准一维共聚物的电子结构研究

在紧束缚近似下,建立了共聚物 (- PPP_x )—( PA_y)- 的物理模型,研究了组成共聚物的均聚物单体对体系晶格结构、能带结构等的影响,发现共聚物的带隙可通过改变均聚物的配比或均聚物之间的相互作用来加以调制. 关键词： 共聚物 界面耦合 带隙     

First-principles study of the electron transport through conjugated molecular wires with different carbon backbones

The nonequilibrium Green’s function approach in combination with density-functional theory is used to perform ab initio quantum-mechanical calculations of the electron transport properties of polyacetylene, polythiophene, poly(phenylene vinylene), poly(p-phenylene ethynylene), and poly(p-phenylene) molecules sandwiched between two gold electrodes. The results demonstrate that the conjugation path has a profound effect on the electron transport property of the molecular wires. Among the five molecular wires, polyacetylene is the most conductive one. The conductivities of the five molecular wires decrease with an order of polyacetylene > polythiophene > poly(phenylene vinylene) > poly(p-phenylene ethynylene) > poly(p-phenylene). The conductivities of polyacetylene and polythiophene are much higher than those of poly(phenylene vinylene), poly(p-phenylene ethynylene), and poly(p-phenylene). The difference of electron transport behaviors of these molecular wires are analyzed in terms of the electronic structures, the transmission spectra, and the spatial distributions of molecular orbitals.     

Unified Hamiltonian for conducting polymers

Two transferable physical parameters are incorporated into the Su-Schrieffer-Heeger Hamiltonian to model conducting polymers beyond polyacetylene: the parameter γ scales the electron-phonon coupling strength in aromatic rings and the other parameter ε specifies the heterogeneous core charges. This generic Hamiltonian predicts the fundamental band gaps of polythiophene, polypyrrole, polyfuran, poly-(p-phenylene), poly-(p-phenylene vinylene), and polyacenes, and their oligomers of all lengths, with an accuracy exceeding time-dependent density functional theory. Its computational costs for moderate-length polymer chains are more than eight orders of magnitude lower than first-principles approaches.     

Voltage-modulated millimeter-wave spectroscopy on a polymer diode: mesoscopic charge transport in conjugated polymers

We present a new technique to determine the carrier mobility mu in semiconducting, undoped, conjugated polymers in the millimeter-wave frequency range, 10-500 GHz. This method probes charge conduction on mesoscopic length scales, a regime inaccessible to other transport experiments. The experiment is based on the detection of millimeter-wave absorption of field-induced charge in polymer diodes, and is applied to poly( p-phenylene vinylene). We demonstrate that locally mu can be as high as 10(-4) m(2)/V s, and deduce the typical hopping parameters in the mesoscopic high- mu regions in the material.     

Organic quantum well and superlattice characteristics in quasi-one-dimensional multiblock copolymers

A tight-binding calculation was presented to describe multiblock copolymers, such as [...-(PA)x-(PPP)y-...] composed of PA (polyacetylene) and PPP (poly(p-phenylene). It is found that a copolymer has a quantum well and superlattice characteristics, and evident is the effect of the composite lengths, the interfacial couplings and the electron-phonon interactions on the electronic properties of a copolymer. The quantum tunneling, the Franz-Keldysh effect and the quantum confinement can be generated under an applied electric field. These results were compared to those of traditional inorganic quantum well and superlattice systems.     

导电聚合物自组装纳米器件

导电聚合物自20世纪70年代以来得到了广泛的研究．然而，关于聚合物纳米器件的研究则鲜有报导．从纳米尺度上研究导电聚合物，不仅有利于从更小的尺度上解析聚合物的光电性能、电荷传输机理，也可以将导电聚合物和纳米电子学有机地结合起来，发展聚合物纳米电子学的研究．文章介绍了最近由胡文平等采用自组装的方法构筑的聚合物纳米器件和在纳米器件中观察到的一些有趣的现象．     

Quenching of fluorescence of conjugated poly(p-phenylene) polymers by benzil and dimethylaminobenzil molecules

We have studied the mechanisms for quenching of the fluorescence of conjugated poly(p-phenylene) polymers by benzil and dimethylaminobenzil molecules. We have shown that molecules in the diketone series are quenching agents for the fluorescence of the indicated polymers, and can serve as singlet-triplet converters capable of populating the triplet state of the polymer. We have observed that the efficiency of quenching of the fluorescence of the studied polymers depends considerably on the presence of bulky side groups in the polymer or in the activator molecules. Based on analysis of the data obtained, we conclude that in the case of a rigid planar structure for the polymer, a significant contribution to quenching of its fluorescence comes from not only singlet-singlet energy transfer but also charge transfer, leading to formation of intermolecular complexes (exciplexes). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 756–762, November–December, 2006.     

