"Self-assembled monolayers (SAMs) are organized molecular assemblies that are formed by spontaneous adsorption of a compound in solution to a surface (e.g. alkanethiols on gold). The design, preparation, and characterization of several self-assembled monolayers and multilayers on surfaces (gold, indium tin oxide and quartz) are described. The systems were chosen based on their ability to form ordered films and to perform a given device function. SAMs were fabricated with selected functional groups at the air-monolayer interface, capable of complexing metal ions (e.g. dicarboxypyridine, dicarboxybenzene, imidazole, 4-hydroxypyridine) with the purpose of using these SAMs to construct multilayered films. Deposition of a second layer consisting of metal ions (e.g. Cu(II), Co(II) and Fe(III)), occurs by non-covalent metal ligand binding interactions between the metal ion layer and the different organic ligands on the surface. Deposition of subsequent layers was achieved by the incorporation of the appropriate organic ligands and metal ions. These monolayers and multilayered films were characterized by contact angle measurements, ellipsometry, grazing angle FT-IR, cyclic voltammetry and impedance spectroscopy following deposition of each layer on the film. Electrochemical analysis of the multilayered films shows alternating insulating/conducting behavior (cyclic voltammetry) and alternating changes in films capacitance (impedance spectroscopy) depending on the outermost layer of the film. Films capped with an organic layer show low conductivity, while films capped with a metal layer show conducting behavior. The electrochemical behavior of the films is related to the degree of “leakiness” or electrolyte solution permeation through the film, which is high for films with metal layers as the top layer and decreases once the film is capped with an organic layer. The alternating conducting/insulating behavior of the films allows for fabrication of multilayered thin films of variable thickness and tunable conducting properties. Ordered films were fabricated with up to seven layers of dicarboxypyridine and Cu(II), and 4-hydroxypyridine and Fe(III) metal-ligand units. The construction of these films provides an example of molecular films that could function as molecular wires or junctions due to their controllable electrochemical properties. Photocurrent generating films were fabricated by incorporation of chromophore groups (e.g. pyrene, porphyrins) into the multilayered structures. These films generate cathodic or anodic current upon photoexcitation of the chromophores. The monolayers functionalized with different organic ligands were also used to study lanthanide complexation on the surfaces. Successful deposition of different lanthanide ions was achieved from DMSO solutions. Monolayers of a bicyclic structure, 4, 7, 13, 16-tetraoxa-1,10,21-triaza-bicycle[8.8.5] tricosane-19,23-dione, attached to a hexadecanethiol molecule were used to study the ability of metal ion detection on the surface using electrochemical (cyclic voltammetry and impedance spectroscopy) techniques. The SAMs show higher complexation affinity for Li+ than for Na+ or K+. Preliminary studies were also carried out to investigate the ability of different SAMs to cell adhesion interactions. Future experiments will help elucidate a systematic relation of cell adherence and the bulk and molecular-level properties of the functionalized surfaces. The different multilayered films described in this dissertation served as preliminary models for different molecular scale device applications. Current work is focused in the design and preparation of more efficient photocurrent generating films, highly selective sensors for different types of ions, surfaces for cell adhesion and microbial interactions, and the study of other potential applications such as the design of micro and nanofluidic devices. "

The aim of the thesis was to elucidate the effect of confinement of amorphous phase of apolymer above its glass transition temperature being in contact with another polymer in a rigid state.Confinement is unavoidably connected with surfaces enforcing confinement. It is very difficult to separate theeffect of confinement from the effect of interfaces because both effects arise parallel and coincide. Multilayeredfilms were chosen as the base material for the studies because they contain multifold number of confined layerand response from confinement and interfaces is multifold increased. Hoping that some of experimentaltechniques are more sensitive to interfaces while others to confinement we selected the following:microcalorimetry, SSNMR, direlectrical spectroscopy and dynamic shear rheology. We have searched for theinfluence of PS on dynamics of phenyl rings of PC for PC/PS film with ratio 70/30 in the temperature rangefrom 296 K to 393 K employing PILGRIM pulse sequence. .We show that above the glass transition temperatureof PS, the PC component became more flexible. It is at the first glance the effect of