Cette thèse s'inscrit dans le cadre du développement des technologies CMOS 32/28nm chez STMicroelectronics. Elle porte sur l'étude d'empilements de grille métal/diélectrique high-k élaborés selon une stratégie d'intégration Gate First, où le couple TiN/HfSiON est introduit avec une couche interfaciale SiON et une encapsulation de la grille TiN par du polysilicium. Cette étude s'est principalement focalisée sur l'analyse des interactions entre les différentes couches constituant les empilements, en particulier des additifs lanthane et aluminium, employés pour moduler la tension de seuil Vth des transistors NMOS et PMOS respectivement. Les analyses physico-chimiques réalisées au cours de ces travaux ont permis de mettre en évidence la diffusion en profondeur des éléments La et Al à travers le diélectrique de grille HfSiON sous l'effet du recuit d'activation des dopants à 1065°C. Les résultats obtenus ont montré que ce processus de diffusion entraine une réaction du lanthane et de l'aluminium avec la couche interfaciale de SiON pour former un silicate stable La(ou Al)SiO au profit de la couche de SiON. L'analyse des propriétés électrique des structures MOS a permis de révéler que la présence d'atomes La ou Al proximité de l'interface HfSiON/SiON conduit à la présence d'un dipôle généré à cette interface, qui a pour effet de décaler le travail de sortie effectif de la grille métallique. / This thesis is part of the development of CMOS technologies 32/28nm STMicroelectronics. It focuses on the study of stacks of metal / high-k dielectric prepared by an integration strategy Gate First , where the couple TiN / HfSiON gate is introduced with an interfacial layer SiON and encapsulation of TiN gate polysilicon by . The study was mainly focused on the analysis of interactions between the various layers forming the stacks , in particular lanthanum and aluminum additives , used for modulating the threshold voltage Vth of the PMOS and NMOS transistors respectively . The physico-chemical analyzes in this work helped to highlight the depth distribution of the elements La and Al through the HfSiON gate dielectric under the influence of dopant activation annealing at 1065 ° C. The results obtained showed that this diffusion process causes a reaction of lanthanum and aluminum with the interfacial layer of SiON to form a stable silicate La ( or Al ) SiO benefit of the SiON layer . The analysis of electrical properties of MOS structures revealed that the presence of the atoms near the Al or HfSiON / SiON interface leads to the presence of a dipole generated at this interface , which has the effect of shifting actual output work of the metal gate.

Neste trabalho pós de CaCu3Ti4O12 foram preparados por reação em estado sólido e por técnicas de solução: complexação de cátions e coprecipitação dos oxalatos. Foram realizados estudos de formação de fase, densificação e propriedades dielétricas das cerâmicas sinterizadas. Para efeito comparativo, ta is propriedades foram determinadas em amostras puras e contendo dissilicato de lítio (LSO) e fluoreto de lítio (LiF) como aditivos de sinterização. O principal objetivo foi verificar o efeito do uso dos diferentes aditivos de sinterização na microestrutura, densificação e propriedades dielétricas do CCTO. Os principais resultados revelaram que pós preparados por técnicas de solução apresentam fase única após calcinação em condições selecionadas. Foi verificado que os aditivos influenciam na densificação, possibilitando obter cerâmicas com 95% da densidade teórica do CCTO a 1025°C. As amostras preparadas por diferentes técnicas apresentam propriedades similares, com exceção das características microestruturais. A permissividade elétrica determinada à temperatura ambiente é da ordem de 104 independentemente do método de síntese. As menores perdas dielétricas foram obtidas para amostras contendo LiF como aditivo de sinterização. / In this work the effects of the method of synthesis and sintering additives on the microstructure and dielectric properties of CCTO were investigated. Powder mixtures were prepared by the cation complexation and coprecipitation methods, and by mixing of the starting oxides, for comparison purposes. Lithium dissilicate (LSO) and lithium fluoride (LiF) were used as sintering aids. The main results revealed that powders prepared by solution techniques have single phase after calcination at selected conditions. The additives were found to influence the densification allowing for obtaining high relative density (≥ 95%) at 1025ºC. Specimens prepared by different methods show similar properties except on microstructure features. The electric permittivity is of the order of 104 for all investigated specimens independent on the method of synthesis. The dielectric loss is found to be lower for specimens prepared with LiF as sintering aid.

