Versatile functional poly(3‐hexylthiophene) for hybrid particles synthesis by the grafting onto technique: Core@shell ZnO nanorods

We demonstrate an efficient strategy to anchor poly(3‐hexylthiophene) (P3HT) onto zinc oxide (ZnO) surfaces. Synthesis of a novel triethoxysilane‐terminated regioregular P3HT is herein reported and supported by thorough characterization. Three triethoxysilane‐terminated P3HTs of different molar masses were prepared via a hydrosilylation reaction from allyl‐terminated P3HT. MALDI‐TOF and ¹H NMR were performed to characterize the polymer and show that around 80% of the chains are end‐functionalized. These polymers were then grafted onto the ZnO nanorods to create a macromolecular self‐assembled monolayer. This versatile technique could be subsequently applied to different metal oxide surfaces, such as silicon, titanium, or indium‐tin oxide, and represents a new one‐pot strategy based on triethoxysilane coupling reaction. Importantly, the influence of the molar mass on the grafting density and the polymer shell thickness was studied via thermo gravimetric analysis and transmission electron microscopy. The optical properties of the hybrid materials were determined by UV–visible absorption and photoluminescence to show a quenching effect of P3HT fluorescence by ZnO when grafted. This electronic transfer associated with an improved miscibility of the ZnO@P3HT, makes these hybrid materials suitable candidates for photovoltaic applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 30–38     

Fabrication of large-scale ripples on fluorine-doped tin oxide films by femtosecond laser irradiation

The large-scale uniform self-organized ripples are fabricated on fluorine-doped tin oxide （FTO） coated glass by femtosecond laser. They can be smoothly linked in a horizontal line with the moving of XYZ stage by setting its velocity and the repetition rate of the laser. The ripple-to-ripple linking can also be realized through line-by-line scanning on a vertical level. The mechanism analysis shows that the seeding effect plays a key role in the linking of ripples.     

Synthesis and characterization of highly conjugated side‐group‐substituted benzo[1,2‐b:4,5‐b′]dithiophene‐based copolymer for use in organic solar cells

A new donor–acceptor (D–A) conjugated copolymer based on benzo[1,2‐b:4,5‐b′]dithiophene (BDT) and thieno[3,4‐c]pyrrole‐4,6‐dione (TPD) was synthesized via a Stille cross‐coupling reaction. A highly conjugated thiophene‐based side group, tris(thienylenevinylene) (TTV), was incorporated into each BDT unit to generate the two‐dimensional D–A copolymer (PBDT‐TTV). An alkoxy‐substituted BDT‐based TPD copolymer (PBDT‐OR) was synthesized using the same polymerization method for comparison. PBDT‐TTV thin films produced two distinct absorption peaks. The shorter wavelength absorption (458 nm) was attributed to the BDT units containing the TTV group, and the longer wavelength band (567–616 nm) was attributed to intramolecular charge transfer between the BDT donor and the TPD acceptor. The highest occupied molecular orbital energy levels of PBDT‐OR and PBDT‐TTV were calculated to be −5.53 and −5.61 eV, respectively. PBDT‐TTV thin films harvested a broad solar spectrum covering the range 300–700 nm. A comparison with the PBDT‐OR films revealed stronger interchain π–π interactions in the PBDT‐TTV films and, thus, a higher hole mobility. A polymer solar cell device prepared using PBDT‐TTV as the active layer was found to exhibit a higher power conversion efficiency than a device prepared using PBDT‐OR under AM 1.5 G (100 mW/cm²) conditions. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 653–660     

Hybrid inorganic–organic poly(carborane‐siloxane‐arylacetylene) structural isomers with in‐chain aromatics: Synthesis and properties

Structural isomers of thermo‐oxidatively stable poly(carborane‐siloxane‐arylacetylene) (PCSAA), namely, m‐PCSAA and p‐PCSAA, were synthesized by the reaction of the dimagnesium salts of m‐diethynylbenzene or p‐diethynylbenzene with 1,7‐bis(chlorotetramethyldisiloxyl)‐m‐carborane. The developed polymers have exceptional thermo‐oxidative properties similar to their diacetylene counterpart poly(carborane‐siloxane‐acetylene), PCSA. Thermal treatment of either of the PCSAAs results in a fully crosslinked thermoset by 500 °C resulting from the cycloaddition reactions involving the acetylene and aryl functionalities and subsequent formation of bridging disilylmethylene entities as discerned from Fourier transform infrared, ¹³C and ²⁹Si solid‐state NMR, and XPS studies. X‐ray diffraction analysis revealed that the thermosets obtained from p‐PCSAA possess enhanced crystallinity when compared to that obtained from m‐PCSAA possibly due to more efficient packing interactions of the p‐diethynylbenzene groups during thermoset formation. The presence of the aryl groups in the backbone of the PCSAAs' chains appeared to have enhanced the storage and bulk moduli of their thermosets when compared to the thermoset of PCSA. Dielectric studies of m‐PCSAA and p‐PCSAA revealed segmental relaxation peaks, α, above their glass transition temperatures with p‐PCSAA exhibiting a broader peak with a slower relaxation rate than m‐PCSAA. © 2013 Wiley Periodicals, Inc.^? J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2638–2650     

Flexible active matrix addressed displays manufactured by printing and coating techniques

A flexible electrochromic active matrix addressed display, including 8 × 8 pixels, is demonstrated by using solution processing based on standard printing and coating manufacturing techniques. Each organic electrochromic display (OECD) pixel and its corresponding organic electrochemical transistor (OECT) are located on different sides of the flexible PET substrate. Electronic vias generated through the plastic substrate connects each OECD pixel with one addressing OECT. When comparing this display with actively addressed OECDs with all its components located on the same side, the present approach based on this electronic via substrate provides an enhanced pixel resolution and a relatively more simplified manufacturing process. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Charge-transfer complex coupled between polymer and H-aggregate molecular crystals

Crystal needles of N,N′-bis(1-ethylpropyl)-3,4,9,10-perylenebis(dicarboximide) (EPPTC) are produced through p-stacking and are embedded in the thin film of poly(9,9-din-hexylfluorenyl-2,7-diyl) (PFO) when the blend solution of EPPTC and PFO in p-xylene is spin-coated onto a glass substrate. Charge transfer (CT) complex is resolved from the spectroscopic response of the blend film, which is generated only when the PFO molecules are excited. Thus, the PFO molecules are specified as donors and the H-aggregated EPPTC as acceptors in the formation of CT state (CTS). The emission resulting from the CTS in the red is further recognized by its much longer lifetime than both the intrinsic emission of the individual EPPTC molecules and that of their pure aggregates. Near-field analysis verifies that the CTS form on the boundary between the PFO and the crystal phases. The CT exciton forms by bounding the hole left on HOMO of the donor (PFO) and the indirectly transferred electron to the H-aggregate state of EPPTC, which transits back to the ground state by emitting a photon at about 650 nm. This introduces special physics in the heterojunctions that are coupled with the H-aggregates and mechanisms important for the design of organic photovoltaic devices. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013