Correlations between Conjugation Length, Macromolecular Dynamics, and Photophysics of Phenylene-Vinylene/Aliphatic Multiblock Copolymers

This work reports a detailed spectroscopy study of a series of multiblock conjugated nonconjugated copolymers built by p-phenylene vinylene type units (PV) and octamethylene spacers, namely, poly(1,8-octanedioxy-2,6-dimethoxy-1,4-phenylene-1,2-ethenylene) (LaPPS18). The relative proportions of the PV and aliphatic segments were estimated on the basis of solid-state NMR and Raman spectroscopy. The overall structure was characterized by wide angle X-ray diffraction; H-1 wide-line dipolar chemical shift correlation (DIPSHIFT), and centerband-only detection of exchange (CODEX) NMR data, that together with glass transition temperatures allowed us to identify the groups involved in the molecular dynamics. These different structural properties were used to explain the photoluminescence properties in terms of peak position and spectral profile

Photophysical properties of a fluorene-bipyridine copolymer and its complexes with europium

The synthesis and structural characterization of a europium complexed fluorene-bipyridine copolymer are described. A level of ion insertion of 80% in molar basis was achieved, and theoretical calculations showed that it required a twist of 179 degrees (49 kJ) between the pyridine units. Spectroscopy data showed that no electronic coupling between the main backbone and the complexation sites had occurred, but these hindered the interchain aggregation observed in the non complexed polymer. Preliminary electroluminescence studies showed that the EL and PL spectra are consistent, and that the ion had a trapping effect in the charge transport. (C) 2011 Elsevier B.V. All rights reserved.

Synergetic Effect of Efficient Energy Transfer and 3D pi-pi Stack for White Emission Based on the Block Copolymers Containing Nonconjugated Spacer

A series of block copolymers containing nonconjugated spacer and 3D pi-pi stacking structure with simultaneous blue-, green-, and yellow-emitting units has been synthesized and characterized. The dependence of the energy transfer and electroluminescence (EL) properties of these block copolymers on the contents of oligo(phenylenevinylene)s has been investigated. The block copolymer (GEO8-BEO-YEO4) with 98.8% blue-emitting oligomer (BEO), 0.8% green-emitting oligomer (GEO), and 0.4% yellow-emitting oligomer (YEO) showed the best electroluminescent performance, exhibiting a maximum luminance of 2309 cd/m(2) and efficiency of 0.34 cd/A. The single-layer-polymer light-emitting diodes device based on GEO2-BEO-YEO4 emitted greenish white light with the CIE coordinates of (0.26, 0.37) at 10 V. The synergetic effect of the efficient energy transfer and 3D pi-pi stack of these block copolymers on the photoiuminescent and electroluminescent properties are investigated.

Processing of polycaprolactone and polycaprolactone-based copolymers into 3D scaffolds and their cellular responses

Synthetic polymers have attracted much attention in tissue engineering due to their ability to modulate biomechanical properties. This study investigated the feasibility of processing poly(varepsilon-caprolactone) (PCL) homopolymer, PCL-poly(ethylene glycol) (PEG) diblock, and PCL-PEG-PCL triblock copolymers into three-dimensional porous scaffolds. Properties of the various polymers were investigated by dynamic thermal analysis. The scaffolds were manufactured using the desktop robot-based rapid prototyping technique. Gross morphology and internal three-dimensional structure of scaffolds were identified by scanning electron microscopy and micro-computed tomography, which showed excellent fusion at the filament junctions, high uniformity, and complete interconnectivity of pore networks. The influences of process parameters on scaffolds' morphological and mechanical characteristics were studied. Data confirmed that the process parameters directly influenced the pore size, porosity, and, consequently, the mechanical properties of the scaffolds. The in vitro cell culture study was performed to investigate the influence of polymer nature and scaffold architecture on the adhesion of the cells onto the scaffolds using rabbit smooth muscle cells. Light, scanning electron, and confocal laser microscopy showed cell adhesion, proliferation, and extracellular matrix formation on the surface as well as inside the structure of both scaffold groups. The completely interconnected and highly regular honeycomb-like pore morphology supported bridging of the pores via cell-to-cell contact as well as production of extracellular matrix at later time points. The results indicated that the incorporation of hydrophilic PEG into hydrophobic PCL enhanced the overall hydrophilicity and cell culture performance of PCL-PEG copolymer. However, the scaffold architecture did not significantly influence the cell culture performance in this study.

