This thesis is an attempt to understand ways to improve thermo-mechanical and structural properties of nano-structured materials. A detailed study on computational design and analysis of metallic nanowires is carried out. Molecular dynamic simulation method is applied. In particular, FCC metallic nanowires, NiAl, and CuZr nanowires are studied. Various bottom-up approaches are suggested with improved structural and thermo¬mechanical properties. In the first part of the thesis, Cu nanowires are considered. Existence of a novel and stable pentagonal multi-shell nanobridge structure of Cu under high strain rate tensile loading is reported. Such a structure shows enhanced mechanical properties. A three-fold pseudo-elastic-plastic shape recovery mechanism in such nanowires is established. This study also shows that the length of the pentagonal nanobridge structures can be characterized by its inelastic strain. It is also reported that an initial FCC structure is transformed into a new HCP structure. The evidence of HCP structure is confirmed with the help of experimental data published in the literature. Subsequent to the above study, a novel mechanism involving coupled temperature-stress dependent reorientation in FCC nanowires is investigated. A detailed map is generated for size dependent stress-temperature induced solid-solid reorientation in Cu nanowires. In the second part of the thesis, deformation mechanisms in NiAl based intermetallic nanowires are studied. A novel mechanism of temperature and cross-section dependent pseudo-elastic/pseudo-plastic shape and strain recovery by an initial B2 phase of NiAl nanowire is reported. Such a recoverable strain, which is as high as ~ 30%, can potentially be utilized to realize various types of shape memory and strain sensing phenomena in nano-scale devices. An asymmetry in tensile and compressive yield strength behavior is also observed, which is due to the softening and hardening of the nanowires under tensile and compressive loadings, respectively. Two different deformation mechanisms dominated by twinning under tension and slip under compression are found. Most interestingly, a superplastic behavior with a failure strain of up to 700% in the intermetallic NiAl nanowires is found to exist at a temperature of 0.36Tm. Such superplastic behavior is attributed to the transformation of the nanowire from a crystalline phase to an amorphous phase after yielding of the nanowire. In the last part the work, another type of nanowires having Cu-Zr system is considered. A novel stress induced martensitic phase transformation from an initial B2 phase to BCT phase in a CuZr nanowire under tensile loading is reported. It is further shown that such a stress induced martenistic phase transformation can be achieved under both tensile as well as compressive loadings. Tensile-compressive asymmetry in the stress-strain behavior is observed due to two different phase transformation mechanisms having maximum transformation strains of ~ 5% under compressive loading and ~ 20% under tensile loading. A size and temperature dependent tensile phase transformation in the nanowire is also observed. Small nanowires show a single step tensile phase transformation whereas the nanowires with larger size show a two step deformation mechanism via an intermediate R-phase hardening followed by R-phase yielding. A study of energetic behavior of these nanowires reveals uniform distribution of stress over the nanowire cross-section and such stress distribution can lead to a significant improvement in its thermo-mechanical properties. Similar improvement is demonstrated by designing the nanowires via manipulating the surface configuration of B2-CuZr system. It is found that the CuZr nanowires with Zr atoms at the surface sites are energetically more stable and also give a uniform distribution of stresses across the cross-section. This leads to the improvement in yield strength as well as failure strain. An approach to design energetically stable nano-structured materials via manipulating the surface configurations with improved thermo-mechanical properties is demonstrated which can help in fundamental understanding and development of similar structures with more stability and enhanced structural properties. Further ab-initio and experimental studies on the confirmation of the stability of the nanowires via manipulating the surface site is an open area of research and related future scopes are highlighted in the closure.

