La1/8Ca7/8MnO3/Sr0.95Nb0.05TiO3异质结的整流特性和磁输运性质

在5%Nb掺杂的SrTiO3衬底上用磁控溅射法外延生长了La1/aCa7/aMnO3薄膜形成异质结,该异质结有类似于传统P-n结的整流特性.磁场下扩散电压减小,当温度低于130 K以下,扩散电压的减小非常明显.这和在此温度以下,La1/8Ca7/aMnO3出现自旋倾斜态密切相关.我们计算出异质结的结电阻和磁致电阻(MR),在不同大小的正负偏压,不同磁场下,都得到负的MR值.我们给出界面附近的La1/8Ca7/8MnO3的能带结构并分析了外加磁场对洪德耦合,Jahn-Teller畸变等机制的作用,来解释该异质结的磁输运行为.结果有助于了解高Ca掺杂锰氧化物异质结的性质.     

Chemical kinetics at high pressure

Abstract

Numerous studies have demonstrated the importance to include pressure as a kinetic parameter in the elucidation of inorganic reaction mechanisms. These studies have specially led to a better understanding and a systematic classification of solvent exchange and ligand substitution reactions of octahedral complexes of transition metal elements. The mechanistic picture for substution reactions on square planar complexes is well established and involves a concurrent bimolecular attack by solvent and the nucleophile on the substrate with a considerable discrimination among different entering groups. The search for factor promoting the conversion of the normal associative mode of activation into a dissociative process has then attracted much attention. Two attempts to induce dissociation, as studied by high-pressure NMR, are presented: one is to prevent the formation by means of sterically hindered ligands, the other one is to promote bond weakening at the leaving group.     

Significantly improved photovoltaic performances of the dithiophene‐benzothiadiazole‐alt‐fluorene copolymers by incorporating carbazole units in fluorene moiety

To exploit an effective way to improve polymeric photovoltaic performance, a series of dithiophene‐benzothiadiazole‐alt‐fluorene copolymers containing carbazole groups at C‐9 positions of the alternating fluorene units (PFO‐FCz‐DBT) were synthesized and characterized. The effect of the carbazole groups on the optophysical, electrochemical, and photovoltaic properties of these copolymers was investigated. By comparison, this type of copolymers with carbazole units exhibited significantly improved photovoltaic properties than poly(2,7‐(9,9‐dioctyl‐fluorene)‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole) (PFO‐DBT) in the bulk heterojunction solar cells. A maximum power‐conversion efficiency (PCE) of 2.41% and a highest short‐circuit current density (J_sc) of 9.68 mA cm^?2 were obtained for the PFO‐FCz‐DBT30, which are about two times higher than the corresponding levels for the PFO‐DBT30. This work demonstrated that introducing a hole‐transporting carbazole unit into copolymer is a simple and effective method to improve the J_sc and PCE. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Bandgap engineering of indenofluorene‐based conjugated copolymers with pendant donor‐π‐acceptor chromophores for photovoltaic applications

Three narrow‐band‐gap conjugated copolymers based on indenofluorene and triphenylamine with pendant donor‐π‐acceptor chromophores were successfully synthesized by post‐functionalization approach. All the polymers have good solubility in common solvents and excellent thermal stability. The photophysical properties, energy levels and band gaps of the polymers were well manipulated by introducing different acceptor groups onto the end of their conjugated side chains. By using different acceptor groups, the band gaps of the polymers were narrowed from 1.86 to 1.53 eV by lowering their lowest unoccupied molecular orbital levels, whereas their relatively deep highest occupied molecular orbital levels of approximately ?5.35 eV were maintained. Bulk‐heterojunction solar cells with these polymers as electron donors and (6,6)‐phenyl‐C₇₁‐butyric acid methyl ester as acceptor showed power conversion efficiencies as high as 3.1% and high open circuit voltages more than 0.88 eV. The relationships between the performance and film morphology, energy levels, charge mobilities were discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Low band gap copolymers consisting of porphyrins,thiophenes, and 2,1,3‐benzothiadiazole moieties for bulk heterojunction solar cells

