Novel NIR-absorbing conjugated polymers for efficient polymer solar cells: effect of alkyl chain length on device performance

Three low bandgap conjugated polymers, i.e., PDTPBT-C8, PDTPBT-C6 and PDTPBT-C5, which consist of alternating N-alkyl dithieno[3,2-b: 2',3'-d] pyrrole and 2,1,3-benzothiadiazole units and carry 1-octylnonyl, 1-hexylheptyl and 1-pentylhexyl as side chains, respectively, were synthesized. These polymers show strong absorption in the wavelength range of 600-900 nm with enhanced absorption coefficient as the length of alkyl chain decreases. The film morphology of the polymers and 1-(3-methoxycarbonyl) propyl-1-phenyl-[6,6]-C-61 (PCBM) blends is also dependent on the alkyl chain length. As the length decreases, the film becomes more uniform and the domian size decreases from 400-900 nm for PDTPBT-C8 to similar to 50 nm for PDTPBT-C5.

Dendritic Superstructures and Structure Transitions of Asymmetric Poly(L-lactide-b-ethylene oxide) Diblock Copolymer Thin films

The evolution of morphologies of isothermally crystallized thin films with different thicknesses of poly(L-lactide-bethylene oxide) diblock copolymer was observed by optical microscopy (OM) and atomic force microscopy (AFM). Dendritic superstructures stacked with lamellae were investigated in thin films with similar to 200 nm to similar to 400 nm thickness. The lamellar structure was a lozenge- or truncated-lozenge-shaped single crystal of PLLA confirmed by AFM observations. The contour of the dendritic superstructures is hexagonal, and two types of sectors, [110] and [100], can be classified in terms of the chain-folding and crystal growth directions. These phenomena Are due to the interplay of the crystallization of the PLLA block, the microphase separation of the block copolymer, and the effect of the film thickness.

Microphase Separation of Mixed Polymer Brushes: Dependence of the Morphology on Grafting Density, Composition, Chain-Length Asymmetry, Solvent Quality, and Selectivity

Microphase separation of binary mixed A/B polymer brushes exposed to different solvents is studied using Single-Chain-in-Mean-Field simulations. Effects of solvent quality and selectivity, grafting density, composition, and chain-length asymmetry are systematically investigated, and diagrams of morphologies in various solvents are constructed as a function of grafting density and composition or chain-length asymmetry. The structure of the microphase segregated morphologies lacks long-range periodic order, and it is analyzed quantitatively Using Minkowski measures.

Synthesis and Crystal Structure of a New 3D Copper B-Paradodecatungstate Compound: [Na-2(H2O)(8)][Na-8(H2O)(20)][Cu(en)(2)][W12O42] center dot 3H(2)O

A new polyoxotungstate complex [Na-2(H2O)(8)][Na-8(H2O)(20)][Cu(en)(2)][W12O42] center dot 3 H2O (1) (en = ethylenediamine) has been synthesized in aqueous solution and characterized by elemental analysis, IR spectroscopy and TG analysis, together with a single crystal X-ray diffraction study. In compound 1, the Cu(en)(2)(2+) complex cation links the [W12O42](12-) anions to form a I D chain, and the ID chains are further interconnected with Na-8(H2O)(20)(8+) and Na-2(H2O)(8)(2+) cations to construct a new 3D framework.

Naphthyl and thionaphthyl end-capped oligothiophenes as organic semiconductors: Effect of chain length and end-capping groups

