Dans cette étude, des revêtements Cr-Si-N sont réalisés à l’aide d’un procédé hybride arc-magnétron. L’étude préliminaire de validation du procédé montre que, malgré une dureté moindre que celle des revêtements type Ti-Si-N, les revêtements type Cr-Si-N présentent une très bonne résistance à l’oxydation à haute température. Les revêtements à base de Cr2N sont moins durs que ceux à base de CrN. Quelle que soit la nature du nitrure synthétisé, l’enrichissement en silicium des couches conduit à une augmentation du paramètre de maille due à la substitution de l’azote par le silicium. L’enrichissement en silicium des couches à base de CrN conduit également à un maximum de dureté de 50-60 GPa pour des teneurs de l’ordre de 6-8 %at. Si. Quant aux revêtements à base de Cr2N, l’ajout de silicium entraîne une légère décroissance, sensiblement linéaire, de la dureté. La présence de silicium au sein des couches conduit à améliorer la stabilité de la dureté ainsi que la résistance à l’oxydation à haute température pour les deux types de revêtements. La croissance des grains, la déstabilisation de CrN en Cr2N et l’interdiffusion du fer et du silicium sont les paramètres principaux associés à la chute de dureté des revêtements à haute température / IIn this study, Cr-Si-N coatings are synthesized by an arc-magnetron hybrid process. In spite of a lower hardness of Cr-Si-N coatings in comparison with Ti-Si-N ones synthesised in a preliminary study performed to validate the deposition device, Cr-Si-N coatings present a higher resistance to high temperature oxidation. The Cr2N-based coatings are softer than those based on CrN. Si addition yields an increase of the lattice constant attributed to the substitution of N by Si. In CrN-based coatings, the maximum hardness of about 50-60 GPa is obtained for 6-8 at. % Si. For Cr2N-based coatings, the hardness decreases linearly with the Si content. Si addition improves both hardness stability and oxidation resistance at high temperature for both coatings. Grains growth, CrN destabilisation into Cr2N and interdiffusion of Fe and Si are the main parameters which govern the loss of hardness after annealing at high temperature of the coatings

The basic necessities to sustain life are – air, water and food. Although the harmful effects due to contaminated food or water are dangerous to life, these can be reduced/avoided by controlling the intake. Whereas, in case of air, the same amount of control cannot be exercised as there is very little, one can do in case of inhalation. Maximum damage to life is due to air contamination which can be detected and prevented by using gas sensors. The proper use of these sensors not only save lives, but also minimizes social and financial loss. The objective of this thesis work is to study and explore the use of p-type semiconducting material such as CuO, as a promising gas sensing material for organic compounds (VOCs), compatible with existing silicon fabrication technology. The Thesis consist of 7 chapters: Chapter 1 covers the general introduction about gas sensors, sensor parameters, criteria for the selection of sensing material, suitability of CuO as sensing material and a brief literature survey. The second chapter includes the selection of substrate, cleaning procedures and suitable deposition method. The deposition method used in the present thesis work is DC/RF magnetron sputtering. The reactive magnetron sputtering is employed during the deposition of CuO sensing films. It also includes basic introduction about some of the common material characterization techniques. This is followed by Chapter 3 which includes the optimization of sputtering process parameters such as applied power, working pressure, Ar-O2 ratio and substrate temperature for CuO sensing film and the effect of these on surface morphology. Information on the optimized sputtering parameters for electrode film (silver and gold) deposition has also been included in this chapter. In order to study the sensing behavior of the sensor, suitable testing set-up is necessary. This leads us to Chapter 4 that discusses the development of an in-house built sensor testing setup and its automization using MATLAB. The automated testing set-up facilitates off-time data plotting as well as real-time data plotting during the sensing process. To demonstrate the working of the set-up, some initial results obtained are also included in this chapter. After ascertaining the functioning of the automated gas sensor testing set-up, detailed study on the sensing behavior of nanostructured CuO films was performed. This information along with the necessary details is included in Chapter 5. The sensing response of nanostructured CuO films has been studied for different VOCs such as alcohol, toluene and benzene. The study carried out on the effect of different surface additives like multi-walled carbon nanotubes (MWNTs), gold or platinum on ethanol sensing has also been included in this chapter. During the use of MWNTs as surface additives, different concentrations of MWNTs – 0.01 mg, 0.05 mg and 0.1 mg have been dispersed on the CuO sensing film. The sample with lowest concentration of MWNTs exhibited highest sensitivity and lower response time. It is due to the fact that, higher concentrations of MWNTs do not result into uniform dispersion over the CuO films and cover the sensing film almost completely. Operating temperature is the most important factor affecting the performance of a gas sensor. In order to maintain the operating temperature for the portable sensor, the sensor is usually integrated with a heater. The chapter 6 deals with heater optimization including design, simulation and fabrication. In this chapter, microheater as well as macro-heaters were simulated and fabricated. The fabricated macro-heater is bonded with the sensor by eutectic bonding. One of the bonded samples was studied for its sensing response. The final chapter of the thesis deals with the conclusion of present research work and the possible further work on CuO gas sensor.

