Synthesis, multiscale-multiphase characterization and applications of thiophene-based biohybrids

Biohybrid derivatives of π-conjugated materials are emerging as powerful tools to study biological events through the (opto)electronic variations of the π-conjugated moieties, as well as to direct and govern the self-assembly properties of the organic materials through the organization principles of the bio component. So far, very few examples of thiophene-based biohybrids have been reported. The aim of this Ph. D thesis has been the development of oligothiophene-oligonucleotide hybrid derivatives as tools, on one side, to detect DNA hybridisation events and, on the other, as model compounds to investigate thiophene-nucleobase interactions in the solid state. To obtain oligothiophene bioconjugates with the required high level of purity, we first developed new synthetic ecofriendly protocols for the synthesis of thiophene oligomers. Our innovative heterogeneous Suzuki coupling methodology, carried out in EtOH/water or isopropanol under microwave irradiation, allowed us to obtain alkyl substituted oligothiophenes and thiophene based co-oligomers in high yields and very short reaction times, free from residual metals and with improved film forming properties. These methodologies were subsequently applied in the synthesis of oligothiophene-oligonucleotide conjugates. Oligothiophene-5-labeled deoxyuridines were synthesized and incorporated into 19-meric oligonucletide sequences. We showed that the oligothiophene-labeled oligonucletide sequences obtained can be used as probes to detect a single nucleotide polymorphism (SNP) in complementary DNA target sequences. In fact, all the probes showed marked variations in emission intensity upon hybridization with a complementary target sequence. The observed variations in emitted light were comparable or even superior to those reported in similar studies, showing that the biohybrids can potentially be useful to develop biosensors for the detection of DNA mismatches. Finally, water-soluble, photoluminescent and electroactive dinucleotide-hybrid derivatives of quaterthiophene and quinquethiophene were synthesized. By means of a combination of spectroscopy and microscopy techniques, electrical characterizations, microfluidic measurements and theoretical calculations, we were able to demonstrate that the self-assembly modalities of the biohybrids in thin films are driven by the interplay of intra and intermolecular interactions in which the π-stacking between the oligothiophene and nucleotide bases plays a major role.

On Designing Compliant Actuators Based On Dielectric Elastomers

Dielectric Elastomers (DE) are incompressible dielectrics which can experience deviatoric (isochoric) finite deformations in response to applied large electric fields. Thanks to the strong electro-mechanical coupling, DE intrinsically offer great potentialities for conceiving novel solid-state mechatronic devices, in particular linear actuators, which are more integrated, lightweight, economic, silent, resilient and disposable than equivalent devices based on traditional technologies. Such systems may have a huge impact in applications where the traditional technology does not allow coping with the limits of weight or encumbrance, and with problems involving interaction with humans or unknown environments. Fields such as medicine, domotic, entertainment, aerospace and transportation may profit. For actuation usage, DE are typically shaped in thin films coated with compliant electrodes on both sides and piled one on the other to form a multilayered DE. DE-based Linear Actuators (DELA) are entirely constituted by polymeric materials and their overall performance is highly influenced by several interacting factors; firstly by the electromechanical properties of the film, secondly by the mechanical properties and geometry of the polymeric frame designed to support the film, and finally by the driving circuits and activation strategies. In the last decade, much effort has been focused in the devolvement of analytical and numerical models that could explain and predict the hyperelastic behavior of different types of DE materials. Nevertheless, at present, the use of DELA is limited. The main reasons are 1) the lack of quantitative and qualitative models of the actuator as a whole system 2) the lack of a simple and reliable design methodology. In this thesis, a new point of view in the study of DELA is presented which takes into account the interaction between the DE film and the film supporting frame. Hyperelastic models of the DE film are reported which are capable of modeling the DE and the compliant electrodes. The supporting frames are analyzed and designed as compliant mechanisms using pseudo-rigid body models and subsequent finite element analysis. A new design methodology is reported which optimize the actuator performances allowing to specifically choose its inherent stiffness. As a particular case, the methodology focuses on the design of constant force actuators. This class of actuators are an example of how the force control could be highly simplified. Three new DE actuator concepts are proposed which highlight the goodness of the proposed method.