the interface because there isno significant confinement of thicker PC layers. Dielectric relaxation spectroscopy measurements in our studyclearly provide evidence for deviations from a simple 2-phase structure in multilayered films PC/PS that is worthto be analyzed more in the future. The dielectric response of the multilayer samples was also modeled andcompared with experimental results. We obtained again discrepancies between the simulated spectra and themeasured spectra for multilayer films. Knowing the exact composition and viscoelastic behaviour of eachcomponent, the theoretical viscoelastic behavior of composites has been predicted numerically. Then,rheological tests have been made, and confronted with numerical predictions, to detect the confinement effect.The upper limit of thickness beyond which PS in confined layers at rubbery state becomes stiffer than in bulk isabout 150/200 nm. It appeared that the shear modulus of the thinnest PS layers (10 nm) is nearly 2.5 times largerthan that for bulk PS sample. We can note that Tg of PS layers also begins to increase beyond this upper limit ofthickness.. None of the experiment could clearly deliver the information about the effect of confinement orinterface on the behavior of PS layers alone. The results obtained here point out that separation of the effects ofconfinement and interfaces remains very difficult.

Made available in DSpace on 2016-12-12T20:15:50Z (GMT). No. of bitstreams: 1 Alex Kraisch.pdf: 2282404 bytes, checksum: 128e624fc8b71f2bc7d95efb2b375527 (MD5) Previous issue date: 2013-03-21 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / There is a relevant potential for multilayered films in many areas of technological interest once they may combine in just one sample convenient mechanical, optical, electrical and magnetic properties, resulting in an upgrade of the original monolayer films. However, it is quite important to take into account that its production evolves chemical and crystallographic compatibility of the materials and a correct understanding of the stresses and deformations that result from the contact between different materials with quite different characteristics. The objective of this work is to build a three-dimensional model that may describe the relation between the stress in a multilayered film deposed on a thick substrate and the curvature of the sample. It is used the minimization of the deformation energy of the sample in elastic regime. This method is quite simple which is a advantage when compared with tensor procedures, allowing an easier identification of the terms as well as the reduction of the complexity of the calculations. The work starts by the motivation for the study of the stress in monolayer and multilayered films, followed by a presentation of the theoretical and experimental implications of the theme. Then, a more complete description of the methodology used and of the model itself is presented, including the identification of the corrections terms for the well-known Stoney equation. Finally, it is presented a validation of the model, by means of a comparison between its results and the values obtained by other theoretical models, taking as standard results obtained by finite element simulation that favors the model presented in this work. / Filmes compostos por múltiplas camadas de diferentes materiais possuem um potencial considerável para aplicações de interesse tecnológico, na medida em que a combinação dos materiais pode produzir coberturas com propriedades mecânicas, ópticas ou magnéticas superiores às obtidas com uma única camada de um único material. Também é evidente que sua produção envolve questões importantes como a compatibilidade cristalográfica e química, bem como uma correta caracterização das tensões e deformações em cada camada, evitando assim fissuras e delaminação entre as camadas. O objetivo desse trabalho é a construção de um modelo tridimensional que descreva a relação entre tensões e deformações em filmes finos depositados em multicamadas sobre substratos espessos. O método utilizado é o da minimização de energia de deformação da amostra em regime elástico. Esse método possui como vantagem significativa sua maior simplicidade em relação a abordagem tensorial, o que reduz a complexidade dos cálculos e permite uma mais fácil identificação dos termos envolvidos. Após a apresentação da motivação ao estudo do problema, bem como das diversas questões que envolvem a análise experimental e teórica do mesmo, é feita uma descrição mais completa da metodologia utilizada e do modelo teórico que é o foco deste trabalho. A seguir, é feita aplicação do modelo para amostras que se deformam como uma casca esférica e cilíndrica, com a identificação dos termos de correção à equação de Stoney. Finalmente, é feita uma comparação entre os valores obtidos pelo modelo e outros modelos teóricos, tomando-se como padrão os valores obtidos segundo uma simulação por elementos finitos, com um resultado favorável ao modelo proposto neste trabalho.