Two series of oligothiophenes (OThs), NaTn and TNTn (n = 2-6 represents the number of thiophene rings), end-capped with naphthyl and thionaphthyl units have been synthesized by means of Stille coupling. Their thermal properties, optical properties, single crystal structures, and organic field-effect transistor performance have been characterized. All oligomers display great thermal stability and crystallinity. ne crystallographic structures of NaT2, NaT3, TNT2, and TNT3 have been determined. The crystals of NaT2 and NaT3 are monoclinic with space group P2(1)/C, while those of TNT2 and TNT3 are triclinic and orthorhombic with space groups P-1(-) and P2(1)2(1)2(1), respectively. All oligomers adopt the well-known herringbone packing-mode in crystals with packing parameters dependent on the structure of the end-capping units and the number of thiophene rings. The shorter intermolecular distance in NaT3 compared to NaT2 indicates that the intermolecular interaction principally increases with increasing molecular length. X-ray diffraction and atomic force microscopy (AFM) characterization indicate that the NaTn oligomers can form films with better morphology and high molecular order than TNTn oligomers with the same number of thiophene rings. The NaTn oligomers exhibit mobilities that are much higher than those for TNTn oligomers (0.028-0.39 cm(2) V-1 s(-1) versus 0.010-0.055 cm(2) V-1 s(-1), respectively).

Synthesis and chain-length dependent properties of monodisperse oligo(9,9-di-n-octylfluorene-2,7-vinylene)s

A series of monodisperse oligo(9,9-di-n-octylfluorene-2,7-vinylene)s (OFVs) with fluorene units up to 11 has been synthesized following a divergent approach. Chain length was found to affect not only photophysical properties but also thermal properties. Absorption and photoluminescence spectra are red-shifted with increasing chain length. The effective conjugated length has been extrapolated to be as long as 19 fluorene vinylene units, indicative of a well-conjugated system. With the number of fluorene units > 5, the oligomers exhibit nematic mesomorphism. Glass transition temperature (T-g) and clearing point temperature (T-c) increase with increasing molecular length and with those of OFV11 up to 71 and 230 degrees C, respectively. The oligomers can form uniform films by solution casting for fabrication of light-emitting diodes. With a device structure of ITO/ PEDOT:PSS/OFV11/Ca/Al, a current efficiency of 0.8 cd.A(-1) at a brightness of 1300 cd.m(-2) along with a maximum brightness of 2690 cd.m(-2) have been realized. This performance is notably superior to that of the corresponding polymer.

Synthesis and characterization of white-light-emitting polyfluorenes containing orange phosphorescent moieties in the side chain

Two orange phosphorescent iridium complex monomers, 9-hexyl-9-(iridium (III)bis(2-(4'-fluorophenyl)-4-phenylquinoline-N, C-2')(tetradecanedionate-11,13))-2,7-dibromofluorene (Br-PIr) and 9-hexyl-9-(iridium(III)bis(2-(4'-fluorophenyl)-4-methylquinoline-N, C-2')(tetradecanedionate-11,13))-2,7-dibromofluorene (Br-MIr), were successfully synthesized. The Suzuki polycondensation of 2,7-bis(trimethylene boronate)-9,9-dioctylfluorene with 2,7-dibromo-9,9-dioetylfluorene and Br-Plr or Br-MIr afforded two series of copolymers, PIrPFs and MIrPFs, in good yields, in which the concentrations of the phosphorescent moieties were kept small (0.5-3 mol % feed ratio) to realize incomplete energy transfer. The photoluminescence (PL) of the copolymers showed blue- and orange-emission peaks. A white-light-emitting diode with a configuration of indium tin oxide/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/PIr05PF (0.5 mol % feed ratio of Br-PIr)/Ca/Al exhibited a luminous efficiency of 4.49 cd/A and a power efficiency of 2.35 lm/W at 6.0 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.46, 0.33). The CIE coordinates were improved to (0.34, 0.33) when copolymer MIr10PF (1.0 mol % feed ratio of Br-MIr) was employed as the white-emissive layer. The strong orange emission in the electroluminescence spectra in comparison with PL for these kinds of polymers was attributed to the additional contribution of charge trapping in the phosphorescent dopants.

