Highly asymmetric phase diagram of a poly(1,2-octylene oxide)-poly(ethylene oxide) diblock copolymer system comprising a brush-like poly(1,2-octylene oxide) block

The phase diagram of a series of poly(1,2-octylene oxide)-poly(ethylene oxide) (POO-PEO) diblock copolymers is determined by small-angle X-ray scattering. The Flory-Huggins interaction parameter was measured by small-angle neutron scattering. The phase diagram is highly asymmetric due to large conformational asymmetry that results from the hexyl side chains in the POO block. Non-lamellar phases (hexagonal and gyroid) are observed near f(PEO) = 0.5, and the lamellar phase is observed for f(PEO) >= 0.5.

3,6-Di(furan-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione and bithiophene copolymer with rather disordered chain orientation showing high mobility in organic thin film transistors

Pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione or diketopyrrolopyrrole (DPP) is a useful electron-withdrawing fused aromatic moiety for the preparation of donor-acceptor polymers as active semiconductors for organic electronics. This study uses a DPP-furan-containing building block, 3,6-di(furan-2-yl)pyrrolo[3,4- c]pyrrole-1,4(2H,5H)-dione (DBF), to couple with a 2,2′-bithiophene unit, forming a new donor-acceptor copolymer, PDBFBT. Compared to its structural analogue, 3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (DBT), DBF is found to cause blue shifts of the absorption spectra both in solution and in thin films and a slight reduction of the highest occupied molecular orbital (HOMO) energy level of the resulting PDBFBT. Despite the fact that its thin films are less crystalline and have a rather disordered chain orientation in the crystalline domains, PDBFBT shows very high hole mobility up to 1.54 cm 2 V-1 s-1 in bottom-gate, top-contact organic thin film transistors.

A study of diphenylfumaronitrile and furan-substituted diketopyrrolopyrrole alternating copolymer and its thin-film transistors

A fused aromatic furan-substituted diketopyrrolopyrrole and novel diphenylfumaronitrile conjugated building blocks are used for the synthesis of an alternating copolymer (DPFN-DPPF) via Suzuki polycondensation. In this paper, the first attempt to use the diphenylfumaronitrile building block for the synthesis of conjugated polymer is described. The number-average and weight-average molecular weights calculated for DPFN-DPPF are 20?661 and 66?346 g mol-1, respectively. The optical bandgap calculated for DPFN-DPPF is 1.53 eV whereas the highest occupied molecular orbital (HOMO) value calculated by photoelectron spectroscopy in air (PESA) is 5.50 eV. The calculated HOMO value is lower, which is suitable for stable organic electronic devices. DPFN-DPPF polymer is used as an active layer in bottom-contact bottom-gate organic thin-film transistor devices and the thin film exhibits a hole mobility of 0.20 cm2 V-1 s-1 in air.

Furan substituted diketopyrrolopyrrole and thienylenevinylene based low band gap copolymer for high mobility organic thin film transistors

A novel solution processable donor-acceptor (D-A) based low band gap polymer semiconductor poly{3,6-difuran-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4- c]pyrrole-1,4-dione-alt-thienylenevinylene} (PDPPF-TVT), was designed and synthesized by a Pd-catalyzed Stille coupling route. An electron deficient furan based diketopyrrolopyrrole (DPP) block and electron rich thienylenevinylene (TVT) donor moiety were attached alternately in the polymer backbone. The polymer exhibited good solubility, film forming ability and thermal stability. The polymer exhibits wide absorption bands from 400 nm to 950 nm (UV-vis-NIR region) with absorption maximum centered at 782 nm in thin film. The optical band gap (Eoptg) calculated from the polymer film absorption onset is around 1.37 eV. The π-energy band level (ionization potential) calculated by photoelectron spectroscopy in air (PESA) for PDPPF-TVT is around 5.22 eV. AFM and TEM analyses of the polymer reveal nodular terrace morphology with optimized crystallinity after 200 °C thermal annealing. This polymer exhibits p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices. The highest hole mobility of 0.13 cm 2 V -1 s -1 is achieved in bottom gate and top-contact OTFT devices with on/off ratios in the range of 10 6-10 7. This work reveals that the replacement of thiophene by furan in DPP copolymers exhibits such a high mobility, which makes DPP furan a promising block for making a wide range of promising polymer semiconductors for broad applications in organic electronics.

