Estudo da deposição de filmes finos de BaTi(1-X)Zr(X)O3 por meio de planejamento Box-Behnken

Ferroelectric ceramics with perovskite structure (ABO3) are widely used in solid state memories (FeRAM’s and DRAM's) as well as multilayered capacitors, especially as a thin films. When doped with zirconium ions, BaTiO3-based materials form a solid solution known as barium zirconate titanate (BaTi1-xZrxO3). Also called BZT, this material can undergo significant changes in their electrical properties for a small variation of zirconium content in the crystal lattice. The present work is the study of the effects of deposition parameters of BaTi0,75Zr0,25O3 thin films by spin-coating method on their morphology and physical properties, through an experimental design of the Box-Behnken type. The resin used in the process has been synthesized by the polymeric precursor method (Pechini) and subsequently split into three portions each of which has its viscosity adjusted to 10, 20 and 30 mPa∙s by means of a rotary viscometer. The resins were then deposited on Pt/Ti/SiO2/Si substrates by spin-coating method on 15 different combinations of viscosity, spin speed (3000, 5500 and 8000 rpm) and the number of deposited layers (5, 8 and 11 layers) and then calcined at 800 ° C for 1 h. The phase composition of the films was analyzed by X-ray diffraction (XRD) and indexed with the JCPDS 36-0019. Surface morphology and grain size were observed by atomic force microscopy (AFM) indicating uniform films and average grain size around 40 nm. Images of the cross section of the films were obtained by scanning electron microscopy field emission (SEM-FEG), indicating very uniform thicknesses ranging from 140-700 nm between samples. Capacitance measurements were performed at room temperature using an impedance analyzer. The films presented dielectric constant values of 55-305 at 100kHz and low dielectric loss. The design indicated no significant interaction effects between the deposition parameters on the thickness of the films. The response surface methodology enabled better observes the simultaneous effect of variables.

Structure and dynamics of thin colloidal films

This thesis begins by studying the thickness of evaporative spin coated colloidal crystals and demonstrates the variation of the thickness as a function of suspension concentration and spin rate. Particularly, the films are thicker with higher suspension concentration and lower spin rate. This study also provides evidence for the reproducibility of spin coating in terms of the thickness of the resulting colloidal films. These colloidal films, as well as the ones obtained from various other methods such as convective assembly and dip coating, usually possess a crystalline structure. Due to the lack of a comprehensive method for characterization of order in colloidal structures, a procedure is developed for such a characterization in terms of local and longer range translational and orientational order. Translational measures turn out to be adequate for characterizing small deviations from perfect order, while orientational measures are more informative for polycrystalline and highly disordered crystals. Finally, to obtain an understanding of the relationship between dynamics and structure, the dynamics of colloids in a quasi-2D suspension as a function of packing fraction is studied. The tools that are used are mean square displacement (MSD) and the self part of the van Hove function. The slow down of dynamics is observed as the packing fraction increases, accompanied with the emergence of 6-fold symmetry within the system. The dynamics turns out to be non-Gaussian at early times and Gaussian at later times for packing fractions below 0.6. Above this packing fraction, the dynamics is non-Gaussian at all times. Also the diffusion coefficient is calculated from MSD and the van Hove function. It goes down as the packing fraction is increased.

Fabrication of sub-10 nm lamellar structures by solvent vapour annealing of block copolymers

