncoated detectors, the coated one presented a memory effect reduction of a factor of 1000. Simulations and measurements of the expected light collection efficiency of a coated detector were also performed, since it is important that this property is not degraded by the coating. It was shown that a smooth coating, with a similar refractive index as the one of the plastic, should not significantly affect the light collection and resolution. The resolution of the complete coated detector was also measured, showing a resolution comparable to uncoated detectors. The work conducted in this thesis proved that this coating approach is a viable solution to the memory effect problem, given that the results are reproducible, and that the quality of the coating is maintained over time.

Thin films of cobalt oxide, iron oxide and niobium oxide, and nanostructured thin films of iron oxide, titanium oxide and multilayered iron oxide/titanium oxide have been deposited by Atomic Layer Deposition (ALD). The metal oxides were grown using the precursor combinations CoI2/O2, Fe(Cp)2/O2, NbI5/O2 and TiI4/H2O. The samples were analysed primarily with respect to phase content, morphology and growth characteristics. Thin films deposited on Si (100) were found to be amorphous or polycrystalline, depending on deposition temperature and the oxide deposited; cobalt oxide was also deposited on MgO (100), where it was found to grow epitaxially with orientation (001)[100]Co3O4||(001)[100]MgO. As expected, the polycrystalline films were rougher than the amorphous or the epitaxial films. The deposition processes showed properties characteristic of self-limiting ALD growth; all processes were found to have a deposition temperature independent growth region. The deposited films contained zero or only small amounts of precursor residues. The nanostructured films were grown using anodic aluminium oxide (AAO) or carbon nanosheets as templates. Nanotubes could be manufactured by depositing a thin film which covers the pore walls of the AAO template uniformly; free-standing nanotubes retaining the structure of the template could be fabricated by removing the template. Multilayered nanotubes could be obtained by depositing multiple layers of titanium dioxide and iron oxide in the pores of the AAO template. Carbon nanosheets were used to make titanium dioxide nanosheets with a conducting graphite backbone. The nucleation of the deposited titanium dioxide could be controlled by acid treatment of the carbon nanosheets.

In the industry of metal cutting tools the conditions are extreme; the temperature can vary thousand degrees rapidly and the pressure can be tremendously high. To survive this kind of stress the cutting tool must be both hard and tough. In order to obtain these properties different coatings are used on a base of cemented carbide, WC-Co. Common coatings are hard ceramics like titanium nitride and titanium carbon-nitride with an outer layer of aluminium oxide. In this thesis the possibility of using titanium dioxide as an interlayer between titanium carbon-nitride and aluminium oxide to control the morphology and phase of aluminium oxide is investigated. Of the different aluminium oxide phases only the alpha-Al2O3 is stable. The titanium carbon-nitride coatings are made by CVD (chemical vapour deposition); also the alumina is deposited by CVD. The titanium dioxide was deposited by atomic layer deposition (ALD) which is a sequential CVD technique that allows a lower deposition temperature and better control of the film growth than CVD. The obtained thin films were analyzed using XRD, Raman spectroscopy, ESCA and SEM. To test the adhesion of the coatings the samples were sand blasted. A thin interlayer of titanium dioxide causes the aluminium oxide to grow as alpha-Al2O3, thinner TiO2 gave better adhesion.

The atomic layer deposition (ALD) growth of titania thin films was studied for the infiltration of silica photonic crystals. Titania thin films were grown in a custom-built ALD reactor by the alternating pulsing and purging of TiCl4 and water vapor. The conformal nature of ALD growth makes it an ideal candidate for the infiltration of the complex opal structure. Titania is a high refractive index material, which makes it a popular material for use in photonic crystal (PC) applications. Photonic crystals are periodic dielectric structures that forbid the propagation of light in a certain wavelength range. This forbidden range is known as the photonic band gap (PBG). A refractive index contrast of at least 2.8 is required for a complete PBG in an inverted opal structure. Therefore, the rutile structure of titania is more desirable for use in PCs due to its higher index of refraction than the anatase or brookite structure. The growth mechanisms and film properties of the TiO2 thin films were studied. Investigation of the growth mechanisms revealed saturated growth rate conditions for multiple temperature regions. Film characterization techniques included XRD, SEM/EDS, XPS, AFM, reflectivity, and index of refraction measurements. Post growth heat treatment was performed to study the conversion from the as-deposited crystal structure to the rutile structure. After optimization of the deposition process, the infiltration of silica opals for PC applications was attempted. The filling fraction was optimized by increasing the pulse and purge lengths at a deposition temperature of 100oC. Although the silica opals were successfully infiltrated using ALD of TiO2, the long range order of the PC was destroyed after the heat treatment step required to achieve the high index rutile structure.

