Carbon nanoribbons are today of great interest as graphene segments with modulable electronic properties. Whilst top down techniques give giant ribbons, bottom-up organic synthesis may lead to exactly designed nanoribbons of controlled geometries. The Scholl reaction is a precious chemical tool for that purpose since it yields efficiently to the graphitization of long and flexible polyphenylene precursors.Surprisingly, twisted structures may be obtained preferentially even if less crowded isomers are also feasible. It has been shown that, against all expectation, even a strong steric hindrance has no marked effect on regioselectivity and highly twisted polycyclic aromatic hydrocarbons are sometimes preferentially formed, whereas their flat and more symmetrical isomers are only obtained in minority. Highly twisted structures such as hexabenzotriphenylene (HBTP) may then be obtained very easily from flexible polyphenylene precursors.After discovering this unexpected regioselectivity, we used it on purpose to form polyhelicenic species. Attempts to prepared hexaphenanthrotriphenylene (HPTP) were unsuccessful due to reactivity issues when synthesizing the corresponding flexible precursors. By using a new versatile strategy leading to an advanced common precursor, several C3-symmetrical flexible substrates have been synthesized and submitted to Scholl reaction. The expected [6]helicenes were not obtained and rearranged products were formed instead, but TMS-bearing HBTP could be prepared, as well as a hexabenzocoronene (HBC) which exceptionnal solubility is due to the distortion of the aromatic core under the effect of bulky tert-butyl substituents in bay regions.The easily formed [5]helicene fragment has been incorporated in the design of twisted carbon nanoribbons that would be composed of a succession of such motifs. As a test reaction, the corresponding monomer and dimer have been synthesized with an excellent yield and fully characterized. Their X-ray structures have even been determined, giving interesting information about their configuration. A more general strategy has then been developed and optimized for the systematic synthesis of longer oligomers of twisted nanoribbons. Using this technique, the trimer and tetramer have been synthesized and characterized by mass spectrometry.

Graphene is foreseen to be the basis of future electronics owing to its ultra thin structure, extremely high charge carrier mobility,  high thermal conductivity etc., which are expected to overcome the size limitation and heat dissipation problem in silicon based transistors. But these great prospects are hindered by the metallic nature of pristine graphene even at charge neutrality point, which allows to flow current even when a transistor is switched off. A part  of the thesis is dedicated to invoke electronic band gaps in graphene to overcome this problem. The concept of quantum confinement has been employed to tune the band gaps in graphene by  dimensional confinement along with the functionalization of the edges of these confined nanostructures. Thermodynamic stability of the functionalized zigzag edges with hydrogen, fluorine and reconstructed edges has been presented in the thesis. Keeping an eye towards the same goal of band gap opening,  a different route has been considered by admixing insulating hexagonal boron nitride (h-BN) with semimetal graphene. The idea has been implemented in two  dimensional h-BN-graphene composites and three dimensional stacked heterostructures. The study reveals the possibility of tuning band gaps by controlling the admixture. Occurrence of defects in graphene has significant effect on its electronic properties. By random insertion of defects, amorphous graphene is studied, revealing a semi-metal to a metal transition. The field of molecular electronics and spintronics aims towards device realization at the molecular scale. In this thesis, different aspects of magnetic bistability in organometallic molecules have been explored in order to design  practical spintronics devices. Manipulation of spin states in organometallic molecules, specifically metal porphyrin molecules, is achieved by controlling surface–molecule interaction. It has been shown that by strain engineering in defected graphene, the magnetic state of adsorbed molecules can be changed. The spin crossover between different spin states can also be achieved by chemisorption on magnetic surfaces. A significant part of the thesis demonstrates that the surface-molecule interaction not only changes the spin state of the molecule, but allows to manipulate magnetic anisotropies and spin dipole moments via modified ligand fields. Finally, in collaboration with experimentalists, a practical realization of switching surface–molecule magnetic interactions by external magnetic fields is demonstrated.

