Electronic and magnetic properties of armchair and zigzag graphene nanoribbons

The electronic properties, band gap, and ionization potential of zigzag and armchair graphene nanoribbons are calculated as a function of the number of carbon atoms in the ribbon employing density functional theory at the B3LYP6-31G* level. In armchair ribbons, the ionization potential and band gap show a gradual decrease with length. For zigzag ribbons, the dependence of the band gap and ionization potential on ribbon length is different depending on whether the ribbon has an unpaired electron or not. It is also found that boron and nitrogen zigzag and armchair doped graphene nanoribbons have a triplet ground state and could be ferromagnetic.     

Scaling of excitons in graphene nanoribbons with armchair shaped edges

The scaling behavior of band gaps and fundamental quantities of exciton, i.e., reduced mass, size, and binding strength, in three families of quasi one-dimensional graphene nanoribbons with hydrogen passivated armchair shaped edge (AGNRs) are comprehensively investigated by density functional theory with quasi-particle corrections and many body, i.e., electron-hole, interactions. Compared with single-walled carbon nanotubes (SWCNTs) where the scaling character features a single exponent, each family of AGNRs has its own single exponent, due to its intrinsic zero curvature, which also accounts for the absent "family spreading" of optical transition energies in the smaller width region in the Kataura plots of AGNRs as compared to those of SWCNTs. Moreover, the scaling relation between exciton binding strength and the geometric parameter is established.     

电场和应力作用下氮钝化扶手型氧化锌纳米带的电子结构和磁特性

采用密度泛函理论(DFT)方法,在LDA+U水平下详细研究了电场和应力作用下氮钝化扶手型氧化锌纳米带(NA8-ZnONRs)的电子结构和磁特性。对体系的电子结构和磁性进行详细的计算,结果表明：本征扶手型氧化锌纳米带(A8-ZnONRs)是无磁性P型半导体。氮钝化后NA8-ZnONRs具有铁磁金属性,其磁性主要来源于N2p轨道(2.56μ_B)和O2p轨道(0.69μ_B)电子的自旋极化,总磁矩为3.21μ_B。NA8-ZnONRs体系对X方向电场有较强的响应,通过调节X方向电场的幅度,可以有效调节体系的磁矩。在X方向电场作用下体系仍具有铁磁金属性,磁性也主要来源于N2p和O2p轨道电子的自旋极化。施加X方向应力作用后,体系仍表现为铁磁金属性。与NA8-ZnONRs纳米带磁矩相比,体系的总磁矩均发生了较大幅度的增长,表明体系对应力作用具有较明显的相应。但随着应力幅度的调节,总磁矩的变化较平坦。表明施加应力可以有效调节体系的磁矩,但在较小应力范围内,体系对应力变化的相应不明显。     

Oxygen-promoted synthesis of armchair graphene nanoribbons on Cu(111)

We report the systematic investigation of the effects of oxygen on the synthesis of 3 p sub-family armchair graphene nanoribbons(3 p-AGNRs),which revealed a strong catalytic effect with a reduction in the reaction temperature by approximately 180 K without degradation of the AGNRs.Poly(para-phenylene)(3-AGNR)was generated through Ullmann-type coupling of4,4’’-dibromo-p-terphenyl on Cu(111),which was then converted into wider 3 p-AGNRs via lateral fusion.Scanning tunneling microscopy(STM)and X-ray photoelectron spectroscopy demonstrated the formation of different ribbons up to 12-AGNR,which contained regions exhibiting increased STM contrast that we attribute to the intercalation of Br atoms during lateral fusion.     

