One-dimensional Silicon and Germanium Nanostructures With No Carbon Analogues

In this work we report new silicon and germanium tubular nanostructures with no corresponding stable carbon analogues. The electronic and mechanical properties of these new tubes were investigated through ab initio methods. Our results show that the structures have lower energy than their corresponding nanoribbon structures and are stable up to high temperatures (500 and 1000 K, for silicon and germanium tubes, respectively). Both tubes are semiconducting with small indirect band gaps, which can be significantly altered by both compressive and tensile strains. Large bandgap variations of almost 50% were observed for strain rates as small as 3%, suggesting possible applications in sensor devices. They also present high Young's modulus values (0.25 and 0.15 TPa, respectively). TEM images were simulated to help the identification of these new structures

Inorganic Graphenylene: A Porous Two-Dimensional Material With Tunable Band Gap

By means of ab initio calculations we investigate the possibility of existence of a boron nitride (BN) porous two-dimensional nanosheet which is geometrically similar to the carbon allotrope known as biphenylene carbon. The proposed structure, which we called Inorganic Graphenylene (IGP), is formed spontaneously after selective dehydrogenation of the porous Boron Nitride (BN) structure proposed by Ding et al. We study the structural and electronic properties of both porous BN and IGP and it is shown that, by selective substitution of B and N atoms with carbon atoms in these structures, the band gap can be significantly reduced, changing their behavior from insulators to semiconductors, thus opening the possibility of band gap engineering for this class of two-dimensional materials

Structure and Dynamics of Boron Nitride Nanoscrolls

Carbon nanoscrolls (CNSs) are structures formed by rolling up graphene layers into a papyruslike shape. CNNs have been experimentally produced by different groups. Boron nitride nanoscrolls (BNNSs) are similar structures using boron nitride instead of graphene layers. In this work we report molecular mechanics and molecular dynamics results for the structural and dynamical aspects of BNNS formation. Similarly to CNS, BNNS formation is dominated by two major energy contributions, the increase in the elastic energy and the energetic gain due to van der Waals interactions of the overlapping surface of the rolled layers. The armchair scrolls are the most stable configuration while zigzag scrolls are metastable structures which can be thermally converted to armchair. Chiral scrolls are unstable and tend to evolve to zigzag or armchair configurations depending on their initial geometries. The possible experimental routes to produce BNNSs are also addressed

Self-assembly Of Nitpp On Cu(111): A Transition From Disordered 1d Wires To 2d Chiral Domains.

The growth and self-assembling properties of nickel-tetraphenyl porphyrins (NiTPP) on the Cu(111) surface are analysed via scanning tunnelling microscopy (STM), X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT). For low coverage, STM results show that NiTPP molecules diffuse on the terrace until they reach the step edge of the copper surface forming a 1D system with disordered orientation along the step edges. The nucleation process into a 2D superstructure was observed to occur via the interaction of molecules attached to the already nucleated 1D structure, reorienting molecules. For monolayer range coverage a 2D nearly squared self-assembled array with the emergence of chiral domains was observed. The XPS results of the Ni 2p(3/2) core levels exhibit a 2.6 eV chemical shift between the mono- and multilayer configuration of NiTPP. DFT calculations show that the observed chemical shifts of Ni 2p(3/2) occur due to the interaction of 3d orbitals of Ni with the Cu(111) substrate.1718344-1835

The AFLOW Fleet for Materials Discovery

The traditional paradigm for materials discovery has been recently expanded to incorporate substantial data driven research. With the intent to accelerate the development and the deployment of new technologies, the AFLOW Fleet for computational materials design automates high-throughput first principles calculations, and provides tools for data verification and dissemination for a broad community of users. AFLOW incorporates different computational modules to robustly determine thermodynamic stability, electronic band structures, vibrational dispersions, thermo-mechanical properties and more. The AFLOW data repository is publicly accessible online at aflow.org, with more than 1.7 million materials entries and a panoply of queryable computed properties. Tools to programmatically search and process the data, as well as to perform online machine learning predictions, are also available.Comment: 14 pages, 8 figure