Orientador: Douglas Soares Galvão / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-10T18:28:40Z (GMT). No. of bitstreams: 1 Sato_Fernando_D.pdf: 7711328 bytes, checksum: 22c01d9be26cdd21cf062f6b8f62cde0 (MD5) Previous issue date: 2007 / Resumo: Neste trabalho utilizamos métodos de física computacional para descrever o comportamento estrutural de formação de cadeias atômicas lineares suspensas (LACs) (i ) e de uma estrutura orgânica sobre superfície metálica (ii ). Ambos os temas foram desenvolvidos sobre o ponto de vista de física computacional e comparados com resultados experimentais específicos provenientes da estreita colaboração em grupos experimentais. Desenvolvemos uma metodologia para estudo sistemático da formação de nanofios (i ) metálicos a partir de aglomerados (clusters) compostos por átomos puros (Au, Ag, Cu) e a partir de ligas bi-metálicas (Au-Ag). A metodologia se baseou nas equações de movimento de Newton (método de dinâmica molecular clássica) utilizando um potencial parametrizado de origem quântica, denominado potencial de ligações fortes com aproximação de segundos momentos (TB-SMA). Com a metodologia desenvolvida foi possível realizar um estudo estatístico da formação de cadeias atômicas lineares suspensas, a verificação de aglomerados até então somente vistos em estudos direcionados a clusters, a observação de defeitos de empilhamento e a previsão de novas estruturas. Estudamos aspectos da geometria de uma molécula orgânica denominada Violeta Lander (ii ) (VL) com métodos clássicos e semi-empíricos no vácuo. A VL é uma das moléculas da classe das moléculas de Lander. Após a descrição geométrica, colocamos a VL sobre uma superfície de Cu[110] para verificar posições e conformações de estabilidade através de métodos clássicos de mecânica molecular. Para entender o comportamento dinâmico da VL sobre uma superfície de Cu[110] utilizamos um método clássico de dinâmica molecular utilizando o potencial Universal Force Field (UFF). A relevância desta parte do trabalho reside no fato de investigarmos, pela primeira vez, um caso análogo ao efeito chave-fechadura não biológico estudado no ambiente experimental e teórico de simulação. Ambos os trabalhos nos remetem para o campo da nanociência, servindo de base para futuras aplicações em nanotecnologia, tais como contatos elétricos e interação de sistemas orgânicos sobre superfície metálica / Abstract: In this work we use tools of computational physics to describe the structural and formation behavior of metallic nanowires (i ) and an organic structure on metallic surface (ii ). Both subjects had been developed under computational physics point of view and compared to specific experimental data from our close collaborations with experimental and theoretical groups. In this part of the work we developed a methodology for systematic study of the formation of metallic nanowires (i ) from clusters composed by pure atoms (Au, Ag and Cu) and from bi-metallic alloys (Au-Ag). The methodology was based on the Newton equations of motion (traditional method of molecular dynamics) together with a parametrized potential of quantum origin, named Tight-binding potential with second moment approximations (TB-SMA). With the developed methodology it was possible to carry out a statistical study of suspended linear atomic chains formation from clusters and to predict new structures and defects, stacking faults, among others. We also studied aspects of the geometry of an organic molecule called Violet Lander (VL) (ii ) with classic and semi-empirical methods in vacuum and also deposited over copper [110]. The VL is one of molecules of the Lander molecules class. The great relevance of this part of the work is because we addressed and explained the rst non-biological lock-key eect in the experimental and theoretical environment. Both the works have a great nanoscience appeal, being one of its bases. It will have great importance in future applications of nanotechnology as electric contacts and organic-metallic interaction based devices / Doutorado / Física da Matéria Condensada / Doutor em Ciências

The principal aim of this thesis is to study the electrical transport properties of metal nanowires. Specifically, we have focussed on investigating the resistance fluctuations of Ag and Cu nanowires of diameters ranging from 15nm to 200nm and studied the instabilities that set in when the diameter is reduced below a certain range. The nanowires were grown electrochemically inside polycarbonate and alumina templates. X-ray diffraction studies on the samples showed the presence of a HCP 4H phase in the Ag nanowires in addition to the usual FCC phase, which is seen in bulk Ag. The relative ratios of these two phases were a maximum for nanowires of diameter 30nm. The X-ray diffraction studies also showed that the samples were of high chemical purity. TEM studies revealed that the wires are single crystalline in nature. Once the wires are released from the template, the wires of diameter 15nm were seen to break down spontaneously into globules due to Rayleigh instability. Wires of larger diameter tended to neck down to smaller radius but did not break down completely into globules. Both the Ag and Cu nanowire arrays had a fairly linear temperature dependence of resistance down to about 100K and reached a residual resistance below 40-50K. The temperature dependence of resistance could be fitted to a Bloch-Grüneisen formula over the entire temperature range. We found that n = 5 gave the best fit for the wires of all diameters showing that the dominant contribution to the temperature dependence of the resistivity in theses nanowires come from electron-acoustic phonon interactions. The resistivities of the wires were seen to increase as the wire diameter was decreased. This increase in the resistivity of the wires could be attributed to surface scattering of conduction electrons. In nanowires of diameter 15nm of both Ag and Cu, the relative variance of resistance fluctuations <(ΔR)2>/R2 showed a prominent peak at around ~ 220K for the Ag nanowire and ~ 260K for the Cu wire. Ag wires of diameter 20nm showed a much-reduced peak in noise at a somewhat higher temperature while this feature was completely absent in wires of larger diameter as also for the reference Ag film. The noise in wires of diameter larger than 20nm was similar to that of the reference film. For wires of diameter 15nm as we approach T*, the power spectral density showed a severe deviation from 1/f nature. We could establish that the extra fluctuation seen in the nanowires of the narrowest diameters could originate from the Rayleigh instability. The measured resistance fluctuation was found to have a magnitude similar to that estimated from a simple model of a wire showing volume preserving fluctuation. In the temperature range T ≤ 100K we observed very large non-Gaussian resistance fluctuations in a narrow temperature range for Ag and Cu wires of diameter 30nm with the fluctuations becoming much smaller as the diameter of the wires deviated from 30nm. In wires of diameter larger than 50nm the noise was almost independent of temperature in this range. The power spectrum of the resistance fluctuations also developed a large additional low frequency component near TP. We could establish that the appearance of this noise at a certain temperature (~30 – 50K) is due to the onset of martensite strain accommodation in these nanowires. To summarize, we measured the resistance and resistance fluctuations of Ag and Cu nanowires of diameters ranging from 15nm to 200nm in the temperature range 4.2-300K. The temperature dependence of resistance could be fitted to a Bloch-Grüneisen formula over the entire temperature range of measurement (4.2K-300K). The contribution of electron-phonon scattering to the resistivity was found to be similar to that of bulk. The defect free nature of our samples allowed us to identify two novel sources of noise in these nanowires. At high temperatures Rayleigh instability causes the noise levels in wires of diameter around 15nm to increase. At lower temperatures the formation of martensite state leads to an increase in noise in wires of small diameters.

