Orientador: José Manoel Balthazar / Banca: Átila Madureira Bueno / Banca: Bento Rodrigues de pontes Junior / Resumo: Desde 1986, quando Binnig et al (1986) criaram o microscópio de força atômica (AFM), esse aparelho se tornou um dos mais importantes microscópios de varredura (SPM), sendo usado para análise de DNA, nanotubos, etc. (Rützel et al, 2006). O AFM tem como componente principal uma microviga, com uma ponteira em uma das extremidades, que vibra próximo de sua frequencia de ressonância para mandar sinais a um fotodetector que traduz esse sinal e gera as imagens da superfície da amostra. O modo de operação tapping é o mais usado, e o comportamento caótico é muito comum nesse modo de operação, por esse motivo, AFM se tornou um assunto muito importante no mundo científico. Nesse trabalho, a microviga é modelada com o uso das equações de Bernoulli, as interações entre ela e a amostra são modeladas usando o potencial de Lennard Jones. Simulações numéricas detectam movimento caótico no sistema, a necessidade de estabilizá-lo nos leva a usar os seguintes métodos: Método do Balanço Harmônico, sincronização de Sistemas Não Lineares, Método das Equações de Estado Dependentes de Riccati (SDRE), Método de Realimentação de Sinal Atrasado. Por fim, a aplicação dos métodos se mostra eficiente, com pequeno erro e fácil implementação / Abstract: Since 1986, when Binnig et al (1986) created the atomic force microscope (AFM), this unit became one of the most important scanning probe microscopes (SPM) being used for DNA analysis, nano tubes, etc. (Rutzel et al, 2006). The AFM has as a main component, a micro cantilever, with a tip at its free end, which vibrates near its resonance frequency to send signals to a photo detector that translates the signal and generates images of the sample surface. The tapping mod of operation is the most widely used and chaotic behavior is very common in this mode, therefore, AFM has become a very interesting subject in the scientific world. In this work, the micro cantilever is modeled using Bernoulli's equation and the interactions between the tip and the sample are modeled using the Lennard Jones potential. Numerical simulations detect chaotic motion in the system and the need to stabilize it leads us to use the following methods, Harmonic Balance Method; Synchronization of Nonlinear Systems; the State Dependent Riccati Equation control method (SDRE); the Method of Feedback Delay. Finally, the application of the methods proved to be effective, with small error and easy implementation / Mestre

Metrological data from sample surfaces can be obtained by using a variety of profilometry methods. Atomic Force Microscopy (AFM), which relies on contact inter-atomic forces to extract topographical images of a sample, is one such method that can be used on a wide range of surface types, with possible nanometer range resolution. However, AFM images are commonly distorted by convolution, which reduces metrological accuracy. This type of distortion is more significant when the sample surface contains high aspect ratio features such as lines, steps or sharp edges - structures commonly found in semiconductor devices and applications. Aiming at mitigating these distortions and recovering metrology soundness, we introduce a novel image deconvolution scheme based on the principle of stereo imaging. Multiple images of a sample, taken at different angles, allow for separation of convolution artifacts from true topographic data. As a result, perfect sample reconstruction and probe shape estimation can be achieved in certain cases. Additionally, shadow zones, which are areas of the sample that cannot be probed by the AFM, are greatly reduced. Most importantly, this technique does not require a priori probe characterization. It also reduces the need for slender or sharper probes, which, on one hand, induce less convolution distortion but, on the other hand, are more prone to wear and damage, thus decreasing overall system reliability. / Singapore-MIT Alliance (SMA)

