Cutting forces and wear analysis of Si3N4 diamond coated tools in high speed machining

Si3N4 tools were coated with a thin diamond film using a Hot-Filament Chemical Vapour Deposition (HFCVD) reactor, in order to machining a grey cast iron. Wear behaviour of these tools in high speed machining was the main subject of this work. Turning tests were performed with a combination of cutting speeds of 500, 700 and 900 m min−1, and feed rates of 0.1, 0.25 and 0.4 mm rot−1, remaining constant the depth of cut of 1 mm. In order to evaluate the tool behaviour during the turning tests, cutting forces were analyzed being verified a significant increase with feed rate. Diamond film removal occurred for the most severe set of cutting parameters. It was also observed the adhesion of iron and manganese from the workpiece to the tool. Tests were performed on a CNC lathe provided with a 3-axis dynamometer. Results were collected and registered by homemade software. Tool wear analysis was achieved by a Scanning Electron Microscope (SEM) provided with an X-ray Energy Dispersive Spectroscopy (EDS) system. Surface analysis was performed by a profilometer.

Adhesion and wear behaviour of NCD coatings on Si3N4 by micro-abrasion tests

Nanocrystalline diamond (NCD) coatings offer an excellent alternative for tribological applications, preserving most of the intrinsic mechanical properties of polycrystalline CVD diamond and adding to it an extreme surface smoothness. Silicon nitride (Si3N4) ceramics are reported to guarantee high adhesion levels to CVD microcrystalline diamond coatings, but the NCD adhesion to Si3N4 is not yet well established. Micro-abrasion tests are appropriate for evaluating the abrasive wear resistance of a given surface, but they also provide information on thin film/substrate interfacial resistance, i.e., film adhesion. In this study, a comparison is made between the behaviour of NCD films deposited by hot-filament chemical vapour deposition (HFCVD) and microwave plasma assisted chemical vapour deposition (MPCVD) techniques. Silicon nitride (Si3N4) ceramic discs were selected as substrates. The NCD depositions by HFCVD and MPCVD were carried out using H2–CH4 and H2–CH4–N2 gas mixtures, respectively. An adequate set of growth parameters was chosen for each CVD technique, resulting in NCD films having a final thickness of 5 m. A micro-abrasion tribometer was used, with 3 m diamond grit as the abrasive slurry element. Experiments were carried out at a constant rotational speed (80 r.p.m.) and by varying the applied load in the range of 0.25–0.75 N. The wear rate for MPCVD NCD (3.7±0.8 × 10−5 m3N−1m−1) is compatible with those reported for microcrystalline CVD diamond. The HFCVD films displayed poorer adhesion to the Si3N4 ceramic substrates than the MPCVD ones. However, the HFCVD films show better wear resistance as a result of their higher crystallinity according to the UV Raman data, despite evidencing premature adhesion failure.

Desenvolvimento de células solares de Si nano-estruturado para aplicação em azulejos solares

Dissertação apresentada para a obtenção do Grau de Mestre em Engenharia de Materiais, pela Universidade Nova de Lisboa,Faculdade de Ciências e Tecnologia

Optimisation of doped microcrystalline silicon films deposited at very low temperatures by Hot-Wire CVD

In this paper we present new results on doped μc-Si:H thin films deposited by hot-wire chemical vapour deposition (HWCVD) in the very low temperature range (125-275°C). The doped layers were obtained by the addition of diborane or phosphine in the gas phase during deposition. The incorporation of boron and phosphorus in the films and their influence on the crystalline fraction are studied by secondary ion mass spectrometry and Raman spectroscopy, respectively. Good electrical transport properties were obtained in this deposition regime, with best dark conductivities of 2.6 and 9.8 S cm -1 for the p- and n-doped films, respectively. The effect of the hydrogen dilution and the layer thickness on the electrical properties are also studied. Some technological conclusions referred to cross contamination could be deduced from the nominally undoped samples obtained in the same chamber after p- and n-type heavily doped layers.