L'utilisation de matériaux transparents et conducteurs a subi une croissance exponentielle lors de la dernière décennie, puisque faisant partie intégrante de nombreux dispositifs optoélectroniques tels que les écrans tactiles & les cellules solaires. Parmi ces matériaux, l'oxyde d'indium-étain occupe la quasi-totalité du marché puisqu'il associe une conductivité élevée et une transparence supérieure à 90% sous forme de film mince. Cependant, le développement de technologies flexibles pousse à rechercher des alternatives à son utilisation car son cout élevé et sa faible flexibilité le rendent incompatible. Au milieu des alternatives carbonées (graphène et nanotubes), les nanomatériaux métalliques ou les polymères conducteurs se présentent comme des alternatives intéressantes : bas cout et facilité à mettre en forme pour les polymères conducteurs, hautes performances pour les nanofils métalliques. Cette thèse présente la mise en œuvre de ces matériaux alternatifs par la méthode originale d'électrofilage et l'étude de leurs propriétés optoélectroniques. La maitrise des conditions de mise en forme (champ, débit, paramètres environnementaux) et l'optimisation des solutions utilisées (rhéologie, concentration en polymère, co-solvants) nous a permis d'obtenir 2 types de nanostructures : des nanofibres 100% polymériques à base de PEDOT:PSS et des nanofibres composites PVP:Nanofils d'argent. L'étude des propriétés opto-électroniques des réseaux ainsi obtenus a aussi été étudiée / The use of transparent and conductive materials has been growing exponentially in the last decade as they are part of many optoelectronic devices such as touch screens and solar cells. Among these materials, Indium-Tin Oxide (ITO) is the market reference since it combines a low resistivity and a high transparency up to 90% in the form of thin film. However, the growing in the development of flexible technologies created a real need in alternatives as ITO has poor mechanical properties. Carbon nanotubes and graphene are potential substitutes, but metallic nanowires and conductive polymers have been developed for their high performances and low cost respectively.This thesis presents the implementation of these alternatives by the original method of electrospinning and the study of their optoelectronic properties. The optimization of the experimental setup (field, rate, environmental parameters) and solutions (rheology, polymer concentration, co-solvents) allowed us to obtain 2 different kinds of nanostructures: fully polymeric with PEDOT:PSS and composite with PVP and silver nanowires. The study of the optoelectronic properties of the resulting networks has also been investigated

Dans cette thèse nous avons réalisé une étude théorique concernant les mécanismes de formation et les propriétés de transport électronique de fils de section atomique d’Au et de Pt.Pour cela, nous avons utilisé un Hamiltonien de Liaisons Fortes donnant accès aux propriétés électroniques et à l’énergie totale. Lors de nos simulations de traction de nanofils cristallins en Dynamique Moléculaire nous avons observé la formation de structures assimilables `a des nanotubes dont la chiralité évolue au cours de la déformation. En poursuivant la traction, nous avons observé la formation de structures planes (ou rubans) dans le cas de l’Au et du Pt. Ces rubans permettent de former des fils de section atomique pour l’Au mais pas pour le Pt, la différence étant liée aux propriétés mécaniques des éléments. Les calculs réalisés sur les propriétés de transport ont mis en évidence des effets d’interférence destructive induits par la géométrie du système. / In this thesis we study the formation mechanisms and the electronic transport propertiesof Au and Pt atomic wires. We have used a Tight Binding Hamiltonian giving access to theelectronic structure and to the total energy. By performing traction simulations of cristallinenanowires by Molecular Dynamics we observe the formation of structures similar to nanotubeswhose chirality evolve during the deformation. Following the traction process we observe theformation of planar structures (or ribbons) for both Au and Pt. These ribbons give rise to theformation of wires of atomic section for Au but not for Pt, the different behavior is related withthe different elastic properties of the two elements. Our preliminary results on the electronictransport properties show interference effects induced by the geometry which can cancel out theconductance.