CASTRO, Luan Veira de. Transporte balístico em dispositivos de grafeno nanoestruturados. 2015. 83 f. Dissertação (Mestrado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2015. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2016-01-05T20:08:10Z No. of bitstreams: 1 2015_dis_lvcastro.pdf: 15542997 bytes, checksum: 6f4e517b4e288990d33f8f864427ecd6 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2016-01-05T20:08:23Z (GMT) No. of bitstreams: 1 2015_dis_lvcastro.pdf: 15542997 bytes, checksum: 6f4e517b4e288990d33f8f864427ecd6 (MD5) / Made available in DSpace on 2016-01-05T20:08:23Z (GMT). No. of bitstreams: 1 2015_dis_lvcastro.pdf: 15542997 bytes, checksum: 6f4e517b4e288990d33f8f864427ecd6 (MD5) Previous issue date: 2015 / In this dissertation, we studied the electronic properties of a graphene nanoestructure under influence of external fields. We considered the application of an uniform transversal electric field and an uniform perpendicular magnetic field. Using a nearest-neighbor Tigh-binding model, we investigated how those fields change the band structure and the local density of states (LDOS) of the system. Then, we studied the transport properties of nanostructures. We assumed ballistic transport due to the long mean free path of graphene. Through a numerical model that it consists in solving the Tight-binding Hamiltonian in real space and the combination of the boundary conditions between the central region and the reservoir, we calculated the transmission coefficients for two specifics systems: First, for a graphene ribbon under the influence of a transversal electric field in a region of finite length; Next, for a three terminal ballistic junction (JBTT) of graphene under the influence of a transversal electric field in the region immediately before the junction. / Nesta dissertação, estudamos as propriedades eletrônicas de nanoestruturas de grafeno submetidas a campos externos. Consideramos a aplicação de um campo elétrico uniforme transversal e um campo magnético uniforme perpendicular à estrutura. Utilizando um modelo Tight-binding com hopping de primeiros vizinhos, vimos como esses campos modificam a estrutura de bandas e a densidade local de estados (LDOS) do sistema. Em seguida, estudamos as propriedades de transporte das nanoestruturas. Consideramos transporte balístico devido ao longo livre caminho médio do grafeno. Através de um modelo numérico que consiste em resolver o Hamiltoniano Tight-binding no espa ̧co real e combinar condições de contorno entre a região central e os reservatórios, calculamos os coeficientes de transporte para dois sistemas específicos: Primeiro, para uma nanofita de grafeno submetida a um campo elétrico transversal em uma região de extensão finita. Em seguida, para uma junção balística de três terminais (JBTT) de grafeno submetida a um campo elétrico transversal na região imediatamente adjacente à junção.

Our vision is as yet unsurpassed by machines because of the sophisticated representations of objects in our brains. This representation is vastly different from a pixel-based representation used in machine storages. It is this sophisticated representation that enables us to perceive two faces as very different, i.e, they are far apart in the “perceptual space”, even though they are close to each other in their pixel-based representations. Neuroscientists have proposed distances between responses of neurons to the images (as measured in macaque monkeys) as a quantification of the “perceptual distance” between the images. Let us call these neuronal dissimilarity indices of perceptual distances. They have also proposed behavioural experiments to quantify these perceptual distances. Human subjects are asked to identify, as quickly as possible, an oddball image embedded among multiple distractor images. The reciprocal of the search times for identifying the oddball is taken as a measure of perceptual distance between the oddball and the distractor. Let us call such estimates as behavioural dissimilarity indices. In this thesis, we describe a decision-theoretic model for visual search that suggests a connection between these two notions of perceptual distances. In the first part of the thesis, we model visual search as an active sequential hypothesis testing problem. Our analysis suggests an appropriate neuronal dissimilarity index which correlates strongly with the reciprocal of search times. We also consider a number of alternative possibilities such as relative entropy (Kullback-Leibler divergence), the Chernoff entropy and the L1-distance associated with the neuronal firing rate profiles. We then come up with a means to rank the various neuronal dissimilarity indices based on how well they explain the behavioural observations. Our proposed dissimilarity index does better than the other three, followed by relative entropy, then Chernoff entropy and then L1 distance. In the second part of the thesis, we consider a scenario where the subject has to find an oddball image, but without any prior knowledge of the oddball and distractor images. Equivalently, in the neuronal space, the task for the decision maker is to find the image that elicits firing rates different from the others. Here, the decision maker has to “learn” the underlying statistics and then make a decision on the oddball. We model this scenario as one of detecting an odd Poisson point process having a rate different from the common rate of the others. The revised model suggests a new neuronal dissimilarity index. The new dissimilarity index is also strongly correlated with the behavioural data. However, the new dissimilarity index performs worse than the dissimilarity index proposed in the first part on existing behavioural data. The degradation in performance may be attributed to the experimental setup used for the current behavioural tasks, where search tasks associated with a given image pair were sequenced one after another, thereby possibly cueing the subject about the upcoming image pair, and thus violating the assumption of this part on the lack of prior knowledge of the image pairs to the decision maker. In conclusion, the thesis provides a framework for connecting the perceptual distances in the neuronal and the behavioural spaces. Our framework can possibly be used to analyze the connection between the neuronal space and the behavioural space for various other behavioural tasks.