Low-temperature saturation of dephasing in heavily doped conjugated polymers

Based on our low temperature (down to 0.5 K) electronic transport studies of heavily doped polyacetylene and magnetotransport results reported for other heavily doped conjugated polymers, we demonstrate that the low-temperature saturation of electron dephasing found for metallic and semiconducting materials is also exhibited in conducting polymers. Such behavior explained by a model, which involves electron dephasing by two-level systems of a special type originating from initially symmetric defect configurations where the symmetry is partially lifted by disorder.     

Conformational dynamics of photoexcited conjugated molecules

Time-dependent photoexcitation and optical spectroscopy of pi-conjugated molecules is described using a new method for the simulation of excited state molecular dynamics in extended molecular systems with sizes up to hundreds of atoms. Applications are made to poly(p-phenylene vinylene) oligomers. Our analysis shows self-trapping of excitations on about six repeat units in the course of photoexcitation relaxation, identifies specific slow (torsion) and fast (bond-stretch) nuclear motions strongly coupled to the electronic degrees of freedom, and predicts spectroscopic signatures of molecular conformations.     

Electronic confinement in quasi—one—dimensional triblock copolymers

A tight-binding calculation to describe the triblock copolymer xPA(polyacetylene)/nPPP (poly(p-phenylene))/yPA or xPPP/nPA/yPPP is presented. The interfacial coupling between homopolymer segments is attributed to the hopping of π-electrons and the coupling of σ-bonds. The dependence of the band gap of triblock copolymers on the interfacial couplings or on the composite segment lengths is studied. The influence of composite segment lengths on the electron density is also studied. For nPPP/xPA/nPPP structures, the band gap varies with PA segment length over a wide range of 1.32－2.74eV. For nPA/xPPP/nPA structures,the band gap is invariant with PPP segment length. It is found that a spontaneous tunnelling phenomenon could take place in nPA/xPPP/nPA structures. Furthermore, the polaron caused by doping an electron into nPA/xPPP/nPA will tend to be confined in one of the well (PA) parts. This kind of confinement may increase the electron－hole recombination probability.     

显微拉曼光谱研究导电高分子复合微米管

利用氧化铝模板在三氟化硼乙醚溶液中电化学聚合苯和噻吩制得聚苯/聚噻吩复合微米管。通过扫描电子显微镜和显微拉曼光谱研究了复合微米管的形态与结构。结果表明:复合微米管具有三个明显的区域,它们分别是聚苯区,聚苯/聚噻吩复合区和聚噻吩区。     

From polymer films to organic nanoparticles suspensions by means of excimer laser ablation in water

This study highlights the preparation of organic nanoparticles (NP) by laser ablation (LA) of polymeric materials in water. Experiments focused on poly(ethylene terephtalate) (PET) were carried out with the KrF laser pulse (248 nm). Size distribution and concentration of nanoparticles were deduced from suspensions turbidity measurements with the aid of Mie model, by Atomic Force Microscopy (AFM) on the basis of a statistical study and Scanning Electron Microscopy (SEM). The obtained results show that assemblies of spherical NP with a mean diameter 50 nm were synthesised. Composition and surface chemistry of NP were investigated using the Confocal Micro-Raman Spectroscopy (CMRS) and X-ray Photoelectron Spectroscopy (XPS). It indicates that NP are graphitic carbon rich and have a polymeric structure like polyacetylene. The possible mechanisms responsible of NP synthesis by under water LA of polymers was briefly discussed by investigating other polymers targets.     