Les électrodes transparentes (ET) sont présentes dans de nombreux dispositifs optoélectroniques. Par exemple, on peut les trouver au sein de cellules solaires, d'écrans tactiles, d'OLEDs ou encore de films chauffants transparents. Les propriétés physiques de ces électrodes influencent l'efficacité de ces dispositifs. Les ET sont fabriquées à partir de matériaux transparents conducteurs (TCM) dont le développement a débuté dans les années 1950 notamment avec les oxydes métalliques. Parmi ces oxydes transparents conducteurs (TCO), l'oxyde d'étain-indium (ITO) est celui le plus communément utilisé dans les cellules solaires et les écrans de télévision ou de smartphones. Cependant, de nouvelles exigences telles qu'une réduction des coûts, la flexibilité et la fabrication à faible température et/ou faible coût, ont orienté les recherches vers de nouveaux TCM, notamment à base de nanostructures. Parmi ces matériaux émergents, les réseaux de nanofils métalliques, en particulier de nanofils d'argent, présentent déjà des propriétés optiques et électriques approchant celles de l'ITO, c'est-à-dire une conductivité électrique et une transparence élevées. Ces deux propriétés sont cependant intrinsèquement liées à la densité de nanofils constituant le réseau, et lorsque la conductivité augmente, la transparence diminue. Des traitements post-dépôt existent et permettent d'augmenter la conductivité électrique des ET sans changer la densité du réseau. Plusieurs de ces méthodes d'optimisation ont été étudiées pendant ce travail de thèse, en particulier le recuit thermique, analysé minutieusement afin de comprendre les différents mécanismes de réduction de la conductivité électrique induits par la température. L'examen des effets thermiques a soulevé la question de l'instabilité des nanofils en température, qui est aussi abordée et discutée dans ce document. Le paramètre clé de la densité de nanofils optimale menant au meilleur compromis entre transparence et conductivité a été recherché pour des nanofils de différentes dimensions. La taille des nanofils a en effet un fort impact sur les propriétés du réseau. Ainsi, les propriétés électriques, dans le cadre de la théorie de la percolation, les propriétés optiques comme la transmittance et le facteur de haze, et même l'instabilité thermique ont été reliées aux dimensions des nanofils ainsi qu'à la densité du réseau en utilisant des modèles physiques simples. En ce qui concerne les applications de ces ET émergentes, des études ont été menées sur l'application des réseaux de nanofils d'argent comme film chauffant transparent, et les résultats sont rapportés à la fin de ce document. Les limitations soulevées par cette application, comme les limites de stabilités électrique et thermique ont aussi été abordées. Pour finir, des études préliminaires menées sur de nouvelles applications comme des antennes transparentes ou le blindage électromagnétique transparent utilisant les nanofils d'argent sont présentées. / Transparent electrodes (TE) are used in a variety of optoelectrical devices. Among them, solar cells, flat panel displays, touch screens, OLEDs and transparent heaters can be cited. The physical properties of the TE influence the efficiency of the device as a whole. Such electrodes are fabricated from transparent conducting materials (TCM) that have been undergoing development since the 1950s, initially from metallic oxides. Among these transparent conducting oxides (TCO), indium tin oxide (ITO) is the most commonly used in solar cells, and television or smartphone screens. However requirements such as cost reduction, flexibility and low cost/temperature fabrication techniques have oriented the researches toward emerging TCM, mostly using nanostructures. Among them, metallic nanowire networks, and in particular silver nanowires (AgNW), already present optical and electrical properties approaching those of ITO, i.e. a high electrical conductivity and a high transparency. These two properties are intrinsically linked to the network density, therefore a tradeoff has to be considered knowing that when conductivity increases, transparency decreases. Some post-deposition treatments do exist, allowing an increase of the TE electrical conductivity without changing the network density. Several of these optimization methods have been thoroughly studied during this thesis work, especially thermal annealing. This method have been investigated in details to understand the different thermally-induced mechanisms of conductivity improvement. In addition, the investigation of thermal effects raised the question of thermal instability of the nanowires, which is also addressed and discussed in this document. The key issue of density optimization, allowing the best tradeoff between transparency and conductivity, has been investigated for nanowires with different dimensions. Nanowire size has a strong impact on the network properties. Thus, electrical properties, within the framework of percolation theory, optical properties such as transmittance or haziness, and even thermal instability have been linked to the nanowires' dimensions and the network density by using simple physical models. Regarding the application of these emerging TE, studies were conducted on the application of AgNWs as transparent heaters, and the results are reported at the end of the document. Limitations arising from this application, like thermal and electrical stabilities, have also been addressed. To finish, preliminary studies conducted on new applications such as transparent antennas and transparent electromagnetic shielding using AgNW are presented.

