Photo-thermal Processing of Semiconductor Fibers and Thin Films

Furnace processing and rapid thermal processing (RTP) have been an integral part of several processing steps in semiconductor manufacturing. The performance of RTP techniques can be improved many times by exploiting quantum photo-effects of UV and vacuum ultraviolet (VUV) photons in thermal processing and this technique is known as rapid photo-thermal processing (RPP). As compared to furnace processing and RTP, RPP provides higher diffusion coefficient, lower stress and lower microscopic defects. In this work, a custom designed automated photo assisted processing system was built from individual parts and an incoherent light source. This photo-assisted processing system is used to anneal silica clad silicon fibers and deposit thin-films. To the best of our knowledge, incoherent light source based rapid photo-thermal processing (RPP) was used for the first time to anneal glass-clad silicon core optical fibers. X-ray diffraction examination, Raman spectroscopy and electrical measurements showed a considerable enhancement of structural and crystalline properties of RPP treated silicon fibers. Photons in UV and vacuum ultraviolet (VUV) regions play a very important role in improving the bulk and carrier transport properties of RPP-treated silicon optical fibers, and the resultant annealing permits a path forward to in situ enhancement of the structure and properties of these new crystalline core optical fibers. To explore further applications of RPP, thin-films of Calcium Copper Titanate (CaCu3Ti4O12) or CCTO and Copper (I) Oxide (Cu2O) were also deposited using photo-assisted metal-organic chemical vapor deposition (MOCVD) on Si/SiO2 and n-Si substrate respectively. CCTO is one of the most researched giant dielectric constant materials in recent years. The given photo-assisted MOCVD approach provided polycrystalline CCTO growth on a SiO2 surface with grain sizes as large as 410 nm. Copper (I) oxide (Cu2O) is a direct band gap semiconductor with p-type conductivity and is a potential candidate for multi-junction solar cells. X-ray diffraction study revealed a preferred orientation, as (200) oriented crystals of Cu2O are grown on both substrates. Also, electrical characterization of Cu2O/n-Si devices showed the lowest saturation current density of 1.5x10-12 A/cm2 at zero bias. As a result, photo-assisted thermal processing has the potential of making the process more effective with enhanced device performance

Agenda: Second International Workshop on Thin Films for Electronics, Electro-Optics, Energy and Sensors (TFE3S)

University of Dayton’s Center of Excellence for Thin Film Research and Surface Engineering (CETRASE) is delighted to organize its second international workshop at the University of Dayton’s Research Institute (UDRI) campus in Dayton, Ohio, USA. The purpose of the new workshop is to exchange technical knowledge and boost technical and educational collaboration activities within the thin film research community through our CETRASE and the UDRI

Characterization of Nanomaterials for Thermal Management of Electronics

Recently, there has been a growing interest in flexible electronic devices as they are light, highly flexible, robust, and use less expensive substrate materials. Such devices are affected by thermal management issues that can reduce the device’s performance and reliability. Therefore, this work is focused on the study of the thermal properties of nanomaterials and the methods to address such issues. The goal is to enhance the effective thermal conductivity by adding nanomaterials to the polymer matrix or by structural modification of nanomaterials. The thermal conductivity of copper nanowire/polydimethylsiloxane and copper nanowire/polyurethane composites were measured and showed more than threefold enhancement compared to the thermal conductivity values of the neat polymers. Furthermore, identical heat sources were used on the neat polymer as well as the composite samples, and the resulting thermal images were taken, which showed that the resulting hot spot was significantly less severe for the composite sample, demonstrating the potential of copper nanowire/polymer composite as a substrate for flexible electronics with better heat spreading capability. In addition, the thermal properties of cellulose nanocrystals-poly (vinyl alcohol) composite films with different structural configurations of cellulose nanocrystals (such as isotropic and anisotropic configurations) were investigated as an alternative to commonly used petroleum-based materials for potential application in the thermal management of flexible electronic devices. Also, the in-plane thermal conductivity of the anisotropic composite film was as high as ~ 3.45 W m-1 K-1 in the chain direction. Moreover, the composite films showed ~ 4-14 fold higher in-plane thermal conductivity than most polymeric materials used as substrates for flexible electronics. A high degree of cellulose nanocrystal orientation and the inclusion of poly (vinyl alcohol) were the reasons for such improvements. In addition, thermal images showed that the cellulose nanocrystals-poly (vinyl alcohol) composite films had better heat dissipation capability compared to the neat poly (vinyl alcohol) films, indicating its potential application for flexible electronic devices. In another study, thermal properties of nanodiamond films obtained through a solution-based directed covalent assembly were studied as a low-cost and greener alternative to the nanodiamond films grown via chemical vapor deposition method for thermal management of electronics. The results obtained showed cross-plane thermal conductivity as high as 3.50 +/- 0.54 W m-1 K-1 for nanodiamond film of 139.1 +/- 19.5 nm thick. Such a low cross-plane thermal conductivity value can be attributed to higher porosity and poor interface quality compared to that of the nanodiamond films grown via chemical vapor deposition method. Hence, there is still more room for improvement for such nanodiamond films. The above chapters were focused on the study of the thermal properties of various types of nanomaterials for thermal management of electronic devices. In the next chapter, a technique for the fabrication of a device, that is capable of performing characterization nanomaterials was presented. In this work, suspended beam microdevices for electrothermal characterization of nanomaterials were fabricated through a standard photolithography technique that is less time-consuming, less expensive and much simpler than the methods used by other research groups in the past. The agreement of the measured in-plane thermal conductivity of the suspended central silicon nitride bare bridge with the literature validated the microdevice, setup, and the experimental procedure. Furthermore, these microdevices can be used to measure other important thermoelectric properties of nanomaterials such as the Seebeck coefficient, electrical conductivity, and thermoelectric figure of merit