In this work, we demonstrate the bottom-up on-surface synthesis of poly(para-dibenzo[bc,kl]-coronenylene) (PPDBC), a zigzag edge-encased analog of poly(para-phenylene) (PPP), and its lateral fusion into zigzag edge-extended graphene nanoribbons (zeeGNRs). Toward this end, we designed a dihalogenated di(meta-xylyl)anthracene monomer displaying strategic methyl groups at the substituted phenyl ring and investigated its applicability as precursor in the thermally induced surface-assisted polymerization and cyclodehydrogenation. The structure of the resulting zigzag edge-rich (70%) polymer PPDBC was unambiguously confirmed by scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM). Remarkably, by further thermal treatment at 450 °C two and three aligned PPDBC chains can be laterally fused into expanded zeeGNRs, with a ribbon width of nine (N = 9) up to 17 (N = 17) carbon atoms. Moreover, the resulting zeeGNRs exhibit a high ratio of zigzag (67%) vs armchair (25%) edge segments and feature electronic band gaps as low as 0.9 eV according to gaps quasiparticle calculations.

Structurally precision graphene nanoribbons (GNRs) have attracted great interest considering their prospective applications as organic carbon materials for nanoelectronics. The electronic properties of GNRs not only critically depend on the edge structure and width but also on the heteroatom type, doping position, and concentration. Motivated by the recent undisputable progress in the synthesis of stable boron-doped polycyclic aromatic hydrocarbons (B-PAHs), considerable efforts have been devoted to the precision synthesis of the corresponding boron-doped GNRs (B-GNRs) via bottom-up synthesis approach in recent years in view of the extraordinary ability of boron doping on modulating their physiochemical properties. In this review, an overview of the bottom-up organic synthesis of B-GNRs, including the precursor design and synthesis, structure characterization of the resulting B-GNRs, and investigation of their electronic properties is provided. Moreover, the future challenges and perspectives regarding the bottom-up synthesis of B-GNRs are also discussed. The authors hope that this review will further stimulate the synthesis and device integrations of B-GNRs with a combined effort from different disciplines.

No description available.