Tuning of the electronic properties of H‐passivated armchair graphene nanoribbons by mild border oxidation: Theoretical study on periodic models

We report the results of a DFT study of the electronic properties, intended as highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies, of periodic models of H‐passivated armchair graphene nanoribbons (a‐GNRs) as that synthetized by bottom‐up technique, functionalized by vicinal dialdehydic groups. This material can be obtained by border oxidation in mild and easy to control conditions with ¹Δ_g O₂ as we reported in our previous paper (Ghigo et al., ChemPhysChem 2015, 16, 3030). The calculations show that the two models of border oxidized a‐GNRs (model A, 0.98 nm and model B, 1.35 nm wide) present LUMO and HOMO energies lowered by an extend roughly linearly dependent on the amount of oxygen chemically bound. The frontier orbital energy variations dependence on the % wt of oxygen bound are, for model A: ?0.12 eV for the LUMO and ?0.05 eV for the HOMO; for model B: ?0.15 eV (HOMO) and ?0.06 eV (LUMO). © 2016 Wiley Periodicals, Inc.     

A single-molecule nanopore device detects DNA polymerase activity with single-nucleotide resolution

The ability to monitor DNA polymerase activity with single-nucleotide resolution has been the cornerstone of a number of advanced single-molecule DNA sequencing concepts. Toward this goal, we report the first observation of the base-by-base DNA polymerase activity with single-base resolution at the single-molecule level. We describe the design and characterization of a supramolecular nanopore device capable of detecting up to nine consecutive DNA polymerase-catalyzed single-nucleotide primer extensions with high sensitivity and spatial resolution (相似文献   

Measurements of single-molecule electromechanical properties

The electromechanical properties of a single molecule covalently attached to two gold electrodes are studied by simultaneously measuring the conductance and the force during the stretching of the molecule. The conductance, the spring constant of the molecular junction, and the dependence of the conductance on the stretching force are determined. Like the conductance, the spring constant of a molecule depends also on the molecule-electrode contacts. The forces required to break the molecule-gold contacts are 1.5 nN for alkanedithiols and 0.8 nN for 4,4' bipyridine, indicating that the breakdowns take place at the Au-Au bond and at the N-Au bond, respectively.     

Density functional study on the increment of carrier mobility in armchair graphene nanoribbons induced by Stone-Wales defects

Armchair graphene nanoribbons and their derived structures containing Stone-Wales defects are investigated using a self-consistent field crystal orbital method based on density functional theory. The investigation indicates that both the nanoribbons and the defective structures are semiconductors. A low concentration of middle Stone-Wales defects generally increases the carrier mobility, calculated using deformation potential theory, while edge Stone-Wales defects decrease it. The largest increment of the carrier mobility is as high as 170%, which is explained by the lighter carrier effective mass with crystal orbital analysis.     

Synthesis and optical properties of CdS nanoribbons

Rapid production of single crystalline CdS nanoribbons with hexagonal wurtzite phase has been achieved by thermal evaporation of CdS powder on Si wafers. The flow rate of the carrier (Ar) gas along with the synthesis temperature plays an important role in defining the size and shape of the CdS nanoribbons. Scanning electron and transmission electron microscopic observations revealed the nanoribbons to have a flat end as well as side surfaces which will make it ideal for optoelectronic devices such as nanolasers and light emitting diodes based on individual nanoribbons. The nanoribbons have widths within 200-400 nm and lengths approximately a few hundred micrometers. Room-temperature photoluminescence measurements show green emission centered at approximately 525 nm which may be ascribed to the near band edge emission. The Raman spectra of the CdS nanoribbons show peaks around 304, 609, 915, and 1220 cm(-1) corresponding to the first-, second-, third-, and fourth-order longitudinal optical phonon modes, respectively.     

A microfluidic approach for investigating the temperature dependence of biomolecular activity with single-molecule resolution

We present a microfluidic approach for single-molecule studies of the temperature-dependent behavior of biomolecules, using a platform that combines microfluidic sample handling, on-chip temperature control, and total internal reflection fluorescence (TIRF) microscopy of surface-immobilized biomolecules. With efficient, rapid, and uniform heating by microheaters and in situ temperature measurements within a microfluidic flowcell by micro temperature sensors, closed-loop, accurate temperature control is achieved. To demonstrate its utility, the temperature-controlled microfluidic flowcell is coupled to a prism-based TIRF microscope and is used to investigate the temperature-dependence of ribosome and transfer RNA (tRNA) structural dynamics that are required for the rapid and precise translocation of tRNAs through the ribosome during protein synthesis. Our studies reveal that the previously characterized, thermally activated transitions between two global conformational states of the pre-translocation (PRE) ribosomal complex persist at physiological temperature. In addition, the temperature-dependence of the rates of transition between these two global conformational states of the PRE complex reveal well-defined, measurable, and disproportionate effects, providing a robust experimental framework for investigating the thermodynamic activation parameters that underlie transitions across these barriers.     