Abstract This work presents a method for the fabrication of Li₂MoO₄ ceramics at room-temperature based on utilizing a small amount of water with Li₂MoO₄ powder. The densification of the ceramic takes place during pressing. Thus the shape and size of the final ceramic compact can easily be managed by controlling the mould dimensions and the amount of material. Post-processing at 120 °C is applied to remove residual water from the compact. This post-processing temperature can be chosen to be suitable to the other materials integrated, such as the substrate or electrodes, as long as the post-processing time is adequate to remove the residual water. The dielectric properties (relative permittivity of 5.1 and a loss tangent value of 0.00035 at 9.6 GHz) after optimization of the powder particle size, sample pressing pressure, and post-processing time were similar to those achieved for Li₂MoO₄ ceramics fabricated by sintering at 540 °C. The dielectric properties of Li₂MoO₄ ceramics were also modified using composite methods. For example, an addition of 10 volume-% of BaTiO₃ increased the relative permittivity from 6.4 to 9.7 and the loss tangent value from 0.0006 to 0.011 at 1 GHz. To investigate the thermal dependence of the permittivity, different amounts of rutile TiO₂ were incorporated into a Li₂MoO₄ ceramic matrix fabricated with the method described in this work. As the amount of TiO₂ increased from 10 to 30 volume-%, the thermal coefficient of permittivity decreased from 180 ppm/°C to -170 ppm/°C. The low processing temperature made the fabrication approach introduced here feasible for silver electrode integration without the formation of extra phases, which were observed in sintered samples with similar compositions in another study. A patch antenna was realized utilizing a Li₂MoO₄ ceramic disk fabricated by the room-temperature method. The antenna operating at ~4 GHz showed reasonably good performance. A relative humidity of 80% lowered the resonant frequency by 3.25% from the initial value, and reduced the total and radiation efficiencies of the antenna by ~2 dB. The changes were slowly reversible. Use of a silicone conformal coating reduced the shift of the resonant frequency to 1.26% from the initial value and also reduced the effect on efficiencies to ~1 dB. The use of the coating also speeded up the reversibility of the changes when the humidity was decreased. / Tiivistelmä Tässä työssä esitellään menetelmä, jolla Li₂MoO₄-keraameja voidaan valmistaa huoneenlämpötilassa. Menetelmä hyödyntää pientä määrää Li₂MoO₄-vesiliuosta ja sen kiteytymistä. Keraami tiivistyy kappaletta puristettaessa, joten sen koko ja muoto ovat sama kuin muotilla riippuen vain keraamin määrästä. Kappaleeseen jäänyt vesi poistetaan lämpökäsittelyllä yleensä 120 celsiusasteessa. Jälkikäsittelylämpötila voidaan valita muiden integroitavien materiaalien mukaan, kuten alusta- tai elektrodimateriaalin, kunhan jälkikäsittelyaikaa muokataan vastaavasti, jotta kaikki vesi poistuu. Optimoimalla Li₂MoO₄-jauheen partikkelikokoa, puristuspainetta ja jälkikäsittelyaikaa saavutettiin samankaltaiset dielektriset ominaisuudet taajuudella 9,6 GHz (suhteellinen permittiivisyys 5,1 ja häviötangentti 0,00035) kuin Li₂MoO₄-keraameilla, jotka on sintrattu 540 celsiusasteessa. Li₂MoO₄-keraamien dielektrisiä ominaisuuksia muokattiin myös lisäaineilla. Esimerkiksi 10 tilavuus-% BaTiO₃-jauhetta kasvatti suhteellista permittiivisyyttä taajuudella 1 GHz arvosta 6,4 arvoon 9,7 ja häviötangenttia arvosta 0,0006 arvoon 0,011. Myös eri määriä TiO₂-jauhetta (rutiili) lisättiin Li₂MoO₄-matriisiin permittiivisyyden lämpötilariippuvuuden tutkimiseksi. TiO₂-jauheen määrän kasvaessa 10 tilavuusprosentista 30 tilavuusprosenttiin laski permittiivisyyden lämpötilariippuvuus arvosta 180 ppm/°C arvoon -170 ppm/°C. Matalan käsittelylämpötilan ansiosta työssä esitelty valmistusmenetelmä soveltui käytettäväksi hopeaelektrodien kanssa. Aiemman tutkimuksen mukaan nämä komposiittimateriaalit muodostivat ei-toivottuja faaseja sintrattaessa hopean kanssa. Menetelmällä valmistettua Li₂MoO₄-keraamikiekkoa käytettiin mikroliuska-antennin valmistuksessa. Taajuudella 4 GHz toimivan antennin suorituskyky oli suunnitellun kaltainen. 80 prosentin suhteellinen ilmankosteus laski resonanssitaajuutta 3,25 % alkuperäisestä arvosta ja vähensi antennin kokonais- ja säteilytehokkuutta noin 2 dB. Muutokset palautuivat hitaasti. Silikonisuojalakan käyttö vähensi taajuuden laskua 1,26 prosenttiin alkuperäisestä arvosta ja tehokkuudet laskivat vain noin 1 dB. Suojalakan käyttö nopeutti muutosten palautuvuutta ilmankosteuden laskiessa.

