Aujourd’hui, le principal facteur limitant le photovoltaïque est le prix élevé du kWh produit par les modules PV. Pour faire face à cette difficulté, les recherches actuelles se concentrent autour de plusieurs leviers et solutions alternatives : la réduction du coût énergétique avec notamment la réduction du coût de la matière première, qui consiste en la diminution de l’épaisseur des wafers de silicium, ou encore l’élaboration de cellules en couches minces de silicium. Ce dernier procédé a pour but de s’affranchir de l’étape de sciage des blocs de silicium, nécessaire pour la réalisation de plaquette photovoltaïque de faible épaisseur. C’est cette dernière approche qui nous a conduits à proposer un procédé d’élaboration de couches minces à l’aide d’un plasma et du chauffage du substrat. Par ailleurs, quel que soit le procédé choisi pour atteindre la cristallinité et la pureté exigées pour le grade solaire, il est nécessaire de disposer de technique analytique multiélémentaire pour contrôler l’évolution de la pureté en fonction des paramètres. La LIBS que nous avons développée au laboratoire offre l’opportunité de répondre à ces attentes : très basses limites de détection tout en permettant un suivi en ligne du silicium à l’état solide ou en fusion. / Today, the main limiting factor of PV is the high price of electricity production by the PV modules. To cope with this difficulty, current researches focus on several ways and alternatives solutions: reducing energy costs including reducing the cost of the raw material, which consists in reducing the thickness of silicon wafers or in the development of cells in thin silicon layers. The latter process is intended to overcome the sawing step of silicon ingots which is necessary for the realization of photovoltaic wafer. It is this very approach that led us to develop a method to prepare thin films by using plasma and heating the substrate. Moreover, whatever the method chosen to achieve the required crystallinity and purity for solar grade, it is necessary to have a multi-elements analytical technique to control the evolution of purity. In our laboratory, we have developed LIBS which can meet these expectations, i-e very low detection limits while allowing online tracking of silicon in solid or liquid state.

The integration of copper (Cu) and dielectric materials has been outlined in the International Technology Roadmap for Semiconductors (ITRS) as a critical goal for future microelectronic devices. A necessity toward achieving this goal is the development of diffusion barriers that resolve the Cu and dielectric incompatibility. The focus of this research examines the potential use of tungsten nitride as a diffusion barrier by characterizing the interfacial properties with Cu and evaluating its process capability for industrial use. Tungsten nitride (β-W2N) development has been carried out using a plasma enhanced chemical vapor deposition (PECVD) technique that utilizes tungsten hexafluoride (WF6), nitrogen (N2), hydrogen (H2), and argon (Ar). Two design of experiments (DOE) were performed to optimize the process with respect to film stoichiometry, resistivity and uniformity across a 200 mm diameter Si wafer. Auger depth profiling showed a 2:1 W:N ratio. X-ray diffraction (XRD) showed a broad peak centered on the β-W2N phase. Film resistivity was 270 mohm-cm and film uniformity < 3 %. The step coverage (film thickness variance) across a structured etched dielectric (SiO2, 0.35 mm, 3:1 aspect ratio) was > 44 %. Secondary ion mass spectroscopy (SIMS) measurements showed good barrier performance for W2N between Cu and SiO2 with no intermixing of the Cu and silicon when annealed to 390o C for 3 hours. Cu nucleation behavior and thermal stability on clean and nitrided tungsten foil (WxN = δ-WN and β-W2N phases) have been characterized by Auger electron spectroscopy (AES) and thermal desorption spectroscopy (TDS) under controlled ultra high vacuum (UHV) conditions. At room temperature, the Auger intensity ratio vs. time plots demonstrates layer by layer Cu growth for the clean tungsten (W) surface and three-dimensional nucleation for the nitride overlayer. Auger intensity ratio vs. temperature measurements for the Cu/W system indicates a stable interface up to 1000 K. For the Cu /WxN/W system, initial Cu diffusion into the nitride overlayer is observed at 550 K.