Transport properties of armchair graphene nanoribbon junctions between graphene electrodes

The transmission properties of armchair graphene nanoribbon junctions between graphene electrodes are investigated by means of first-principles quantum transport calculations. First the dependence of the transmission function on the size of the nanoribbon has been studied. Two regimes are highlighted: for a small applied bias transport takes place via tunneling and the length of the ribbon is the key parameter that determines the junction conductance; at a higher applied bias resonant transport through the HOMO and LUMO starts to play a more determinant role, and the transport properties depend on the details of the geometry (width and length) of the carbon nanoribbon. In the case of the thinnest ribbon it has been verified that a tilted geometry of the central phenyl ring is the most stable configuration. As a consequence of this rotation the conductance decreases due to the misalignment of the π orbitals between the phenyl ring and the remaining part of the junction. All the computed transmission functions have shown a negligible dependence on different saturations and reconstructions of the edges of the graphene leads, suggesting a general validity of the reported results.     

Ligand-to-metal ratio controlled assembly of tetra- and hexanuclear clusters towards single-molecule magnets

A simple template-mediated route, starting from triethalolamine 1, sodium hydride or caesium carbonate, and iron(III) chloride led to the six- and eight-membered iron coronates [Na c [Fe6[N(CH2CH2O)3]6]]+ (2) and [Cs c (Fe8[N(CH2CH2O)3]8]]+ (3). In the reaction of N-methyldiethanolamine 4 (H2L1) or N-(2,5-dimethylbenzyl)iminodiethanol 6 (H2L2) with calcium hydride followed by addition of a solution of iron(III) chloride, the neutral unoccupied coronands [Fe6Cl6(L1)6] (5) and [Fe6Cl6(L2)6] (7) were formed. Subsequent exchange of the chloride ions of 7 by bromide or thiocyanate ions afforded the ferric wheels [Fe6Br6(L2)6] (8) or [Fe6(NCS)6(L2)6] (9), respectively. Titration experiments of solutions of dianion (L1)2- with iron(III) chloride in THF revealed interesting mechanistic details about the self-assembling process leading to 5. At an iron/ligand ratio of 1:1.5 star-shaped tetranuclear [Fe[Fe(L1)2]3] (11) was isolated. However, at an iron/ligand ratio of 1:2, complex 11 was transformed into the ferric wheel 5. It was shown, that the interconversion of 5 and 11 is reversible. Based on the mechanistic studies, a procedure was developed which works for both the synthesis of homonuclear 11 and the star-shaped heteronuclear clusters [Cr[Fe(L1)2]3] (12) and [Al[Fe(L1)2]3] (13). The structures of all new compounds were determined unequivocally by single-crystal X-ray analyses.     

High resolution gas chromatographic determination of permanent gases with a helium ionization detector

The capability of the helium ionization detector (HID) to operate in connection with capillary columns for trace gas analyses has been evaluated. Two different capillary columns were considered: a PLOT fused silica column with molecular sleve and a thick film WCOT glass column with PS-255. The determination of trace impurities in gases can be achieved with evident advantages over classical adsorption columns, even using a split injection system. Direct on-column injections also have been investigated with promising results.     

Synthesis and magnetic properties of manganite multiple heterostructure nanoribbons

The fabrication and applications of two-dimensional complex oxide heterostructures have gained great attention. However, the achievement of these materials in one-dimensional form with multiple interfaces is still elusive. Here, we report the growth of manganite CaMn(3)O(6)/CaMn(2)O(4) heterostructure nanoribbons via the use of CaMnO(3) powders as the precursor for the molten-salt process. In contrast with the antiferromagnetism in CaMn(3)O(6) and CaMn(2)O(4) in the bulk, magnetization measurements indicate the coexistence of a ferromagnetic phase with a spin-glass-like component in CaMn(3)O(6)/CaMn(2)O(4) heterostructure nanoribbons. An asymmetric magnetization hysteresis loop observed in the applied magnetic field H≤ 3 T is attributed to the coupling between the antiferromagnetic phase and the ferromagnetic or spin-glass-like phase in CaMn(3)O(6)/CaMn(2)O(4) heterostructure nanoribbons.     