Fabrication of nanoscale patterns through the bottom-up approach of self-assembly of phase-separated block copolymers (BCP) holds promise for nanoelectronics applications. For lithographic applications, it is useful to vary the morphology of BCPs by monitoring various parameters to make “from lab to fab” a reality. Here I report on the solvent annealing studies of lamellae forming polystyrene-blockpoly( 4-vinylpyridine) (PS-b-P4VP). The high Flory-Huggins parameter (χ = 0.34) of PS-b-P4VP makes it an ideal BCP system for self-assembly and template fabrication in comparison to other BCPs. Different molecular weights of symmetric PS-b-P4VP BCPs forming lamellae patterns were used to produce nanostructured thin films by spin-coating from mixture of toluene and tetrahydrofuran(THF). In particular, the morphology change from micellar structures to well-defined microphase separated arrangements is observed. Solvent annealing provides a better alternative to thermal treatment which often requires long annealing periods. The choice of solvent (single and dual solvent exposure) and the solvent annealing conditions have significant effects on the morphology of films and it was found that a block neutral solvent was required to realize vertically aligned PS and P4VP lamellae. Here, we have followed the formation of microdomain structures with time development at different temperatures by atomic force microscopy (AFM). The highly mobilized chains phase separate quickly due to high Flory-Huggins (χ) parameter. Ultra-small feature size (~10 nm pitch size) nanopatterns were fabricated by using low molecular weight PSb- P4VP (PS and P4VP blocks of 3.3 and 3.1 kg mol-1 respectively). However, due to the low etch contrast between the blocks, pattern transfer of the BCP mask is very challenging. To overcome the etch contrast problem, a novel and simple in-situ hard mask technology is used to fabricate the high aspect ratio silicon nanowires. The lamellar structures formed after self-assembly of phase separated PS-b-P4VP BCPs were used to fabricate iron oxide nanowires which acted as hard mask material to facilitate the pattern transfer into silicon and forming silicon nanostructures. The semiconductor and optical industries have shown significant interest in two dimensional (2D) molybdenum disulphide (MoS2) as a potential device material due to its low band gap and high mobility. However, current methods for its synthesis are not ‘fab’ friendly and require harsh environments and processes. Here, I also report a novel method to prepare MoS2 layered structures via self-assembly of a PS-b-P4VP block copolymer system. The formation of the layered MoS2 was confirmed by XPS, Raman spectroscopy and high resolution transmission electron microscopy.

3D nanoimprint technology for NIR Fabry-Pérot filter arrays

Im Rahmen dieser Arbeit wird die Herstellung von miniaturisierten NIR-Spektrometern auf Basis von Fabry-Pérot (FP) Filter Arrays behandelt. Bisher ist die kostengünstige Strukturierung von homogenen und vertikal erweiterten Kavitäten für NIR FP-Filter mittels Nanoimprint Technologie noch nicht verfügbar, weil die Qualität der Schichten des Prägematerials unzureichend ist und die geringe Mobilität der Prägematerialien nicht ausreicht, um die vertikal erweiterten Kavitäten zu füllen. Diese Arbeit konzentriert sich auf die Reduzierung des technischen Aufwands zur Herstellung von homogenen und vertikal erweiterten Kavitäten. Zur Strukturierung der Kavitäten wird ein großflächiger substratkonformer UV-Nanoimprint Prozess (SCIL - Substrate Conformal Imprint Lithoghaphy) verwendet, der auf einem Hybridstempel basiert und Vorteile von harten und weichen Stempeln vereint. Um die genannten Limitierungen zu beseitigen, werden alternative Designs der Kavitäten untersucht und ein neues Prägematerial eingesetzt. Drei Designlösungen zur Herstellung von homogenen und erweiterten Kavitäten werden untersucht und verglichen: (i) Das Aufbringen des Prägematerials mittel mehrfacher Rotationsbeschichtung, um eine höhere Schichtdicke des Prägematerials vor dem Prägeprozess zu erzeugen, (ii) die Verwendung einer hybriden Kavität bestehend aus einer strukturierten Schicht des Prägematerials eingebettet zwischen zwei Siliziumoxidschichten, um die Schichtdicke der organischen Kavität zu erweitern und (iii) die Optimierung des Prägeprozesses durch Verwendung eines neuen Prägematerials. Die mit diesen drei Ansätzen hergestellten FP-Filter Arrays zeigen, hohe Transmissionen (beste Transmission > 90%) und kleine Linienbreiten (Halbwertsbreiten <5 nm).