Integration of pentacene-based thin film transistors via photolithography for low and high voltage applications

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2012.Cataloged from PDF version of thesis.Includes bibliographical references.An organic thin film transistor (OTFT) technology platform has been developed for flexible integrated circuits applications. OTFT performance is tuned by engineering the dielectric constant of the gate insulator and the insulator/semiconductor interface. Full integration is enabled by a low temperature photolithographic patterning process that is compatible with flexible substrates. Devices and circuits for low voltage [ ... ] and high [ ... ] voltage applications are demonstrated. Both the low and high voltage OTFTs are made from the same set of materials and processes. Low voltage operation is achieved by the use of BZN (Bi1.5Zn1Nb1.5O7) which maintains a high dielectric constant (40) at low processing temperatures. With surface treatments and back channel encapsulation for patterning, OTFTs having two distinct threshold voltages (VT > 0 V and VT 300 V) with a lower controlling voltage (VG <20 V). An offset drain/source structure enables high voltage operation. A high voltage organic thin film transistor (HVOTFT) has been fabricated. As organic semiconductors and related devices are known for their compatibility with flexible media and/or large areas, the HVOTFT would be suitable for high voltage switching on such media. Gate insulator engineering is used to tune the threshold voltage and drain current in these devices. HVOTFTs of channel length 10 [mu]m and offset length 20 [mu]m suffer from non-saturating current behavior that is similar to the short channel effects reported in short channel OTFTs and Si-based MOSFETs, and a metastable charge injection similar to that reported in a-Si based HVTFTs.by Melissa Alyson Smith.Ph.D

Development of elastomeric composite materials for the realization of piezoresistive sensors