No description available.

In this thesis, we study some aspects of the transmission of a monochromatic electromagnectic plane wave inciding into some configurations of multilayered films. Using a transfer matrix formalism, we firstly investigate the case of a binary sequence of N dielectric layers distributed in a random way, where the layer parameters follow the Bragg condition (nAdA = nBdB). We could observe that the mode for which the optical thickness of the layers corresponds to half-wavelength is insensitive to disorder and fully transparent. The average transmission in a frequency range around this resonance decays as 1/N1/2, and the localization length diverges quadratically as this resonance mode is approached. In the vicinity of the quarter-wavelength, the localization length diverges logarithmically and the frequency averaged transmission exhibits an stretched exponential dependence on the total thickness. At the quarter-wavelength resonance, the Lyapunov exponent for different realizations of disorder has a Gaussian distribution leading to distinct scaling laws for the geometric and arithmetic averages of the transmission. The scaling laws for the half-and quarter-wavelength modes are analogous to those found in electronic onedimensional Anderson models with random dimers and pure off-diagonal disorder, respectively, which are known to display similar violations of the usual exponential Anderson localization. These scale behavior were compared with the case of a disordered structure where one kind of constituint material is a metamaterial. We observe that the spectrally averaged transmission in a frequency range around the fully transparent resonant mode is shown to decay faster as the number of layer increases (1/N). The interplay of strong localization and the emergence of resonant modes within the gap leads to a non-monotonous disorder dependence of the transmission that reaches a minimum at an intermediate disorder strength. Using the same layer parameters of the first case, we investigate the influence of a binary aperiodic incommensurated sequence of layers. The aperiodicity is introduced by considering the sequence of refractive indices to follow a sinusoidal function whose phase ϕ varies as a power-law of the layer index (ϕ ∝ jν). For ν > 1 the resulting sequence is effectivelly uncorrelated leading to the usual Anderson localization of light. The crossover from a uniform structure at ν = 0 to a quasi-periodic structure at ν = 1 is signaled by a minimum at the spectrally averaged transmission. We perform a spectral analysis of the refractive index sequence to show its close connection to the main features exhibited by the averaged optical transmittance. The last case studied is about the inclusion of a cholesteric liquid crystal (ChLC) in the film composition. We considered a single-pitched ChLC multilayered system with quasiperiodic Fibonaccian phase defects as well as an alternate sequence of single-pitched ChLC and isotropic dielectric layers. Using the Berreman 4 × 4 matrix formalism, we numerically obtain the reflection spectrum and the chromaticity diagram of these structures. The associated chromaticity is shown to depend on the incidence angle. However, for the ChLC Fibonaccian phase defect system, the color shift can be controlled by the defect angle α. For the F4 generation and α = π/3, the chromaticity of the reflected light remains close to the white color region for a wide range of incidence angles, followed by a blue-shift at intermediate incidence angles. This is the setup that produces the nearest omnidirectional red-green-blue condition for the reflection spectrum. On the other hand, the structure with alternate ChLC and isotropic layers exhibits a complex sequence of color shifts when the incidence angle is increased. / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Nesta