Neue konjugierte Polyarylene mit Leiterstruktur

Zusammenfassung: Im Rahmen der Arbeit wird über die Darstellung neuartiger, konjugierter Polyarylene mit Leiterstruktur berichtet. Über eine zweistufige Synthese wurde ein ethylenüberbrücktes Leiterpolymer (LPDP) hergestellt. Dabei wurde das Vorläuferpolymer mit Samarium(II)jodid unter milden Bedingungen zum Leiterpolymeren cyclisiert. Erste Untersuchungen zeigen, daß LPDP im Gegensatz zum 'gewinkelten Polyacen' eine sehr vielversprechende Elektrolumineszenz-Eigenschaft besitzt. Durch den Einbau chiraler Alkylsubstituenten in entsprechenden meta-Phenylen-Analoga der Leiterpolymere vom Polyacen-Typ wurde versucht, eine Vorzugsdrehrichtung der helikalen Leiterpolymere im Laufe der polymeranalogen Cyclisierung zu induzieren. Es zeigt sich, daß für eines der chiralen Derivate ein CD-Effekt im Bereich der Absorption der helikalen Polyacen-Hauptkette auch auf molekularer Ebene auftritt. Weiterhin wird die erfolgreiche Synthese eines neuen, heteroaromatischen Leiterpolymeren, LPPPT, beschrieben, welches alternierend aus 1,4-Phenylen- und 2,5-Thienylen-Einheiten aufgebaut ist. Eine LED in der Konfiguration ITO/LPPPT/Al zeigt eine orange Lichtemission. Die Quanteneffizienz der freien Ladungsträgerbildung für LPPPT wurde in Experimenten zur Ladungstraegergeneration im elektrischen Feld (Coronaentladung) zu ca. 1 % bei 10E7 V/m bestimmt. Letztlich wurde die Synthese eines neuen, heteroaromatischen Leiterpolymeren mit Carbazol-Einheiten, LPPPC, in der Hauptkette beschrieben, das alternierend aus 1,4-Phenylen- und Carbazol-3,6-diyl-Einheiten aufgebaut ist. Untersuchungen am LPPPC ergaben, daß das Polymer gute Lochleitereigenschaften besitzt, daneben weisen dünne Filme von LPPPC auch photovoltaische Eigenschaften auf.

Synthesis of hexa-peri-hexabenzocoronenes - from building blocks to functional materials

Discotic hexa-peri-hexabenzocoronene (HBC) derivatives have attracted intensive scientific interest due to their unique optoelectronic properties, which depends, to a large extend, upon the attached functional groups. The presented work covers the synthesis of novel HBC building blocks and new HBC derivatives as functional materials. The traditional preparation of HBC derivatives requires elaborate synthetic techniques and tremendous effort. Especially, more than 10 synthetic steps are usually necessary to approach HBCs with lower symmetries. In order to simplify the synthetic work and reduce the high costs, a novel synthetic strategy involving only four steps was developed based on 2,3,5,6-tetraphenyl-1,4-diiodobenzene intermediates and palladium catalyzed Suzuki cross coupling reactions. In order to introduce various functionalities and expand the diversity of multi-functionalizations, a novel C2v-symmetric dihalo HBC building block 2-47, which contains one iodine and one bromine in para positions, was prepared following the traditional intermolecular [4+2] Diels-Alder reaction route. The outstanding chemical selectivity between iodo and bromo groups in this compound consequently leads to lots of HBC derivatives bearing different functionalities. Directly attached heteroatoms will improve the material properties. According to the application of intramolecular Scholl reaction to a para-dimethoxy HPB, which leads to a meta-dimethoxy HBC, a phenomenon of phenyl group migration was discovered. Thereby, several interesting mechanistic details involving arenium cation intermediates were discussed. With a series of dipole functionalized HBCs, the molecular dynamics of this kind of materials was studied in different phases by DSC, 2D WAXD, solid state NMR and dielectric spectroscopies. High charge carrier mobility is an important parameter for a semiconductive material and depends on the degree of intramolecular order of the discotic molecules in thin films for HBC derivatives. Dipole – dipole interaction and hydrogen bonds were respectively introduced in order to achieve highly ordered supramolecular structure. The self-assembly behavior of these materials were investigated both in solution and solid state. Depending upon the different functionalities, these novel materials show either gelating or non-linear optical properties, which consequently broaden their applications as functional materials. In the field of conceivable electronic devices at a molecular level, HBCs hold high promise. Differently functionalized HBCs have been used as active component in the studies of single-molecular CFET and metal-SAMs-metal junctions. The outstanding properties shown in these materials promise their exciting potential applications in molecular devices.

