双掺杂碳纳米管电子场发射性能的密度泛函研究

采用第一性原理的密度泛函理论(DFT)研究了(5,5)碳纳米管(CNT)顶端硼(B)、氮(N)、硅(Si)等元素双掺杂体系的电子场发射性能.结果表明,在外电场下,各种双掺杂CNT帽端态密度(DOS)向价带移动.电子轨道分布变化显著,电荷分布明显局城化.根据电子态密度、差分电荷密度、最高分子占据轨道(HOMO)/最低分子非占据轨道(LUMO)分布等计算结果可预期Si双掺杂后更有利于场致电子发射.     

Single-walled carbon nanotube growth from highly activated metal nanoparticles

We demonstrate that any metal, even gold, silver, and copper, can act as a catalyst for SWCNT synthesis in chemical vapor deposition (CVD). Metal nanoparticles 3 nm or less in diameter, introduced into CVD ambience immediately after heat treatment at 800-950 degrees C in air, produce SWCNTs. The activation method is effective for copper and various noble metals as well as for iron-family elements. This implies that any metal particle may produce SWCNTs when its size becomes 1-3 nm. In other words, carbon atoms can form SWCNTs in a self-assembling fashion on nanoparticles without the specific functions of iron-family elements.     

Template synthesis and growth mechanism of metal nanowire/carbon nanotube heterojunctions

Copper (Cu) and Cobalt (Co) with remarkable difference in the catalytic activity for the growth of carbon nanotubes (CNTs) have been used to prepare metal-nanowire/CNT heterojunctions. The ordered arrays of Cu nanowire/CNT (CuNW/CNT) and Co nanowire/CNT (CoNW/CNT) heterojunctions were prepared by combining electrochemical deposition and chemical vapor deposition. The interfaces between CNTs and Cu or Co nanowires have been examined and compared. At the interface of CuNW/CNT heterojunction, the tip of CuNW is encapsulated by carbon material (named "cap") and connected the CNT consisting of amorphous carbon (a-C). Two-segment CuNW/amorphous CNT (CuNW/a-CNT) hybrid nanostructure was obtained for the CuNW/CNT heterojunctions due to low catalytic activity of Cu. It is also interesting that a hollow gap was observed between the "cap" and the CuNW. By contrast with the case of Cu, multi-walled CNT (MWCNT) was achieved and no hollow gap was observed at the interface of CoNW/CNT heterojunctions. Three-segment CoNW/MWCNT/a-CNT hybrid nanostructure was observed for the CoNW/CNT heterojunctions because of high catalytic activity of Co. Because no stable copper carbides are observed, we infer that the growth mechanism of CuNW/CNT heterojunctions is different from that of CoNW/CNT. Possible growth models of CuNW/CNT and CoNW/CNT heterojunctions are proposed based on experimental results, respectively.     

Density functional theory studies of Cu-zeolite de-NOx catalysts

Summary Recent progress in the modelling of exchanged Cu sites and their interactions with small molecules, based on DFT cluster calculations, is briefly reviewed.     

Density functional theory investigation of the mechanical properties of single-walled carbon nanotubes

We detail the results of our first-principles study based on density functional theory on the elastic properties of (6, 6) single-walled carbon nanotubes (SWCNTs) in both periodic and non-periodic systems. The Young’s modulus and the shear modulus of nanotubes were evaluated through applying axial and torsion strains on periodic, H-, and C-capped nanotubes. Based on our first-principles calculations, the Young’s modulus of the periodic nanotube tens to increase as the nanotube’s length increases, and finally approaches a constant value at long tube lengths. It was found that the Young’s modulus characteristic of H- and C-capped nanotubes exhibit contradictory behaviors during compression with the periodic nanotube. Our calculations also predict that the Young’s and Shear moduli of C-capped nanotubes are larger than those of other types of nanotubes.     

Density functional theory study of optical transitions in semiconducting single-walled carbon nanotubes

We present a density functional theory study of optical transitions in semiconducting single-walled carbon nanotubes. We utilize recently developed exchange-correlation functionals in a set of 21 tubes that includes large and chiral nanotubes. The novel TPSSh meta-generalized gradient approximation hybrid functional accurately reproduces optical excitations with mean absolute errors of 0.024 and 0.065 eV for first and second transitions, respectively. We also report predictions for higher order optical transitions.     