tese, estudamos vários aspectos da transmissividade de uma onda eletromagn ética plana monocromática incidindo sobre algumas configurações de filmes de multicamadas. Aplicando o formalismo de matriz de transferência, inicialmente tratamos o caso de uma sequencia binária de N camadas dielétricas distribuidas aleatoriamente, cujas características das camadas obedecem à condição de Bragg (nAdA = nBdB). Vemos que o modo para o qual o caminho óptico das camadas corresponde a meio comprimento de onda da luz incidente é insensível à desordem e completamente transparente. A média da transmissão na região de frequência ao redor desta ressonância cai com 1/N1/2 e o comprimento de localização diverge quadraticamente à medida que a frequência da luz se aproxima desta ressonância. Na vizinhança dos modos de quarto de onda, o comprimento de localização diverge logaritmicamente e a média espectral da transmissão apresenta uma dependência com N do tipo exponencial alongada. Ainda neste modo, o expoente de Lyapunov para diferentes realizações de desordem apresenta uma distribuição Gaussiana, levando a leis de escala distintas para as médias geométrica e aritmética da transmissão. As leis de escala para os modos de meio e quarto de onda apresentam-se análogas às obtidas no modelo eletrônico 1D de Anderson com dímeros aleatórios e com desordem nos termos de hopping do hamiltoniano respectivamente. Estes sistemas são conhecidos por apresentarem uma violação similar para a localização exponencial de Anderson usual. Estes comportamentos de escala foram comparados ao caso de uma estrutura desordenada onde uma das camadas é constituida por metamaterial. Vimos que a média espectral da transmissão ao redor do modo completamente transmissível decai de maneira mais rápida com o aumento do número de camadas (1/N). A ação conjunta da forte localização e do surgimento de modos ressonantes dentro da banda proibida leva a uma dependência não-monotônica da transmissão com o grau de desordem, que atinge um mínimo para um grau de desordem intermediário. Utilizando os mesmos parâmetros de construção do primeiro caso, investigamos a influência de uma distribuição binária de camadas aperiódica incomensurável. A aperiodicidade é introduzida baseando-se em uma lei senoidal cuja fase ϕ varia como uma lei de potência do índice das camadas (ϕ ∝ jν). Para ν > 1, a sequência resultante é efetivamente descorrelacionada, levando à localização de Anderson usual da luz. A transição de uma estrutura uniforme em ν = 0 para uma estrutura quasi-periódica em ν = 1 é assinalada por um mínino na média espectral da transmissão. Realizamos uma análise espectral do sequência de índices de refração para mostrar sua íntima relação com o comportamento encontrado para a média da transmissão. O último caso de multicamada estudado trata-se da utilização de cristal líquido colestérico (ChLC) na composição do filme. Consideramos uma estrutura de ChLC com ângulos de defeito que obedecem uma sequência quasi-periódica de Fibonacci assim como uma estrutura formada por camadas alternadas de ChLC e dielétrico isotrópico. Utilizando o formalismo matricial de Berreman, obtivemos o espectro de reflexão e o diagrama cromático destas estruturas. A cromaticidade associada apresentou dependência com o ângulo de incidência. No entanto, para o caso com ângulo de defeito Fibonnaciano, o deslocamento cromático pode ser controlado pelo ângulo de defeito α. Para a geração F4 com α = π/3, a cromaticidade da luz refletida se mantém próxima à região do branco para um largo intervalo de ângulos de incidência, seguido por um deslocamento para o azul em incidências intermediários. Esta configuração se aproxima de um refletor RGB omnidirecional. Por outro lado, a estrutura com camadas alternadas exibe uma sequência complexa de deslocamentos cromáticos com o aumento do ângulo e incidência.