共价有机骨架衍生碳基材料的制备及其电化学性能

设计具有多孔结构、比表面积大的高性能电极材料对于发展高能量密度的超级电容器尤为重要.本文报道以共价有机骨架材料为前驱体,通过简单热处理构建出一种氮掺杂的多孔碳纳米材料作为超级电容器电极材料.该材料显示出高导电性和高表面积,其应用于超级电容器作为负极时表现出高的面积比容量.在电流密度为1mA·cm-2时,其面积比容量可达...     

Electronic structures and transport properties of fluorinated boron nitride nanoribbons

By applying the nonequilibrium Green's functions and the density-functional theory, we investigate the electronic structures and transport properties of fluorinated zigzag-edged boron nitride nanoribbons. The results show that the transition between half-metal and semiconductor in zigzag-edged boron nitride nanoribbons can be realized by fluorination at different sites or by the change of the fluorination level. Moreover, the negative differential resistance and varistor-type behaviors can also be observed in such fluorinated zigzag-edged boron nitride nanoribbon devices. Therefore, the fluorination of zigzag-edged boron nitride nanoribbons will provide the possibilities for a multifunctional molecular device design.     

Controlled synthesis and photoluminescence properties of ZnS nanowires and nanoribbons

Rapid synthesis of wurtzite ZnS nanowires and nanoribbons has been achieved by a simple thermal evaporation of ZnS powder onto Si substrate in the presence of Au catalyst. A vapor-liquid-solid process is proposed for the formation of the ZnS nanostructures. The flow rate of the inert carrier Ar gas along with the temperature play an important role in defining the morphology of the ZnS nanostructures. The morphological change of the ZnS nanostructures and their growth sequence were studied through scanning electron microscopy. Room-temperature photoluminescence measurements showed intense blue emission at approximately 398 nm from both the nanowires and the nanoribbons.     

Electronic properties of capped, finite-length armchair carbon nanotubes in an electric field

This study investigates the electronic properties of finite-length armchair carbon nanotubes in an electric field (E) using a single-pi-band tight-binding model. Three different tip configurations are considered, namely, open ends with hydrogen terminations (H-terminations), one end capped with half of C60 fullerene and the other end open with H-terminations, and both ends capped with half of C60 fullerene. In general, the electronic states and energy gaps of low-energy electronic structures are highly sensitive to changes in the direction and magnitude of the applied electric field and to the tip configuration. The present results show that the electric field induces a strong modulation of the state energies and energy gaps of the current nanotubes, changes their energy spacings, and prompts the occurrence of semiconductor-metal transitions (SMTs). It is found that the SMTs occur more frequently as the direction of the electric field approaches the symmetry axis or when its magnitude becomes sufficiently large. The present results also indicate that the Fermi levels and energy gaps of the three nanotubes considered in this study are strongly influenced by the cap configuration. Finally, the convergent decay behavior of the energy gap which is observed as the length of the nanotube is increased is also strongly dependent on the tip configuration.     

Position effects of single vacancy on transport properties of single layer armchair h-BNC heterostructure

Based on certain single layer armchair h-BNC heterostructures, six molecular devices with different positions of single vacancy atoms are investigated to explain the modulating process of negative differential resistance (NDR) behaviors and rectifying performance. The results show that NDR behaviors can be observed clearly with vacancy atoms near the interface of graphene nano-ribbon and BN nano-ribbon, and rectifying performance can be enhanced obviously when there are vacancy atoms in the moiety of the BN nano-ribbon. The first-principles analysis of the microscopic nature reveals that strength of electronic transmission, evolutions of molecular orbitals and distributions of molecular states are the intrinsic responses to these transport properties.