Émanant d’une collaboration entre le laboratoire CNRS du GREMI et le CEA le Ripault, l’objectif de cette thèse est de réaliser une étude exhaustive sur les conditions d’élaboration des électrodes de pile à combustible PEMFC par procédés plasma, dont l’enjeu est d’améliorer l’activité électro-catalytique du catalyseur employé qu’est le platine (Pt). A même quantité, la répartition du platine sur son support se révèle être un critère déterminant sur les performances délivrées par les PEMFCs. De cette observation, plusieurs axes de recherche ont été proposés et chacun d’entre eux a permis d’obtenir de nouveaux résultats. Le régime de pulvérisation magnétron à haute puissance pulsée (HiPIMS) est étudié dans le cas de dépôt de matériaux nobles pures (Pt, Au, Pd) et alliés (Pt5Pd95 et Pt50Pd50) et a permis de révéler une vapeur métallique ionisée conséquente lors du dépôt (10 % à 90 % selon l’élément). Les résultats obtenus sur le régime HiPIMS ont permis la modification de la distribution d’une faible quantité fixée de Pt (20 μg.cm−2) déposée sur la profondeur des couches de diffusion des gaz (GDL), améliorant incidemment les performances des PEMFCs (+80 % à 0.65 V, la tension à puissance nominale). Ce résultat est complété par ceux obtenus sur l’élaboration de catalyseur alliés, notamment sur la disposition du matériel catalytique au niveau de la structure des agrégats (+93 % à 0.65 V pour Pt5Pd95 en dépôts successifs). Une autre étude a permis d’étudier la modification de répartition du Pt en contact avec la membrane électrolyte. La surface de membrane échangeuses de proton est alors initialement structurée. Ces structurations de surface des membranes montrent une amélioration globale des performances PEMFCs pour les architectures CCB (Catalyst Coated Backing) et CCM (Catalyst Coated Membrane) d’un facteur 1.3 jusqu’à 12, respectivement. / From a collaboration between the CNRS laboratory of the CEA and GREMI Ripault, the objective of this thesis is to conduct a complete study on the conditions for producing electrodes of PEM fuel cell by plasma processes in order to improve the electro-catalytic activity of the catalyst (Pt). The platinum atoms on its support appears to be a one of the most important factor determining the performance delivered by the PEMFCs. From this observation, several lines of research have been proposed and each of them has yielded new results. The High Power Impulse Magnetron Sputtering (HiPIMS) process is studied in case of depositions of noble materials (Pt, Au, Pd) and alloy (Pt5Pd95 and Pt50Pd50) and revealed an ionized metal vapor consequent upon deposition (10 % to 90 % depending of the element). The results obtained on the HIPIMS process have allowed a change in the distribution of a small fixed amount of Pt (20 μg.cm−2) deposited on the depth of the gas diffusion layer (GDL), incidentally improving the performance of PEMFCs (+80% at 0.65 V, the voltage at rated power). This result is complemented by those obtained on the development of allied catalysts, especially with the arrangement of the catalytic material on the aggregates structure (+93 % at 0.65 V for Pt5Pd95 in successive deposits). In order to modify the Pt atoms distribution on the membrane support, another study has been realized. The surface of the proton exchange membrane has been structurated before the Pt deposition. Such structuration have shown an increase of the overall performance of PEMFCs in the case of CCB (Catalyst Coated Backing) and CCM (Catalyst Coated Membrane) architecture with an improvement factor of 1.3 up to 12, respectively.