Tailoring molecular weight of the conjugated model polymer MEH-PPV and its structure-property relations

In der vorliegenden Arbeit wurden Struktur-Eigenschaftsbeziehungen des konjugierten Modell-Polymers MEH-PPV untersucht. Dazu wurde Fällungs-fraktionierung eingesetzt, um MEH-PPV mit unterschiedlichem Molekulargewicht (Mw) zu erhalten, insbesondere MEH-PPV mit niedrigem Mw, da dieses für optische Wellenleiterbauelemente optimal geeignet ist Wir konnten feststellen, dass die Präparation einer ausreichenden Menge von MEH-PPV mit niedrigem Mw und geringer Mw-Verteilung wesentlich von der geeigneten Wahl des Lösungsmittels und der Temperatur während der Zugabe des Fällungsmittels abhängt. Alternativ dazu wurden UV-induzierte Kettenspaltungseffekte untersucht. Wir folgern aus dem Vergleich beider Vorgehensweisen, dass die Fällungsfraktionierung verglichen mit der UV-Behandlung besser geeignet ist zur Herstellung von MEH-PPV mit spezifischem Mw, da das UV-Licht Kettendefekte längs des Polymerrückgrats erzeugt. 1H NMR and FTIR Spektroskopie wurden zur Untersuchung dieser Kettendefekte herangezogen. Wir konnten außerdem beobachten, dass die Wellenlängen der Absorptionsmaxima der MEH-PPV Fraktionen mit der Kettenlänge zunehmen bis die Zahl der Wiederholeinheiten n  110 erreicht ist. Dieser Wert ist signifikant größer als früher berichtet. rnOptische Eigenschaften von MEH-PPV Wellenleitern wurden untersucht und es konnte gezeigt werden, dass sich die optischen Konstanten ausgezeichnet reproduzieren lassen. Wir haben die Einflüsse der Lösungsmittel und Temperatur beim Spincoaten auf Schichtdicke, Oberflächenrauigkeit, Brechungsindex, Doppelbrechung und Wellenleiter-Dämpfungsverlust untersucht. Wir fanden, dass mit der Erhöhung der Siedetemperatur der Lösungsmittel die Schichtdicke und die Rauigkeit kleiner werden, während Brechungsindex, Doppelbrechung sowie Wellenleiter-Dämpfungsverluste zunahmen. Wir schließen daraus, dass hohe Siedetemperaturen der Lösungsmittel niedrige Verdampfungsraten erzeugen, was die Aggregatbildung während des Spincoatings begünstigt. Hingegen bewirkt eine erhöhte Temperatur während der Schichtpräparation eine Erhöhung von Schichtdicke und Rauhigkeit. Jedoch nehmen Brechungsindex und der Doppelbrechung dabei ab.rn Für die Schichtpräparation auf Glassubstraten und Quarzglas-Fasern kam das Dip-Coating Verfahren zum Einsatz. Die Schichtdicke der Filme hängt ab von Konzentration der Lösung, Transfergeschwindigkeit und Immersionszeit. Mit Tauchbeschichtung haben wir Schichten von MEH-PPV auf Flaschen-Mikroresonatoren aufgebracht zur Untersuchung von rein-optischen Schaltprozessen. Dieses Verfahren erweist sich insbesondere für MEH-PPV mit niedrigem Mw als vielversprechend für die rein-optische Signalverarbeitung mit großer Bandbreite.rn Zusätzlich wurde auch die Morphologie dünner Schichten aus anderen PPV-Derivaten mit Hilfe von FTIR Spektroskopie untersucht. Wir konnten herausfinden, dass der Alkyl-Substitutionsgrad einen starken Einfluss auf die mittlere Orientierung der Polymerrückgrate in dünnen Filmen hat.rn