Ordering-induced micro-bands in thin films of a main-chain liquid crystalline chloro-poly(aryl ether ketone)

Micro-banded textures developed from thin films of a main-chain thermotropic liquid crystalline chloro-poly(aryl ether ketone) in the melt were investigated using transmission electron microscopy (TEM). selective area electron diffraction, and atomic force microscopy techniques. The micro-banded textures were formed in the copolymer thin films after annealing at temperatures between 320 and 330degreesC, where a highly ordered smectic crystalline phase is formed without mechanical shearing. The micro-banded textures displayed a sinusoidal-like periodicity with a spacing of 150 nm and an amplitude of 2 rim. The long axis of the banded texture was parallel to the b-axis of an orthorhombic unit cell. In the convex regions, the molecular chains exhibited a homeotropic alignment, i.e. the chain direction was parallel to the film normal. In the concave re-ions, the molecular chains possessed a tilted alignment. In addition to the effects of annealing temperatures and times, the thickness of the film played a vital role in the formation of the banded texture. A possible formation mechanism of this banded texture vas also suggested and discussed. It was suggested that the micro-bands were formed during cooling.

Control of self-organized low-dimensional morphology in Poly(styrene-b-4vinylpyridine)/polystyrene blend thin films

The surface morphologies of poly(styrene-b-4vinylpyridine) (PS-b-P4VP) diblock copolymer and homopolystyrene (hPS) binary blend thin films were investigated by atomic force microscopy as a function of total volume fraction of PS (phi(PS)) in the mixture. It was found that when hPS was added into symmetric PS-b-P4VP diblock copolymers, the surface morphology of this diblock copolymer was changed to a certain degree. With phi(PS) increasing at first, hPS was solubilized into the corresponding domains of block copolymer and formed cylinders. Moreover, the more solubilized the hPS, the more cylinders exist. However, when the limit was reached, excessive hPS tended to separate from the domains independently instead of solubilizing into the corresponding domains any longer, that is, a macrophase separation occurred. A model describing transitions of these morphologies with an increase in phi(PS) is proposed. The effect of composition on the phase morphology of blend films when graphite is used as a substrate is also investigated.

Electric-field-induced molecular alignment of side-chain liquid-crystalline polyacetylenes containing biphenyl mesogens

Electric-field-induced molecular alignments of side-chain liquid-crystalline polyacetylenes [-{HC=C[(CH2)(m)OCO-biph-OC7H15]}-, where biph is 4,4'-biphenylyl and m is 3 (PA3EO7) or 9 (PA9EO7)] were studied with X-ray diffraction and polarized optical microscopy. An orientation as high as 0.84 was obtained for PA9EO7. Furthermore, the molecular orientation of]PA9EO7 was achieved within a temperature range between the isotropic-to-smectic A transition temperature and 115 degreesC, and this suggested that the orientational packing was affected by the thermal fluctuation of the isotropic liquid and the mobility of the mesogenic moieties. The maximum achievable orientation for PA9EO7 was much greater than that for PA3EO7. This was the first time that the electric-field-induced molecular orientation of a side-chain liquid-crystalline polymer with a stiff backbone was studied.

Effects of chain flexibility on polymer conformation in dilute solution studied by lattice Monte Carlo simulation

Effects of chain flexibility on the conformation of homopolymers in good solvents have been investigated by Monte Carlo simulation. Bond angle constraint coupled with persistence length of polymer chains has been introduced in the modified eight-site bond fluctuation simulation model. The study about the effects of chain flexibility on polymer sizes reveals that the orientation of polymer chains under confinement is driven by the loss of conformation entropy. The conformation of polymer chains undergoing a gradual change from spherical iso-diametric ellipsoid to rodlike iso-diametric ellipsoid with the decrease of polymer chain flexibility in a wide region has been clearly illustrated from several aspects. Furthermore, a comparison of the freely jointed chain (FJC) model and the wormlike chain (WLC) model has also been made to describe the polymer sizes in terms of chain flexibility and quasi-quantitative boundary toward the suitability of the models.