The diploma thesis deals with the treatment of polycaprolactone (PCL) nanofibers. PCL fibers were subjected to the deposition of plasma amine polymers in a low pressure pulsed radiofrequency capacitively coupled discharge using cyclopropylamine monomer (CPA). Collagen as an extracellular matrix (ECM) protein was immobilized and cell proliferation on the modified nanofiber surface was monitored. Untreated PCL fibers were also subjected to the deposition of an antibacterial copper layer, and the fibers were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and energy dispersive spectroscopy (EDX).

The master’s thesis deals with the theory of thin film technology, especially creating these layers. The work includes the distribution of vacuum deposition techniques for physical (PVD) and chemical (CVD). The main aim is to create a theme in different ways of implementation by using magnetron sputtering device, and these motives evaluated in terms of the quality of sputtering.

This thesis is focused on the description of the method of reactive sputtering of thin films. Currently, there are many ways how to create thin films and there are many applications of thin films in various industrial sectors. In this paper at the first are listed the issue of thin films, followed by an overview of the deposition techniques and of the chemical analysis of deposited thin films. It also describes the four-point measurement method of sheet resistance, mechanical test of adhesion and optical properties. At the end of the theoretical part are described the material composition of the deposited films. The goal of the practical part is to optimize the deposition process of the mixed layer of indium tin oxide (In2O3: SnO2) and contribute to the overall understanding of the influence of annealing on the layer. There were created six series of samples with that applied layers. First, the work focused on examining of the influence of annealing on the throughput in the whole measuring range, and then comparing the series due to the transmittance in the visible light spectrum. Furthermore were compared the value of sheet resistance of unannealed and subsequently annealed samples.