Charge transport study of high mobility polymer thin-film transistors based on thiophene substituted diketopyrrolopyrrole copolymers

In this paper, we report on the device physics and charge transport characteristics of high-mobility dual-gated polymer thin-film transistors with active semiconductor layers consisting of thiophene flanked DPP with thienylene-vinylene-thienylene (PDPP-TVT) alternating copolymers. Room temperature mobilities in these devices are high and can exceed 2 cm2 V-1 s-1. Steady-state and non-quasi-static measurements have been performed to extract key transport parameters and velocity distributions of charge carriers in this copolymer. Charge transport in this polymer semiconductor can be explained using a Multiple-Trap-and-Release or Monroe-type model. We also compare the activation energy vs. field-effect mobility in a few important polymer semiconductors to gain a better understanding of transport of DPP systems and make appropriate comparisons.

Design and modification of three-component randomly incorporated copolymers for high performance organic photovoltaic applications

In this study we report the molecular design, synthesis, characterization, and photovoltaic properties of a series of diketopyrrolopyrrole (DPP) and dithienothiophene (DTT) based donor-acceptor random copolymers. The six random copolymers are obtained via Stille coupling polymerization using various concentration ratios of donor to acceptor in the conjugated backbone. Bis(trimethylstannyl)thiophene was used as the bridge block to link randomly with the two comonomers 5-(bromothien-2-yl)-2,5-dialkylpyrrolo[3,4-c]pyrrole-1, 4-dione and 2,6-dibromo-3,5-dipentadecyl-dithieno[3,2-b;2′,3′-d] thiophene. The optical properties of these copolymers clearly reveal a change in the absorption band through optimization of the donor-acceptor ratio in the backbone. Additionally, the solution processability of the copolymers is modified through the attachment of different bulky alkyl chains to the lactam N-atoms of the DPP moiety. Applications of the polymers as light-harvesting and electron-donating materials in solar cells, in conjunction with PCBM as acceptor, show power conversion efficiencies (PCEs) of up to 5.02%.

Synthesis of diketopyrrolopyrrole based copolymers via the direct arylation method for p-channel and ambipolar OFETs

In this paper, we have synthesized two novel diketopyrrolopyrrole (DPP) based donor-acceptor (D-A) copolymers poly{3,6-dithiophene-2-yl-2,5-di(2-octyl)- pyrrolo[3,4-c]pyrrole-1,4-dione-alt-1,5-bis(dodecyloxy)naphthalene} (PDPPT-NAP) and poly{3,6-dithiophene-2-yl-2,5-di(2-butyldecyl)-pyrrolo[3,4-c]pyrrole-1,4- dione-alt-2-dodecyl-2H-benzo[d][1,2,3]triazole} (PDPPT-BTRZ) via direct arylation organometallic coupling. Both copolymers contain a common electron withdrawing DPP building block which is combined with electron donating alkoxy naphthalene and electron withdrawing alkyl-triazole comonomers. The number average molecular weight (Mn) determined by gel permeation chromatography (GPC) for polymer PDPPT-NAP is around 23 400 g mol-1 whereas for polymer PDPPT-BTRZ it is 18 600 g mol-1. The solid state absorption spectra of these copolymers show a wide range of absorption from 400 nm to 1000 nm with optical band gaps calculated from absorption cut off values in the range of 1.45-1.30 eV. The HOMO values determined for PDPPT-NAP and PDPPT-BTRZ copolymers from photoelectron spectroscopy in air (PESA) data are 5.15 eV and 5.25 eV respectively. These polymers exhibit promising p-channel and ambipolar behaviour when used as an active layer in organic thin-film transistor (OTFT) devices. The highest hole mobility measured for polymer PDPPT-NAP is around 0.0046 cm2 V-1 s-1 whereas the best ambipolar performance was calculated for PDPPT-BTRZ with a hole and electron mobility of 0.01 cm2 V-1 s-1 and 0.006 cm2 V-1 s-1.

Synthesis, characterization and comparative OFET behaviour of indenofluorene-bithiophene and terthiophene alternating copolymers

The synthesis of alternating copolymers of tetraalkylindenofluorene with bithiophene and terthiophene using Suzuki polycondensation route is reported. We report on the optical and electrochemical properties of these copolymers. AFM analysis of the microscopic morphology of thin deposits showed that the copolymer with terthiophene units produced the more ordered films, with well-defined fibrillar structures, resulting from highly-regular dense packing due to strong π-π interchain interactions, in contrast to the amorphous bithiophene copolymer. Upon testing these materials in FETs the terthienyl copolymers displayed the higher charge mobilities among the studied compounds, with values of over 10-4 cm2 V-1 s-1 being obtained.