Real-time monitoring of the silicidation process of tungsten filaments at high temperature used as catalysers for silane decomposition

The scope of this work is the systematic study of the silicidation process affecting tungsten filaments at high temperature (1900ºC) used for silane decomposition in the hot-wire chemical vapour deposition technique (HWCVD). The correlation between the electrical resistance evolution of the filaments, Rfil(t), and the different stages of the their silicidation process is exposed. Said stages correspond to: the rapid formation of two WSi2 fronts at the cold ends of the filaments and their further propagation towards the middle of the filaments; and, regarding the hot central portion of the filaments: a initial stage of silicon dissolution into the tungsten bulk, with a random duration for as-manufactured filaments, followed by the inhomogeneous nucleation of W5Si3 (which is later replaced by WSi2) and its further growth towards the filaments core. An electrical model is used to obtain real-time information about the current status of the filaments silicidation process by simply monitoring their Rfil(t) evolution during the HWCVD process. It is shown that implementing an annealing pre-treatment to the filaments leads to a clearly repetitive trend in the monitored Rfil(t) signatures. The influence of hydrogen dilution of silane on the filaments silicidation process is also discussed.

Emission of carbon nanofiber (CNF) from CNF-containing composite adsorbents

In spite of numerous applications of carbon nanofibers (CNFs) in a variety of fields, the potential release of airborne CNF during their special application, which could lead to workers or end-users exposure, has not been well investigated. In this study, the potential release of CNF from an organic vapour respirator cartridge was evaluated by carbon analysis and microscopy analysis. The cartridge consisted of an AC (Activated Carbon)/CNF composite adsorbent and different types of particulate filters. The composite adsorbent CNF were prepared by chemical vapour deposition (CVD). Air was passed through the prepared cartridge for 12 hours at 12 l/min and particles were collected on sampling filters suitable for measuring organic and elemental carbon (OC/EC) by carbon analysis based on the NIOSH 5040 method. Breakthrough of CNFs was also checked by scanning and transmission electron microscopy (SEM/TEM). This study found only minimal amounts of released elemental carbon while passing the air through the cartridge. Meanwhile TEM photos showed a few CNF structures for AC/CNF composite adsorbents which were not in the critical range in terms of length, aspect ratio, or number. [Authors]

Investigation of defect formation and electronic transport in microcrystalline silicon deposited by hot-wire CVD

We have investigated doped and undoped layers of microcrystalline silicon prepared by hot-wire chemical vapour deposition optically, electrically and by means of transmission electron microscopy. Besides needle-like crystals grown perpendicular to the substrate's surface, all of the layers contained a noncrystalline phase with a volume fraction between 4% and 25%. A high oxygen content of several per cent in the porous phase was detected by electron energy loss spectrometry. Deep-level transient spectroscopy of the crystals suggests that the concentration of electrically active defects is less than 1% of the undoped background concentration of typically 10^17 cm -3. Frequency-dependent measurements of the conductance and capacitance perpendicular to the substrate surface showed that a hopping process takes place within the noncrystalline phase parallel to the conduction in the crystals. The parasitic contribution to the electrical circuit arising from the porous phase is believed to be an important loss mechanism in the output of a pin-structured photovoltaic solar cell deposited by hot-wire CVD.

Studies on grain boundaries in nanocrystalline silicon grown by Hot-Wire CVD

The use of a tantalum wire in hot-wire chemical vapour deposition (HWCVD) has allowed the deposition of dense nanocrystalline silicon at low filament temperatures (1550 °C). A transition in the crystalline preferential orientation from (2 2 0) to (1 1 1) was observed around 1700 °C. Transmission electron microscopy (TEM) images, together with secondary ion mass spectrometry (SIMS) measurements, suggested that no oxidation occurred in materials obtained at low filament temperature due to the high density of the tissue surrounding grain boundaries. A greater concentration of SiH 3 radicals formed at these temperatures seemed to be responsible for the higher density.