In the past two decades depth-sensing indentation has becomea widely used technique to measure the mechanical properties ofmaterials. This technique is particularly suitable for thecharacterisation of materials at sub-micro or nano scale thoughthere is a tendency to extend its application to the micro ormacro scale. The load-penetration depth curve of depth-sensingindentation is a characteristic of a material and can be usedfor analysing various mechanical properties in addition tohardness. This thesis deals with the mechanicalcharacterisation of bulk materials, thin films and coatings,gradient materials, and composites using depth-sensingindentation. Finite element method has been resorted to as atool to understand the indentation behaviour of materials. The piling-up or sinking-in behaviour of materials plays animportant role in the accurate determination of materialsproperties using depth-sensing indentation. Finite elementsimulations show that the piling-up or sinking-in behaviour isdetermined by the material parameters, namelyE/σyratio and strain hardening exponent orexperimental parameterhe/hmaxratio, and the contact friction. Anempirical model has been proposed to relate the contact area ofindentation to theE/σyratio and thehe/hmaxratio and used to predict thepiling-up orsinking-in of materials. The existence of friction is found toenhance the sinking-in tendency of materials. A generalrelationship between the hardness and the indentationrepresentative stress valid for both soft and hard materialshas been obtained. A possible method to estimate the plasticproperties of bulk materials has been suggested. Measuring the coating-only properties requires theindentation to be done within a critical penetration depthbeyond which substrate effect comes in. The ratio of thecritical penetration depth to the coating thickness determinedby nanoindentation is independent of coating thickness andabout 0.2 for gold / nickel, 0.4 for aluminium / BK7 glass, and0.2 for diamond-like-carbon / M2 steel and alumina / nickel.Finite element simulations show that this ratio is dependent onthe combination of the coating and the substrate and moresensitive to differences in the elastic properties than in theplastic properties of the coating/substrate system. Thedeformation behaviour of coatings, such as, piling-up of thesoft coatings and cracking of the hard coatings, has also beeninvestigated using atomic force microscope. The constraint factors, 2.24 for WC phase and 2.7 for WC-Cocemented carbides, are determined through nanoindentation andfinite element simulations. A modified hardness model of WC-Cocemented carbides has been proposed, which gives a betterestimation than the Lee and Gurland hardness model. Finiteelement method has also been used to investigate theindentation behaviour of WC-Co gradient coatings. Keywords:depth-sensing indentation, nanoindentation,finite element method, atomic force microscope, mechanicalproperties, hardness, deformation, dislocations, cracks,piling-up, sinking-in, indentation size effect, thin coatings,composite, gradient materials, WC-Co, diamond-like-carbon,alumina, gold, aluminium, nickel, BK7 glass, M2 steel.

The fabrication characteristic of etching and deposition of focused ion beam (FIB) on the submicron structure of silica and quartz glass was investigated. FIB has several advantages such as high sensitivity, high material removal rate, and direct fabrication in some selected areas without the use of etching mask, etc. In this study, silicon and quartz glass materials etched by FIB were used for fast fabrication of 3-D submicron structures to investigate the differences between the samples before and after fabrication. The expansion effect of silicon with sputtered platinum on surface is compared with Pyrex glass with sputtered chromium on surface. The result shows the side wall of structure in the center wouldn¡¦t be vertical after etching and trimming on the quartz glass and the silicon substrate. Trenches with different depth and width on the surface of silicon were etched by FIB and measured by Atomic Force Microscope. Lines with different interval were deposited by FIB on the surface of quartz glass and were measured by Atomic Force Microscope.

<p>Nucleic acids are subjected to many different mechanical loadings inside. These loadings could cause large deformations and conformational changes to these molecules. This is why the mechanical properties of nucleic acids are so important to their functions. Here we use a newly designed and built high-performance AFM force spectrometer, supplemented with molecular dynamics simulations and NMR spectroscopy to investigate the relationship between mechanical properties and structure of different nucleic acids.</p><p>To test the mechanical properties of nucleic acids, we successfully designed and purpose-built a single molecule puller, an instrument to physically stretch single molecules, at a fraction of the cost of a commercial AFM instrument. This instrument has similar force noise to hybrid instruments, while also exhibiting significantly lower drift, on the order of five times lower. This instrument allows the measurement of subtle transitions as a molecule is stretched. With the addition of a lock-in amplifier, we possibly could obtain better force resolution, the order of femtonewtons. </p><p>We find that helical structure does indeed have an effect on the mechanical properties of double-stranded DNA. As the A-form double helix has a shorter, wider structure compared to the B-form helix, its force spectra exhibit a shorter initial length before the overstretching force plateau, compared to B-form DNA. Contrarily, the Z-form double helix has a narrower, more extended helical structure than B-form DNA, and we see this fact manifest in the force spectra of Z-DNA, which has a longer initial length before the overstretching force plateau. Also, interestingly, we find that neither A, nor Z-DNA force spectra display the second melting force plateau. Indicating this plateau is not necessarily cause by melting of strands apart, but rather a feature of B-DNA. </p><p>To better understand the forces that stabilized these different structures, specifically base stacking, we also mechanically characterize different single-stranded helical polynucleotides using AFM based force spectroscopy. We expand on previous studies by confirming that single helical polynucleotides undergo a force transition at a force of ~20 pN as they are uncoiled, and also demonstrating, that when stretched beyond this force transition, the molecules behave differently depending on base sequence and backbone sugar. Specifically, the force spectra of poly-adenylic acid possess a linear force region, which persists to ~300 pN, after the force plateau. We also observe that poly-deoxyadenylic acid is comparatively stiffer than other polynucleotides after undergoing two force transitions. By supplementing our force spectroscopic data with MD simulations and NMR spectroscopy, we find that base stacking in adenine is quite strong, persisting above 100 pN. We find that initial helical structure, which is defined by base stacking and backbone sugar, guides the stretching pathway of the polynucleotides. This finding can possibly be extrapolated to the elasticity of double-stranded DNA.</p> / Dissertation