Molekulare und supramolekulare Eigenschaften von neuen Donor-Akzeptor-Polymeren

Die organische Halbleitertechnologie befindet sich seit Jahrzehnten im Focus des Interesses, da sie eine kostengünstige und umweltverträgliche Alternative zu anorganischen Silizium-basierten Halbleitern darstellt. Die Möglichkeit der gezielten Funktionalisierung von definierten Strukturen durch synthetische Methoden, welche eine große Vielfalt an Materialien ermöglicht, steht dabei besonders im Vordergrund. Die Modifikation von physikalischen Eigenschaften ermöglicht dabei eine stark erleichterte Anpassung für den geplanten Anwendungsbereich. Im Rahmen der vorliegenden Dissertation wurden organische Halbleitermaterialien basierend auf Cyclopenta[2,1-b:3,4-b']dithiophen (CDT) dargestellt und hinsichtlich ihrer strukturellen und elektronischen Eigenschaften untersucht. In Kombination mit Benzo[c][1,2,5]thiadiazol (BTZ) und weiteren Akzeptoren wurden zunächst Donor(D)-Akzeptor(A)-Polymere synthetisiert und Struktur-Eigenschaft-Beziehungen aufgestellt. So konnte ein sehr hochmolekulares Polymer CDT-BTZ-Polymer (Mn = 36 kg mol-1, PDI = 2.6) erhalten werden, welches sich durch eine hohe lamellare Ordnung und eine gemessene Ladungsträgermobilität in FETs von über 5.0 cm2V-1s-1 bei Raumtemperatur auszeichnete; bei niedrigen Temperaturen (240 K) war letztgenannte 6.5 cm2V-1s-1. Aufgrund dieses hohen Ladungstransports und der Abwesenheit niedermolekularer Polymerketten innerhalb des Polymers konnte erstmals eine Messung eines HALL-Effektes bewerkstelligt werden. Dies war der erste Beweis eines Band-artigen Ladungstransportes an einem Polymerhalbleiter. Des Weiteren wurde durch synthetische Veränderung der Grundstruktur des Polymers zu längeren Alkylketten eine anisotrope Anordnung der Polymerketten erreicht und die Ladungsträgermobilität (6.5 cm2V-1s-1 bei Raumtemperatur) weiter gesteigert. Darauf aufbauend wurde der Einfluss von stereoisomeren Seitenketten an CDT-BTZ-Polymeren auf Packungsverhalten, Parametern (Sperrstrom, Einschaltstrom) in FETs und Löslichkeit in organischen Lösungsmitteln untersucht. Durch cis-trans-Isomerisierung der Seitenketten wurde hier eine neue Methode zur Optimierung des Packungsverhaltens von Polymeren in dünnen Filmen und Lösung gefunden. Zuletzt wurden D-π-A-Farbstoffen, welche CDT als Verbrückungseinheit (π) beinhalten, dargestellt. Durch Variation von D und A konnten Struktur-Eigenschaft-Beziehungen in der Anwendung in Solarzellen (Feststoffsolarzellen, Flüssigsolarzellen) gefunden werden. Die Untersuchungen der photoinduzierten Absorption und der Photolumisenzenzquantenausbeute lieferten dabei Erklärungen für physikalische Prozesse wie Ladungsinjektion- und rekombination.

Estudo da cristalinidade de filmes finos de nitreto de índio e simulado pelo pacote de programas Wien2k

Neste trabalho, foi utilizado o método de deposição assistida por feixe de íons (IBAD na sigla em inglês) para produção de filmes finos de nitreto de índio em substratos de silício (111) e Safira-C. Variando as condições de deposição e utlilizando a técnica de difração de raios-X, investigou-se com o intuito de obter os parâmetros que resultam em filmes finos com melhor grau de cristalinidade. Os filmes produzidos a 380C apresentaram alta cristalinidade, superior àqueles a 250C. Temperaturas muito superiores a 380C não ocasionam a formação de filme cristalino de InN, como foi observado ao utilizar a temperatura de 480C; o mesmo se observa ao utilizar temperatura ambiente. Na temperatura considerada adequada ,de 380C, obteve-se que a utilização de Ra, ou seja, a razão de fluxo de partículas entre o nitrogênio e índio, em torno de 2,3 permite obter um melhor grau de cristalinização, o qual decresce conforme se diverge desse valor. A comparação entre difratogramas de amostras produzidas com e sem a evaporação prévia de titânio, o qual é possível observar um deslocamento dos picos do InN, indicam que o efeito Gettering permite a redução de impurezas no filme, principalmente de oxigênio. Utilizou-se a técnica de Retroespalhamento de Rutherford para obtenção da composição dos elementos e o perfil de profundidade. Notou-se uma forte mistura dos elementos do substrato de silício e safira com o nitreto de índio mesmo próximos a superfície. A presença indesejável de impurezas, principalmente o oxigênio, durante a deposição de filmes finos é praticamente inevitável. Desta forma, cálculos ab initio baseados na Teoria do Funcional da Densidade (DFT) foram realizados para investigar defeitos isolados e complexos de oxigênio no nitreto de índio e a sua influência nas propriedades óticas. Considerou-se diferentes concentrações de oxigênio (x=2,76, 8,32, 11,11 e 22,22%) aplicando-se o método PBEsolGGA e TB-mBJ para o tratamento da energia e potencial de troca e correlação. Obteve-se que é energeticamente favorável o oxigênio existir principalmente como defeito carregado e isolado. Os resultados utilizando a aproximação de TB-mBJ indicam um estreitamento do bandgap conforme a concentração de oxigênio aumenta. Entretanto, a alta contribuição do efeito de Moss-Burstein resulta num efetivo alargamento do band gap, gerando valores de band gap ótico maiores que no do bulk de nitreto de índio.