In the late eighties, a new class of materials, known as photonic crystals (PCs), emerged enabling the propagation and generation of light to be potentially manipulated with unprecedented control. PCs consist of a periodic modulation of dielectric constant in one, two, or three dimensions, which can result in the formation of directional or omni-directional photonic band gaps (PBGs), spectral regions where light propagation is forbidden, and more remarkably, novel dispersion characteristics. Since PC properties scale with the dimension of the wavelength of interest, significant technological constraints must be fully addressed to manufacture 3D PBG materials for optical or infrared applications such as displays, lightning, and communications. PCs enable the unraveling of unique optical phenomena such as PBGs, spontaneous emission rate manipulation, sub-wavelength focusing, and superprism effects. This research focuses on the feasibility to achieve omni-directional PBGs in synthetic opal-based 3D PCs through precise nanoscale control to the original dielectric architecture. In particular, the optical response to the conformal deposition of dielectric layers using atomic layer deposition (ALD) within the porous template is strongly emphasized. Geometrical models were developed to faithfully model the manipulation of the synthetic opal architecture by ALD and then used in electromagnetic algorithms to predict the resulting optical properties. From these results, this research presents and investigates a scheme used to greatly enhance and adjust the PBG width and position, as well as simultaneously reducing the dielectric contrast threshold at which the PBG forms. This Thesis demonstrates that the unique opal architectures offered by ALD not only supports the formation of larger PBGs with high index materials; but also enables the use of optically transparent materials with reduced refractive index. Additionally, slight alteration of these structures facilitates the incorporation of non-linear (NL) electro-optical (EO) material for dynamic tuning capabilities and potentially offers a pathway for fabricating multi-functional photonic devices. Finally, low-temperature ALD was investigated as a means to manipulate band gaps and dispersion effects in 2D PC silicon slab waveguides and 3D organic biologically-derived templates. The results indicate the unique ability of ALD to achieve composite structures with desirable (large PBGs) or novel (slow light) optical properties.

Vor dem Hintergrund der in der Mikroelektronik-Fertigung heute verbreiteten Kupfertechnologie werden in der vorliegenden Arbeit drei neuartige metallorganische Verbindungen, nämlich phosphitstabilisierte Kupfer(I)-Trifluoracetat-Komplexe vorgestellt und hinsichtlich ihrer Anwendbarkeit für die chemische Gasphasenabscheidung (CVD) von Kupfer untersucht. Im einzelnen handelt es ich um die Substanzen Tris(trimethylphosphit)kupfer(I)trifluoracetat (METFA), Tris(triethylphosphit)kupfer(I)trifluoracetat (ETTFA) und Tri(tris(trifluorethyl)phosphit)kupfer(I)trifluoracetat (CFTFA). Mit den Substanzen erfolgen CVD-Experimente auf TiN und Cu bei Temperaturen <400°C. Die Precursoren werden dabei mittels eines Flüssigdosiersystems mit Verdampfereinheit der Reaktionskammer zugeführt. Während METFA wegen seiner ausreichend geringen Viskosität unverdünnt verwendet werden kann, kommen für ETTFA und CFTFA jeweils Precursor-Acetonitril-Gemische zum Einsatz. Mit keinem der Neustoffe können auf TiN geschlossene Kupferschichten erzeugt werden, während dies auf Kupferunterlagen in Verbindung mit Wasserstoff als Reduktionsmittel gelingt. Die Abscheiderate beträgt hierbei 2-3nm/min; der spezifische Widerstand der Schichten bewegt sich zwischen 4μΩcm und 5μΩcm. Mit allen Substanzen werden besonders an dünnen, gesputterten Kupferschichten Agglomerationserscheinungen und Lochbildung beobachtet. Im Fall von CFTFA treten zusätzlich Schäden am darunterliegenden TiN/SiO₂-Schichtstapel auf. Vergleichende Untersuchungen mit der für die Cu-CVD etablierten Substanz (TMVS)Cu(hfac) ergeben sowohl auf Cu als auch auf TiN geschlossene Kupferschichten. Dabei liegen die Abscheideraten bei Temperaturen zwischen 180°C und 200°C im allgemeinen deutlich über 100nm/min. Ein Vergleich dieser Resultate mit den Ergebnissen für die Neustoffe legt nahe, dass den untersuchten Kupfer(I)-Trifluoracetaten keine ausreichende Tauglichkeit für Cu-CVD-Prozesse in der Mikroelektronik-Technologie bescheinigt werden kann. Die im Vergleich zu (TMVS)Cu(hfac) höhere thermische Stabilität der Precursoren und ihre Fähigkeit, mit Wasserstoff als Reaktionspartner auf Cu geschlossene Kupferschichten erzeugen zu können, deutet jedoch auf ihre eventuelle Eignung für ALD-Prozesse hin. Daher widmet sich die Arbeit in einem abschließenden Kapitel dem Thema der Atomic Layer Deposition (ALD), wobei nach einem allgemeinen Überblick besonders auf für die Mikroelektronik relevante ALD-Prozesse eingegangen wird.