Research on the characterisation and understanding of pulsed magnetron discharges used for the deposition of thin, especially dielectric, films has been carried out between 2003 and 2008 at Chemnitz University of Technology. This thesis is a collection and summary of the original research during this period. In the main part of the thesis, work published in peer-reviewed scientific papers is summarised and yet unpublished results are given in more detail. Different aspects highlighted in the publications are described in a general context of the characterisation of the pulsed discharges for the principal understanding. The cross-linking of the published results is addressed and where necessary extensions to the publications are given. The main part is organised in three sections. In the first one, basics of pulsed magnetron discharges, their application, and important questions are summarised. The second section describes general results and physics of the discharges that have been obtained during the research work. It also emphasises the successful development or modifications of experimental techniques for the time-resolved characterisation. The third section addresses the possibilities to modify and control the process by external parameters that are typically accessible during the application or required by it. An appendix to the thesis comprises selected published research work which is made available as reprints of the original publications. Other publications which are not included as reprints are referenced to in the main part. / Untersuchungen zur Charakterisierung und zum Verständnis gepulster Magnetronentladungen, die zur Abscheidung von dünnen Schichten, besonders von dielektrischen Schichten, verwendet werden, wurden in den Jahren 2003 bis 2008 an der Technischen Universität Chemnitz durchgeführt. Diese Arbeit ist eine Sammlung und Zusammenfassung von neuen Forschungsergebnissen, die in diesem Zeitraum gewonnen wurden. Im Hauptteil der Habilitationsschrift werden die Arbeiten, die in referierten wissenschaftlichen Zeitschriften erschienen sind, zusammengefasst und noch unveröffentlichte Ergebnisse ausführlicher beschrieben. Verschiedene Aspekte, die in den Veröffentlichungen herausgestrichen wurden, werden in einem allgemeinen Zusammenhang der Charakterisierung gepulster Entladungen für ein prinzipielles Verständnis dargestellt. Querverbindungen zwischen den veröffentlichten Ergebnissen werden herausgearbeitet und wo nötig werden Erweiterungen der Originalveröffentlichungen vorgenommen. Der Hauptteil der Habilitationsschrift ist in drei Abschnitte unterteilt. Im ersten Teil werden Grundzüge gepulster Entladungen, ihre Anwendung und wesentliche Fragestellungen zusammengefasst. Der zweite Abschnitt beschreibt allgemeine Ergebnisse und die Physik der Entladungen, die während der Forschungsarbeit herausgearbeitet wurden. Er stellt auch die erfolgreiche Neuentwicklung oder Modifikation von Messtechniken zur zeitaufgelösten Charakterisierung heraus. Der dritte Abschnitt befasst sich mit den Möglichkeiten, den Beschichtungsprozess durch externe Parameter, die typischerweise während der Prozessanwendung zugänglich oder auch erforderlich sind, zu modifizieren und zu steuern. Der Anhang der Schrift beinhaltet ausgewählte Originalveröffentlichungen, die in Form von Reprints zugänglich gemacht werden. Andere Veröffentlichungen, die nicht im Anhang enthalten sind, werden im Hauptteil zitiert.

Research on the characterisation and understanding of pulsed magnetron discharges used for the deposition of thin, especially dielectric, films has been carried out between 2003 and 2008 at Chemnitz University of Technology. This thesis is a collection and summary of the original research during this period. In the main part of the thesis, work published in peer-reviewed scientific papers is summarised and yet unpublished results are given in more detail. Different aspects highlighted in the publications are described in a general context of the characterisation of the pulsed discharges for the principal understanding. The cross-linking of the published results is addressed and where necessary extensions to the publications are given. The main part is organised in three sections. In the first one, basics of pulsed magnetron discharges, their application, and important questions are summarised. The second section describes general results and physics of the discharges that have been obtained during the research work. It also emphasises the successful development or modifications of experimental techniques for the time-resolved characterisation. The third section addresses the possibilities to modify and control the process by external parameters that are typically accessible during the application or required by it. An appendix to the thesis comprises selected published research work which is made available as reprints of the original publications. Other publications which are not included as reprints are referenced to in the main part. / Untersuchungen zur Charakterisierung und zum Verständnis gepulster Magnetronentladungen, die zur Abscheidung von dünnen Schichten, besonders von dielektrischen Schichten, verwendet werden, wurden in den Jahren 2003 bis 2008 an der Technischen Universität Chemnitz durchgeführt. Diese Arbeit ist eine Sammlung und Zusammenfassung von neuen Forschungsergebnissen, die in diesem Zeitraum gewonnen wurden. Im Hauptteil der Habilitationsschrift werden die Arbeiten, die in referierten wissenschaftlichen Zeitschriften erschienen sind, zusammengefasst und noch unveröffentlichte Ergebnisse ausführlicher beschrieben. Verschiedene Aspekte, die in den Veröffentlichungen herausgestrichen wurden, werden in einem allgemeinen Zusammenhang der Charakterisierung gepulster Entladungen für ein prinzipielles Verständnis dargestellt. Querverbindungen zwischen den veröffentlichten Ergebnissen werden herausgearbeitet und wo nötig werden Erweiterungen der Originalveröffentlichungen vorgenommen. Der Hauptteil der Habilitationsschrift ist in drei Abschnitte unterteilt. Im ersten Teil werden Grundzüge gepulster Entladungen, ihre Anwendung und wesentliche Fragestellungen zusammengefasst. Der zweite Abschnitt beschreibt allgemeine Ergebnisse und die Physik der Entladungen, die während der Forschungsarbeit herausgearbeitet wurden. Er stellt auch die erfolgreiche Neuentwicklung oder Modifikation von Messtechniken zur zeitaufgelösten Charakterisierung heraus. Der dritte Abschnitt befasst sich mit den Möglichkeiten, den Beschichtungsprozess durch externe Parameter, die typischerweise während der Prozessanwendung zugänglich oder auch erforderlich sind, zu modifizieren und zu steuern. Der Anhang der Schrift beinhaltet ausgewählte Originalveröffentlichungen, die in Form von Reprints zugänglich gemacht werden. Andere Veröffentlichungen, die nicht im Anhang enthalten sind, werden im Hauptteil zitiert.