Piezoresistive materials, able to sense geometrical deformation through variations of the electrical resistance, attracted an increasing interest in the scientific and industrial comparts during the last forty years, which increased significantly with the advent of nanostructured carbon-based conductive materials. These light, highly conductive and easy-to-obtain fillers have broadened the spectrum of materials that had been used up to that time, opening up the possibility of greater development of multifunctional materials. In particular, the carbonaceous fillers, homogeneously dispersed within a polymer matrix, immediately represented a valid alternative to the metals used in the field of piezoresistive systems. In the context of polymer nanocomposites and piezoresistive materials, a significant challenge for the scientific community is represented the by the achievement of an effective percolation pathway, which allows the passage of an electric current at the lowest percentage of filler (percolation threshold), and provides a direct correlation of the external forces in with the electrical resistance variations. Generally, the piezoresistive materials based on the exploitation of the polymer-based composites are designed by homogeneously dispersing the carbonaceous filler in the polymeric matrix. However, it is well known that a simple approach to reduce the content of filler and realize a conductive composite can be obtained by exploiting the concept of segregation of filler in the polymeric matrix. When the filler is not randomly dispersed, but segregated to build up a three-dimensional network, the electrical conductivity can be obtained with a significantly lower content of the carbonaceous filler. Amongst the several techniques for the realization of piezoresistive systems, in the last decade, the Additive Manufacturing (3D printing) technologies have aroused the greatest interest. The 3D printing processes lead to a considerable reduction in costs and times as compared with the traditional technologies of processing of polymers. Furthermore, as regards prototyping, they allow an almost total freedom to create even complex shapes and geometries in an automated and effective way. In particular, Selective Laser Sintering (SLS) is one of the most interesting technology, able to build up easily the segregated filler network, starting from polymeric powder adequately prepared. It is focused on the sintering of polymeric particles by a laser in the classic layer-by-layer mode. Many polymers can be used, from elastomeric to thermosetting, as well as conductive fillers. In this PhD research project, it was investigated the possibility of obtaining piezoresistive materials printed with 3D SLS using thermoplastic polyurethane (TPU) as a polymer matrix and graphene nanoparticles (GE) and multiwalled carbon nanotubes (MWCNTs) as conductive filler. The main objective of the doctoral research was to investigate the potential of SLS to create porous conductive materials with segregated distribution of the conductive filler, by evaluating the effect of different geometries and porosities (from 20% to 80%) and different shape of the conductive filler (i.e. 1D filler and 2D filler). Again, the aim was to evaluate, based on the complete characterization of the materials, what is the effect of the technology used, finding a possible correlation with the printed geometries. Thus, in the first part of the project, porous systems were printed using TPU modified with 1wt% of GE and starting from Diamond (D), Gyroid (G) and Schwarz (S) geometries for the building up of systems with regular porosity. The resulting three-dimensional porous structures show an effective conductive network due to the segregation of the graphene nanoplatelets previously assembled on the TPU powder surface in between the sintered elastomeric particles. The results confirm that GE nanoplatelets improve the thermal stability of the TPU matrix, while also increasing its glass transition temperature. Furthermore, porous structures made from S geometry show higher elastic modulus values in comparison with D and G based structures. After cyclic compression tests, all porous structures show robust negative piezoresistive behavior, regardless of their porosity and geometry, with exceptional sensitivity to deformation. Gauge Factor (GF) values of 12.4 at 8% deformation are obtained for S structures with 40 and 60% porosity, while GF values up to 60 are obtained for deformations lower than 5%. The thermal conductivity of TPU/GE structures significantly decreases with increasing porosity, while the effect of the structure architecture is less relevant. The second part of the project focused on the characterization of 3D printed TPU products with MWCNTs and a mixture of the two fillers, again at 1wt% but with a proportion of 70/30 wt/wt MWCNTs/GE with geometries D and G, in order to investigate a possible synergistic effect of the two conductive fillers. The results showed that the porous structures based on TPU with 1wt% MWCNTs/GE exhibit excellent electrical conductivity and mechanical strength. In particular, all the porous structures show a robust negative piezoresistive behavior, as demonstrated by the GF values that reach values of about -13 at 8% deformation. Moreover, the G20 porous structures (20% porosity) show microwave absorption coefficients ranging from 0.70 to 0.91 in the 12-18 GHz region and close 1 in the THz (300 GHz - 1 THz) frequency region. The results show that the simultaneous presence of MWCNT and GE brings a significant improvement in the specific functional properties of porous structures, which are proposed as potential piezoresistive actuators with relevant electromagnetic interference (EMI) shielding properties