To sustain future civilization, the development of alternative clean-energy technologies to replace fossil fuels has become one of the most crucial and challenging problems of the last few decades. The thin film solar cell is one of the major photovoltaic technologies that is promising for renewable energy. The current commercial thin film PV technologies are based on \(Cu(In,Ga)Se_2\) and CdTe. Despite their success in reducing the module cost below $1/Wp, these absorber materials face limitations due to their use of scarce (In and Te) and toxic (Cd) elements. One promising candidate for an alternative absorber material is tin monosulfide (SnS). Composed of cheap, non-toxic and earth-abundant elemental constituents, SnS can potentially provide inexpensive PV modules to reach the global energy demand in TW levels. Because of the high volatility of sulfur and various oxidation states of tin, non- stoichiometric chemical composition, traces of other phases \((i.e. Sn, Sn_2S_3, and SnS_2)\), and elemental impurities (e.g. oxygen) are usually observed in SnS films obtained from various reported deposition techniques. First, we present a process to prepare pure, stoichiometric, single-phase SnS films from atomic layer deposition (ALD). The as-deposited SnS films exhibit several attractive properties, including suitable energy band gaps \((E_{g,}~ 1.1 – 1.3 eV)\), a large absorption coefficient \((\alpha > 10^4 cm^{˗1})\), and a proper carrier concentration \(([p] ~ 10^{15} – 10^{16} cm^{˗3})\). Then, heterojunction solar cells were fabricated from p-type SnS and n-type zinc oxysulfide (Zn(O,S)). A record high active-area efficiency of 2.46 % was achieved via conduction band offset engineering by varying the oxygen-to-sulfur ratio in Zn(O,S). Finally, we address two approaches potentially used for improving a device efficiency of the SnS solar cell. First, via doping to create an n-type SnS, a p-n homojunction device could be made. We present the processes and the results of doping SnS films with antimony and chlorine, potential n-type dopants. Second, by post-deposition heat treatment, an improvement in the transport properties of SnS film can be achieved. We discuss the effect of temperature and an annealing ambient \((N_2, H_2S\), and sulfur) on grain growth and the electrical properties of annealed SnS films. / Chemistry and Chemical Biology

Tin(II) sulfide (SnS) is an earth-abundant, inexpensive, and non-toxic absorber material for thin film solar cells. SnS films are deposited by atomic layer deposition (ALD) through the reaction of a tin precursor, bis(N,N'-diisopropylacetamidinato)tin(II), and hydrogen sulfide. The SnS films demonstrate excellent surface morphology, crystal structure, phase purity, stoichiometry, elemental purity, and optical and electrical properties. / Engineering and Applied Sciences

Für die Beschichtung von Bauelementen im Bereich der Elektronik erlangt das Beschichtungsverfahren der Atomlagenabscheidung zunehmend an Bedeutung. Dieses Verfahren überzeugt hier durch seine Fähigkeit sehr homogene Schichten mit einer Dicke von wenigen nm auch auf Strukturen mit hohen Aspektverhältnissen zu erzeugen. Diese Arbeit beschäftigt sich mit der Atomlagenabscheidung von Aluminiumoxid unter Verwendung der Präkursoren Trimethylaluminium und Wasser. Hauptaufgabe dieser Arbeit ist die Modellierung eines experimentellen Prozessaufbaus mit kommerzieller Simulationssoftware. Anhand der Simulationsergebnisse können Aussagen zur Optimierung des ALD-Prozesses getroffen werden. Die durchgeführten Untersuchungen zeigen, dass für die Simulation eines ALD-Prozesses sehr lange Rechenzeiten erforderlich sind. Insbesondere konnte ein tieferes Verständnis der automatischen Zeitschrittweitenregulierung der Software bei transienten Simulationen gewonnen werden. Die Dauer der Spülschritte wurde durch die Simulationsergebnisse als ausreichend bestätigt. Des Weiteren kann die Verwendung der zur Anlage gehörigen Gasdusche anhand der Simulationsergebnisse nicht empfohlen werden.