Orientador: Daniel Mario Ugarte / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-16T08:26:46Z (GMT). No. of bitstreams: 1 LagosParedes_MaureenJoel_D.pdf: 15612188 bytes, checksum: 76b816022716e5ae1bb5de0ff150c8ca (MD5) Previous issue date: 2010 / Resumo: Fios metálicos de tamanho atômico (NF's) apresentam novos efeitos químicos e físicos devido ao seu tamanho reduzido, onde pode-se destacar a condutância quântica. NF's são usualmente gerados através de um procedimento simples: duas superfícies metálicas são colocadas em contato e depois afastadas. Nos últimos estágios do estiramento antes da ruptura, um fio de alguns átomos de diâmetro é gerado enquanto a condutância é medida. Este tipo de abordagem apresenta um cenário que permite o estudo da condutância e do processo de deformação mecânica do NF. O objetivo desta tese consiste no estudo dos efeitos do arranjo atômico na condutância quântica e deformação mecânica de NF's gerados por alongamento. O arranjo atômico dos NF's foi estudado por microscopia eletrônica de transmissão de alta resolução resolvida no tempo. A condutância foi medida utilizando um sistema de quebra controlada de junções operado em ultra alto vácuo. Os experimentos foram realizados a ~ 150 K e 300 K. Neste trabalho de tese NF's de diversos tipos de morfologia, tamanho e composição química foram estudados. O estudo do efeito do arranjo atômico no processo de deformação mecânica foi realizado, principalmente, em nanotarugos (NR's) de ouro de ~ 1 nm de diâmetro. Foi verificado que a temperatura modifica drasticamente o comportamento mecânico dos NR's. Também, foi mostrado que o tamanho e a forma do NR sob deformação têm um papel determinante no processo de deformação mecânica. Além disso, foi realizado o estudo detalhado da formação de uma estrutura anômala que consiste em um nanotubo de seção transversal quadrada. Isto mostra a importância de considerar os efeitos de superfície no arranjo atômico de NF's sob deformação. O estudo da influência do arranjo atômico na deformação mecânica de NF's de ligas de ouro e cobre também foi realizada, onde foram observados eventos de segregação na escala atômica, devido a efeitos de superfície, e variações significativas no comportamento mecânico em relação a NF's puros. A origem na formação de distâncias anômalas em cadeias suspensas de ouro também foi analisada. Os resultados obtidos indicam que o carbono é o agente contaminante que induz a formação de distancias 3.2 Å. Finalmente, estudos dos efeitos do arranjo atômico na condutância de NF's de ouro e prata em função da temperatura foram realizados. Os resultados experimentais mostraram que a temperatura modifica significativamente o comportamento estrutural dos NF's formando defeitos estruturais a baixas temperaturas. As medidas de condutância a ~ 150 K também mostraram variações significativas. A partir da informação estrutural de microscopia, modelos geométricos foram estabelecidos para correlacionar a informação de condutância com o arranjo atômico através de cálculos teóricos de condutância / Abstract: Atomic-size metallic nanowires (NWs) display new physical and chemical effects, for example the quantum conductance. NWs can be usually generated by means of a simple experimental procedure: two metallic surfaces are put into contact and then they are retracted in a controlled way. During the last stages before the rupture, a wire containing a few atoms is created and its conductance can be measured simultaneously during the elongation process. This approach represents a scenario which allows us to study its conductance and mechanical properties. This thesis aims to study the thermal energy effects on NW's atomic arrangement and the corresponding influence on quantum conductance and mechanical deformation. The atomic arrangement was studied using time-resolved high resolution transmission electron microscopy. The conductance was measured using an experimental technique called mechanically controllable break junctions. Experiments were performed at ~ 150 K and 300 K. In this work were studied NW's that exhibit different morphologies, sizes and chemical composition. Firstly, the study of the atomic arrangement influence on the mechanical deformation was developed on one-nm wide gold nanorods (NRs). It was found that temperature induces drastic changes in the NR mechanical behavior. Moreover, it was shown that the NR size and shape play an essential role during the process of mechanical deformation. Second, the detailed study of the formation of anomalous silver square-cross section nanotube was performed. This revealed the strong influence of surface effects on atomic arrangement. Third, the study of atomistic aspects associated with mechanical deformation of gold-copper alloy NWs was also developed. Segregation events at atomic scale, induced by surface effects, and significant variations of the nanoalloy mechanical behavior were observed. Fourth, the analysis of the origin of formation of anomalous interatomic distances in suspended gold atom chains was performed. Our results indicate that carbon represents the most probable contaminant which induces the generation of anomalous distances (3.2 Å). Finally, the study of the atomic arrangement effects on conductance of gold and silver NWs as function of temperature was developed. Our experimental results revealed that thermal energy induces drastic changes of structural behavior, generating planar defects at low temperatures. Conductance measurements obtained at ~150 K also display significant variations. Considering structural information derived from microscopy observations, simple geometric models were defined and the conductance was calculated theoretically in order to correlate the gold and silver NW conductance and structural information / Doutorado / Física da Matéria Condensada / Doutor em Ciências