Bimodal Gate Oxide Breakdown in Sub-100 nm CMOS Technology

In the last three decades, the electronic industry has registered a tremendous progress. The continuous and aggressive downsizing of the transistor feature sizes (CMOS scaling) has been the main driver of the astonishing growth and advancement of microelectronic industry. Currently, the CMOS scaling is almost reaching its limits. The gate oxide is now only a few atomic layers thick, and this extremely thin oxide causes a huge leakage current through the oxide. Therefore, a further reduction of the gate oxide thickness is extremely difficult and new materials with higher dielectric constant are being explored. However, the phenomena of oxide breakdown and reliability are still serious issues in these thin oxides. Oxide breakdown exhibits a soft breakdown behavior at low voltages, and this is posing as one of the most crucial reliability issues for scaling of the ultra-thin oxides. In addition, the stress-induced leakage current (SILC) due to oxide has emerged as a scaling problem for the non-volatile memory technologies. In this dissertation, a percolation modeling approach is introduced to study and understand the dramatic changes in the conductivity of a disordered medium. Two different simulation methods of percolative conduction, the site and bond percolation, are studied here. These are used in simulating the post-breakdown conduction inside the oxide. Adopting a Monte-Carlo method, oxide breakdown is modeled using a 2-D percolation theory. The breakdown statistics and post-breakdown characteristics of the oxide are computed using this model. In this work, the effects of different physical parameters, such as dimension and the applied stress are studied. The simulation results show that a thinning of oxide layer and increasing the oxide area result in softening of breakdown. It is observed that the breakdown statistics appear to follow Weibull characteristics. As revealed by simulations, the Weibull slope changes linearly with oxide thickness, while not having a significant change when the area is varied and when the amount of the applied stress is varied. It is shown that the simulation results are well correlated with the experimental data reported in the literature. In this thesis, studying the conduction through the oxide using percolation model, it was discovered that a critical or a quasi-critical phenomenon occurs depending on the oxide dimensions. The criticality of the phase-transition results in a hard breakdown while the soft breakdown occurs due to a quasi-critical nature of percolation for ultra-thin oxides. In the later part of the thesis, a quantum percolation model is studied in order to explain and model the stress induced leakage current. It is explained that due to the wave nature of electrons, the SILC can be modeled as a tunneling path through the stressed oxide with the smaller tunneling threshold compared to the virgin oxide. In addition to the percolation model, a Markov chain theory is introduced to simulate the movement of electron as a random walk inside the oxide, and the breakdown is simulated using this random-walk of electron through the accumulated traps inside the oxide. It is shown that the trapping-detrapping of electrons results in an electrical noise in the post-breakdown current having 1/f noise characteristics. Using simulation of a resistor network with Markov theory, the conductance of the oxide is computed. An analytical study of a 2-D site percolation system is conducted using recursive methods and useful closed-form expressions are derived for specialized networks

POLYMER COMPOSITES FOR SENSING AND ACTUATION

This thesis concerns materials for polymer actuators and mechanical sensors. Polymer actuators are a class of artificial muscle with promising actuation performance; however, they are currently limited by the materials used in their fabrication. The metal-foil type mechanical strain gauges are commercially available and well understood; however, typically have gauge factors less than 5.5 [1], cannot be patterned into custom shapes, and only monitor small areas. New materials provide opportunities to improve the performance of both polymer actuators and mechanical sensors. The aim of this research was to develop, characterize, and implement such materials. Specifically, this thesis describes novel composites of exfoliated graphite (EG) blended with elastomeric hosts. The mechanical and electrical properties of these composites were tailored for two specific applications by modifying the EG loading and the elastomer host: compliant electrodes and strain gauges. Compliant electrodes were demonstrated that had ultimate tensile strains greater than 300% and that could withstand more than 106 strain cycles. Composites fabricated with polydimethylsiloxane (PDMS) exhibited conductivities up to 0.2 S/cm, and having tangent moduli less than 1.4 MPa. This modulus is the lowest reported for loaded elastomers above the percolation threshold. Conductivity was increased to more than 12.5 S/cm by fabricating composites with polyisoprene (latex) elastomers, and the tangent moduli remained less than 5 MPa. Actuation strains of polymer actuators were increased 3 fold using the composites as electrodes, compared to using carbon-grease electrodes. This was due to the composites ability to be spincoated with thin insulating layers of PDMS, allowing 30% higher electric fields to be applied. Strain gauges fabricated with these composites exhibited gauge factors (GFs) > 27,000, to the authors knowledge this is the highest GF ever reported. The effects of humidity, temperature and strain were investigated