Compósitos de polímero-cerâmica para condensadores incorporados

A necessidade de produção de dispositivos eletrónicos mais eficientes e a sua miniaturização tem sido um dos principais desígnios da indústria eletrónica. Assim surgiu a necessidade de melhorar o desempenho das designadas placas de circuito impresso, tornando-as simultaneamente mais flexíveis, com menos ruído, mais estáveis face a variações bruscas de temperatura e que permitam operar numa vasta gama de frequências e potências. Para tal, uma das estratégias que tem vindo a ser estudada é a possibilidade de incorporar os componentes passivos, nomeadamente condensadores, sob a forma de filme diretamente no interior da placa. Por forma a manter uma elevada constante dielétrica e baixas perdas, mantendo a flexibilidade, associada ao polímero, têm sido desenvolvidos os designados compósitos de matriz polimérica. Nesta dissertação procedeu-se ao estudo do comportamento dielétrico e elétrico da mistura do cerâmico CaCu3Ti4O12 com o copolímero estireno-isoprenoestireno. Foram preparados filmes com diferentes concentrações de CCTO, recorrendo ao método de arrastamento, em conjunto com o Centro de Polímeros da Eslováquia. Foram também preparados filmes por spin-coating para as mesmas concentrações. Usaram-se dois métodos distintos para a preparação do pó de CCTO, reação de estado sólido e sol-gel. Foi realizada a caraterização estrutural (difração de raios-X. espetroscopia de Raman), morfológica (microscopia eletrónica de varrimento) e dielétrica aos filmes produzidos. Na caracterização dielétrica determinou-se o valor da constante dielétrica e das perdas para todos os filmes, à temperatura ambiente, bem como na gama de temperatura entre os 200 K e os 400 K, o que permitiu identificar existência de relaxações vítreas e subvítreas, e assim calcular as temperaturas de transição vítrea e energias de ativação, respetivamente. Foram realizados testes de adesão e aplicada a técnica de análise mecânica dinâmica para o cálculo das temperaturas de transição vítrea nos filmes preparados pelo método de arrastamento. Estudou-se ainda qual a lei de mistura que melhor se ajusta ao comportamento dielétrico do nosso compósito. Verificou-se que é a lei de Looyenga generalizada a que melhor se ajusta à resposta dielétrica dos compósitos produzidos.

Design of functional hybrid coatings with anti-biofouling, self-cleaning and anti-reflecting applications

263 p.

Detection of explosive vapors using organic thin-film transistors

Field effect transistors (FETs) based on organic materials were investigated as sensors for detecting 2,4,6-trinitrotoluene (TNT) vapors. Several FET devices were fabricated using two types of semiconducting organic materials, solution processed polymers deposited by spin coating and, oligomers (or small molecules) deposited by vacuum sublimation. When vapors of nitroaromatic compounds bind to thin films of organic materials which form the transistor channel, the conductivity of the thin film increases and changes the transistor electrical characteristic. The use of the amplifying properties of the transistor represents a major advantage over conventional techniques based on simple changes of resistance in polymers frequently used in electronic noses.

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.

Studio di parametri fondamentali di transistor elettrochimici organici microfabbricati

Questo elaborato tratta il ruolo dei transistor elettrochimici microfabbricati (OECTs) nel campo della Bioelettronica. Nello specifico, il focus della tesi ruota attorno alla categoria di OECTs basati su poli(3,4-etilenediossitiofene)(PEDOT) con drogaggio a base di poli(3,4-etilenediossitiofene)(PSS) a dare il PEDOT:PSS. Nella struttura del seguente elaborato, il primo capitolo è dedicato all’introduzione dei polimeri conduttori organici; materiali che hanno suscitato interesse grazie alle loro proprietà conduttive coniugate a un’alta stabilità, costi di produzione convenienti e alta riproducibilità; infine la biocompatibilità e le proprietà di trasduzione di informazioni attinenti al campo della biologia in segnale elettronico li ha resi lo strumento di maggior interesse nel campo della bioelettronica. Particolare focus è posto sulla categoria degli OECTs basati su PEDOT:PSS, sulle loro caratteristiche, la modellizzazione ed il ruolo del polimero d’interesse. Ciò è trattato nel secondo capitolo assieme ai regimi di funzionamento di questi dispositivi. Nel seguito si sono riportate le procedure seguite per la realizzazione dei dispositivi studiati: dalla preparazione del substrato ai processi litografici mirati alla creazione di un pattern per il circuito, fino alla deposizione per spin-coating del polimero in soluzione. Si sono descritti e chiariti il ruolo degli elementi del dispositivo, quali elettrodi ed elettrolita nella conducibilità del canale. Si è proceduto a descrive il set up strumentale e la strumentazione. Nell’ultimo capitolo si descrivono le misure sperimentali svolte e si commentano i risultati. Le misure svolte sul dispositivo constano innanzitutto della caratterizzazione dello stesso, previa analisi a vari voltaggi forniti sul gate e per varie geometrie del canale.

Antireflection coatings from analogy between electron scattering and spin precession

We use the analogy between scattering of a wave from a potential, and the precession of a spin-half particle in a magnetic field, to gain insight into the design of an antireflection coating for electrons in a semiconductor superlattice. It is shown that the classic recipes derived for optics are generally not applicable due to the different dispersion law for electrons. Using the stability conditions we show that a Poisson distribution of impedance steps is a better approximation than is a Gaussian distribution. Examples are given of filters with average transmissivity exceeding 95% over an allowed band.