Les travaux de thèse sont axés sur le développement de nouvelles techniques de caractérisation basées sur la variation de la réponse d’un résonateur, réponse modifiée par les propriétés diélectriques ou métalliques d’un matériau sous test. La première méthode utilise la microscopie microonde en champ proche pour la caractérisation résonante et non destructive de matériaux diélectriques dans la bande ISM (2,45 GHz).Celle-ci permet de déterminer les propriétés électromagnétiques (permittivité relative, tangente de pertes) des échantillons diélectriques solides de faible volumepar rapport à la longueur d’onde de mesure, et cela sans aucun traitement préalable. La connaissance de ces paramètres est essentielle pour fournir des informations critiques nécessaires pour la conception, la modélisation et la fabrication de circuits microondes. Une deuxième approche vise l’étude et le développement d’un nouveau capteur à base de céramique, économique, sensible, et pouvant s’intégrer dans un système sans fil pour la détection et la caractérisation du degré de corrosion. Ces nouveaux capteurs fournissent des informations sur l'état de l'équipement opérationnel d’une structure cible afin d'assurer la sécurité de cette dernière et par conséquent celle de leurs utilisateurs. Pour ces deux axes d’études, des simulations sur des logiciels de calcul électromagnétique ont été effectuées puis validées par des mesures expérimentales. / This Ph. D thesis focuses on the development of new characterization techniques of dielectric and metallic materials in the ISM band (2.45 GHz). The first proposed method is based on non-destructive near field microave microscopy. This technique allows the determination of the electromagnetic properties (permittivity, loss tangent) of solid dielectric samples of small volume without prior treatment. The knowledge of these parameters is essential to provide critical information needed for accurately designing, modeling and manufacturing microwave circuits. A second study focuses on the development of a new, ceramic based, sensitive and economic sensor that can be integrated in a wireless system for the detection and characterization of the corrosion evolution. These new sensors provide information about the state of the operational equipment of the target structure in order to ensure the safety of these structures and therefore that of their users. In these two studies, simulations on electromagnetic calculation software have been performed and validated by experimental measurements.

Depuis les années 1960, les scientifiques se sont intéressés à l’étude d’effets biologiques provoqués par des champs électromagnétiques impulsionnels. Les premiers effets ont été observés avec des impulsions dont la durée va de quelques microsecondes à quelques millisecondes. Ce phénomène, appelé électroporation, est de nos jours utilisé dans des thérapies anticancéreuses appelées électrochimiothérapies. Les études en laboratoires avec des impulsions ont continuées, mais avec des impulsions de plus en plus courtes, notamment des impulsions pouvant atteindre une durée de quelques centaines de picosecondes avec des amplitudes de forts niveaux (100MV/m). Ces études sont encore émergentes et nécessitent d’être poursuivies, mais pour cela, il est nécessaire de concevoir des moyens d’expérimentations électromagnétiques fiables. Ce travail de thèse consistait à concevoir deux applicateurs de champ électrique : un applicateur in vitro, dans le but d’illuminer des cellules contenues dans des éprouvettes et un applicateur in vivo dans le but de prévoir de futures thérapies non invasives pour le patient. Pour l’applicateur in vitro, les différents résultats obtenus en simulations et expérimentalement sont très encourageant et montrent qu’il est déjà possible d’effectuer des expérimentations biologiques avec. Pour l’applicateur in vivo, qui s’agit de l’antenne PSIRA initialement développée par C. E. Baum, plusieurs problématiques ont été soulevées. Tout d’abord, il a été montré que les tissus biologiques tels que la peau où les muscles ont des permittivités relatives élevées et de fortes pertes pour des fréquences de l’ordre de quelques GHz et au-delà. Afin de maximiser la pénétration de champ électrique à l’intérieur de ces tissus, il a été décidé d’immerger l’antenne dans un milieu de forte permittivité, tels que la glycérine et l’eau. Ces liquides possèdent également des pertes diélectriques non négligeables. Ces pertes ont un fort impact négatif sur les performances de l’antenne. Pour rendre ce système opérationnel plusieurs modifications doivent être opérées, notamment en changeant le milieu d’immersion par un milieu sans pertes. / Since the years 1960, scientists have been interested to the study of biologic effects caused by pulsed electrical fields. The first effects were obtained with microseconds pulses and milliseconds pulses. This phenomenon has been called electroporation and it’s used in anticancerous therapies called electrochimiotherapies. Laboratory studies are continuing, but with shorter pulses like high level subnanoseconds pulses (100MV/m). These studies are emerging and must be pursued, but it’s necessary to design reliable electromagnetic systems. The goal of this thesis was to design two electrical field applicators: an in vitro applicator, to illuminate biologic cells contained in test tube and an in vivo applicator to predict future non invasive therapies. For the in vitro applicator, simulations and experimental results are very encouraging and biological experimentations would be possible with this system. For the applicator in vivo, which is the PSIRA antenna designed par C. E. Baum, many problems are highlighted. First, biological tissues like skin and muscle have high permittivity and high dielectric losses with frequencies in the order of GHz and behind. To maximize electric field penetration in these backgrounds it was decided to submerge the antenna in high permittivity background too, like glycerin and water. These liquids have high dielectric losses which have a strong negative impact on the antenna performances. To make this system operational, some modifications must be done, like changing the actual background with a no losses background.