Printed and drawn flexible electronics based on cellulose nanocomposites

Sustainability, flexibility, and low-power consumption are key features to meet the growing re- quirements of simplicity and multifunctionality of low-cost, disposable/recyclable smart electronic -of- -based composites hold po- tential to fulfill such demands when explored as substrate and/or electrolyte-gate, or as active channel layer on printed transistors and integrated circuits based on ionic responses (iontronics). In this work, a new generation of reusable, healable and recyclable regenerated cellulose hydro- gels with high ionic conductivity and conformability, capable of being provided in the form of stick- ers, are demonstrated. These hydrogels are obtained from a simple, fast, low-cost, and environ- mental-friendly aqueous alkali salt/urea dissolution method of native cellulose, combined with eration and simultaneous ion incorporation with acetic acid. Their electrochemical properties can be also merged with the mechanical robustness, thermal resistance, transparency, and smooth- - strate. Beyond gate dielectrics, a water-based screen-printable ink, composed of CMC binder and com- mercial zinc oxide (ZnO) semiconducting nanoparticles, was formulated. The ink enables the printing of relatively smooth and densely packed films on office paper with semiconducting func- tionality at room temperature. The rather use of porous ZnO nanoplates is beneficial to form per- colative pathways at lower contents of functional material, at the cost of rougher surfaces. The engineered cellulose composites are successfully integrated into flexible, recyclable, low- voltage (<3.5 V), printed electrolyte-gated office paper or on the ionically modified nanopaper. Ubiquitous calligraphy accessories are used -the- out on the target substrate, where are already printed the devices. Such concept paves the way for a worldwide boom of creativity, where we can freely create personal electronic kits, while having fun at it and without generating waste.Sustentabilidade, flexibilidade e baixo consumo energético são características chave para atender aos crescentes requisitos de simplicidade e multifuncionalidade de sistemas eletrónicos inteligentes de baixo custo, das- Compósitos à base de celulose têm potencial para atender a tais necessidades quando explora- dos como substrato e/ou porta-de-eletrólito ou como camada de canal ativo em transístores impressos e circuitos integrados baseados em respostas iónicas (iontronics). Neste trabalho, é demonstrada uma nova geração de hidrogéis reutilizáveis, reparáveis e recicláveis baseados em celulose regenerada, que apresentam alta condução iónica e conformabilidade, podendo ser fornecidos na forma de adesivos. Estes hidrogéis são obtidos a partir de um método simples, rápido, barato e amigo do ambiente que permite a dissolução de celulose nativa em soluções aquosas com mistura de sal alcalino e ureia, combinado com carboximetil celulose (CMC) para melhorar a sua robustez, seguido da regeneração e simultâneo enriquecimento iónico com ácido acético. As suas propriedades eletroquímicas podem ser combinadas com a inbase de celulose micro/nanofibrilada para obter um substrato eletrolítico semelhante a papel. Para além de portas-dielétricas, foi formulada uma tinta aquosa compatível com serigrafia, composta por CMC como espessante e nanopartículas semicondutoras de ZnO. A tinta permite a impressão de filmes pouco rugosos e densamente percolados sobre papel de escritório, e com funcionalidade semicondutora à temperatura ambiente. O uso alternativo de nanoplacas porosas de ZnO é benéfico para criar caminhos percolativos com menores teores de material funcional, apesar de se obter filmes rugosos. Os compósitos à base celulose foram integrados com sucesso em transístores e portas lógicas porta-eletrolítica, os quais foram impressos em papel de escritório ou no "nanopapel" iconicamente modificado. Acessórios de caligrafia permitem a fácil e rápida padronização de pistas condutoras/resistivas, desenhando-as no substrato alvo, onde estão impressos os dispositivos. Este conceito despoleta um mundo criativo, onde é possível criar livremente kits eletrónicos customizados de forma divertida e sem gerar resíduos