Les nanorubans de carbone présentent aujourd’hui un grand intérêt en tant que segments de graphène aux propriétés électroniques modulables. Alors que des techniques de synthèse destructives top down donnent des rubans de très grande taille, d’autres techniques constructives bottom up, par synthèse organique, pourraient former des nanorubans bien définis de géométries contrôlées. Dans cette optique, la réaction de Scholl est un outil chimique précieux car elle permet la graphénisation de longs précurseurs flexibles de type polyphénylène.Etonnamment, des structures distordues peuvent être obtenues majoritairement même si des isomères plans moins encombrés sont a priori favorisés. Nous avons ainsi montré que contre toute attente même un encombrement stérique important n’a aucun effet notoire sur la régiosélectivité et que des composés aromatiques polycycliques courbés sont préférentiellement formés. Ainsi, des structures particulièrement tordues, tel que l’hexabenzotriphénylène (HBTP) peuvent être facilement obtenues à partir de précurseurs de type polyphénylène.Après avoir découvert cette régiosélectivité inattendue, nous en avons tiré parti pour former des composés de type polyhélicène. Plusieurs tentatives de formation de l’hexaphénanthrotriphénylène (HPTP) furent infructueuses à cause de problèmes de réactivité lors des synthèses des précurseurs flexibles correspondants. En mettant au point une stratégie de synthèse versatile fondée sur un précurseur commun, plusieurs substrats flexibles de symétrie C3 ont été synthétisés puis soumis à la réaction de Scholl. Des produits de réarrangement ont cependant été obtenus au détriment des [6]hélicènes attendus. Toutefois, un HBTP fonctionnalisé par des groupements TMS a pu être efficacement préparé, ainsi qu’un hexabenzocoronène (HBC) dont l’exceptionnelle solubilité est due à la distorsion du coeur aromatique sous l’effet des groupements encombrants situés dans les régions baie.Ce fragment [5]hélicène favorisé a enfin été incorporé dans la formulation de nanorubans de carbone tordus, alors composés d’une succession de ce motif. En tant que réactions test, les synthèses du monomère et du dimère correspondants ont été effectuées avec d’excellents rendements et les deux composés entièrement caractérisés. Leurs structures ont été déterminée par diffraction de rayons X sur monocristaux et ont fourni d’intéressantes informations complémentaires quant à leurs configurations. Une stratégie plus générale a enfin été développée et optimisée pour la synthèse systématique d’oligomères plus longs de nanorubans de carbone tordus. En utilisant cette technique les trimère et tétramère correspondants ont été synthétisés et caractérisés par spectrométrie de masse. / Carbon nanoribbons are today of great interest as graphene segments with modulable electronic properties. Whilst top down techniques give giant ribbons, bottom-up organic synthesis may lead to exactly designed nanoribbons of controlled geometries. The Scholl reaction is a precious chemical tool for that purpose since it yields efficiently to the graphitization of long and flexible polyphenylene precursors.Surprisingly, twisted structures may be obtained preferentially even if less crowded isomers are also feasible. It has been shown that, against all expectation, even a strong steric hindrance has no marked effect on regioselectivity and highly twisted polycyclic aromatic hydrocarbons are sometimes preferentially formed, whereas their flat and more symmetrical isomers are only obtained in minority. Highly twisted structures such as hexabenzotriphenylene (HBTP) may then be obtained very easily from flexible polyphenylene precursors.After discovering this unexpected regioselectivity, we used it on purpose to form polyhelicenic species. Attempts to prepared hexaphenanthrotriphenylene (HPTP) were unsuccessful due to reactivity issues when synthesizing the corresponding flexible precursors. By using a new versatile strategy leading to an advanced common precursor, several C3-symmetrical flexible substrates have been synthesized and submitted to Scholl reaction. The expected [6]helicenes were not obtained and rearranged products were formed instead, but TMS-bearing HBTP could be prepared, as well as a hexabenzocoronene (HBC) which exceptionnal solubility is due to the distortion of the aromatic core under the effect of bulky tert-butyl substituents in bay regions.The easily formed [5]helicene fragment has been incorporated in the design of twisted carbon nanoribbons that would be composed of a succession of such motifs. As a test reaction, the corresponding monomer and dimer have been synthesized with an excellent yield and fully characterized. Their X-ray structures have even been determined, giving interesting information about their configuration. A more general strategy has then been developed and optimized for the systematic synthesis of longer oligomers of twisted nanoribbons. Using this technique, the trimer and tetramer have been synthesized and characterized by mass spectrometry.