Abstract The dielectric properties of material are of importance in various industrial and scientific applications of measurement technology. These properties are usually measured by microwave sensors, methods that provide an average result of the entire sample volume. However, the need to know the dielectric properties of single particles has increased in various segments. Dielectrophoresis (DEP) as a method provides a way to determine dielectric properties, such as permittivity and conductivity, of single particles with good precision by using a sufficiently simple system. In this thesis the DEP platform consists of four electrodes with hyperbolic edge geometry. Geometry produces a linear electric field gradient which leads to a constant DEP force in the active region and ensures fairly straightforward determination of particle properties by means of their DEP mobility. Particle mobility is dependent on particle size, the slope of the electric field gradient, the conductivity of the carrier fluid and the frequency of the electric field. For this thesis has been studied particle characterization on a 2D platform, particle 3D behavior, simultaneous multiphenomena observation and the applicability of transparent indium-tin-oxide (ITO) electrode material to DEP platforms. Experiments were made with polystyrene particles, using carrier fluids of varying conductivity. Electrode transparency enabled holographic 3D imaging and thus also the observation of particle behavior in the depth direction. This 3D imaging revealed the restricted working distance from the electrode plane, as well as the mobility of particles in the depth dimension under the DEP force. It was also observed that there was only a marginal difference between 3D mobility and 2D mobility inside the active region. The dielectric properties of the polystyrene particles were determined and found to differ from those of solid polystyrene, and thus the properties of the carrier fluid have a distinctive effect on particle properties. The measurement achieved good precision in a single particle measurement and thus the total particle consistency could be very low. The main restrictions of the DEP method are the limited working distance and restricted range of particle sizes: based on the results of this thesis, with a fixed size platform the particle size may not vary by more than tenfold. / Tiivistelmä Materiaalin dielektriset ominaisuudet ovat merkittäviä monissa teollisissa sekä tieteellisissä mittausteknisissä sovelluksissa. Yleensä nämä ominaisuudet mitataan mikroaaltosensoreilla, joilla mitataan näytetilavuuden keskiarvo. Tarve tietää yksittäisen partikkelin dielektriset ominaisuudet on kuitenkin lisääntynyt useilla segmenteillä. Dielektroforeesi (DEP) on menetelmä, jolla voidaan toistettavasti mitata yksittäisen partikkelin permittiivisyys ja johtavuus suhteellisen yksinkertaisella mittaussysteemillä. Tässä työssä DEP-alusta koostuu neljästä elektrodista, joilla on hyperbelin muotoinen elektrodin reunan muoto. Geometria tuottaa lineaarisen sähkökentän gradientin, mikä johtaa vakio DEP-voimaan alustan aktiivisella alueella. Niinpä partikkelin ominaisuuksien määrittely niiden liikkuvuuden perusteellä on suoraviivaista. Liikkuvuus on riippuvainen partikkelin koosta, sähkökentän gradientin kulmakertoimesta, kantajaliuoksen johtavuudesta sekä käytetyn sähkökentän taajuudesta. Työssä on tutkittu partikkelin karakterisointia 2D-alustalla, partikkelin 3D-käyttäytymistä, samanaikaista moni-ilmiötarkkailua sekä indium-tina-oksidi (ITO) elektrodimateriaalin soveltuvuutta DEP-alustoihin. Kokeet tehtiin polystyreenipartikkeleilla käyttäen eri johtavuuksisia kaliumkloridi-kantajaliuoksia. Elektrodien läpinäkyvyys mahdollisti holografisen 3D-kuvantamisen, jonka avulla havaittiin alustan rajallinen toimintaetäisyys sekä partikkelin syvyyssuuntainen liike DEP-voiman vaikutuksesta. Kuitenkin 3D- ja 2D-liikkeen välillä havaittiin vain vähäinen ero. Määritellyt partikkelin dielektriset ominaisuudet eroavat kiinteän polystyreenin arvoista, jolloin kantajaliuoksen ominaisuuksilla on merkittävä vaikutus määriteltyihin partikkelin ominaisuuksiin. Mittauksilla saavutettiin hyvä toistettavuus jopa yksittäisen partikkelin mittauksista, niinpä näytteen partikkelipitoisuus voi olla erittäin pieni. DEP-menetelmän merkittävimpiä rajoitteita ovat rajallinen toimintaetäisyys sekä rajallinen partikkelikoon variaatio, mikä voi olla yhdellä DEP-alustalla noin kymmenkertainen.