Orientador: Daniel Mario Ugarte / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-08T07:13:58Z (GMT). No. of bitstreams: 1 LagosParedes_MaureenJoel_M.pdf: 3881181 bytes, checksum: 517e8507ccdf35f0fa7a7f9fcb4b3b84 (MD5) Previous issue date: 2007 / Resumo: O estudo de fios metálicos de tamanho atômico (NF's) tem atraído grande interesse devido aos novos efeitos químicos e físicos neles observados. Entre esses novos fenômenos podemos destacar a quantização da condutância, efeito que deve ser fundamental no desenho dos novos nanodispositivos eletrônicos. NF's são usualmente gerados através de um procedimento simples de deformação mecânica: duas superfícies metálicas são colocadas em contato e depois afastadas. Nos últimos estágios do estiramento antes da ruptura, um fio de alguns átomos de diâmetro é gerado enquanto a condutância é medida. Os NF's têm sido estudados por diferentes grupos e, em diversas condições de temperatura (4 - 300 K) e pressão (de ambiente a UHV). Os resultados apresentam importantes variações e, têm gerado interpretações muito controversas. Devemos enfatizar que muitas interpretações têm sido feitas sem considerar que a deformação estrutural dos NF's deve depender fortemente da temperatura. Nesta tese estudamos as propriedades estruturais e eletrônicas NF's e, em particular analisamos a influência de efeitos térmicos no arranjo atômico, e sua manifestação na condutância. A estrutura dos NF's foi estudada por microscopia eletrônica de transmissão de alta resolução resolvidas no tempo. A condutância foi medida utilizando um sistema de quebra controlada de junções operado em ultra-alto-vácuo. Os experimentos foram realizados a ~150 e 300 K. Nossos resultados mostraram que, à temperatura ambiente os NF's são sempre cristalinos e livre de defeitos nas regiões mais finas; e deformam unicamente ao longo dos eixos cristalográficos [111], [100] e [110]. A baixa temperatura duas importantes diferenças foram observadas: (i) NF's de ouro apresentam defeitos, principalmente falhas de empilhamento e maclas. (ii) NF's alongados na direção [110] evoluem em cadeias atômicas, de comportamento mecânico muito diferente da temperatura ambiente, onde quebram abruptamente. Segundo as imagens de microscopia eletrônica, discordâncias parciais (Shockley) geram falhas de empilhamento; e cadeias de átomos suspensos são observados a ~150 e 300 K. Histogramas globais de condutância adquiridos a baixa temperatura revelaram: (i) aumento da intensidade do pico ~1 Go; (ii) leve diminuição da condutância devido ao aumento de defeitos; e (iii) a existência de uma sub-estrutura no pico ~2 Go, indicando a formação de dois arranjos atômicos estáveis. Resumidamente, nossos resultados mostram que a formação de defeitos é um evento freqüente a ~150 K. Provavelmente, mais defeitos na estrutura devem acontecer para temperaturas menores (4 - 10 K). Portanto, uma importante mudança na evolução da condutância durante a elongação de NF's deve ser esperado a baixa temperatura. Assim, a comparação direta de medidas de transporte de NF's realizadas a diferentes temperaturas pode levar a sérias discrepâncias. Esperamos ter contribuído a melhorar a compreensão e interpretação de experimentos de transporte realizados em diferentes condições, de modo tal, a gerar um modelo único e coerente que explique as propriedades físicas de NF's metálicos / Abstract: The study of atomic-size metal nanowires (NW's) is attracting a great interest due to occurrence a novel physical and chemical phenomena. Among these new phenomena, we can mention conductance quantization that will certainly influence the design of nanodevices. NW's are usually generated by means of a simple procedure: two metallic surfaces are put into contact and, then retracted. Just before rupture atomic-size NW's are formed, and the conductance is measured during the wire elongation. The interpretation of the results is troublesome, because conductance is measured during the modification of the atomic structure. This kind of experimental study has been performed by many research groups and, a quite wide range of temperatures (4 - 300 K) and vacuum condition have been used (from ambient to UHV). In fact, the results display significant variation, what has generated several controversial interpretations. It must be emphasized that many models have been derived without taking into account that the NW structural deformation should be significantly dependent on temperature. In this Thesis research work, we have studied the structural and electronic properties of gold NW's, in particular addressing how thermal effects influence the atomistic aspects of the NW deformation and how this