Comportement multifonctionnel des composites comportant des nano/micro renforts

Due to the outstanding mechanical electrical and thermal properties, carbon nanotubes (CNTs) received worldwide attentions and intensive investigations in last decades. CNTs are greatly potential in applications such as energy storage and microelectronics. The one dimensional structure, high aspect ratio and low density, promote CNTs serving as the excellent fillers in composites field. However, due to the strong interactions, CNTs are usually difficult to be dispersed and aligned in a polymer matrix. Designing the CNTs construction reasonably is an effective way to ameliorate the dispersion states of CNTs in matrix. These specific hybrid constructions allowed CNTs arrays synthesized vertically onto the substrates through catalyst chemical vapor deposition method. These CNT arrays effectively overcome the problem of CNTs aggregation and promote the interconnection among CNTs, leading to a considerable improvement of multi-functional properties of composites. Graphite nanoplatelets (GNPs) served as substrate make their synthesizing products-GNP-CNTs hybrids (GCHs) possess distinct merits of all-carbon composition, totally-conductive coupling structure and the low intrinsic density. These GCHs constructions provide a great improvement in the dielectric and electrical properties of composites. However, the relationship between GCHs organization and synthesizing conditions during CVD process and the influence of the addition of GCHs to internal conductive networks have not been reported in detail. These mentioned issues will be investigated and discussed in this thesis, which is divided into four chapters:The first chapter makes a general review of the structure, properties, application and synthesis of CNTs and GNP substrates, and the main procedures of fabricating composites and surface functionalization of CNTs. Moreover, a short introduction of the development of micro-nano hybrids applied to the functional composites is made. Most importantly, the developing electrical states and (di) electrical characteristics of composites with ever-increasing conducting filler loading are reviewed in detail at the last part.The second chapter discusses firstly the synthesis process through the CCVD approach and the relationship between CVD parameters and the corresponding construction of GCHs, where the temperature, gas composition and reaction time were controlled. The constructions CNT arrays are dependent on the synthesis conditions. Furthermore, the results obtained from analysis can provide a structural foundation for the huge application potential of GCHs constructions. The third chapter introduces the poly(vinylidene fluoride)-based nanocomposites containing GCH particles, the dielectric properties of which are improved more greatly than the ternary composites loading equivalent mixture of GNPs and CNTs. The composites achieved by dispersing GCH particles into matrix using the mechanical melt-mixing process, showing a strongly reduced percolation threshold (5.53 vol %) and the relatively high thermal stability. Their improved dielectric properties can be attributed to the formed microcapacitor networks and the change of crystalline formation of matrix, caused by well-designed CNT arrays constructions. The fourth chapter investigates the advanced GCHs/ polydimethylsilicone (PDMS) composites with high piezo-resistive performance at wide temperature range. The synthesized GCHs can be well dispersed in the matrix through the mechanical blending process. The flexible composite shows an ultra-low percolation threshold (0.64 vol%) and high piezo-resistive sensitivity (gauge factor ~103 and pressure sensitivity ~ 0.6 kPa-1). Particularly, the much improvements of electrical properties achieved in GCHs/PDMS composites compared with composites filled with equivalent CNT, GNP or mixture of CNTs/GNPs. Slight motions of finger can be detected and distinguished accurately using the composites film as typical wearable sensor.En raison de leurs propriétés mécaniques, électriques et thermiques exceptionnelles, les nanotubes de carbone (NTC) ont reçu une importante attention mondiale. Les NTC ont un grand potentiel dans différents domaines d'applications tels que le stockage d'énergie et la microélectronique. Grâce à leur structure unidimensionnelle, leur important facteur d'aspect et leur faible densité, les NTC servent comme charges dans les composites. Par contre, en raison des fortes interactions entre eux, il est difficile de les disperser et de les aligner dans une matrice de polymère.Il est connu qu'une bonne conception d'hybrides, constitués de NTC verticalement lignés sur des substrats, améliore de manière significative la dispersion de ces derniers dans la matrice. Ces hybrides sont préparés par le procédé de dépôt chimique en phase vapeur (CVD). Une fois, ces hybrides sont dispersés dans la matrice du composite cela conduit à une nette amélioration des propriétés multifonctionnelles de ce composite. Les substrats utilisés dans cette thèse sont les nanoplaquettes de graphite (NPG) pour donner des hybrides NPG-NTC que nous appellerons par la suite GCHs. Les GCHs ont l'avantage d'avoir une faible densité et une structure totalement conductrice qui améliore les propriétés diélectriques et électriques des composites.Dans l'état de l'art, les relations entre l'organisation des GCHs et les conditions de synthèse par CVD et entre l'ajout des GCHs dans les composites et les réseaux conducteur interne dans les composites n'ont jamais été étudiées. Pour cela, dans cette thèse, nous allons soigneusement étudier et discuter ces problèmes mentionnés.Dans le premier chapitre, nous présentons une revue générale de la structure, des propriétés, des applications et de la synthèse des NTC et des NPG. Nous présentons aussi les procédures de l'intégration des nanoparticules dans des matrices polymères et les méthodes de fonctionnalisation des NTC. Nous discutons aussi des états électriques et les caractéristiques (di)électriques des composites en fonction de la quantité de la charge conductrice.Le deuxième chapitre présente tout d'abord la synthèse des NTC sur les NPG par CVD. Ensuite, l'influence des paramètres de la CVD, la température, la composition du gaz et le temps de la réaction, ont été étudié. Les résultats qualitatifs et quantitatifs obtenus d'après les caractérisations des ces hybrides peuvent servir comme base de données pour l'intégration et l'influence des ces hybrides dans les composites.Le troisième chapitre présente les composites binaires polyvinylidene fluoride/GCHs et leurs propriétés diélectriques qui sont nettement améliorées par rapport aux composites ternaires composés de polyvinylidene fluoride/NPG/NTC. Les composites obtenus par dispersion des GCHs dans la matrice à l'aide du procédé d'extrusion-injection, présentent un seuil de percolation fortement réduit (5,53 vol%) et une stabilité thermique relativement élevée. Leurs propriétés diélectriques améliorées peuvent être attribuées à des réseaux sous forme de micro-condensateurs et le changement de la cristallinité de la matrice peut être attribué à la bonne conception des hybrides.Le quatrième chapitre étudie les composites GCHs/polydiméthylsiloxane (PDMS) avec la haute performance piézo-résistive dans une large gamme de température. Le composite présente un seuil de percolation ultra-bas et une grande sensibilité piézo-résistive. En particulier, les autres améliorations des propriétés électriques obtenues dans les composites GCHs/PDMS par rapport à celles des composites à base de NTC/PDMS, de NPG/PDMS ou encore de NTC-NPG/PDMS. Les légers mouvements des doigts peuvent être détectés grâce à l'usage de ces films composites en tant que capteurs de mouvement

