Insights into the Control of Optoelectronic Properties in Mixed-Stacking Charge-Transfer Complexes

Although cocrystallization has provided a promising platform to develop new organic optoelectronic materials, it is still a big challenge to purposely design and achieve specific optoelectronic properties. Herein, a series of mixed-stacking cocrystals (TMFA, TMCA, and TMTQ) were designed and synthesized, and the regulatory effects of the acceptors on the co-assembly behavior, charge-transfer nature, energy-level structures, and optoelectronic characteristics were systematically investigated. The results demonstrate that it is feasible to achieve effective charge-transport tuning and photoresponse switching by carefully regulating the intermolecular charge transfer and energy orbitals. The inherent mechanisms underlying the change in these optoelectronic behaviors were analyzed in depth and elucidated to provide clear guidelines for future development of new optoelectronic materials. In addition, due to the excellent photoresponsive characteristics of TMCA, TMCA-based phototransistors were investigated with varying light wavelength and optical power, and TMCA shows the best performance among all reported cocrystals under UV illumination.     

Silver(I)-mediated reaction of trimethylsilylated arylacetylenes with sulfonyl chlorides:Unexpected formation of vinvl sulfones

A novel reaction of trimethylsilylated arylacetylenes with sulfonyl chlorides was performed in the presence of silver nitrate or triflate.Conjugated vinyl sulfones as dramatic products were obtained in moderate yields and with Z-selectivity.A free radical mechanism has been proposed to account for the formation of the products.     

Brush macro‐RAFT agent mediated dispersion polymerization of styrene in the alcohol/water mixture

Dispersion RAFT polymerization of styrene in the alcohol/water mixture mediated with the brush macro‐RAFT agent of poly[poly(ethylene oxide) methyl ether vinylphenyl‐co‐styrene] trithiocarbonate [P(mPEGV‐co‐St)‐TTC] with similar molecular weight but different chemical composition is investigated. Well‐controlled RAFT polymerization including an initial slow homogeneous polymerization and a subsequent fast heterogeneous polymerization at almost complete monomer conversion is achieved. The molecular weight of the synthesized block copolymer increases linearly with the monomer conversion, and the polydispersity is relatively narrow (PDI < 1.3). The RAFT polymerization kinetics is dependent on the chemical composition in the brush macro‐RAFT agents, and those with high content of hydrophobic segment lead to fast RAFT polymerization. The growth of the block copolymer nano‐objects during the RAFT polymerization is explored, and various block copolymer nano‐objects such as nanospheres, worms, vesicles and large‐compound‐micelle‐like particles are prepared. The parameters such as the chemical composition in the brush macro‐RAFT agent, the chain length of the solvatophobic block, the concentration of the feeding monomer and the solvent character affecting the size and morphology of the block copolymer nano‐objects are investigated. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3177–3190     

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     

Extraordinary terahertz transmission through subwavelength spindle-like apertures in NbN filmExtraordinary terahertz transmission through subwavelength spindle-like apertures in NbN filmExtraordinary terahertz transmission through subwavelength spindle-like apertures in NbN filmExtraordinary terahertz transmission through subwavelength spindle-like apertures in NbN film

We studied numerically the temperature dependent extraordinary terahertz transmission through niobium nitride （NbN） film perforated with subwavelength spindle-like apertures. Both the resonant frequency and intensity of extraor- dinary terahertz transmission peaks can be greatly modified by the transition of NbN film from the normal state to the superconducting state. An enhancement of the （~1,0） NbN/magnesium oxide （MgO） peak intensity as high as 200% is demonstrated due to the combined contribution of both the superconducting transition and the excitation of localized surface plasmons （LSPs） around the apertures. The extraordinary terahertz transmission through spindle-fike hole arrays patterned on the NbN film can pave the way for us to explore novel active tuning devices.     

Side chain engineering of naphthalene diimide–bithiophene‐based polymer acceptors in all‐polymer solar cells

Two novel polymeric acceptors based on naphthalene diimide (NDI) and 2.2′‐bithiophene, named as P(NDI2THD‐T2) and P(NDI2TOD‐T2), were designed and synthesized for all polymer solar cells application. The structural and electronic properties of the two acceptors were modulated through side‐chain engineering of the NDI units. The optoelectronic properties of the polymers and the morphologies of the blend films composed of the polymer acceptors and a donor polymer PTB7‐Th were systemically investigated. With thiophene groups introduced into the side chains of the NDI units, both polymers showed wider absorption from 350 nm to 900 nm, compared with the reference polymer acceptor of N2200. No redshift of absorption spectra from solutions to films indicated reduced aggregation of the polymers due to the steric hindrance effect of thiophene rings in the side chains. The photovoltaic performance were characterized for devices in a configuration of ITO/PEDOT:PSS/PTB7‐Th:acceptors/2,9‐bis(3‐(dimethylamino)propyl)anthra[2,1,9‐def:6,5,10‐def]diisoquinoline‐1,3,8,10(2H,9H)‐tetraone (PDIN)/Al. With the addition of diphenyl ether as an additive, the power conversion efficiencies (PCEs) of 2.73% and 4.75% for P(NDI2THD‐T2) and P(NDI2TOD‐T2) based devices were achieved, respectively. The latter showed improved J_sc, Fill Factor (FF), and PCE compared with N2200 based devices. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3679–3689     

Non-specular reflection of self-collimated beams in photonic-crystal-made prism and waveguide system

We demonstrate a dual-beam-reflection phenomenon for a Gaussian beam illuminating at a Kretschmann configuration composed of a photonic-crystal-made prism and a dielectric waveguide. One reflection beam has a positive shift and the other has a negative shift. The finite-difference time-domain (FDTD) shows that the specific phenomenon takes place only when the corresponding quasi-guided mode supported in the Kretschmann configuration is excited. Field profile of the quasi-guided mode demonstrates a strong localized stationary field in the dielectric waveguide. We found that the maximum positive lateral shift (LS) is 14.27a (where a is the lattice constant), corresponding to 3.07 times of the incident wavelength, which is 0.7135 times of the beam waist and much larger than that in some previous reports.     

Microwave-assisted one-pot three-component polymerization of alkynes,aldehydes and amines toward amino-functionalized optoelectronic polymers

We present a microwave-assisted one-pot polymerization with three-components of alkynes, aldehydes and amines for the synthesis of new amino-functionalized optoelectronic polymers. The polymerization of diynes(1a-1c), dialdehydes(2a and 2b) and dibenzylamine catalyzed by InCl_3 was carried out smoothly within 1h under microwave radiation, yielding four soluble polymers with high molecular weights. The resulting polymers P1 and P2 could be easily dissolved in alcohol and thus utilized as the cathode interlayer for polymer solar cells(PSCs). Compared with the control device, the PSCs with P1 and P2 as the cathode interlayer and PTB7-Th:PC_(71)BM as the photoactive layer exhibited significantly higher power conversion efficiencies(PCEs) of 9.49% and 9.16%, respectively. These results suggest that this polycoupling reaction is an efficient approach to construct three-component polymers for the practical applications.     

Breaking the diffraction limit in far field by planar metalens

正Optical lens is of fundamental importance in both scientific researches and industrial communities,especially for the aspects of optical focusing and imaging.In traditional optics,the light modulation property is limited by the Rayleigh Criterion(0.61λ/NA),and therefore the development of an ideal lens that produces sub-diffraction limit focusing and imaging has been a dream of lens makers all the time.Intensive effort