influences the quantum conductance behavior. The structure of NW's has been studied by means of time-resolved high resolution transmission electron microscopy; the NWs transport measurements were based on a mechanically controlled break junction operated in ultra-high-vacuum. The experiments were performed at ~150 and 300 K. Our results have shown that at room temperature the atomic-size NW's. are always crystalline and free of defects, and the atomic structure is spontaneously deformed such that one of the [111]/[100]/[110] crystallographic axis becomes approximately parallel to the stretching direction. Low temperature observations revealed two important differences: i) Au NWs show extended defects, mainly stacking faults and, twinning; ii) NWs elongated along the [110] axis evolve to suspended atomic chains, while at room temperature they break abruptly. Partial Schockley dislocations generate the staking faults; suspended atoms chains are both observed at ~150 and 300 K. The global histograms of conductance at ~150 K showed that: i) a increase of the 1 Go peak intensity; ii) slight reduction of the NWs conductance due to scattering at defects and; iii) the peak at ~2 Go shows a sub structure, what is due to the occurrence of two different atomic arrangements with similar conductance. Briefly, our results revealed that the formation of defects is very frequent in NWs generated at ~150 K; the occurrence of more defects should be expected when NWs are studied at cryogenic temperatures. Then, a significant modification of the NW conductance behavior should be expected at low temperature. In these terms, the direct comparison of conductance measurements realized at different temperature regimes can lead to serious discrepancies. We hope that this work contribute to improve the interpretation and understanding of NW transport studies in order to develop a coherent and complete model that explain the physical properties of atomic-size metal NWs / Mestrado / Física da Matéria Condensada / Mestre em Física

Orientador: Daniel Mario Ugarte / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-08T07:13:40Z (GMT). No. of bitstreams: 1 LagosParedes_MaureenJoel_M.pdf: 10524108 bytes, checksum: 4c8c3fb76ef4ed87845ad6eb88cf42e9 (MD5) Previous issue date: 2007 / Resumo: O estudo de fios metálicos de tamanho atômico (NF's) tem atraído grande interesse devido aos novos efeitos químicos e físicos neles observados. Entre esses novos fenômenos podemos destacar a quantização da condutância, efeito que deve ser fundamental no desenho dos novos nanodispositivos eletrônicos. NF's são usualmente gerados através de um procedimento simples de deformação mecânica: duas superfícies metálicas são colocadas em contato e depois afastadas. Nos últimos estágios do estiramento antes da ruptura, um fio de alguns átomos de diâmetro é gerado enquanto a condutância é medida. Os NF's têm sido estudados por diferentes grupos e, em diversas condições de temperatura (4 - 300 K) e pressão (de ambiente a UHV). Os resultados apresentam importantes variações e, têm gerado interpretações muito controversas. Devemos enfatizar que muitas interpretações têm sido feitas sem considerar que a deformação estrutural dos NF's deve depender fortemente da temperatura. Nesta tese estudamos as propriedades estruturais e eletrônicas NF's e, em particular analisamos a influência de efeitos térmicos no arranjo atômico, e sua manifestação na condutância. A estrutura dos NF's foi estudada por microscopia eletrônica de transmissão de alta resolução resolvidas no tempo. A condutância foi medida utilizando um sistema de quebra controlada de junções operado em ultra-alto-vácuo. Os experimentos foram realizados a ~150 e 300 K. Nossos resultados mostraram que, à temperatura ambiente os NF's são sempre cristalinos e livre de defeitos nas regiões mais finas; e deformam unicamente ao longo dos eixos cristalográficos [111], [100] e [110]. A baixa temperatura duas importantes diferenças foram observadas: (i) NF's de ouro apresentam defeitos, principalmente falhas de empilhamento e maclas. (ii) NF's alongados na direção [110] evoluem em cadeias atômicas, de comportamento mecânico muito diferente da temperatura ambiente, onde quebram abruptamente. Segundo as imagens de microscopia eletrônica, discordâncias parciais (Shockley) geram falhas de empilhamento; e cadeias de átomos suspensos são observados a ~150 e 300 K. Histogramas globais de condutância adquiridos a baixa temperatura revelaram: (i) aumento da intensidade do pico ~1 Go; (ii) leve diminuição da condutância devido ao aumento de defeitos; e (iii) a existência de uma sub-estrutura no pico ~2 Go, indicando a formação de dois arranjos atômicos estáveis. Resumidamente, nossos resultados mostram que a formação de defeitos é um evento freqüente a ~150 K. Provavelmente, mais defeitos na estrutura devem acontecer para temperaturas menores (4 - 10 K). Portanto, uma importante mudança na evolução da condutância durante a elongação de NF's deve ser esperado a baixa temperatura. Assim, a comparação direta de medidas de transporte de NF's realizadas a diferentes temperaturas pode levar a sérias discrepâncias. Esperamos ter contribuído a melhorar a compreensão e interpretação de experimentos de transporte realizados em diferentes