Measurement of residual stress by load and depth sensing indentation with spherical indenters

A new experimental technique is presented for making measurements of biaxial residual stress using load and depth sensing indentation (nanoindentation). The technique is based on spherical indentation, which, in certain deformation regimes, can be much more sensitive to residual stress than indentation with sharp pyramidal indenters like the Berkovich. Two different methods of analysis were developed: one requiring an independent measure of the material's yield strength and the other a reference specimen in the unstressed state or other known reference condition. Experiments conducted on aluminum alloys to which controlled biaxial bending stresses were applied showed that the methods are capable of measuring the residual stress to within 10-20% of the specimen yield stress. Because the methods do not require imaging of the hardness impressions, they are potentially useful for making localized measurements of residual stress, as in thin films or small volumes, or for characterization of point-to-point spatial variations of the surface stress.

Functional alkali tantalate 2D structures for microelectronics and related applications

Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.

Filmes formados pelo copolímero SEBS e nanopartículas de óxidos de ferro : preparação e caracterização

Dissertação (mestrado)—Universidade de Brasília, Instituto de Física, Programa de Pós-Graduação em Física, 2016.

Design and characterization of polymorphs and co-crystals of organic molecular semiconductors

In the last decades, organic semiconductors have attracted attention due to their possible employment in solution-processed optoelectronic and electronic devices. One of the advantages of solution processing is the possibility to process into flexible substrates at low cost. Organic molecular materials tend to form polymorphs, which can exhibit very different properties. In most cases, the control of the crystal structure is decisive to maximize the performance of the final device. Although organic electronics have progressed a lot, n-type organic semiconductors still lag behind p-type, presenting challenges such as air instability and poor solubility. NDI derivatives are promising candidates for applications in organic electronics due to their characteristics. Recently, the structure-properties relationship and the polymorphism of these molecules have gained attention. In the first part of this thesis, NDI-C6 thermal behavior was extensively explored which revealed two different behaviors depending on the annealing process. This study allowed to define the stability ranking of the NDI-C6 bulk forms and to determine the crystal structure of Form γ at 54°C. Additionally, the polymorphic and thermal behavior of thin films of NDI-C6 was also explored. It was possible to isolate pure Form α, Form β, Form γ and a new metastable Form ε. It was also possible to determine the stability ranking of the phases in thin films. OFETs were fabricated having different polymorphs as active layer, unfortunately the performance was not ideal. During the second part of this thesis, core-chlorinated NDIs with fluoroalkyl chains were studied. Initially, the focus was on the polymorphism of CF3-NDI that revealed a solvate form with a very interesting molecular arrangement suggesting the possibility to form charge transfer co-crystals. In the last part of the thesis, the synthesis and characterization of CT co-crystal with different NDI derivatives, and acceptor and as donor BTBT and ditBu-BTBT were explored.

The dynamics of ultra-thin polymer films in different confinements studied by resonance enhanced dynamic light scattering

Die Kontroverse über den Glasübergang im Nanometerbereich, z. B. die Glas¬über¬gangs-temperatur Tg von dünnen Polymerfilmen, ist nicht vollständig abgeschlossen. Das dynamische Verhalten auf der Nanoskala ist stark von den einschränkenden Bedingungen abhängig, die auf die Probe wirken. Dünne Polymerfilme sind ideale Systeme um die Dynamik von Polymerketten unter der Einwirkung von Randbedingungen zu untersuchen, wie ich sie in dieser Arbeit variiert habe, um Einblick in dieses Problem zu erhalten.rnrnResonanzverstärkte dynamische Lichtstreuung ist eine Methode, frei von z.B. Fluoreszenzmarkern, die genutzt werden kann um in dünnen Polymerfilmen dynamische Phänomene

Analysis by finite element calculations of light scattering in laser-textured AZO films for PV thin-film solar cells

In the thin-film photovoltaic industry, to achieve a high light scattering in one or more of the cell interfaces is one of the strategies that allow an enhancement of light absorption inside the cell and, therefore, a better device behavior and efficiency. Although chemical etching is the standard method to texture surfaces for that scattering improvement, laser light has shown as a new way for texturizing different materials, maintaining a good control of the final topography with a unique, clean, and quite precise process. In this work AZO films with different texture parameters are fabricated. The typical parameters used to characterize them, as the root mean square roughness or the haze factor, are discussed and, for deeper understanding of the scattering mechanisms, the light behavior in the films is simulated using a finite element method code. This method gives information about the light intensity in each point of the system, allowing the precise characterization of the scattering behavior near the film surface, and it can be used as well to calculate a simulated haze factor that can be compared with experimental measurements. A discussion of the validation of the numerical code, based in a comprehensive comparison with experimental data is included.

