In this thesis a multilayer actuator structure is developed for the I-SWARM project. In order to build an energy efficient and low voltage actuator system for the 3x3x3 mm3 robot, the resonance drive mode in combination with a ten layer multilayer structure build upon the most suitable substrate material was used. Two different sizes of the locomotion module were built. The first one is five times larger than the small version. It has five active layers and is simpler to work with and to test. The small module has three 2x0.4 mm can-tilevers on a 3x3mm body and ten active layers. The multilayer process involve easily defined flexible printed circuit (FPC) board as substrate material, spin coating piezoelectric poly(vinylidenefluoride- tetrafluoroethylene) P(VDF-TrFE) as active stack material, and evaporated aluminum electrodes on each active polymer layer. By using different shadow masks for each electrode layer, special inter con-tact areas can be contacted from above after the polymer has been removed by an Inductively Coupled Plasma (ICP) etch. The contours of the locomo-tion module was etched in a Reactive Ion Etch (RIE) equipment. Both the cupper layer in the FPC and the electrode layers of the active stack, were used as etch mask. The deflections of the cantilevers were measured at low voltages to ensure as realistic drive voltage as possible for the I-SWARM robot. The large struc-ture showed a 250 µm deflection at 4 V and 170 Hz resulting in a Q-value of 19. The deflection of the small structure was 8 µm at 3.3 V and 5000 Hz and the measured Q-value was 31.

Amphiphilic block copolymers based on poly(ethylene glycol) (PEG) and poly(vinylidene fluoride) (PVDF) were synthesized by RAFT polymerization. The commercial poly(ethylene glycol) methyl ether (Me-PEG-OH, 20 Kg/mol) and difunctional polyethylene glycol (OH-PEG-OH, 20 Kg/mol) were used to synthesize diblock copolymers (Me-PEG-b-PVDF), and triblock copolymers (PVDF-b-PEG-b-PVDF) respectively. For the synthesis, the esterification reaction followed by the SN2 reaction was employed to make macro CTA (Me-PEG-XA, XA-PEG-XA, XA refers to the xanthate group). The macro CTAs were used further for VDF polymerization in dimethyl carbonate (DMC) inside the autoclave. Different molecular weights of the PVDF block (whether in the diblocks or the tribolcks) were obtained based on changes in the reaction time. The resulting block copolymers were molecularly characterized by FT-IR, 1H,19F-NMR, and SEC. The thermal properties were studied by DSC and TGA. Furthermore, the crystalline phase characterization was investigated by XRD and FT-IR. Being the obtained block copolymers are amphiphilic, their self-assembly was achieved by nanoprecipitation in DMF/water, and they were analyzed by DLS and TEM.

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The focus of this thesis is the critical review of Additive Printing (AP) or 3D-printing, and optimization strategies for the introduction of new materials. During the course of tenure, four classes of solids were investigated to determine the hurdles presented from each system. Specifically, the investigation developed techniques for optimization of ink production, green-film deposition, and laser sintering parameters surrounding the Optomec AJP system (AJP). In the assessment, statistical experimental design, analysis and material characterization techniques have been utilized. Final recommendations disseminate current best practices for new ink and material development, along with factor analysis of input variables for phase and material properties, along with insights for future research of these systems. The first chapter provides a general introduction to the field of AP. The second chapter focuses specifically on Optomec aerosol-jet process (AJP) techniques, and expands the discussion to process parameters, information concerning the fabrication/characterization procedure followed for each system, and includes: a detailed description of the materials investigated. This is important because printing parameters, optimization, and approach may be divergent for optimization within each strain; and is meant as an aid to resolve some technical issues for future investigators. The third chapter is fully dedicated to the results concerning the fabrication and the characterization of amorphous boron powder to film. Chapter four discusses future research options, ideas and directions. Appendices are provided for any which wish to investigate the orthogonal arrays used, or the combinatorial effects resulting in the attributes of the material system final products. / Master of Science

Poly(vinylidene fluoride) (PVDF) receives an increasing amount of attention because it exhibits the strongest piezoelectric response of any commercially available polymer. These piezoelectric properties have proved useful as actuators and sensors. Current manufacturing processes limit PVDF to thin films and restricting their uses largely to sensors. Further applications utilizing the changes in mechanical properties of piezoelectric polymers are being realized. Evaluating to what extent the mechanical properties will change with applied electric field and finding new ways to manufacture PVDF will lead to new applications of piezoelectric polymers. In-situ mechanical testing of biased piezoelectric PVDF films successfully measured changes in loss and storage modulus. In-situ creep testing measured an increase in stiffness while in-situ dynamic mechanical analysis (DMA) measured and overall decrease in loss and storage modulus. Differences in results between the two experiments are attributed to orientation of the polymer and piezoelectric forces acting on the equipment. DMA results are accepted as being the most accurate and measured changes of over 20% in elastic modulus. Results were believed to be greatly influence by attached electrodes and actuation forces. Cryogenic mechanical milling successfully converted a phase PVDF powder to b phase as measured with wide-angle x-ray diffraction. This is the first recorded instance of b phase powders forming from the a phase through ball milling. These b phase powders maintained their crystal structure during compression molding at 70°C. / Master of Science