Stability of hydrogenated nanocrystalline silicon thin-film transistors

Hydrogenated nanocrystalline silicon thin-films were obtained by catalytic chemical vapour deposition at low substrate temperatures (150°C) and high deposition rates (10 Å/s). These films, with crystalline fractions over 90%, were incorporated as the active layers of bottom-gate thin-film transistors. The initial field-effect mobilities of these devices were over 0.5 cm 2/V s and the threshold voltages lower than 4 V. In this work, we report on the enhanced stability of these devices under prolonged times of gate bias stress compared to amorphous silicon thin-film transistors. Hence, they are promising candidates to be considered in the future for applications such as flat-panel displays.

Electronic transport in low temperature nanocrystalline silicon thin-film transistors obtained by Hot-Wire CVD

Hydrogenated nanocrystalline silicon (nc-Si:H) obtained by hot-wire chemical vapour deposition (HWCVD) at low substrate temperature (150 °C) has been incorporated as the active layer in bottom-gate thin-film transistors (TFTs). These devices were electrically characterised by measuring in vacuum the output and transfer characteristics for different temperatures. The field-effect mobility showed a thermally activated behaviour which could be attributed to carrier trapping at the band tails, as in hydrogenated amorphous silicon (a-Si:H), and potential barriers for the electronic transport. Trapped charge at the interfaces of the columns, which are typical in nc-Si:H, would account for these barriers. By using the Levinson technique, the quality of the material at the column boundaries could be studied. Finally, these results were interpreted according to the particular microstructure of nc-Si:H.

Thin Film Transistors obtained by Hot-Wire CVD

Hydrogenated microcrystalline silicon films obtained at low temperature (150-280°C) by hot wire chemical vapour deposition at two different process pressures were measured by Raman spectroscopy, X-ray diffraction (XRD) spectroscopy and photothermal deflection spectroscopy (PDS). A crystalline fraction >90% with a subgap optical absortion 10 cm -1 at 0.8 eV were obtained in films deposited at growth rates >0.8 nm/s. These films were incorporated in n-channel thin film transistors and their electrical properties were measured. The saturation mobility was 0.72 ± 0.05 cm 2/ V s and the threshold voltage around 0.2 eV. The dependence of their conductance activation energies on gate voltages were related to the properties of the material.

Sistema RTP: uma técnica poderosa para o monitoramento da formação de nanotubos de carbono durante o processo por deposição de vapor químico

In this work, a TPR (Temperature Programmed Reduction) system is used as a powerful tool to monitor carbon nanotubes production during CVD (Chemical Vapour Deposition), The experiments were carried out using catalyst precursors based on Fe-Mo supported on Al2O3 and methane as carbon source. As methane reacts on the Fe metal surface, carbon is deposited and H2 is produced. TPR is very sensitive to the presence of H2 and affords information on the temperature where catalyst is active to form different forms of carbon, the reaction kinetics, the catalyst deactivation and carbon yields.