Orientador: Luiz Carlos Barbosa / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-04T02:12:11Z (GMT). No. of bitstreams: 1 RodriguezGonzalez_Eugenio_D.pdf: 364438828 bytes, checksum: 833cf28a97722cd3503a95105edbd795 (MD5) Previous issue date: 2004 / Resumo: Esta tese foi dedicada a fabricação de filmes finos, quantum dots e multicamadas de materiais semicondutores IV-VI pela técnica de "pulsed-laser deposititon"(PLD). Na primeira parte do trabalho é detalhada a construção de uma instalação "home made" para PLD. O arranjo experimental construído esta baseado fundamentalmente num sistema de câmara de vácuo bombeado até ~ 1 x 10-7 mbar mediante uma bomba turbo-molecular. A ablação do alvo é produzida utilizando o segundo harmônico de um laser Quantel Nd:Yag (532 nm, 5ns, 20Hz, 165mJ/pulso) operando em modo Q-Switch. O feixe laser pulsado é focalizado a 45° sobre o alvo mediante uma lente de 30 cm de foco. O suporte do alvo é mantido girando durante a ablação para evitar a deterioração do mesmo produzido pela irradiação múltipla do feixe no mesmo lugar. Posteriormente fabricamos e caracterizamos filmes finos de PbTe e HgTe pela técnica de PLD. Foi estudada a influência dos parâmetros de crescimento, tais como a distância alvo- substrato, a fluência do laser e a pressão do gás ambiente nas propriedades morfológicas dos filmes. Escolhendo os parâmetros de crescimento adequados, foram obtidos filmes policristalinos, altamente orientados a praticamente livres de "splashing". Foi feito um estudo da dinâmica de expansão do plasma gerado pela ablação de PbTe através da análise da radiação emitida pela pluma. Medidas de espectroscopia de emissão óptica resolvida no tempo e no espaço revelaram a presença no plasma de espécies não ionizadas (PbI, TeI) e ionizadas uma vez (PblI, TelI). A velocidade das espécies não varia para pressões de argônio até 0,1 mbar, o qual sugere que a pluma se expande sem interações com as moléculas do gás ambiente nesta faixa de pressões. Para pressões acima de 0,5 mbar, aparece uma região de aumento na intensidade de emissão da pluma entre o alvo e o substrato. Esta região está associada ao aumento na densidade de espécies produzida por uma compressão da pluma. Foi proposto um modelo para explicar este fato. Finalmente reportamos a fabricação de multicamadas de SiO2 e QDs de PbTe. As nanopartículas do material semicondutor foram crescidas por "laser ablation" de um alvo de PbTe. A matriz vítrea foi fabricada pela técnica "Plasma EnhancedChemical Vapor Deposition" (PECVD) utilizando o tetrametilortossilicato (TMOS) como precursor. A altemância entre as duas técnicas foi controlada por computador através de una interface usando o código Lab View. Imagens "cross section" de Microscopia Eletrônica de Transmissão (TEM) mostram camadas de quantum dots separadas entre si por camadas de SiO2. Foi estudada a influência do tempo de crescimento e da fluência do laser na densidade, tamanho e distribuição de tamanho das nanopartículas. Embora a maior parte das partículas observadas por HRTEM apareceram orientadas na Jireção (200), o padrão de difração de elétrons da multicamada revelou que não existe orientação preferencial para o crescimento dos QDs. Foram medidas a absorção, a luminescência e o tempo de relaxação das multicamadas / Abstract: This thesis was dedicated to the fabrication of thin films, quantum dots and multilayer ofIV-VI semi conducting materiaIs by pulsed-Iaser deposition (PLD). In the first part we report on the construction of a "home made" facility for pulsed laser deposition. The basic experimental set-up fabricated for PLD consists of a vacuum chamber pumped to a base pressure of ~ 1 x 10-7 mbar by a turbo molecular pump. Laser ablation of the target is performed using the second harmonic of a Q-Switched Quantel Nd:Y AG laser (532 nm, 5ns, 20Hz, 1 65mJ/pulse). The pulsed laser beam is focused on an incidence angle of 45° on a target, using a 30 cm lens. The target holder is rotated around the target normal in arder to reduce target degradation by multiple irradiation of a single spot. Afterwards we report on the fabrication and characterization of PbTe and HgTe thin films by pulsed laser deposition in an argon atmosphere. The influence of the growth parameter like target-substrate distance, laser fluence, backing gas pressure and substrate temperature on the structural and morphological properties of the films was studied. Highly oriented, polycrystalline and almost splashing free films were fabricated provided the correct parameter were chosen. We also investigated the expansion dynamics of the plasma induced by the laser ablation of PbTe by analyzing the light emitted from the plume. Space and time-resolved optical spectroscopy measurements indicate the presence of both, neutral (PbI, TeI) and ionized (PbII, TeII) species. The velocities of the species remain unchanged for oxygen pressures up to 0.1 mbar, which suggest that the expansion of the plume occurs without further collisions with the foreign gas in this pressure range. For pressures of 0.5 an above, a region of increasing emission intensity between target and substrate is found when a gas environment is present. This region is related to an increasing of the species density and a compression of the plume. A model to explain this feature was proposed. Finally, we report on the fabrication of SiO2/PbTe multilayers. The gemi conducting nanoparticles were grown by laser ablation of a PbTe target. The glass matrix was fabricated by a plasma chemical vapor deposition (PECVD) method using tetramethoxysilane (TMOS) as precursor. This alternating growth was achieved with a computer-controlled interface using a Lab View code. Cross-section TEM image clearly showed QD' s layer well separated from each other with glass matrix layers. The influence of the ablation time and the laser fluence on the density and size distribution of the quantum dots was studied. Despite most of the nanoparticles observed by HRTEM were oriented in the (200) or (220) directions, electron diffiaction patterns of the multilayer reveal that there is no preferential orientation of the QD's. Absorption, photo luminescence and relaxation time of the multilayer were also too measured / Doutorado / Física / Doutor em Ciências