Le but de la thèse était de comprendre l’effet du confinement en épaisseur nanométrique sur lespropriétés d’un polymère amorphe au-dessus de sa transition vitreuse. Le confinement est inévitablement lié auxeffets de surface générant le confinement et on imagine immédiatement la difficulté qu’il y a à séparer les effetsde confinement et d’interfaces. Des films multi-nanocouches alternées de PS et PC obtenus par un procédéspécifique d’extrusion ont été choisis pour l’étude car l’effet du confinement comme celui des interfaces sontmultipliés et plus facilement détectable. En espérant que des techniques expérimentales soient plus sensibles àl’un des effets, nous avons plus particulièrement sélectionné la calorimétrie, la RMN, la spectroscopiediélectrique et la rhéologie dynamique en cisaillement. En RMN du solide, nous avons pu montrer que lamobilité des cycles phénoliques du PC augmente dans des films PC/PS en proportions respectives 70/30 pourdes températures supérieures à la température de transition vitreuse du PS. Cet effet peut être plutôt attribué àl’interface sachant que l’épaisseur des couches de PC est plus importante. Les essais de relaxation diélectriquemontre clairement un écart entre les réponses des films multi-couches et ceux pour les structures bi-composants.Ces résultats ont été confirmés par les écarts obtenus entre la réponse diélectrique simulée des films multi-couches obtenue à partir des réponses propres du PC et PS et celle mesurée. Ces résultats sont très prometteurs,mais demandent des études supplémentaires pour une analyse en profondeur. Connaissant le comportementrhéologique dynamique en cisaillement des matériaux PS et PC, celui des films multi-couches a été prédit. Ilapparait que le module élastique du PS augmente significativement lorsque l’épaisseur des couches de PSdescend en dessous d’un seuil plutôt élevée : 150 à 200 nm. En dessous de ce seuil, la transition vitreuse du PSmesurée par calorimétrie augmente également sensiblement. Aucune des modélisations proposées ne permetd’expliquer avec suffisamment de fidélité les résultats expérimentaux. / The aim of the thesis was to elucidate the effect of confinement of amorphous phase of apolymer above its glass transition temperature being in contact with another polymer in a rigid state.Confinement is unavoidably connected with surfaces enforcing confinement. It is very difficult to separate theeffect of confinement from the effect of interfaces because both effects arise parallel and coincide. Multilayeredfilms were chosen as the base material for the studies because they contain multifold number of confined layerand response from confinement and interfaces is multifold increased. Hoping that some of experimentaltechniques are more sensitive to interfaces while others to confinement we selected the following:microcalorimetry, SSNMR, direlectrical spectroscopy and dynamic shear rheology. We have searched for theinfluence of PS on dynamics of phenyl rings of PC for PC/PS film with ratio 70/30 in the temperature rangefrom 296 K to 393 K employing PILGRIM pulse sequence. .We show that above the glass transition temperatureof PS, the PC component became more flexible. It is at the first glance the effect of the interface because there isno significant confinement of thicker PC layers. Dielectric relaxation spectroscopy measurements in our studyclearly provide evidence for deviations from a simple 2-phase structure in multilayered films PC/PS that is worthto be analyzed more in the future. The dielectric response of the multilayer samples was also modeled andcompared with experimental results. We obtained again discrepancies between the simulated spectra and themeasured spectra for multilayer films. Knowing the exact composition and viscoelastic behaviour of eachcomponent, the theoretical viscoelastic behavior of composites has been predicted numerically. Then,rheological tests have been made, and confronted with numerical predictions, to detect the confinement effect.The upper limit of thickness beyond which PS in confined layers at rubbery state becomes stiffer than in bulk isabout 150/200 nm. It appeared that the shear modulus of the thinnest PS layers (10 nm) is nearly 2.5 times largerthan that for bulk PS sample. We can note that Tg of PS layers also begins to increase beyond this upper limit ofthickness.. None of the experiment could clearly deliver the information about the effect of confinement orinterface on the behavior of PS layers alone. The results obtained here point out that separation of the effects ofconfinement and interfaces remains very difficult.