Furan containing diketopyrrolopyrrole copolymers : synthesis, characterization, organic field effect transistor performance and photovoltaic properties

In this work, we report design, synthesis and characterization of solution processable low band gap polymer semiconductors, poly{3,6-difuran-2-yl-2,5-di(2- octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-phenylene} (PDPP-FPF), poly{3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1, 4-dione-alt-naphthalene} (PDPP-FNF) and poly{3,6-difuran-2-yl-2,5-di(2- octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-anthracene} (PDPP-FAF) using the furan-containing 3,6-di(furan-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DBF) building block. As DBF acts as an acceptor moiety, a series of donor-acceptor (D-A) copolymers can be generated when it is attached alternatively with phenylene, naphthalene or anthracene donor comonomer blocks. Optical and electrochemical characterization of thin films of these polymers reveals band gaps in the range of 1.55-1.64 eV. These polymers exhibit excellent hole mobility when used as the active layer in organic thin-film transistor (OTFT) devices. Among the series, the highest hole mobility of 0.11 cm 2 V -1 s -1 is achieved in bottom gate and top-contact OTFT devices using PDPP-FNF. When these polymers are used as a donor and [70]PCBM as the acceptor in organic photovoltaic (OPV) devices, power conversion efficiencies (PCE) of 2.5 and 2.6% are obtained for PDPP-FAF and PDPP-FNF polymers, respectively. Such mobility values in OTFTs and performance in OPV make furan-containing DBF a very promising block for designing new polymer semiconductors for a wide range of organic electronic applications.

Isoindigo dye incorporated copolymers with naphthalene and anthracene: promising materials for stable organic field effect transistors

In this paper, we report the design and synthesis of isoindigo based low band gap polymer semiconductors, poly{N,N′-(2-octyldodecyl)-isoindigo-alt- naphthalene} (PISD-NAP) and poly{N,N′-(2-octyldodecyl)-isoindigo-alt- anthracene} (PISD-ANT). A series of donor-acceptor (D-A) copolymers can be prepared where donor and acceptor conjugated blocks can be attached alternately using organometallic coupling. In these polymers, an isoindigo dye acceptor moiety has been attached alternately with naphthalene and anthracene donor comonomer blocks by Suzuki coupling. PISD-NAP and PISD-ANT exhibit excellent solution processibility and good film-forming properties. Gel permeation chromatography exhibits a higher molecular mass with lower polydispersity. UV-vis-NIR absorption of these polymers exhibits a wide absorption band ranging from 300 nm to 800 nm, indicating the low band gap nature of the polymers. Optical band gaps calculated from the solid state absorption cutoff value for PISD-NAP and PISD-ANT are around 1.80 eV and 1.75 eV, respectively. Highest occupied molecular orbital (HOMO) values calculated respectively for PISD-NAP and PISD-ANT thin films on glass substrate by photoelectron spectroscopy in air (PESA) are 5.66 eV and 5.53 eV, indicative of the good stability of these materials in organic electronic device applications. These polymers exhibit p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices in ambient conditions. The highest hole mobility of 0.013 cm2 V-1 s-1 is achieved in top contact and bottom-gate OTFT devices for PISD-ANT, whereas polymer PISD-NAP exhibited a hole mobility of 0.004 cm2 V -1 s-1. When these polymer semiconductors were used as a donor and PC71BM as an acceptor in OPV devices, the highest power conversion efficiency (PCE) of 1.13% is obtained for the PISD-ANT polymer.

4-hexylbithieno[3,2-b:2′3′-e]pyridine: An efficient electron-accepting unit in fluorene and indenofluorene copolymers for light-emitting devices

4-Hexylbithienopyridine has been prepared as a novel electron-accepting monomer for conjugated polymers. To test its electronic properties, alternating copolymers with fluorene and indenofluorene polymers have been prepared. The copolymers displayed reduction potentials about 0.5 V lower than for the corresponding fluorene and indenofluorene homopolymers, indicating much improved electron-accepting properties. Analysis of the microscopic morphology of thin films of the copolymers by AFM shows that they lack the extensive supramolecular order seen with the homopolymers, which is attributed to the bithienopyridine units disrupting the π-stacking. LEDs using these polymers as the emitting layer produce blue-green emission with low turn-on voltages with aluminum electrodes confirming their improved electron affinity. The indenofluorene copolymer displayed an irreversible red shift in emission at high voltages, which is attributed to oxidation of the indenofluorene units. This red shift occurred at higher potentials than for indenofluorene homopolymers in LEDs, suggesting that the heterocyclic moieties offer some protection against electrically promoted oxidation.