Surface Modification of Ceramics

Ceramics are widely used in industrial applications due to their advantageous thermal and mechanical stability. Corrosion of ceramics is a great problem resulting in significant costs. Coating is one method of reducing adversities of corrosion. There are several different thin film deposition processes available such as sol-gel, Physical and Chemical Vapour Deposition (PVD and CVD). One of the CVD processes, called Atomic Layer Deposition (ALD) stands out for its excellent controllability, accuracy and wide process capability. The most commonly mentioned disadvantage of this method is its slowness which is partly compensated by its capability of processing large areas at once. Several factors affect the ALD process. Such factors include temperature, the grade of precursors, pulse-purge times and flux of precursors as well as the substrate used. Wrongly chosen process factors may cause loss of self-limiting growth and thus, non-uniformities in the deposited film. Porous substrates require longer pulse times than flat surfaces. The goal of this thesis was to examine the effects of ALD films on surface properties of a porous ceramic material. The analyses applied were for permeability, bubble point pressure and isoelectric point. In addition, effects of the films on corrosion resistance of the substrate in aqueous environment were investigated. After being exposured to different corrosive media the ceramics and liquid samples collected were analysed both mechanically and chemically. Visual and contentual differences between the exposed and coated ceramics versus the untreated and uncoated ones were analysed by scanning electron microscope. Two ALD film materials, dialuminium trioxide and titanium dioxide were deposited on the ceramic substrate using different pulse times. The results of both film materials indicated that surface properties of the ceramic material can be modified to some extent by the ALD method. The effect of the titanium oxide film on the corrosion resistance of the ceramic samples was observed to be fairly small regardless of the pulse time.

Mécanismes de déformation de nanoparticules d’Au par irradiation ionique

Résumé Dans la présente thèse, nous avons étudié la déformation anisotrope par bombardement ionique de nanoparticules d'or intégrées dans une matrice de silice amorphe ou d'arséniure d’aluminium cristallin. On s’est intéressé à la compréhension du mécanisme responsable de cette déformation pour lever toute ambigüité quant à l’explication de ce phénomène et pour avoir une interprétation consistante et unique. Un procédé hybride combinant la pulvérisation et le dépôt chimique en phase vapeur assisté par plasma a été utilisé pour la fabrication de couches nanocomposites Au/SiO2 sur des substrats de silice fondue. Des structures à couches simples et multiples ont été obtenues. Le chauffage pendant ou après le dépôt active l’agglomération des atomes d’Au et par conséquent favorise la croissance des nanoparticules. Les nanocomposites Au/AlAs ont été obtenus par implantation ionique de couches d’AlAs suivie de recuit thermique rapide. Les échantillons des deux nanocomposites refroidis avec de l’azote liquide ont été irradiés avec des faisceaux de Cu, de Si, d’Au ou d’In d’énergie allant de 2 à 40 MeV, aux fluences s'étendant de 1×1013 à 4×1015 ions/cm2, en utilisant le Tandem ou le Tandetron. Les propriétés structurales et morphologiques du nanocomposite Au/SiO2 sont extraites en utilisant des techniques optiques car la fréquence et la largeur de la résonance plasmon de surface dépendent de la forme et de la taille des nanoparticules, de leur concentration et de la distance qui les séparent ainsi que des propriétés diélectriques du matériau dans lequel les particules sont intégrées. La cristallinité de l’arséniure d’aluminium est étudiée par deux techniques: spectroscopie Raman et spectrométrie de rétrodiffusion Rutherford en mode canalisation (RBS/canalisation). La quantité d’Au dans les couches nanocomposites est déduite des résultats RBS. La distribution de taille et l’étude de la transformation de forme des nanoparticules métalliques dans les deux nanocomposites sont déterminées par microscopie électronique en transmission. Les résultats obtenus dans le cadre de ce travail ont fait l’objet de trois articles de revue. La première publication montre la possibilité de manipuler la position spectrale et la largeur de la bande d’absorption des nanoparticules d’or dans les nanocomposites Au/SiO2 en modifiant leur structure (forme, taille et distance entre particules). Les nanoparticules d’Au obtenues sont presque sphériques. La bande d’absorption plasmon