This master's thesis focuses on composite systems based on varnish combined with different filler ratios of micronized mica. The aim is to analyse impact of the filler on dielectric properties of the varnish, i.e. relative permittivity and loss factor as functions of frequency as well as charging and discharging currents as functions of time. Dielectric mixture formulas are applied on relative permittivity values. Calculated and measured values are compared.

This work deals with measurement capacity and dissipation factor of capacitor with real dielectric in frequency range 20 Hz to 30 MHz. Liquid and solid dielectrics are measured by LCR instruments and by test fixtures, both from company Agilent. Relative permittivity and loss number are calculated for different instruments settings. The general aim is to specify the influence of parameters as frequency, voltage, integration time and thickness of material on the uncertainties of primary and secondary quantities for measurement.

The labor discusses experimental verification of the dielectric properties of pulsed stress slot insulation Isonom NMN. During the pulse stress is investigated in particular component of a complex permittivity depending on frequency and temperature during the electrical stress in the form of pulses of different intensities of electric field supplied.

The dissertation thesis submitted deals with the study of dielectric properties of epoxy nanocomposites containing nanoparticles of inorganic oxides. These nanocomposites may have a promising technologic application for electric insulations in view of their higher resistance against partial discharges; yet information about their behavior in the course of ageing is not available. If at least a partial mass replacement of the currently used epoxy insulation with nanocomposite-based insulations is due to occur, the knowledge of the changes of their dielectric properties in the course of their operation will become indispensable. Within the framework of this dissertation, ensembles of samples of epoxy resins without fillers and with Al2O3, WO3, TiO2 and SiO2 fillers in the form of nanopowders, in concentrations up to 12 wt %, have been prepared. These ensembles have been measured prior to ageing and exposed to long-time (up to 5000 hours) ageing at increased temperatures 200, 250 and 300 °C and in a few cases also at 330 and 360 °C. Samples were measured in the course of ageing roughly in a logarithmic time series after 1, 2, 5, 10, 20, 50, 100, 200, 500, 1000, 2000 and 5000 hours. The measured quantities included complex permittivity , internal resistivity i and loss factor tan at temperatures ranging from -153 °C to +167 °C and in the frequency range 10-2 – 106 Hz. Changes in nanocomposites have been investigated using not just dielectric spectroscopy measurements, but other methods, too, namely Fourier-transformed infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The experiments have proved that materials with different fillers respond to the same concentrations of various fillers in different ways. The addition of nanoparticles, without the addition of microparticles, at a relatively low concentration (max 12 wt %), was not sufficient for reaching fundamental changes in dielectric spectrum; only smaller changes of dielectric strength and shifts of relaxations and in relaxation maps have occurred. Out of more pronounced changes, increase of concentration of the SiO2 filler in the epoxy matrix brings about a decrease of electrical conductivity in the resulting nanocomposite. The TiO2 filler had a different impact. Different TiO2 concentrations make their marked appearance in the region between the relaxation and relaxation. The TiO2-filled nanocomposites do not exhibit the unambiguous dependence of electrical conductivity on nanofiller concentration. It can be concluded that the mere addition of nanoparticles, without the addition of established microparticles, does not change the dielectric spectrum substantially. Generally, a serious problem was the production of the nanocomposite with a uniform distribution of nanoparticles. The preparation of such a nanocomposite was not trivial and, in industrial applications, this issue will require a specific focus, so as to avoid the formation of undesirable aggregates. Within the framework of this research, a methodology for the production of an epoxy nanocomposite has been developed with as high as possible uniformity of nanoparticle distribution.