Synthesis and Functionalization of Silver Nanoparticles for the Preparation of High Permittivity Nanocomposites

Over the last decade, a growing interest in nanochemistry has emerged due to the interesting features of nanomaterials that vary with size, shape and surface structure. In particular, metal nanoparticles have received much attention due to their properties that enable their use in various scientific disciplines. Although metal nanoparticles exhibit a number of properties that differ from bulk, some properties, such as their infinite permittivity, remain unchanged. As a result, metal nanoparticles have also been used to prepare nanocomposites with polymers in order to provide dielectric materials featuring high permittivities which can be used for applications such as energy storage (capacitors) or as materials for the conversion of electrical energy into mechanical motion (actuators). Despite the large number of publications on the preparation of nanocomposites exhibiting high permittivities which have emerged over the years, there is still room for further improvement in the current materials properties. For instance, dielectric losses are still quite high in some materials, and the use of certain types of filler lead to a large deterioration in the mechanical properties of the nanocomposites, especially with increasing filler content. In addition, a large number of the fillers used for the preparation of the nanocomposites feature poor size and shape control as well as poorly defined surface properties thus adding to the complexity of understanding the resulting material properties. This work tries to address some of the current issues concerning the preparation of dielectric materials. Therefore, silver nanoparticles (AgNPs) were used as filler, while polydimethylsiloxane (PDMS) was employed as the polymeric matrix. The advantages of using AgNPs as filler consist of their relative facile preparation, as well as the possibility of controlling their surface properties due to their resistance towards oxidation and corrosion. The possibility of preparing AgNPs in large amounts with control over the average size of the particles was realized by conducting the polyol synthesis of AgNPs in a Segmented Flow Tubular Reactor (SFTR). A SiO2 layer was grown around the AgNPs to prevent the loss of the insulating nature of the composite due to the formation of conductive pathways, and the thickness dependency of the dielectric properties of the core-shell particles was also investigated in this work. Furthermore, the SiO2 shell also provided the possibility of further surface functionalization, which was conducted in order to compatibilize the core-shell particles with the PDMS matrix. PDMS was chosen as the polymeric matrix due to its good electromechanical properties, which include high elasticity, low viscosity as well as low conductivity and low tangent losses (tan ÎŽ). The resulting nanocomposites featured enhanced permittivities compared to PDMS, while further optimization in the reaction conditions as well as in the processing procedure yielded nanocomposites with high flexibility that can undergo strains as high as 800 % at a silver content of 20 vol%. Other properties such as electric conductivity and the tan ÎŽ were kept low which emphasizes the potential of the nanocomposites to being used as flexible dielectric materials