Dynamics of carbon nanotube growth from fullerenes

The growth of double-walled carbon nanotubes from peapods was studied. The transformation was monitored by the decrease of fullerene Raman lines, the growth of inner tube Raman lines, and the development of X-ray diffraction patterns. A visual check of the growth process by HRTEM provided additional information. From the difference in time constants for the bleaching of fullerene Raman lines and for the growth of nanotube Raman lines, the existence of an intermediate phase was concluded that was eventually observed in X-ray diffraction and HRTEM. Time constants for the growth of large diameter inner tubes were up to a factor two larger than for small diameter inner tubes. The results fully support the fullerene coalescence growth model triggered by Stone-Wales transformations.     

Bottom-up growth of carbon nanotube multilayers: unprecedented growth

An unusual growth phenomenon, with no precedent in vapor-phase thin film growth, is described here, for the case of the growth of stacked multiple layers of vertically aligned carbon nanotubes(1-6) on solid substrates. As multiple layers of ordered nanotubes are sequentially deposited from the vapor onto the substrate, each layer nucleates and grows from the original substrate surface at the bottom of the existing multiple stacks of nanotubes. In contrast to conventional understanding of thin film deposition,(7) the mechanism here has similarities to porous oxide film formation on surfaces.(8) The stacked layers of aligned nanotubes act as fully permeable membranes for the downward diffusion of growth precursor vapors, allowing growth to occur at the buried solid interface. The preexisting multiple nanotube stacks lift up to accommodate the vertical growth of fresh layers, allowing the formation of nanotube towers extending in millimeter lengths. Our results provide evidence for a new growth phenomenon, characterized by selective, interface-driven, bottom-up growth of self-assembled nanowires at buried interfaces, covered with weakly adhering thick porous membranes.     

Air-assisted growth of ultra-long carbon nanotube bundles

We report an air-assisted chemical vapor deposition (CVD) method for the synthesis of super-long carbon nanotube (CNT) bundles. By mixing a small amount of air in the vapor phase catalyst CVD process, the catalyst lifetime can be dramatically increased, and extremely long dense and aligned CNT bundles up to 1.5?cm can be achieved. Electron microscopy characterization shows that the injection of air does not damage the CNT structures. Further, we have estimated that individual ultra-long CNTs can carry moderate current densities ～10(5)?A?cm(-2), indicating their possible use in nanoelectronic devices.     

Atomistic simulations of catalyzed carbon nanotube growth

We review the advances made in understanding the mechanism of catalyzed carbon nanotube growth, with the main focus on direct dynamics and molecular dynamics studies of single-walled carbon nanotube (SWNT) growth. These studies have deepened our understanding of the catalytic SWNT nucleation and growth mechanisms, but more accurate and efficient methods are required for a complete investigation at experimental growth conditions.     

Dynamical observation of bamboo-like carbon nanotube growth

The growth dynamics of bamboo-like multiwalled carbon nanotubes (BCNTs) via catalytic decomposition of C2H2 on Ni catalyst at 650 degrees C was observed in real time using an in situ ultrahigh vacuum transmission electron microscope. During BCNT growth, the shape of the catalyst particle changes constantly but remains metallic and crystalline. Graphene sheets (bamboo knots) within the nanotube preferentially nucleate on the multistep Ni-graphite edges at the point where the graphene joins the catalyst particle, where it is stabilized by both the graphene walls and the Ni catalyst surface. The growth of a complete inner graphene layer growth prior to contraction of the Ni catalyst particle due to restoring cohesive forces will result in a complete BCNT knot whereas partial growth of the inner wall will lead to an incomplete BCNT knot.     

Raman studies of new carbon nanotube sample types

Generation of new carbon nanotube sample types, including individualized nanotubes suspended in surfactant solutions and recently synthesized ultralong nanotubes, has enabled new experimental studies that provide useful insight into nanotube structure and photophysical behavior. We present a review of Raman studies performed in our laboratory on these newly available sample types. Results from Raman excitation profile studies of individualized HiPco-produced nanotubes have confirmed fluorescence-based chirality assignments and have revealed chiral-dependences in the Raman scattering cross-sections. These studies have also enabled a direct evaluation of the effects of nanotube bundling on electronic and vibrational structure. Confocal Raman imaging is demonstrated as a useful technique for probing vibrational structure of ultralong nanotubes over large length scales and has resulted in the detection and imaging of a semiconductor-to-metallic nanotube intramolecular junction.     