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / We use first principles calculations based upon the density functional theory to investigate the stability, geometry, electronic and magnetic properties of cibic silicon carbide (SiC) surfaces aligned along the (001) direction (β−SiC(001)) and nanoribbons (SiCNRs). The β−SiC(001) can be terminated in C or Si. For both terminations a great number of possible reconstruction are studied. To study the stability of the β−SiC(001) surface the formation energy is calculated, which shows that the two terminations (C or Si) have similar stability. Surfaces states are find in the bandgap for the two possible terminations. These surfaces states rule the electronic properties of the β−SiC(001) surface, which present metallic or semiconductor characteristics depending on the surface reconstruction. Aiming to saturate the dangling bonds and functionalize the C terminated β− SiC(001) surface, H atoms are adsorbed in the most stable configuration: the β− SiC(001) in the c(2x2) reconstruction where there are C dimers aligned in row and column. First we observe that the H adsorption is exothermic, indicating to a greater stability of the β−SiC(001) surface. Increasing the number of adsorbed H atoms (up to the third layer) we observe the formation of a nanotunnel structure. There tunnels are stable and small cavities present in the subsurface of the β−SiC(001). The semiconductor character of the β−SiC(001) in the presence of nanotunnels is preserved. The top of the valence band and of the boton of the band are surface states localized in hydrogenated C dimers near to the nanotunnel. Adsorbing Fe atoms on the β−SiC(001) surface we observe that the electronic and magnetic properties of the β−SiC(001) surface are strongly modified. There is a strong magnetic moment localized in Fe atoms adsorbed on the β−SiC(001) surface, which can present metallic or half metallic characteristics. The antiferromagnetic (AFM) interaction between the magnetic moments is favorable when compared to the ferromagnetic (FM) interaction. The electronic and magnetic properties of SiCNRs depend on the border structure. The SiCNRs terminated by H atoms and with armchair borders are semiconductor and no magnetic. Whereas the electronic and magnetic properties of SiCNRs terminated by H atoms and with zigzag border depend on the ribbon width and can be metallic or semiconductor. For pristine zigzag SiCNRs, the ferrimagnetic interaction between the borders is the ground state. The adsorption of Fe (atom and dimer) on a SiC sheet give rise to new electronic levels inside the bandgap and lead the SiC sheet to shows magnetic properties. The magnetic moment for Fe adsorbed on a SiC sheet is 2 μB and 6 μB, for a Fe atom or dimer adsorbed, respectively. The adsorption of Fe structures (atoms and dimers) on the SiCNRs is more stable near the borders of the ribbon. Depending on the Fe coverage and the magnetic interactions we can obtain, metallic, half-metallic, semiconductor or even a spin gapless semiconductor (SGS). These results show that functionalized SiC nanostructures are important materials for nanodevices. / Utilizando cálculos de primeiro princípios dentro do formalismo da teoria do funcional da densidade (DFT) realizou-se um estudo da estabilidade, geometria, propriedades eletrônicas e magnéticas de superfícies de carbeto de silício (SiC) cúbica alinhada ao longo da direção (001) (β−SiC(001)) e nanofitas de SiC. A superfície β−SiC(001) apresenta dois tipos de terminação: terminação em C ou em Si. Para cada terminação (C ou Si) foi estudado um grande número de reconstruções possíveis. No estudo da estabilidade da superfície β−SiC(001) calculamos a energia de superfície, que mostrou que as duas terminações (C ou Si) apresentam similar estabilidade. Para as duas terminações a análise das propriedades eletrônicas mostra que estados de superfície estão presentes no gap. Estes estados de superfície regem as propriedades eletrônicas da β−SiC(001) que apresentam comportamento metálico ou semicondutor, dependendo da reconstrução. Com o objetivo de saturar as ligações pendentes na superfície e ao mesmo tempo funcionalizar a superfície, efetuamos o estudo da hidrogenação da superfície β−SiC(001) terminada em C e na reconstrução mais estável que é a c(2x2), onde linhas e colunas de dímeros de C estão presentes. Inicialmente observamos que a adsorção de H é exotérmica indicando uma maior estabilidade da superfície β−SiC(001) hidrogenada. Aumentando o número de H adsorvido (hidrogenação até a terceira camada) foi possível mostrar a formação de nanotúnel na superfície. Os nanotúneis são pequenas cavidades presentes na subsuperfície da β−SiC(001). Na presença dos nanotúneis o carácter semicondutor é preservado. Com adsorção de átomos de Fe na β−SiC(001) as propriedades eletrônicas e magnéticas são fortemente influenciadas. Existe a presença de um forte momento magnético localizados nos átomos de Fe adsorvidos na β−SiC(001), que pode apresentar características metálicas ou meio-metálicas. A interação entre os momentos magnéticos favorece a uma interação do tipo antiferromagnética (AFM) se comparada com a interação do tipo ferromagnética (FM). As propriedades eletrônicas e magnéticas das nanofitas de SiC (SiCNFTs) são dependentes das bordas. As SiCNFTs terminadas em H e com bordas armchair são semicondutoras não magnéticas. No entanto, as propriedades eletrônicas e magnéticas das SiCNFTs terminadas em H e com bordas zigzag dependem da largura da fita e podem ser metálicas ou semicondutoras. Para as SiCNFTs na forma pristina, o estado fundamental ocorre quando há uma interação do tipo ferrimagnética entre as bordas. A adsorção de Fe (átomo e dímero) em uma folha de SiC faz com que novos níveis eletrônicos estejam presentes no gap e a folha de SiC apresenta propriedades magnéticas. O momento magnético para o átomo de Fe adsorvido sobre a folha de SiC é de 2 μB e para um dímero de Fe adsorvido este momento magnético é de 6 μB. A adsorção de Fe (átomo ou dímero) sobre as SiCNFTs é mais estável nas bordas das fitas. Dependendo da cobertura de Fe e das interações magnéticas podemos obter metais, meio-metais, semicondutores ou mesmo semicondutores com polarização de spin e gap nulo (SGS). Estes resultados mostram que nanoestruturas de SiC funcionalizadas são importantes materiais para nanodispositivos.