<p style="text-align: justify;">Kroz istoriju, otkrivanje novih materijala i njihovog dizajna dovodilo je do tehnolo&scaron;kih revolucija. U pro&scaron;lom veku, novi materijali naprednih svojstava uveli su elektronske uređaje u svakodnevni život čoveka. Industrija mikročipova predstavlja ogroman deo svetskog trži&scaron;ta, i traži neprestan razvoj da bi pružila bolje proizvode potro&scaron;ačima. Početkom ovog veka, nova grupa materijala, pod nazivom multiferoici, privukla je pažnju naučno-istraživačkog dru&scaron;tva u svetu. Ovi materijali poseduju jedinstvenu karakteristiku da istovremeno ispoljavaju vi&scaron;e od jedne feroične osobine (feroelektričnost, feromagnetizam, feroelastičnost), a &scaron;to je jo&scaron; važnije, mogu da ostvare interakciju među njima. Naime, magnetizacija multiferoika se može postići primenom spolja&scaron;njeg električnog polja, a takođe se mogu i polarisati primenom spolja&scaron;njeg magnetnog polja. Ovo vrlo interesantno svojstvo otvara potencijlanu primenu u oblasti hibridne računarske memorije, senzora, aktuatora, i dr. Sredinom pro&scaron;log veka, jednofazni multiferoici su prvi privukli pažnju, ali poseldnjih godina, kompozitni multiferoici su pokazali bolje rezultate u pogledu funkcionalnih karakteristika. Trend minijaturizacije je takođe prisutan u ovoj oblasti, stoga su multiferoični tanki filmovi vrlo atraktivni u istraživačkih krugovima ne samo zbog niske potro&scaron;nje električne energije, malog utro&scaron;ka meterijala i malih dimenzija, već i zbog dobre magnetoelektrične interakcije.&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; Glavni cilj ove doktorske disertacije je bio određivanje optimalnog procesa sinteze/depozicije, i vr&scaron;enje strukturne i funkcionalne karakterizacije multiferoičnih vi&scaron;eslojnih tankih filmova, sačinjenih od naizmenično deponovanih feroelektričnih BaTiO₃ i fero/ferimagnetnih NiFe₂O₄ slojeva (uglavnom na silicijumskim supstratima sa slojem platine). Različite strukture slojeva dizajnirane su u cilju određivanja optimalne, koja bi dala najvi&scaron;e vrednosti magnetoelektričnog efekta.&nbsp;&nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; U prvom koraku, sintetisani su stabilni solovi/rastvori prekursora, veličine čestica od nekoliko nanometara, reolo&scaron;kih karakteristika pogodnih za depoziciju tehnikama iz tečne faze. Vi&scaron;eslojni filmovi su dobijeni &quot;spin&quot; procesom nano&scaron;enja, pri čemu je termički tretman svakog sloja na 500 &deg;C bio neophodan radi potpunog otparavanja zaostalog rastvarača. Filmovi bez pukotina, ukupne debljine ispod 1 &mu;m, uniformne debljine sloja (60 nm sloj BaTiO₃ i 40 nm sloj NiFe₂O₄) i ravne povr&scaron;ine mogu biti dobijeni sinterovanjem u temperaturnom opsegu od 750 do 900 &deg;C. Strukturna karakterizacija je potvrdila sistem bez prisustva sekundarnih faza, sačinjen od perovskitnog BaTiO₃ i spinelnog NiFe₂O₄. Dielektrična merenja su bila u saglasnosti sa mikrostrukturnom analizom, i vrednostima dielektrične konstante tipične za nanostrukturni sistem, niske vrednosti dielektričnih gubitaka i male provodljivosti. Uticaj međuslojne polarizacije, koja nalikuje Debajeovoj relaksaciji, izražena kroz povećanje dielektrične konstante uspod 100 kHz, bio je jači u nižoj frekventnoj regiji na povi&scaron;enim temperaturama usled termičke aktivacije nosilaca naelektrisanja u feritnoj fazi. Samo čist BaTiO₃ film je pokazao slab feroelektrični histerezis nepotpune saturacije, malo vi&scaron;e polarizacije filma sinterovanog na 900 &deg;C usled ogrubljivanja strukture. Meuđuslojni efekti su takođe primećeni kod feroelektričnih merenja na sobnoj temperaturi, sa izraženijim prisustvom kada se primeni jače električno polje. Na osnovu dielektričnih i feroelektričnih merenja, zaključeno je da film sa debljim titanatnim i tanjim feritnim slojevima ima najverovatnije najbolji dizajn slojeva. Magnetne histerezisne petlje su snimljene na sobnoj temperaturi za čiste NiFe₂O₄ filmove i vi&scaron;eslojne filmove. Analizom vi&scaron;eslojnih filmova različitog dizajna slojeva, pretpostavljeno je da zatezanje nastalo mehaničkom interakcijom između titanatnih i feritnih slojeva jeste prisutno, i da raste sa povećanjem broja kontaktnih povr&scaron;ina, stoga film sa tanjim titanatnim i feritnim slojevima verovatno predstavlja najbolji izbor sa aspekta megnetnih osobina.