La spintronique utilisant des matériaux semi-conducteurs est un sujet de recherche très actif. Elle permet de combiner le potentiel des semi-conducteurs avec le potentiel des matériaux magnétiques. Le GaN pourrait être un bon candidat pour des applications en spintronique car le temps de relaxation de spin est très long. La spintronique organique est également un domaine de recherche en plein essor en raison de la longue durée de vie de spin des porteurs de charge ainsi que de leur coût relativement bas, de leur flexibilité et de leur diversité chimique. Dans un premier temps, nous montrerons que la polarisation circulaire de la lumière émise par une LED contenant une couche unique de points quantiques InAs / GaAs (QD) InAs / GaAs dopés p peut atteindre environ 18% sans champ magnétique extérieur. Une corrélation claire est établie entre le degré de polarisation de la lumière émise et l’aimantation perpendiculaire de l’injecteur. La polarisation atteint un maximum pour une polarisation appliquée de 2.5 V à 10 K, ce qui correspond à un courant injecté de 6 µA. En outre, nous observons un comportement remarquable de la polarisation pour un température comprise entre 60K et 80K. L’évolution de la polarisation en fonction de la température est discutée à la lumière de la compétition entre le temps de vie de recombinaison radiative τr et le temps de relaxation de spin τs. De plus, nous avons développé un injecteur de spin présentant une anisotropie magnétique perpendiculaire sur GaN. Nous avons d’abord optimisé la croissance de MgO pour différentes températures du substrat. Nous avons ensuite étudié la croissance de Fe puis de Co sur MgO/GaN. L’injecteur de spin Co(0001)/MgO(111) a été retenu car celui-ci permet d’obtenir un anisotropie magnétique perpendiculaire. De plus, les calculs ab initio ont également montré que l’interface Co/MgO(111) présente une grande anisotropie magnétique. Finalement, nous étudions les MFTJ basés sur une barrière de PVDF organique dopée avec des nano-particules de Fe3O4. Nous avons fabriqué avec succès une multicouche de La0.6Sr0.4MnO3/PVDF:Fe3O4/Co, dans laquelle la barrière organique en poly (fluorure de vinylidène) (PVDF) a été dopée avec des nanoparticules ferromagnétiques de Fe3O4. En modifiant la polarisation du PVDF, l’effet tunnel dans la jonction multiferroïque peut être commuté via la partie LSMO/PVDF/Co (polarisation positive) ou via la partie Fe3O4/PVDF/Co (polarisation négative). Cela correspond à une inversion de la magnétorésistance à effet tunnel (TMR) de + 10% à -50%, respectivement. Notre étude montre que les jonctions tunnel multiferroïques organiques dopées avec des particules magnétiques pourraient créer de nouvelles fonctionnalités en jouant sur l’interaction du magnétisme des nanoparticules avec la ferroélectricité de la barrière organique. / Spintronics with semiconductors is very attractive as it can combine the potential of semiconductors with the potential of the magnetic materials. GaN has a long spin relaxation time, which could be of potential interest for spintronics applications. Organic spintronics is also very appealing because of the long spin lifetime of charge carriers in addition to their relatively low cost, flexibility, and chemical diversity. In this thesis, we investigate spin injection in spin LEDs containing either InAs/GaAs quantum dots or InGaN/GaN quantum wells. Moreover, we further study spin polarized transport in organic multiferroic tunnel junctions (OMFTJs). Firstly, we will show that the circular polarization of the light emitted by a LED containing a single layer of p-doped InAs/GaAs quantum dots (QDs) can reach about 18% under zero applied magnetic field. A clear correlation is established between the polarization degree of the emitted light and the perpendicular magnetization of the injector layer. The polarization reaches a maximum for an applied bias of 2.5V at 10K, which corresponds to an injected current of 6 µA. Also, we report a remarkable behavior of the polarization in the temperature region 60-80K. The interpretation of the bias and temperature dependence of the polarization is discussed in light of the competition between radiative recombination time τr and the spin relaxation time τs. In addition, significant efforts have been devoted to developing a perpendicular spin injector on GaN based materials to achieve spin injection without applying a magnetic field. Firstly, the growth of MgO has been investigated at various growth temperatures. Then, we studied the growth of either Fe or Co on MgO/GaN. In contrast to Fe/MgO, the Co/MgO spin injector yields a clear perpendicular magnetic anisotropy. In addition, ab-initio calculations have been performed to understand the origin of the perpendicular magnetic anisotropy at the Co/MgO(111) interface. Finally, we investigate multiferroic tunnel junctions (MFTJs) based on organic PVDF barriers doped with Fe3O4 nano particles. The organic MFTJs have recently attracted much attention since they can combine advantages of spintronics, organic and ferroelectric electronics. We report on the successful fabrication of La0.6Sr0.4MnO3/PVDF:Fe3O4/Co OMFTJ, where the poly(vinylidene fluoride) (PVDF) organic barrier has been doped with ferromagnetic Fe3O4 nanoparticles. By changing the polarization of the ferroelectric PVDF, the tunneling process in OMFTJ can be switched either through the LSMO/PVDF/Co part (positive polarization) or through the Fe3O4/PVDF/Co part (negative polarization). This corresponds to a reversal of tunneling magnetoresistance (TMR) from +10% to -50%, respectively. Our study shows that the doping of OMFTJs with magnetic nanoparticles can create new functionalities of organic spintronic devices by the interplay of nanoparticle magnetism with the ferroelectricity of the organic barrier.