Atomistic simulations of nanoscrolls and other nanostructures

Orientador: Douglas Soares GalvãoTese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb WataghinResumo: Neste trabalho nós investigamos propriedades estruturais, dinâmicas, mecânicas e eletrônicas de diferentes nanoestruturas. A tese está dividida em três partes distintas, na primeira tratamos diversos aspectos relacionados a nanoscrolls formados a partir de diferentes materiais, na segunda investigamos estruturas bidimensionais e porosas de nitreto de boro e, na terceira, estudamos novas estruturas unidimensionais de silício e de germânio. Nanoscrolls são estruturas formadas ao se enrolar materiais lamelares em torno de um eixo bem definido e apresentam propriedades interessantes e únicas. Além de preservarem características eletrônicas e mecânicas encontradas em nanotubos, os nanoscrolls, em função de sua morfologia aberta, apresentam grande flexibilidade radial e extensa área de superfície acessível a solventes, o que os torna candidatos interessantes para aplicações como nanoatuadores, tanto mecânicos quanto elétricos, e como armazenadores de hidrogênio. Inicialmente, abordamos questões relacionadas à síntese de nanoscrolls de carbono e de nitreto de boro, ambos já produzidos em laboratório. Partimos, então, para os primeiros estudos publicados acerca de nanoscrolls formados por nitreto de carbono, estudando sua estabilidade e suas propriedades dinâmicas. Por último, analisamos o empacotamento de nanoscrolls dentro de nanotubos, demonstrando a falha da teoria elástica contínua em tratar este problema devido a efeitos eletrônicos. Estruturas bidimensionais têm sido exaustivamente estudadas desde o isolamento de monocamadas de grafeno e da confirmação de suas propriedades mecânicas e eletrônicas altamente interessantes. Naturalmente, há busca por novos materiais com características semelhantes e, devido à grande semelhança estrutural, o nitreto de boro hexagonal tem despertado grande interesse, apresentando maior estabilidade térmica e química se comparado ao grafeno. Nós desenvolvemos estudos acerca de estuturas bidimensionais e porosas de nitreto de boro com diferentes morfologias. Estas estruturas, além de preservarem propriedades desejáveis do nitreto de boro hexagonal, são caracterizadas por sua baixa densidade e pela existência de largos poros, que podem ser utilizados em aplicações como de filtros seletivos. Nós mostramos, também, a possibilidade de se controlar o gap eletrônico destas estruturas através de substituições por átomos de carbono. Em função de importantes semelhanças entre suas estruturas eletrônicas e a do carbono, silício e germânio são capazes de gerar uma larga gama de nanoestruturas de interesse, análogas às existentes de carbono. Entretanto, há, também, notáveis diferenças, como a manifestação do efeito pseudo-Jahn Teller que se reflete em nanoestruturas com morfologias distintas. Tendo isso em mente, investigamos a possibilidade destas diferenças levarem à existência de estruturas únicas de silício e de germânio, sem análogos de carbono e mostramos estruturas unidimensionais que satisfazem tais condições. Nós estudamos sua estabilidade e suas propriedades mecânicas e eletrônicas, mostrando que seus valores de gap eletrônico podem ser controlados através de tensão e compressãoAbstract: In this work we investigate structural, dynamical, mechanical and electronic properties of different nanostructures. The thesis is organized in three distinct parts, in the first we analyze some aspects related to nanoscrolls made from different materials, in the second we investigate two dimensional porous boron nitride structures and, in the third, we study novel one dimensional silicon and germanium nanostructures. Nanoscrolls are structures formed by rolling layered materials around a well defined axis and present interesting and unique properties. Besides preserving electronic and mechanical properties shown by nanotubes, nanoscrolls, as a consequence of their open ended morphology, present great radial flexibility and large solvent accessible surface area, making them interesting candidates for aplications as nanoactuators, both mechanical and electronic, and as hydrogen storage mediums. Firstly, we approach aspects related to carbon and boron nitride nanoscrolls synthesis processes, both already having been experimentally produced. We then focus on the first published works on nanoscrolls formed from carbon nitride, studying their stability and dynamical properties. Lastly, we analyze the confinement laws of nanoscrolls inside nanotubes, demonstrating the failure of classical continuous elasticity on solving this problem due to electronic effects. Two dimensional nanostructures have been extensively studied since the successful isolation of monolayer graphene and the confirmation of its highly interesting mechanical and electronic properties. Naturally, other materials with similar characteristics are pursued and, due to its large structural similarity, hexagonal boron nitride has been of great interest, presenting higher thermal and chemical stability when compared to graphene. We investigated two dimensional porous boron nitride structures with distinct morphologies. These structures, besides preserving hexagonal boron nitride desirable properties, are characterized by their low density and the presence of large pores, which can be utilized in applications such as selective filters. We also show the possibility of bandgap tuning through carbon atoms substitution. Due to significant similarities between their electronic structures and that of carbon, silicon and germanium are able to generate a plethora of interesting nanostructures, analogous to the existing carbon ones. Nevertheless, there are notable differences, such as the manifestation of the pseudo-Jahn Teller effect which leads to nanostructures with distinct morphologies. With this in mind, we investigate the possibility of these differences leading to the existence of unique silicon and germanium nanostructres, with no carbon analogue and we show one dimensional structures satisfying such conditions. We study their stability and their mechanical and electronic properties, showing that their bandgap values can be controlled by compressive and tensile strainDoutoradoFísicaDoutor em Ciência