</p> / <p>Through history, discovery of new materials and material design have led to technological revolutions. In the last century, new materials with advanced properties have introduced electronic devices in our everyday lives. Microchip industry represents one huge part of world market, and needs constant development to provide better products to consumers. In the beginning of this century, a novel group of materials, called multiferroics, have attracted close attention of research society around the world. These materials have a unique property to express more than one ferroic property simultaneously (feroelectricity, ferromagneticity, ferroelasticity), and more important, to achieve coupling between them. Namely, magnetization of multieferroic may be changed with application of external electric field, and they can be polarized with application of the external magnetic field. This is a very interesting property that opens the potential applications in fields of hybrid computer memory, sensors, actuators, etc. In the middle of last century, single phase multiferroics were the first to trigger interest in this special property, but in recent years, composite multiferroics have shown more promising results in terms of functional properties. The trend of miniaturization is also present in this field, so multiferroic thin films are very attractive for research not only because of low power and material consumption or small size, but also because of strong magnetoelectric coupling.<br />The main goal of this thesis was to determine optimal synthesis/deposition process, and perform structural and functional characterization of multiferroic multilayer thin films, composed of ferroelectric BaTiO3 and ferro/ferrimagnetic NiFe2O4 layers in alternating order (mostly on platinum coated silicon substrates). Different layer structures were designed in order to find optimal one which could show the strongest magnetoelectric effect.<br />In the first step, stable precursor sols/solutions were synthesized, with particle size of a few nanometes, and rheological properties suitable for solution deposition. The multilayered thin films were obtained by spin coating and thermal treatment of each layer on 500 &deg;C was necessary in order to completely evaporate traces of residual solvents. Crack free films with overall thickness below 1 &mu;m, uniform single layer thickness (60 nm of BaTiO3 layer and 40 nm of NiFe2O4) and flat surface can be obtained by sintering in temperature range from 750 to 900 &deg;C. Structural characterization confirmed that secondary phase free system with microstructure on nanometer scale was obtained, composed of perovskite BaTiO3 and spinel NiFe2O4. Dielectric measurements were in agreement with microstructural characterization, showing the values of dielectric constant typical for nanostructured system, low values of dielectric losses and low conductivity. The influence of interfacial polarization, resembling Debye behavior, expressed as a rise of dielectric constant below 100 kHz, was stronger in lower frequency range on higher temperatures due to thermal activation of mobile charge carriers in ferrite phase. Only the pure BaTiO3 films showed weak unsaturated ferroelectric hysteresis loops, with slightly higher polarization of films sintered on 900 &deg;C due to coarsening of the structure. The interface effects were also detected in ferroelectric measurements on room temperatures, showing increased presence when higher field is applied. Regarding dielectric and ferroelectric characterization, it was concluded that the multilayered films with thick titanate and thin ferrite layers may probably have the most promising layer design. Magnetic hysteresis loops were recorded on room temperatures for the pure NiFe2O4 and multilayers films. By analysis of different layer design of multilayers, it was assumed that mechanical straining between the ferrite and titanate layers may be present, and increases with the number of contact surfaces, thus the films with thinner titanate and ferrite layers may probably have the best layer design from aspect of magnetic properties.</p>

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No description available.