condições, de modo tal, a gerar um modelo único e coerente que explique as propriedades físicas de NF's metálicos / Abstract: The study of atomic-size metal nanowires (NW's) is attracting a great interest due to occurrence a novel physical and chemical phenomena. Among these new phenomena, we can mention conductance quantization that will certainly influence the design of nanodevices. NW's are usually generated by means of a simple procedure: two metallic surfaces are put into contact and, then retracted. Just before rupture atomic-size NW's are formed, and the conductance is measured during the wire elongation. The interpretation of the results is troublesome, because conductance is measured during the modification of the atomic structure. This kind of experimental study has been performed by many research groups and, a quite wide range of temperatures (4 - 300 K) and vacuum condition have been used (from ambient to UHV). In fact, the results display significant variation, what has generated several controversial interpretations. It must be emphasized that many models have been derived without taking into account that the NW structural deformation should be significantly dependent on temperature. In this Thesis research work, we have studied the structural and electronic properties of gold NW's, in particular addressing how thermal effects influence the atomistic aspects of the NW deformation and how this influences the quantum conductance behavior. The structure of NW's has been studied by means of time-resolved high resolution transmission electron microscopy; the NWs transport measurements were based on a mechanically controlled break junction operated in ultra-high-vacuum. The experiments were performed at ~150 and 300 K. Our results have shown that at room temperature the atomic-size NW's. are always crystalline and free of defects, and the atomic structure is spontaneously deformed such that one of the [111]/[100]/[110] crystallographic axis becomes approximately parallel to the stretching direction. Low temperature observations revealed two important differences: i) Au NWs show extended defects, mainly stacking faults and, twinning; ii) NWs elongated along the [110] axis evolve to suspended atomic chains, while at room temperature they break abruptly. Partial Schockley dislocations generate the staking faults; suspended atoms chains are both observed at ~150 and 300 K. The global histograms of conductance at ~150 K showed that: i) a increase of the 1 Go peak intensity; ii) slight reduction of the NWs conductance due to scattering at defects and; iii) the peak at ~2 Go shows a sub structure, what is due to the occurrence of two different atomic arrangements with similar conductance. Briefly, our results revealed that the formation of defects is very frequent in NWs generated at ~150 K; the occurrence of more defects should be expected when NWs are studied at cryogenic temperatures. Then, a significant modification of the NW conductance behavior should be expected at low temperature. In these terms, the direct comparison of conductance measurements realized at different temperature regimes can lead to serious discrepancies. We hope that this work contribute to improve the interpretation and understanding of NW transport studies in order to develop a coherent and complete model that explain the physical properties of atomic-size metal NWs / Mestrado / Física da Matéria Condensada / Mestre em Física

This thesis reports transport in ultrathin single crystalline nanowires of gold (∼ 2nm). These nanowires were fabricated using an oriented attachment process whereby nanoparticles of appropriate dimensions join in a linear fashion to form long and stable wires. The main motivation was to study the role of electron-electron interactions on the transport mechanism in case of a metallic system, as one approaches dimensions closer to the Fermi wavelength. The study forms the first of its kind in a simple metallic system of this dimension. Indeed, several new features have been obtained in this regard: Chapter 4 reports a breakdown of Fermi liquid state in such a system opening up possibilities of exotic states constituted by a strongly correlated Tomonaga-Luttinger liquid. We report consistent scaling of current-voltage curves, characteristic of such a phase and even resonant tunneling in such structures. The study reports the first observation of a correlated electron liquid in a metal, which has been observed only in semiconductors and polymer wires till date. Chapter 5 discusses the possibility of tuning the transport mechanism in these wires via a controlled change in the growth process. We show that using appropriate growth mechanisms, we can have a localized ground state as well, where variable range hopping is the dominant transport mechanism. Possibility of structural transitions in ultrathin wires is a field that has garnered considerable interest due to simulations. We present a highly sensitive tool in the form of electrical noise and its higher order statistics that can act as a detector of structural transitions. This has been thoroughly studied in case of conventional shape memory systems in Chapter 6. Preliminary noise studies on the nanowires have been reported in Chapter 7.