<p>In the past two decades depth-sensing indentation has becomea widely used technique to measure the mechanical properties ofmaterials. This technique is particularly suitable for thecharacterisation of materials at sub-micro or nano scale thoughthere is a tendency to extend its application to the micro ormacro scale. The load-penetration depth curve of depth-sensingindentation is a characteristic of a material and can be usedfor analysing various mechanical properties in addition tohardness. This thesis deals with the mechanicalcharacterisation of bulk materials, thin films and coatings,gradient materials, and composites using depth-sensingindentation. Finite element method has been resorted to as atool to understand the indentation behaviour of materials.</p><p>The piling-up or sinking-in behaviour of materials plays animportant role in the accurate determination of materialsproperties using depth-sensing indentation. Finite elementsimulations show that the piling-up or sinking-in behaviour isdetermined by the material parameters, namely<i>E/σ</i><i>y</i>ratio and strain hardening exponent orexperimental parameter<i>h</i><i>e</i><i>/h</i><i>max</i>ratio, and the contact friction. Anempirical model has been proposed to relate the contact area ofindentation to the<i>E/σ</i><i>y</i>ratio and the<i>h</i><i>e</i><i>/h</i><i>max</i>ratio and used to predict thepiling-up orsinking-in of materials. The existence of friction is found toenhance the sinking-in tendency of materials. A generalrelationship between the hardness and the indentationrepresentative stress valid for both soft and hard materialshas been obtained. A possible method to estimate the plasticproperties of bulk materials has been suggested.</p><p>Measuring the coating-only properties requires theindentation to be done within a critical penetration depthbeyond which substrate effect comes in. The ratio of thecritical penetration depth to the coating thickness determinedby nanoindentation is independent of coating thickness andabout 0.2 for gold / nickel, 0.4 for aluminium / BK7 glass, and0.2 for diamond-like-carbon / M2 steel and alumina / nickel.Finite element simulations show that this ratio is dependent onthe combination of the coating and the substrate and moresensitive to differences in the elastic properties than in theplastic properties of the coating/substrate system. Thedeformation behaviour of coatings, such as, piling-up of thesoft coatings and cracking of the hard coatings, has also beeninvestigated using atomic force microscope.</p><p>The constraint factors, 2.24 for WC phase and 2.7 for WC-Cocemented carbides, are determined through nanoindentation andfinite element simulations. A modified hardness model of WC-Cocemented carbides has been proposed, which gives a betterestimation than the Lee and Gurland hardness model. Finiteelement method has also been used to investigate theindentation behaviour of WC-Co gradient coatings.</p><p><b>Keywords:</b>depth-sensing indentation, nanoindentation,finite element method, atomic force microscope, mechanicalproperties, hardness, deformation, dislocations, cracks,piling-up, sinking-in, indentation size effect, thin coatings,composite, gradient materials, WC-Co, diamond-like-carbon,alumina, gold, aluminium, nickel, BK7 glass, M2 steel.</p>