Bond-order potential for transition metal carbide cluster for the growth simulation of a single-walled carbon nanotube

A classical many-body potential for transition metal carbide cluster is developed in the form of the bond-order type potential function. The parameter sets between carbon atoms and several transition metal atoms (Fe, Co and Ni) are constructed by fitting binding energies from Density Functional Theory (DFT) calculations. Using the potential function, clustering process of carbon atoms to a small metal cluster is studied by classical molecular dynamics (MD) simulation. The number of hexagonal rings in the Co cluster increases about twice as fast as in the Fe cluster. This implies that the graphitic lattice interacts more strongly with Co atoms than with Fe atoms. A Co cluster has a crystal structure where metal atoms are regularly allocated and embedded in the hexagonal carbon network in the simulation. In contrast, carbon atoms cover the entire surface in case of the Fe cluster. Additionally, the potential energy surface that a carbon atom feels from a 2D closed-packed facet is examined using a hypothetical FCC(1 1 1) facet of several transition metals. The potential energy minima are distributed on the hexagonal network showing the 2D closed-packed facet can be a template where a graphene is formed.     

Adjoint operator approach to functional reliability analysis of passive fluid dynamical systems

Reliability analysis of passive systems mainly involves quantification of the margin to safety limits in probabilistic terms. For systems represented by complex models, propagating input uncertainty to get the response uncertainty and hence probability information requires intensive computational effort. Here a computationally efficient method for the functional reliability analysis of passive fluid dynamical systems is presented. The approach is based on continuous adjoint operator technique to generate a response surface approximating the given system model from the sensitivity coefficients. A numerical application of this method to the reliability analysis of heat transport in an asymmetrical natural convection loop is demonstrated. Computational efficiency and accuracy compared with the direct Monte-Carlo and forward response surface methods.     

Density functional theory study of piperidine and diazocine compounds

Density functional theory calculations at the B3LYP/6-311G** level were performed to predict the heats of formation (HOFs) for three eight-membered ring compounds and four six-membered ring compounds via designed isodesmic reactions. In the isodesmic reactions designed for the computation of HOFs (CH(3)CH(2))(2)NNO(2) and piperidine were chosen as reference compounds. The HOFs for -NO(2) substituted derivations are larger than those of -NF(2) substituent groups. Thermal stability were evaluated via bond dissociation energies (BDE) at the UB3LYP/6-311G** level. As a whole, the homolysis of CNF(2) or CNO(2) bonds is the main step for bond dissociation of the title compounds. Detonation properties of seven title compounds were evaluated by using the Kamlet-Jacobs equation based on the calculated densities and HOFs. It is found that 3,3,7,7-tetrakis(difluoroamino)octahydro-1,5-dinitro-1,5-diazocine (HNFX) and 3,3,5,5-tetrakis (difluoroamino)-1-nitro piperidine (N-nitro TDFAPP), with predicted density of ca. 2.0 g/cm(3), detonation velocity (D) about 9.9 km/s, and detonation pressure (P) of 47GPa that are lager than those of HMX, are expected to be the novel candidates of high energy density materials (HEDMs). The detonation data of 1,3,3,5,7,7-hexanitro-1,5-diazacyclooctane (HNDZ) and TNBDFAPP show that they meet the requirements for HEDMs.     

The growth of freestanding single carbon nanotube arrays

Regular arrays of freestanding single carbon nanotubes (CNTs) were prepared on Ni dot arrays by dc plasma-enhanced chemical vapour deposition. The size of the Ni dot was reduced for single CNT growth by means of conventional photolithography and a lateral wet-etch process. The vertical alignment of a single CNT was directly dependent on the location of the catalyst metals. Using this method, well-separated and well-defined regular arrays of freestanding CNTs can be fabricated and the process can be scaled up at a lower cost than electron beam lithography, which is encouraging for applications in field emitters and nanoelectrodes.     

半导体非线性光学材料的第一性原理研究

通过第一性原理研究Ⅱ-Ⅳ-Ⅴ2族CKP半导体中的CdSiAs2，计算了其双折射性，量化了双折射性同应力的线性关系，它的负双折射性使之能够通过应力、温度调节以及同CdGeAs2混合来设计非临界位相匹配材料。计算显示，少量的参杂Ge（ 〈5％），能够实现非临界位相匹配I类二次谐波产生（SHG）在CO2激光谱线范围可调谐，它可能具有很高的有效χ^（2）。