NONLINEAR EFFECTS IN MAGNETIC GARNET FILMS AND NONRECIPROCAL OPTICAL BLOCH OSCILLATIONS IN WAVEGUIDE ARRAYS

This dissertation presents detailed experimental and theoretical investigations of nonlinear and nonreciprocal effects in magnetic garnet films. The dissertation thus comprises two major sections. The first section concentrates on the study of a new class of nonlinear magneto-optic thin film materials possessing strong higher order magnetic susceptibility for nonlinear optical applications. The focus was on enlarging the nonlinear performance of ferrite garnet films by strain generation and compositional gradients in the sputter-deposition growth of these films. Under this project several bismuth-substituted yttrium iron garnet (Bi,Y) 3 (Fe,Ga)5 O12(acronym as Bi:YIG) films have been sputter-deposited over gadolinium gallium garnet (Gd 3 Ga5 O12 ) substrates and characterized for their nonlinear optical response. One of the important findings of this work is that lattice mismatch strain drives the second harmonic (SH) signal in the Bi:YIG films, in agreement with theoretical predictions; whereas micro-strain was found not to correlate significantly with SH signal at the micro-strain levels present in these films. This study also elaborates on the role of the film's constitutive elements and their concentration gradients in nonlinear response of the films. Ultrahigh sensitivity delivered by second harmonic generation provides a new exciting tool for studying magnetized surfaces and buried interfaces, making this work important from both a fundamental and application point of view. The second part of the dissertation addresses an important technological need; namely the development of an on-chip optical isolator for use in photonic integrated circuits. It is based on two related novel effects, nonreciprocal and unidirectional optical Bloch oscillations (BOs), recently proposed and developed by Professor Miguel Levy and myself. This dissertation work has established a comprehensive theoretical background for the implementation of these effects in magneto-optic waveguide arrays. The model systems we developed consist of photonic lattices in the form of one-dimensional waveguide arrays where an optical force is introduced into the array through geometrical design turning the beam sideways. Laterally displaced photons are periodically returned to a central guide by photonic crystal action. The effect leads to a novel oscillatory optical phenomenon that can be magnetically controlled and rendered unidirectional. An on-chip optical isolator was designed based on the unidirectionality of the magneto-opticBloch oscillatory motion. The proposed device delivers an isolation ratio as high as 36 dB that remains above 30 dB in a 0.7 nm wavelength bandwidth, at the telecommunication wavelength 1.55 μm. Slight modifications in isolator design allow one to achieve an even more impressive isolation ratio ~ 55 dB, but at the expense of smaller bandwidth. Moreover, the device allows multifunctionality, such as optical switching with a simultaneous isolation function, well suited for photonic integrated circuits.

Influence of substrate surface topography in the deposition of nanostructured diamond-like carbon films by high density plasma chemical vapor deposition

In this work, we have studied the influence of the substrate surface condition on the roughness and the structure of the nanostructured DLC films deposited by High Density Plasma Chemical Vapor Deposition. Four methods were used to modify the silicon wafers surface before starting the deposition processes of the nanostructured DLC films: micro-diamond powder dispersion, micro-graphite powder dispersion, and roughness generation by wet chemical etching and roughness generation by plasma etching. The reference wafer was only submitted to a chemical cleaning. It was possible to see that the final roughness and the sp(3) hybridization degree strongly depend on the substrate surface conditions. The surface roughness was observed by AFM and SEM and the hybridization degree of the DLC films was analyzed by Raman Spectroscopy. In these samples, the final roughness and the sp(3) hybridization quantity depend strongly on the substrate surface condition. Thus, the effects of the substrate surface on the DLC film structure were confirmed. These phenomena can be explained by the fact that the locally higher surface energy and the sharp edges may induce local defects promoting the nanostructured characteristics in the DLC films. (C) 2008 Elsevier B.V. All rights reserved.