The diploma thesis deals with the study of Inter-Laminar Shear Strength (ILSS) of polymer composites, based on unsaturated polyester resin with unidirectionally oriented basalt or glass fibers. The basis of the experimental part is the preparation of composite samples with different types of surface treatment of a fibers (a reinforcement) as well as the surface treatment itself. The untreated, the commercially treated fibers and the plasmatreated fibers used as reinforcement in the polymer composites were analysed by a short beam shear test and their ILSS was determined. The effect of various deposition conditions during Plasma-Enhanced Chemical Vapour Deposition (PECVD) on the value of ILSS of the composite with originally unsized glass or basalt fibers was studied. The impact of aging on the interlaminar shear strength of the composites was investigated for commercially treated glass fibers. The Scanning Electron Microscopy (SEM) is also used in the thesis together with the Energy Dispersive Spectroscopy (EDS). Based on all the results a proposal was made to correct and improve the deposition conditions and thus improve the interphase to achieve the required shear properties of polymer composites.

Semiconducting aromatic-boron carbide composite/alloyed films formed by plasma enhanced chemical vapor deposition from carborane and aromatic precursors have been demonstrated to be excellent detectors for thermal neutrons because of the large 10B cross section. The electronic properties of these films derived from XPS show that the properties of boron carbide can be tuned by co-deposition of aromatic compounds and carborane. Aromatic doping results in narrower indirect band gaps (1.1 - 1.7 eV vs ~3 eV for orthocarborane-derived boron carbide without aromatics) and average charge transport lifetimes (as long as 2.5 ms for benzene-orthocarborane and 1.5 - 2.5 ms for indole-orthocarborane) that are superior to those of boron carbide (35 µs). The films also show enhanced electron-hole separation that is also superior to those of boron carbide where the states at the top of the valence band is made of aromatic components while states at the bottom of the conduction band is a combination of aromatic and carborane moeities. These properties result in greatly enhanced (~850%) charge collection, relative to films without aromatic content, in thermal neutron exposures at zero-bias, and are gamma-blind. Such films are therefore excellent candidates for zero-bias neutron detector applications. These properties also show little variation with increasing aromatic content beyond a critical concentration, indicating that at some point, excess aromatic results in the formation of regions of polymerized aromatic within the film, rather than in additional carborane/aromatic linkages. While previous studies on these aromatic-boron carbide materials indicate the potential for neutron detection due to the narrowed band gap, enhanced electron-hole separation and charge transport lifetimes compared to the boron carbide counterpart, the mechanisms of charge transport and photoconductivity (important for photovoltaic applications) of these materials have remained unexplored. Properties such as narrowed band gap, efficient electron-hole separation and long charge transport lifetimes, are also desirable in photovoltaic applications. This, plus ease of fabrication and environmental robustness makes aromatic-boron carbide films promising candidates for photovoltaic applications. Plasma enhanced chemical vapor deposition (PECVD) has been used to synthesize these aromatic-boron carbide composite films by co-deposition of pyridine, aniline or indole with orthocarborane/metacarborane. Film chemical composition and bonding were characterized by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), variable angle spectroscopic ellipsometry (VASE) and (in collaboration with Dowben Group at UNL) charge transport and photoconductivity measurements. Results show narrowed band gaps (indirect) where the top of the valence band is made up of the aromatic moiety and the conduction band minimum us made of aromatic and carborane moeities, improved charge carrier mobilities that is stoichiometry and frequency dependent (aniline-orthocarborane films). Photoconductivity measurement results obtained from ~2.6:1 indole-orthocarborane film show fourth quadrant conductivity. I(V) curves indicate a photocurrent of 2.36 µA at zero bias, with an appreciable open-circuit voltage of 1V. The ability for these aromatic-boron carbide films to operate at zero bias for both neutron detection and photovoltaic applications is an excellent advantage that indicates low cost of operation of these materials.