Synthesis and characterization of blue-light-emitting poly(aryl ether)s containing oligofluorenes in the main chain

A series of blue light-emitting poly(aryl ether)s (PAEs) containing ter- or pentafluorenes in the main chain have been synthesized via nucleophilic substitution polycondensation reaction. The energy levels of the polymers were tuned by introducing hole-transporting triaryamine groups in the side chains and/or incorporating electron-transporting oxadiazole segments in the main chain. The optical properties of the polymers are dominantly determined by the well-defined oligofluorene segments, and therefore all polymers show high photoluminescence quantum yield. Differential scanning calorimeter (DSC) characterizations indicate that they are vitrified polymers with high glass transition temperature (up to 156 degrees C). The polymers comprising pentafluorenes exhibit electroluminescent properties equal to or better than fully conjugated fluorene homopolymers. With the device structure of ITO/PEDOT:PSS/polymer/Ca/Al, an external quantum efficiency of 1.4% along with Commission Internationale de L'Eclairage (CIE) coordinates of (0.17, 0.09) has

Monte Carlo simulation of miscibility of polymer blends with repulsive interactions: effect of chain structure

The effects of the chain structure and the intramolecular interaction energy of an A/B copolymer on the miscibility of the binary blends of the copolymer and homopolymer C have been studied by means of a Monte Carlo simulation. In the system, the interactions between segments A, B and C are more repulsive than those between themselves. In order to study the effect of the chain structure of the A/B copolymer on the miscibility, the alternating, random and block copolymers were introduced in the simulations, respectively. The simulation results show that the miscibility of the binary blends strongly depends on the intramolecular interaction energy ((ε) over bar (AB)) between segments A and B within the A/B copolymers. The higher the repulsive interaction energy, the more miscible the A/B copolymer and homopolymer C are. For the diblock copolymer/homopolymer blends, they tend to form micro phase domains. However, the phase domains become so small that the blend can be considered as a homogeneous phase for the alternating copolymer/ homopolymer blends. Furthermore, the investigation of the average end-to-end distance ((h) over bar) in different systems indicates that the copolymer chains tend to coil with the decrease Of (ε) over bar (AB) whereas the (h) over bar of the homopolymer chains depends on the chain structure of the copolymers.

Shear induced molecular alignments of a side-chain liquid crystalline polyacetylene containing biphenyl mesogens

Mesomorphic properties of a side chain liquid crystalline polyacetylene, poly(11-{[(4'-heptyloxy-4-biphenylyl)carbonyl]oxy}-1-undecyne) (PA9EO7), are investigated using polarized optical microscope, X-ray diffraction, and transmission electron microscope. Polymer PA9EO7 forms enantiotropic smectic A and smectic B phases. It also exhibits an additional high order smectic phase, a sandwich structure consisting of different molecular packing of biphenyl mesogenic moieties from that of alkyl spacers and terminals, when it is prepared from its toluene solution. Shearing the polymer film at its smectic A phase generates banded texture with the alignment of the backbones parallel to the direction of shear force. While at its high order smectic phase, the mesogen pendants of the polymer are arranged parallel to the direction of shear. The different mesomorphic behaviors arise from different molecular alignments influenced by the fluidity.

An unusual organic-inorganic chain-like hybrid complex [(CuCl)(2)(o-phen)](infinity) (o-phen=o-phenanthroline)

A novel organic-inorganic hybrid complex [(CuCl)(2) (o-phen)](infinity) 1 (o-phen = o-phenanthroline) has been hydrothermally synthesized and structurally characterized by elemental analyses, XPS spectrum, TG analysis, and single-crystal X-ray diffraction. Compound I crystallizes in the monoclinic system, space group P2(1)/n, a = 3.7285(7) Angstrom, b = 19.603(4) Angstrom, c = 16.757(3) Angstrom, beta = 95.83(3)degrees, V = 1218.4(4) Angstrom(3), Z = 4, lambda(MoKalpha) = 0.71073 Angstrom (R(F) = 0.0643 for 2559 reflections). Data were collected on an R-axis RAPID diffractometer at 293 K in the range of 1.60 < θ < 27.48degrees. The title compound exhibits a one-dimensional chain-like scaffolding constructed by the unusual [Cu3Cl3] hexagon motifs by, sharing opposite edges. Only Cu(1) sites of the [Cu3Cl3] hexagon are coordinated with N donors of o-phen groups. Furthermore, the three-dimensional supermolecular architecture is formed by C-H...Cl hydrogen bonds between o-phen groups and CuCl chains.