The aim of the presented work was to deposit cubic boron nitride thin films by magnetron sputtering under simultaneous stress relaxation by ion implantation. An in situ instrument based on laser deflectometry on cantilever structures and in situ ellipsometry, was used for in situ stress measurements. The characteristic evolution of the instantaneous stress during the layered growth of cBN films observed in IBAD experiments, could be reproduced for magnetron sputter deposition. To achieve simultaneous stress relaxation by ion implantation, a complex bipolar pulsed substrate bias source was constructed. This power supply enables the growth of cBN thin films under low energy ion irradiation (up to 200 eV) and, for the first time, the simultaneous implantation of ions with an energy of up to 8 keV during high voltage pulses. It was demonstrated that the instantaneous stress in cBN thin films can be released down to -1.1 GPa by simultaneous ion bombardment during the high voltage pulses. A simultaneous stress relaxation during growth is possible in the total investigated ion energy range between 2.5 and 8 keV. These are the lowest ion energies reported for the stress relaxation in cBN. Since such a substrate bias power supply is easy to integrate in existing process lines, this result is important for industrial deposition of thin films, not only for cubic boron nitride films. It was found that the amount of stress relaxation depends on the number of atomic displacements (displacements per atom: dpa) that are induced by the high energy ion bombardment and is therefore dependent on the ion energy and the high energy ion flux. In practise, this means that the stress relaxation is controlled by the product of the pulse voltage and the pulse duty cycle or frequency. The cantilever bending measurements were complemented on microscopic scale by x-ray diffraction (XRD). The analysis of the cBN (111) lattice distances revealed a pronounced biaxial compressive state of stress in a non-relaxed cBN film with d(111) being larger in out-of-plane than in in-plane direction. Post deposition annealing at 900 ° C of a sample with an ion induced damage of 1.2 dpa, resulted in a complete relaxation of the lattice with equal in-plane and out-of-plane lattice parameters. In the case of medium-energy ion bombardment, the in-plane and out-of-plane lattice parameters approach the value of the annealed sample with increasing ion damage. This is a clear evidence for stress relaxation within the cBN lattice. The stability of cBN under ion bombardment was investigated by IR spectroscopy and XRD. The crystalline cBN was found to be very stable against ion irradiation. However a short-range ordered, sp3/sp2 - mixed phase may exist in the films, which could be preferably converted to a sp2 -phase at high damage values. From the analysis of the near surface region by XANES, it can be concluded the stress relaxation by the energetic ion bombardment is less at the surface than in the bulk film. This is explained with the dynamic profile of the ion induced damage, that reaches the stationary bulk value in 15-20 nm depth, whereas it is decreasing towards the surface. This fits with the results that the stress relaxation is dependent on the amount of ion induced damage. Comparing the results from substrate curvature measurement, XRD, XANES, and IR spectroscopy possible mechanisms of stress relaxation are discussed. Concluding the results, it can be stated that using simultaneous ion implantation for stress relaxation during the deposition it is possible to produce BN films with a high amount of the cubic phase and with very low residual stress.

No description available.