The theme of this work is the preparation and characterization of multilayer barrier coatings to polymer and metal substrates based on SiOx and organic molecules. It deals with the determination of their properties in terms of oxygen permeability and corrosion protection. The starting materials for the preparation of these layers are hexamethyldisiloxane, octafluorocyclobutane and 4,12-dichloro[2.2]paracyclophane. These layers have been prepared with regard to their use as barrier coatings for use in archeology, with the focus on corrosion protection of coated items and other specific requirements museums. For these samples was realized characteristic of both in terms of their physical properties – the ability to resist permeation of oxygen and in terms of their chemical composition. The fourier transformation infrared spectroscopy (FTIR), scanning elektron microscopy (SEM), oxygen transmission rate (OTR), contac angle measurement and corrosion testing were used for the above-mentioned characterisations.

Diplomová práce nastiňuje problémy spojené s výrobou a analýzou tenkých vrstev DLC:H. Tyto vrstvy jsou ve středu zájmu mnoha vědeckých pracovníků již po několik desetiletí. V současné době existuje mnoho technik pro přípravu a analýzu. Příprava DLC vrstev má zásadní vliv na jejich vlastnosti a možnosti použití. Je zde mnoho kritérií jak vrstvy posuzovat. V této práci jsou studovány vlastnosti DLC:H vrstev připravených na substrát krystalického křemíku metodou RF-PECVD a následně jsou studovány mechanické, tribologické a optické vlastnosti. Jsou zde využity techniky jako XPS, Ramanova spektroskopie, reflektometrie, měření tvrdosti a adheze. Část práce se zabývá modelováním DLC z prvních principů. Pro tento účel je využito prvoprincipiálního programu Abinit který je šířen pod GPL. Je studována otázka přípravy vstupních dat s ohledem na konvergenci výsledků. Pozornost je také věnována výpočtu vibračních spekter ve středu Brillouinovy zóny ( bod) a celkové hustotě elektronových stavů clusteru DLC v supercele tvaru krychle. Tyto výsledky mohou být porovnány s experimentálně získanými daty z Ramanovy spektroskopie, respektive z XPS spektra valenčního pásu