de surface (PS) correspondante aux particules distantes est située à 520 nm. Lorsque la distance entre les particules est réduite, l’interaction dipolaire augmente ce qui élargit la bande de PS et la déplace vers le rouge (602 nm). Après irradiation ionique, les nanoparticules sphériques se transforment en ellipsoïdes alignés suivant la direction du faisceau. La bande d’absorption se divise en deux bandes : transversale et longitudinale. La bande correspondante au petit axe (transversale) est décalée vers le bleu et celle correspondante au grand axe (longitudinale) est décalée vers le rouge indiquant l’élongation des particules d’Au dans la direction du faisceau. Le deuxième article est consacré au rôle crucial de la déformation plastique de la matrice et à l’importance de la mobilité des atomes métalliques dans la déformation anisotrope des nanoparticules d’Au dans les nanocomposites Au/SiO2. Nos mesures montrent qu'une valeur seuil de 2 keV/nm (dans le pouvoir d'arrêt électronique) est nécessaire pour la déformation des nanoparticules d'or. Cette valeur est proche de celle requise pour la déformation de la silice. La mobilité des atomes d’Au lors du passage d’ions est confirmée par le calcul de la température dans les traces ioniques. Le troisième papier traite la tentative de formation et de déformation des nanoparticules d’Au dans une matrice d’arséniure d’aluminium cristallin connue pour sa haute résistance à l’amorphisation et à la déformation sous bombardement ionique. Le résultat principal de ce dernier article confirme le rôle essentiel de la matrice. Il s'avère que la déformation anisotrope du matériau environnant est indispensable pour la déformation des nanoparticules d’or. Les résultats expérimentaux mentionnés ci-haut et les calculs de températures dans les traces ioniques nous ont permis de proposer le scénario de déformation anisotrope des nanoparticules d’Au dans le nanocomposite Au/SiO2 suivant: - Chaque ion traversant la silice fait fondre brièvement un cylindre étroit autour de sa trajectoire formant ainsi une trace latente. Ceci a été confirmé par la valeur seuil du pouvoir d’arrêt électronique. - L’effet cumulatif des impacts de plusieurs ions conduit à la croissance anisotrope de la silice qui se contracte dans la direction du faisceau et s’allonge dans la direction perpendiculaire. Le modèle de chevauchement des traces ioniques (overlap en anglais) a été utilisé pour valider ce phénomène. - La déformation de la silice génère des contraintes qui agissent sur les nanoparticules dans les plans perpendiculaires à la trajectoire de l’ion. Afin d’accommoder ces contraintes les nanoparticules d’Au se déforment dans la direction du faisceau. - La déformation de l’or se produit lorsqu’il est traversé par un ion induisant la fusion d’un cylindre autour de sa trajectoire. La mobilité des atomes d’or a été confirmée par le calcul de la température équivalente à l’énergie déposée dans le matériau par les ions incidents. Le scénario ci-haut est compatible avec nos données expérimentales obtenues dans le cas du nanocomposite Au/SiO2. Il est appuyé par le fait que les nanoparticules d’Au ne se déforment pas lorsqu’elles sont intégrées dans l’AlAs résistant à la déformation.

Photoluminescence studies on RF plasma-polymerized thin films

Conjugated polymers in the form of thin films play an important role in the field of materials science due to their interesting properties. Polymer thin films find extensive applications in the fabrication of devices, such as light emitting devices, rechargeable batteries, super capacitors, and are used as intermetallic dielectrics and EMI shieldings. Polymer thin films prepared by plasma-polymerization are highly cross-linked, pinhole free, and their permittivity lie in the ultra low k-regime. Electronic and photonic applications of plasma-polymerized thin films attracted the attention of various researchers. Modification of polymer thin films by swift heavy ions is well established and ion irradiation of polymers can induce irreversible changes in their structural, electrical, and optical properties. Polyaniline and polyfurfural thin films prepared by RF plasmapolymerization were irradiated with 92MeV silicon ions for various fluences of 1×1011 ions cm−2, 1×1012 ions cm−2, and 1×1013 ions cm−2. FTIR have been recorded on the pristine and silicon ion irradiated polymer thin films for structural evaluation. Photoluminescence (PL) spectra were recorded for RF plasma-polymerized thin film samples before and after irradiation. In this paper the effect of swift heavy ions on the structural and photoluminescence spectra of plasma-polymerized thin films are investigated.