Effect of the nature of annealing solvent on the morphology of diblock copolymer blend thin films

The morphologies and structures for the thin film of blend systems consisting of two asymmetric polystyrene-block-polybutadiene (SB) diblock copolymers induced by annealing in the vapor of different solvents, namely, cyclohexane, benzene, and heptane, which have different selectivity or preferential affinity for a certain block, were investigated by tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM). The results revealed that even a slight preferential affinity of good solvent for one block would strongly alter the morphology of the blend thin film.

Novel pH- and temperature-responsive block copolymers with tunable pH-responsive range

A series of novel pH- and temperature-responsive diblock copolymers composed of poly(N-isopropylacrylamide) (PNIPAM) and poly[(L-glutamic acid)-co-(gamma-benzyl L-glutamate)] [P(GA-co-BLG)] were prepared. The influence of hydrophobic benzyl groups on the phase transition of the copolymers was studied for the first time. With increasing BLG content in P(GA-co-BLG) block, the thermal phase transition of the diblock copolymer became sharper at a designated pH and the critical curve of phase diagram of the diblock copolymer shifted to a higher pH region.

"Sandglass"-shaped self-assembly of coil-rod-coil triblock copolymer containing rigid aniline-pentamer

The amphiphilic PEG1 500-b-EM AP-b-PEG1 500 (EM PAP) triblock copolymer of poly(ethylene glycol) (PEG) and emeraldine aniline-pentamer (EM AP) in its concentrated solution can self-assemble into a special shape like "sandglass", as observed by transmission electron microscopy (TEM), field emission scanning electron microscopy (ESEM) and atomic force microscopy (AFM). This "sandglass"- shaped assembly is composed of several "rods" aggregated in the middle, with every "rod" being about 8 VLrn in length and 300 nm in diameter.

Order-Order Transition of C -> sdG -> sL -> S in ABC Triblock Copolymer Thin Film Induced by Solvent Vapor

The morphology transition of polystyrene-block-poly(butadiene)-block-poly(2-vinylpyridine) (SBV) triblock thin film induced in benzene vapor showing weak selectivity for PS is investigated. The order-order transitions (OOT) in the sequence of core-shell cylinders (C), sphere in 'diblock gyroid' (sdG), sphere in lamella (sL) and sphere (S) are observed. The projection along (111) direction in Gyroid phase (sdG(111)) is found to epitaxially grow from C(001) in the film.

Bump-Surface Multicompartment Micelles from a Linear ABC Triblock Copolymer: A Combination Study by Experiment and Computer Simulation

Novel bump-surface multicompartment micelles formed by a linear amphiphilic ABC triblock copolymer via self-assembly in selective solvent were successfully observed both in simulation and experiment. The results revealed that the block A forms the most inner core, and the blocks B and C form the inner and outer layers, respectively, and the bumps were formed by block A and more likely to be born on curving surfaces. Moreover, the micelle shape could be controlled by changing the solvent selectivity of the blocks A and B. Spherical, cylindrical, and discoidal micelles with bumpy surfaces were obtained both in experiment and simulation.

Effect of Shear Flow on the Formation of Ring-Shaped ABA Amphiphilic Triblock Copolymer Micelles

We have investigated the effect of Shear flow on the formation of rill.-shaped ABA triblock copolymer (P4VP(43)-b-PS260-b-P4VP(43)) micelles. The results reveal that Shear flow Plays an important role in the formation of the rings Both ring size and its, distribution are found to be dependent sensitively on the stirring rate. Sizable rings are more likely to be formed at moderate stirring rate, Interestingly, the ring formation mechanism is also dependent oil the Shear flow. Copolymers are likely to form rings via end-to-end cylinder connection at low stirring rates, whereas they tend to form rings via the pathway of the rod-sphere-vesicle-ring it high stirring rates.