Submitted by Maike Costa (maiksebas@gmail.com) on 2016-03-15T13:04:40Z No. of bitstreams: 1 arquivototal.pdf: 6077553 bytes, checksum: 3cad3094833d2fdc458897bedccb4917 (MD5) / Made available in DSpace on 2016-03-15T13:04:40Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 6077553 bytes, checksum: 3cad3094833d2fdc458897bedccb4917 (MD5) Previous issue date: 2014-08-08 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In this work, we investigate in parallel physical and mathematical aspects inherent to the problem of confinement of massless Dirac fermions in graphene nanostructures. In a low energy approach, we propose models to describe confining systems in graphene and study how the choice of boundary conditions of the problem - or, equivalently, of domains of the Dirac operator - affects the physical properties of such systems. In this scenario, we concentrate essentially on the study of the physical behavior of graphene nanorings and nanoribbons in response to aspects such as topology, edge and interface geometry and interactions with external fields. At the same time, a rigorous investigation concerning formal aspects of the problem and the way that they manifest themselves physically is also performed. In light of the theory of linear operators on Hilbert spaces, we analyze the role played by the notion of self-adjointness in the problem and establish sets of boundary conditions physically acceptable in graphene, which mathematically corresponds to the definition of self-adjoint extensions of the Dirac Hamiltonian from the continuum description. Sets proposed in the treatment of some studied configurations are approached in this context. In addition, we present a particular study in which we examine the influence of topological defects on the physics of massive fermions in graphene in the presence of Coulomb and uniform magnetic fields. / Neste trabalho, investigamos paralelamente os aspectos físicos e matemáticos inerentes ao problema do confinamento de férmions de Dirac sem massa em nanoestruturas de grafeno. Em uma abordagem no limite de baixas energias, propomos modelos para descrever sistemas confinantes no âmbito da física do grafeno e estudamos de que modo a escolha das condições de contorno do problema - ou, equivalentemente, dos domínios do operador de Dirac - exercem influência sobre as propriedades físicas de tais sistemas. Neste cenário, concentramo-nos essencialmente no estudo do comportamento físico de nanoanéis e nanofitas de grafeno em resposta a aspectos como topologia, geometria de borda e interface e interações com campos externos. Ao mesmo tempo, também é realizada uma rigorosa investigação acerca dos aspectos formais do problema e do modo como eles se refletem fisicamente. À luz da teoria dos operadores lineares em espaços de Hilbert, analisamos o papel desempenhado pela noção de self-adjointness na modelagem do problema e estabelecemos conjuntos de condições de contorno fisicamente aceitáveis relativamente ao grafeno, o que corresponde matematicamente à definição de extensões auto-adjuntas do Hamiltoniano de Dirac da descrição do contínuo. Conjuntos propostos no tratamento de algumas das configurações estudadas são abordados neste contexto. Além disso, apresentamos um estudo à parte em que examinamos a influência de defeitos topológicos na física de férmions com massa no grafeno na presença de interações de Coulomb e de campos magnéticos uniformes.