Thin films have become very important in the past years as there is a tremendous increase in the need for small-scale devices. Thin films are preferred because of their electrical, mechanical, chemical, and other unique properties. They are often used for coatings, and in the fabrication of Microelectronic devices and Micro-electro Mechanical Systems (MEMS). Internal (residual) stress always exists when a thin film is employed in the device design. Residual and thermal stresses cause membrane bow, altering the anticipated dynamic response of a membrane-based MEMS design. The device may even become inoperable under the high stresses conditions. As a result, the stresses that act upon the membrane should be minimized for optimum operation of a MEMS device. In this research, the fabrication process parameters leading to low stress silicon nitride films were investigated. Silicon nitride was deposited using Plasma Enhanced Chemical Vapor Deposition (PECVD) and the residual stresses on these films were determined using a wafer curvature technique. By adjusting the silane (SiH4) and nitrogen (N2) gas flow rates, and the radiofrequency (RF) power; high quality silicon nitride films with residual stress as low as 11 MPa were obtained. Furthermore, an analytical study was also conducted to explore the effect of thermal stresses between layers of thin films on the MEMS device operation. In this thesis, we concentrated our efforts on three layers of thin films, as that is the most commonly encountered in a membrane based MEMS device. The results obtained from a parametric study of the membrane center deflection indicate that the deflection can be minimized by the appropriate choice of materials used. In addition, our results indicate that thin films with similar coefficient of thermal expansion should be employed in the design to minimize the deflection of the membrane, leading to anticipated device operation and increased yield. A complete understanding of the thermal and residual stress in MEMS structures can improve survival rate during fabrication, thereby increasing yield and ultimately reducing the device cost. In addition, reliability, durability, and overall performance of membrane-based structures are improved when substrate curvature and membrane deflection caused by stresses are kept at a minimum.

This dissertation presents a method for fabricating integrated hollow and solid optical waveguides on planar substrates. These waveguides are antiresonant reflecting optical waveguides (ARROWs), where high-index cladding layers confine light to hollow cores through optical interference. Hollow waveguides that can be filled with liquids or gases are an important new building block for creating highly-integrated optical sensors. The method developed for fabricating these integrated waveguides employs standard processes and materials used in the microelectronics industry, allowing for parallel, low-cost fabrication. Dielectric cladding layers are deposited on a silicon wafer using plasma-enhanced chemical vapor deposition (PECVD). After the lower cladding layers have been deposited, a sacrificial material is deposited and patterned using photolithography to produce the hollow-core shape. After the sacrificial cores are defined, they are coated with additional PECVD dielectric layers to form the sides and tops of the waveguides. Integrated solid-core waveguides can be easily created by etching a ridge into the top dielectric cladding layer. Finally, the ends of the sacrificial cores are exposed and removed with an acid solution, resulting in hollow waveguides. Improved optical performance for integrated ARROW platforms can be achieved by only using a single over-coating for the cladding on the sides and top of the hollow waveguide. Such a structure resulted in 70% improvement in optical throughput for the platforms and increased sensitivity for optical manipulation and fluorescence detection of single particles, including viruses. Reduced loss for the hollow waveguides can be obtained by surrounding the core with a terminal layer of air on the sides and top of the waveguide. Such devices were created by forming the hollow waveguides on top of a pedestal on the silicon substrate. This process produces the ideal geometry for hollow ARROW waveguides, and loss measurements of waveguides with air-filled cores had loss coefficients of 1.54/cm, which is the lowest achieved for air-core ARROWs.

This dissertation presents research on the fabrication of optofluidic sensor platforms, which consist of integrated hollow waveguides and solid waveguides. Antiresonant reflecting optical waveguides (ARROWs) filled with liquids or gases, can be used for high-sensitivity sensing in applications of biotechnology, chemical synthesis, and analytical chemistry. The fabrication method developed for integrated ARROW sensing platforms utilizes standard microfabrication processes and materials. Dielectric cladding layers are deposited on a silicon wafer using plasma-enhanced chemical vapor deposition (PECVD) or sputtering. A sacrificial material is then patterned over the bottom cladding layers by photolithography. Additional dielectric layers are deposited around the core, forming the structure of the waveguides. Integrated solid-core waveguides can be easily created by etching a ridge into the topmost dielectric cladding layer. The hollow core waveguides are then formed by wet etching the sacrificial core material. The coupling efficiency between solid core and hollow core waveguides is extremely important for the platform's overall sensitivity. Efficiencies can be enhanced from 18% to 67% by adjusting the thickness of the thick top oxide. Experimental results prove that optical throughput was improved by 17.1× with this improved interface transmission. Sputtered films were investigated as an alternative to for producing cladding layers. The experimental results reveal that sputtered layers show poor adhesion and mechanical strength which make them unreliable for hollow waveguides with small dimension. High-sensitivity ARROW platforms were obtained by employing hybrid layers (PECVD SiO2 and sputtered Ta2O5) as claddings and building waveguides on self-aligned pedestals. The photolumiscence background was only 1/10 that of previous devices made with SiO2/SiN and the average signal-to-noise ratio was improved by 12×.