Effect of Solvent Molecular Size on the Self-Assembly of Amphiphilic Diblock Copolymer in Selective Solvent

Real-space self-consistent field theory (SCFT) is employed to study the effect of solvent molecular size on the self-assembly of amphiphilic diblock copolymer in selective solvent. The phase diagrams in wide ranges of interaction parameters and solvent molecular size were obtained in present study. The results indicate that the solvent molecular size is a key factor that determines the self-assembly of amphiphilic diblock copolymer. The self-assembled morphology changes from circle-like micelle to line-like micelle, then to loop-like micelle by decreasing the solvent molecular size in a wide range of solvent selectivity. We analyze and discuss this change in terms of the solvent solubility and the entropy contribution.

Self-Assembly of Hyperbranched Multiarmed PEG-PEI-PLys(Z) Copolymer into Micelles, Rings, and Vesicles

Self-assembling of synthesized novel biodegradable hyperbranched amphiphilic poly(ethylene glycol)-polyethylenimine-poly(epsilon-benzyloxycarbonyl-L-lysine) (PEG-PEI-PLys(Z)) in aqueous media is studied. In aqueous media. PLys(Z) is the hydrophobic segment, with PEG and PEI as the hydrophilic segments. It will self-assemble into spherical shape when the selected solvent water is dropped into the common solvent tetrahydrofuran (THF). And when PEG-PEI-PLYS in common solvent is dropped into mixed solvent water and THF, rings will come into King. The spherical and rings are observed by environmental scanning electron microscopy (ESEM) and transmission electron microscopy ITEM). It shows that the size of the sphere is about 100 nm, and the diameter of ring distributes from 400 nm to 10 mu m and bigger with the time roll around.

Formation of Two Kinds of Hexagonally Arranged Structures in ABC Triblock Copolymer Thin Films Induced by a Strongly Selective Solvent Vapor

An order-order transition (OOT) in the sequence of a hexagonally arranged core-shell cylinder to a double-hexagonally arranged dot in polystyrene-block-poly(butadiene)-block-poly(2-vinylpyridine) (SBV) triblock copolymer thin films is reported to be induced upon exposure to a solvent vapor that: is strongly selective for the two end blocks. These two kinds of hexagonally arranged structures could form when the film thickness is 44, 3.23, and 223 nm. When the film thickness is decreased to 13 nm, the ordered structure is absent. The sizes of the cylinder structures formed with the same annealing time in films of different thickness are compared to address the effects of film thickness on the phase structure. The mechanism is analyzed from the total surface area of the blocks and the effective interaction parameter in the solvent vapor.

Effect of block sequence and block length on the stimuli-responsive behavior of polyampholyte brushes: hydrogen bonding and electrostatic interaction as the driving force for surface rearrangement

Diblock polyampholyte brushes with different block sequences (Si/SiO2/poly(acrylic acid)-b-poly (2-vinylpyridine) (PAA-b-P2VP) brushes and Si/SiO2/P2VP-b-PAA brushes) and different block lengths were synthesized by sequent surface-initiated atom transfer radical polymerization (ATRP). The PAA block was obtained through hydrolysis from the corresponding poly(tert-butyl acrylate). The polyampholyte brushes demonstrated unique pH-responsive behavior. In the intermediate pH region, the brushes exhibited a less hydrophilic wetting behavior and a rougher surface morphology due to the formation of polyelectrolyte complex through electrostatic interaction between oppositely charged blocks. In the low pH and high pH regions, the rearrangement of polyampholyte brushes showed great dependence on the block sequence and block length. The polyampholyte brushes with P2VP-b-PAA sequence underwent rearrangement during alternative treatment by acidic aqueous solution (low pH value) and basic aqueous solution (high pH value).