Non-linear transport by solitons in nanofibers of polymers in high magnetic field

Nonlinear local excitations like solitons, polarons, and bipolarons are known to be responsible for physical properties of conducting polymers. Recent experiments on nano-fibers in high electric and magnetic fields provide a further insight by demonstrating an effect of vanishing magnetoconductance (MC) in the polyacetylene (PA)—in contrast to other polymers. Here we present new experimental data and describe the theoretical model based on notion of solitons—dimerization kinks which can carry either the spin or the charge; they are allowed only in the PA with its degenerate ground state. The solitons experience a confinement force due to the interchange coupling which is erased by the electric field and disappears above critical field strength. The unbinding by tunneling allows for the transport of individual solitons, which sweeps off the spins residing at electronic intragap states associated with polarons, hence the vanishing MC.     

XPS study of PBO fiber surface modified by incorporation of hydroxyl polar groups in main chains

Dihydroxy poly(p-phenylene benzobisoxazole) (DHPBO), a modified poly(p-phenylene benzoxazole) (PBO) polymer containing double hydroxyl groups in polymer chains, was synthesized by copolymerization of 4,6-diamino resorcinol dihydrochloride (DAR), purified terephthalic acid (TA) and 2,5-dihydroxyterephthalic acid (DHTA). DHPBO fibers were prepared by dry-jet wet-spinning method. The effects of hydroxyl polar groups on the surface elemental compositions of PBO fiber were investigated by X-ray photoelectron spectroscopy (XPS). The results show that the ratio of oxygen/carbon on the surface of DHPBO fibers is higher than that on the surface of PBO fibers, which indicates the content of polar groups on the surface of DHPBO fiber increase compared with PBO fiber.     

Comparative study of the electronic structure of conjugated polymers

We compare the electronic structures of trans-polyacetylene, poly - (p-phenylene), polypyrrole and polythiophene, computed by an Extended Hückel crystalline orbital scheme. Similarities in the valence and conduction densities of states are analyzed in terms of the connectivity of the different systems.     

Single molecule lifetime fluctuations reveal segmental dynamics in polymers

We present a single molecule fluorescence study that allows one to probe the nanoscale segmental dynamics in amorphous polymer matrices. By recording single molecular lifetime trajectories of embedded fluorophores, peculiar excursions towards longer lifetimes are observed. The asymmetric response is shown to reflect variations in the photonic mode density as a result of the local density fluctuations of the surrounding polymer. We determine the number of polymer segments involved in a local segmental rearrangement volume around the probe. A common decrease of the number of segments with temperature is found for both investigated polymers, poly(styrene) and poly(isobutylmethacrylate). Our novel approach will prove powerful for the understanding of the nanoscale rearrangements in functional polymers.     

Coherent control of optical emission from a conjugated polymer

We have observed that resonant Rayleigh scattering dominates the emission from poly(p-phenylene vinylene) excited with photons at energies below the threshold at which excitonic migration is reduced. The intensity of the resonant emission decays exponentially with a lifetime of up to 450 fs after pulsed excitation. The coherent nature of the emission was confirmed by angular variations in the far-field emission intensity-bright and dark speckles. Persistence of a coherent polarization was demonstrated by coherent control using phase-locked pulses.     

环形聚乙炔分子桥的电导研究

我们选择了由40个CH基团组成的环形聚乙炔链作为分子桥,基于Landauer-Buttiker理论,利用求解散射波函数的方法,研究了这种环状聚乙炔分子桥与金属多端连接的电导随能量的变化关系.结果表明,在给定入射端的条件下,电导在正负能量上是对称的,当各个端口满足旋转对称性时,相对于入射端对称的两个出射端的电导相同.当分子桥耦合较弱时,电导对能量的变化相当敏感.     

Asymmetrically doped polyacetylene

Doped one-dimensional (1D) conjugated polymers, such as polyacetylene, have a conductivity of some metals, like copper. We show that when this polymer is asymmetrically doped, unexpected properties are revealed, when compared to the behavior of the symmetrically standard doped systems (SDS). Depending on the level of imbalance between the chemical potentials of the two involved fermionic species, the polymer can be converted into a 1D partially or fully polarized organic conductor.     

聚对苯乙炔(PPV)的薄膜电致发光特性

聚对苯乙炔[poly(p-phenylene vinylene),缩写为PPV]是一种典型的线性共轭高分子.早在1968年,美国化学家Wessling就宣布合成出了PPV[1],但由于当时对该材料的应用前景不清,故未能引起科学界的重视.80年代中期,Murase等用AsF5及其它多种掺杂剂成功地对PPV进行了掺杂导电研究[2],使其电导率提高了16个数量级,由绝缘体变成了导体.