A new experimental method to characterize the mechanical properties of metallic nanowires is introduced. An accurate and fast mechanical characterization of nanowires requires simultaneous imaging and testing of nanowires. However, there exists no practical experimental procedure in the literature that provides a quantitative mechanical analysis and imaging of the nanowire specimens during mechanical testing. In this study, a customized atomic force microscope (AFM) is placed inside a scanning electron microscope (SEM) in order to locate the position of the nanowires. The tip of the atomic force microscope cantilever is utilized to bend and break the nanowires. The nanowires are prepared by electroplating of nickel ions into the nanoscale pores of the alumina membranes. Force versus bending displacement responses of these nanowires are measured experimentally and then compared against those of the finite element analysis and peridynamic simulations to extract their mechanical properties through an inverse approach.The average elastic modulus of nickel nanowires, which are extracted using finite element analysis and peridynamic simulations, varies between 220 GPa and 225 GPa. The elastic modulus of bulk nickel published in the literature is comparable to that of nickel nanowires. This observation agrees well with the previous findings on nanowires stating that the elastic modulus of nanowires with diameters over 100nm is similar to that of bulk counterparts. The average yield stress of nickel nanowires, which are extracted using finite element analysis and peridynamic simulations, is found to be between 3.6 GPa to 4.1 GPa. The average value of yield stress of nickel nanowires with 250nm diameter is significantly higher than that of bulk nickel. Higher yield stress of nickel nanowires observed in this study can be explained by the lower defect density of nickel nanowires when compared to their bulk counterparts.Deviation in the extracted mechanical properties is investigated by analyzing the major sources of uncertainty in the experimental procedure. The effects of the nanowire orientation, the loading position and the nanowire diameter on the mechanical test results are quantified using ANSYS simulations. Among all of these three sources of uncertainty investigated, the nanowire diameter has been found to have the most significant effect on the extracted mechanical properties.

Made available in DSpace on 2014-06-11T19:28:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-11-10Bitstream added on 2014-06-13T19:58:06Z : No. of bitstreams: 1 rodrigues_ks_me_bauru.pdf: 3671952 bytes, checksum: 95922ebe5feb1ccd5d65c466e158d7a8 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Universidade Estadual Paulista (UNESP) / Desde 1986, quando Binnig et al (1986) criaram o microscópio de força atômica (AFM), esse aparelho se tornou um dos mais importantes microscópios de varredura (SPM), sendo usado para análise de DNA, nanotubos, etc. (Rützel et al, 2006). O AFM tem como componente principal uma microviga, com uma ponteira em uma das extremidades, que vibra próximo de sua frequencia de ressonância para mandar sinais a um fotodetector que traduz esse sinal e gera as imagens da superfície da amostra. O modo de operação tapping é o mais usado, e o comportamento caótico é muito comum nesse modo de operação, por esse motivo, AFM se tornou um assunto muito importante no mundo científico. Nesse trabalho, a microviga é modelada com o uso das equações de Bernoulli, as interações entre ela e a amostra são modeladas usando o potencial de Lennard Jones. Simulações numéricas detectam movimento caótico no sistema, a necessidade de estabilizá-lo nos leva a usar os seguintes métodos: Método do Balanço Harmônico, sincronização de Sistemas Não Lineares, Método das Equações de Estado Dependentes de Riccati (SDRE), Método de Realimentação de Sinal Atrasado. Por fim, a aplicação dos métodos se mostra eficiente, com pequeno erro e fácil implementação / Since 1986, when Binnig et al (1986) created the atomic force microscope (AFM), this unit became one of the most important scanning probe microscopes (SPM) being used for DNA analysis, nano tubes, etc. (Rutzel et al, 2006). The AFM has as a main component, a micro cantilever, with a tip at its free end, which vibrates near its resonance frequency to send signals to a photo detector that translates the signal and generates images of the sample surface. The tapping mod of operation is the most widely used and chaotic behavior is very common in this mode, therefore, AFM has become a very interesting subject in the scientific world. In this work, the micro cantilever is modeled using Bernoulli's equation and the interactions between the tip and the sample are modeled using the Lennard Jones potential. Numerical simulations detect chaotic motion in the system and the need to stabilize it leads us to use the following methods, Harmonic Balance Method; Synchronization of Nonlinear Systems; the State Dependent Riccati Equation control method (SDRE); the Method of Feedback Delay. Finally, the application of the methods proved to be effective, with small error and easy implementation