Laser ablation in titanium implants followed by biomimetic hydroxyapatite coating: Histomorphometric study in rabbits

Titanium surface texture and chemistry modification successfully improves the host response and consequently the bone-to-implant contact surrounding dental implants. The aim of the present study was to investigate, using histomorphometrical-analysis, the effects of titanium surface modification by laser-ablation (Nd:YAG) followed by thin chemical deposition of HA. Forty-eight rabbits received one implant by tibiae of AS-machined (MS), laser-modified (LMS), or biomimetic hydroxyapatite-coated (HA) surface. Bone-to-implant contact (BIC) and bone area (BBT) were evaluated after 4, 8, and 12 weeks, at cortical and cancellous regions. Average BIC in the cortical region was higher (P < 0.001) on the LMS and HA implants for all periods, with no differences between LMS and HA. For the cancellous area, the LMS and HA implants showed higher (P < 0.01) BIC than MS at the initial periods. The LMS and HA showed similar values in the cortical region, but a tendency of higher values for HA in the cancellous region was observed in all periods. For the BBT, the differences were found only between HA and MS after 4 weeks in the cortical region (P < 0.05), and after 12 weeks in the cancellous area (P < 0.05). Our results showed that HA biomimetic coating preceded by laser treatment induced the contact osteogenesis and allowed the formation of a more stable boneimplant interface, even in earlier periods. Microsc. Res. Tech., 2012. (C) 2012 Wiley Periodicals, Inc.

Extreme Harmonic Generation In Electrically Driven Spin Resonance.

We report the observation of multiple harmonic generation in electric dipole spin resonance in an InAs nanowire double quantum dot. The harmonics display a remarkable detuning dependence: near the interdot charge transition as many as eight harmonics are observed, while at large detunings we only observe the fundamental spin resonance condition. The detuning dependence indicates that the observed harmonics may be due to Landau-Zener transition dynamics at anticrossings in the energy level spectrum.

Measurement Of Longitudinal Spin Asymmetries For Weak Boson Production In Polarized Proton-proton Collisions At Rhic.

We report measurements of single- and double-spin asymmetries for W^{±} and Z/γ^{*} boson production in longitudinally polarized p+p collisions at sqrt[s]=510  GeV by the STAR experiment at RHIC. The asymmetries for W^{±} were measured as a function of the decay lepton pseudorapidity, which provides a theoretically clean probe of the proton's polarized quark distributions at the scale of the W mass. The results are compared to theoretical predictions, constrained by polarized deep inelastic scattering measurements, and show a preference for a sizable, positive up antiquark polarization in the range 0.05

Paired Evaluation Of Calvarial Reconstruction With Prototyped Titanium Implants With And Without Ceramic Coating.

To investigate the osseointegration properties of prototyped implants with tridimensionally interconnected pores made of the Ti6Al4V alloy and the influence of a thin calcium phosphate coating. Bilateral critical size calvarial defects were created in thirty Wistar rats and filled with coated and uncoated implants in a randomized fashion. The animals were kept for 15, 45 and 90 days. Implant mechanical integration was evaluated with a push-out test. Bone-implant interface was analyzed using scanning electron microscopy. The maximum force to produce initial displacement of the implants increased during the study period, reaching values around 100N for both types of implants. Intimate contact between bone and implant was present, with progressive bone growth into the pores. No significant differences were seen between coated and uncoated implants. Adequate osseointegration can be achieved in calvarial reconstructions using prototyped Ti6Al4V Implants with the described characteristics of surface and porosity.

Site Specific Spin Dynamics In Bafe2as2: Tuning The Ground State By Orbital Differentiation.

The role of orbital differentiation on the emergence of superconductivity in the Fe-based superconductors remains an open question to the scientific community. In this investigation, we employ a suitable microscopic spin probe technique, namely Electron Spin Resonance (ESR), to investigate this issue on selected chemically substituted BaFe2As2 single crystals. As the spin-density wave (SDW) phase is suppressed, we observe a clear increase of the Fe 3d bands anisotropy along with their localization at the FeAs plane. Such an increase of the planar orbital content is interestingly independent of the chemical substitution responsible for suppressing the SDW phase. As a consequence, the magnetic fluctuations in combination with this particular symmetry of the Fe 3d bands are propitious ingredients for the emergence of superconductivity in this class of materials.