Two novel low band gap conjugated copolymers containing porphyrins, thiophenes, and 2,1,3‐benzothiadiazole ( BTZ ) moieties were synthesized and applied in bulk heterojunction solar cells. The thermal, optical, electrochemical, and photovoltaic properties of the two copolymers were examined to investigate the effect of the introduction of BTZ moiety in the backbone of the porphyrin polymers. The copolymers exhibited good thermal stability and film‐forming ability. The absorption spectra indicated that the BTZ moiety has significant influence on the UV–visible region spectra of the copolymers: with increasing the molar amount of BTZ moieties in conjugated main chain, the absorption in the range of 450–700 nm is largely broadened and red‐shifted compared to the similar polymers without BTZ moiety, and the optical band gaps of copolymers were narrowed to ～1.50 eV. The photoluminescence spectra showed that there is effective charge transfer in the whole conjugated main chain. Cyclic voltammetry displayed that the band gaps were reduced effectively by the introduction of the BTZ moieties. The bulk heterojunction solar cells were fabricated based on the blend of the copolymers and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) in a 1:2 weight ratio. The maximum power conversion efficiency of 0.91% was obtained by using P2 as the electron donor under the illumination of AM 1.5, 100 mW/cm². © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Coloring plane graphs with independent crossings

We show that every plane graph with maximum face size four in which all faces of size four are vertex‐disjoint is cyclically 5‐colorable. This answers a question of Albertson whether graphs drawn in the plane with all crossings independent are 5‐colorable. © 2009 Wiley Periodicals, Inc. J Graph Theory 64: 184–205, 2010     

M@B<Subscript>9</Subscript> and M@B<Subscript>10</Subscript> molecular wheels containing planar nona- and deca-coordinate heavy group 11, 12, and 13 metals (M=Ag,Au, Cd,Hg, In,Tl)

A density functional and ab initio theory investigation on M@B₉ and M@B₁₀ molecular wheels containing planar nona- and deca-coordinate heavy group 11, 12 and 13 metals (M=Ag, Au, Cd, Hg, In, Ti) has been performed. These unusual clusters all prove to be true minima on the potential energy surfaces of the systems and σ+π double aromatic in nature. The first two vertical one-electron detachment energies of M@B₁₀⁻ (M=Ag, Au) anions and first two ionization potentials of M@B₉ (M=Ag, Au) and M@B₁₀ (M=Cd, Hg) neutrals were calculated to aid future experiments. The cluster complexes designed in this work may expend the domain of planar hyper-coordinate elements to include heavy group 11, 12, and 13 metals and serve as interesting candidates to be targeted in experiments. Electronic Supplementary Material  Supplementary material is available for this article at and is accessible for authorized users. Supported by the National Natural Science Foundation of China (Grant No. 20873117)     

A conjecture of Borodin and a coloring of Grünbaum

In 1976, Borodin conjectured that every planar graph has a 5‐coloring such that the union of every k color classes with 1 ≤ k ≤ 4 induces a (k—1)‐degenerate graph. We prove the existence of such a coloring using 18 colors. © 2008 Wiley Periodicals, Inc. J Graph Theory 58:139–147, 2008     

A study on stress intensity factors and singular stress fields of three-dimensional interface crack

By using the finite-part integral concepts and limit technique, the hypersingular integrodifferential equations of three-dimensional (3D) planar interface crack were obtained; then the dominant-part analysis of 2D hypersingular integral was further used to investigate the stress fields near the crack front theoretically, and the accurate formulae were obtained for the singular stress fields and the complex stress intensity factors. After that, a numerical method is proposed to solve the hypersingular integrodifferential equations of 3D planar interface crack, and the problem of elliptical planar crack is then considered to show the application of the method. The numerical results obtained are satisfactory. Project supported by the Foundation of Solid Mechanics Open Research Laboratory of State Education Commission at Tongji University and the National Natural Science Foundation.