Le but de cette thèse était tout d'abord de comprendre les théories physiques qui décrivent la dynamique des polymères à l'échelle macroscopique. Le modèle de Rouse et la théorie d'enchevêtrement de De Gennes décrivent la dynamique des polymères non enchevêtrés et enchevêtrés, respectivement. Nous avons étudiés les différentes transitions entre ces deux régimes en utilisant deux techniques expérimentales: Broadband Dielectric Spectroscopy (BDS) et rhéologie. Les effets d'enchevêtrement sur les spectres diélectriques ont été discutés. Un test complet du modèle de Rouse à été effectué sur en comparant les prédictions de ce modèle pour la dépendance en fréquence de la permittivité diélectrique et du module de cisaillement aux données expérimentales. Ensuite nous avons développés des méthodes bas"s sur la microscopie à force électrostatique afin d'étudier les propriétés diélectriques locales. En utilisant la simulation numérique de la Méthode des Charges Equivalentes la constante diélectrique a été quantifiée à partir de la mesure du gradient de force crée par un potentiel statique entre une pointe et un diélectrique. Cette méthode permet d'imager la constante diélectrique avec une résolution spatial de 40 nm. Le retard de phase de la composante en 2ω de la force ou du gradient de force crée par un voltage alternatif est relié aux pertes diélectriques. En mesurant cette quantité nous avons montré que la dynamique était plus rapide proche d'une interface libre et nous avons développé un mode d'imagerie des pertes diélectriques. Cette méthode simple pourrait être appliqué en biologie ou matière molle en générale afin d'étudier des variations locales de constantes diélectriques. / The aim of this thesis was first to understand the physical theories that describe the dynamics of linear polymers at the macroscopic scale. Rouse and the reptational tube theory describe the large scale dynamics of unentangled and entangled polymers respectively. Using Broadband Dielectric Spectroscopy (BDS) and rheology we have studied the different transition between these two regimes. Effects of entanglement on dielectric spectra will be discussed (Rheologica Acta. 49(5):507-512). Avoiding the segmental relaxation contribution and introducing a distribution in the molecular weight we have been able to perform a comparison of the Rouse model with experiment dielectric and rheological data (Macromolecules 42(21): 8492-8499) Then we have developed EFM-based methods in order to study the local dynamics. Using the numerical simulation of the Equivalent Charge Method, the value of the static dielectric permittivity has been quantified from the measurement of the force gradient created by a VDC potential between a tip and a grounded dielectric (Journal of Applied Physics 106(2):024315). This method allows a quantitative mapping of dielectric properties with a 40 nm spatial resolution and is therefore suitable for the study of nano-defined domains (Physical Review E 81(1): 010801). The electrical phase lags in the 2ω components of the force or force gradient created by VAC voltage, ΔΦ2ω, are related with dielectric losses. Measuring the frequency dependence of ΔΦ2ω Crieder et al (Applied Physics Letters 91(1):013102) have shown that the dynamics at the near free surface of polymer films is faster than the one in bulk. We have used this method in order to visualize the activation of the segmental relaxation with temperature and frequency (Applied Physics Letters 96(21): 213110). All this measurements can be achieved using standard Atomic Force Microscope (and a lock-in) for VAC measurements.

Two-dimensional (2D) layered hexagonal boron nitride (h-BN) has become a very popular material in nanoelectronics in recent years because of its extraordinary chemical stability and thermal conductivity [1]. Recently, h-BN is also commonly used as a dielectric material [2], and research in this area is still in its early stages. The commonly used methods for fabricating h-BN include mechanical exfoliation and chemical vapor deposition (CVD). CVD is a recognized industry-compatible method for producing large-area h-BN. However, studies have shown that multilayer h-BN grown by CVD is polycrystalline and contains multiple local defects [3]. These defects and inhomogeneity cannot be avoided and lead to small amounts of atom-wide amorphous regions that have weak dielectric strength [3]. Although the general characteristics of h-BN prepared by these two fabrication methods can be learned from different works in the literature, it is difficult to study the quality of h-BN without systematically comparing the differences between the two growth methods under the same experimental conditions and with large number of samples. This also makes it difficult for researchers to choose the best-quality h-BN. In this work, the morphological characteristics and electrical properties of mechanically exfoliated h-BN and CVD-grown h-BN from different sources have been compared under different conditions. Commercially available h-BN flakes mechanically exfoliated from NIMS h-BN bulk crystal show no leakage current at electrical fields up to 25.9 MV/cm, and above this applied electrical force, the size of the conductive spots is extremely small (1.99 ± 1.81 nm2). On the contrary, “monolayer” CVD-grown h-BN samples from Graphene Supermarket were shown to be amorphous in ~20% of their area, which makes them appear discontinuous from an electrical point of view, plus they contain large thickness fluctuations up to 6 layers. Moreover, in nanoelectronic measurements collected with a conductive atomic force microscope (CAFM) working in vacuum, mechanically exfoliated h-BN showed better electrical homogeneity and presented later dielectric breakdown compared to the h-BN samples fabricated by the CVD method.