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3D Printing Amorphous Polysiloxane Terpolymers via Vat Photopolymerization
摘要： Photocuring and vat photopolymerization (VP) additive manufacturing (AM) is reported for two families of fully amorphous poly(dimethyl siloxane) (PDMS) terpolymers containing either diphenylsiloxy (DiPhS) or diethylsiloxy (DiEtS) repeating units. A thiol-functionalized PDMS crosslinker enables rapid crosslinking in air using efficient thiol–ene addition. Differential scanning calorimetry and dynamic mechanical analysis (DMA) confirm the absence of crystallinity for the DiPhS-containing systems, while DMA shows a rubbery plateau extending to greater than 200 °C for the DiEtS-containing system. VP-AM of both photopolymer systems afford well-defined 3D geometries, including high aspect ratio structures, which demonstrate feasibility of these photopolymers for the 3D printing of unique geometric objects that require elastomeric performance to temperatures as low as ?120 °C.
关键词： thiol–ene reaction,elastomers,poly(dimethyl siloxane),vat photopolymerization,siloxane terpolymers,3D printing
更新于2025-09-23 15:22:29
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a??Double-Acceptor-Typea?? Random Conjugated Terpolymer Donors for Additive-Free Non-Fullerene Organic Solar Cells
摘要： Random conjugated terpolymers (RCTs) not only promote great comprehension and realization for state-of-the-art high effective non-fullerene polymer solar cells (OSCs) but also offer a simple and practical synthetic strategy. However, the photovoltaic properties of RCTs yet lagged behind that of the donor-acceptor alternating copolymer, especially in the additive-free devices. Hence, we developed two feasible “double acceptor type” random conjugated terpolymers, PBDB-TAZ20 and PBDB-TAZ40. The additive-free OSCs based on PBDB-TAZ20:ITIC and PBDB-TAZ40:ITIC exhibit decent efficiencies of 12.34% and 11.27%, respectively, which both surpass the PBDB-T:ITIC-based device. For the RCTs, the reasonably weakened crystallinity and reduced phase separation degree are demonstrated to help improve charge transport, reduce bimolecular recombination and thus enhance the photovoltaic performance of the additive-free OSCs. The results imply that adding a third moiety into the D-A polymer donors provides a simple but efficient synthetic approach for high-performance OSCs.
关键词： polymer solar cells,crystallinity,non-fullerenes,morphology,random terpolymers
更新于2025-09-23 15:19:57
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Highly Efficient Large Area Organic Photovoltaic Module with 350 nm Thick Active Layer using Random Terpolymer Donor
摘要： Random terpolymers are developed by incorporating small portions of benzodithiophene into a highly crystalline copolymer of terthiophene and difluorobenzothiadiazole, BDT-Th0. The bulk-heterojunction (BHJ) of the copolymer BDT-Th0 is formed by process of rapid solid-liquid phase demixing of polymer crystallites, which results in irregular and unclear phase separation with large polymer aggregation. By contrast, the random terpolymer BDT-Th10 which was prepared using 10% feed molar ratio of a benzodithiophene moiety shows slower and gradual formation of the polymer packing structures without substantial agglomeration from loosely packed pseudo-crystallites in precursor solution. This results in optimal BHJ morphology with appropriate phase separation and improved domain purity. BDT-Th10 achieves high solar cell efficiency of 7.74% by successfully reproducing the optimized BHJ morphology of small cells into 58.5 cm2 sized modules with 350 nm film thickness, whereas the copolymer shows irreproducible property with much decreased efficiency of 4.37%. This result is among the highest efficiency of high-performance large area PSC modules with such a thick active film.
关键词： Random terpolymers,benzodithiophene,bulk-heterojunction,large area modules,polymer solar cells
更新于2025-09-19 17:13:59
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Regio-regular alternating diketopyrrolopyrrole-based D <sub/>1</sub> –A–D <sub/>2</sub> –A terpolymers for the enhanced performance of polymer solar cells
摘要： We designed and synthesized regio-regular alternating diketopyrrolopyrrole (DPP)-based D1–A–D2–A terpolymers (PDPPF2T2DPP-T2, PDPPF2T2DPP-TVT, and PDPPF2T2DPP-DTT) using a primary donor (D1) [3,30-di?uoro-2,20-bithiophene (F2T2)] and a secondary donor (D2) [2,20-bithiophene (T2), (E)-1,2-di(thiophen-2-yl)ethene (TVT), or dithieno[3,2-b:20,30-d]thiophene (DTT)]. A PDPP2DT-F2T2 D–A polymer was synthesized as well to compare optical, electronic, and photovoltaic properties. The absorption peaks of the terpolymers (PDPPF2T2DPP-T2, PDPPF2T2DPP-TVT, and PDPPF2T2DPP-DTT) were longer (lmax ? 801–810 nm) than the peak of the PDPP2DT-F2T2 polymer (lmax ? 799 nm), which is associated with the high-lying HOMO levels of the terpolymers ((cid:2)5.08 to (cid:2)5.13 eV) compared with the level of the PDPP2DT-F2T2 polymer ((cid:2)5.38 eV). The photovoltaic properties of these DPP-based polymers were investigated under simulated AM 1.5G sunlight (100 mW cm(cid:2)2) with a conventional structure (ITO/PEDOT:PSS/polymer:PC71BM/Al). The open-circuit voltages (Voc) of photovoltaic devices containing the terpolymers were slightly lower (0.68–0.70 V) than the Voc of the device containing the PDPP2DT-F2T2 polymer (0.79 V). The short-circuit current (Jsc) of the PDPPF2T2DPP-DTT device was signi?cantly improved (14.14 mA cm(cid:2)2) compared with that of the PDPP2DT-F2T2 device (8.29 mA cm(cid:2)2). As a result, the power conversion e?ciency (PCE) of the PDPPF2T2DPP-DTT device (6.35%) was increased by 33% compared with that of the simple D–A-type PDPP2DT-F2T2 device (4.78%). The highest Jsc and PCE values (the PDPPF2T2DPP-DTT device) were attributed to an optimal nanoscopically mixed morphology and strong interchain packing with a high face-on orientation in the blend ?lm state. The study demonstrated that our strategy of using multiple donors in a regio-regular alternating fashion could ?ne-tune the optical, electronic, and morphological properties of D–A-type polymers, enhancing the performance of polymer solar cells.
关键词： diketopyrrolopyrrole,terpolymers,polymer solar cells,photovoltaic properties,regio-regular
更新于2025-09-12 10:27:22
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Multi C–C/ C–N Coupled Light‐Emitting Aliphatic Terpolymers: N–H Functionalized Fluorophore‐Monomers and High‐Performance Applications
摘要： For circumventing the costly fluorescent labelling, nonconventional multifunctional intrinsically fluorescent aliphatic-terpolymers, i.e., 1, 2, 3, 4, and 5, were synthesized via C–C/ C–N coupled in situ protrusions of fluorophore-monomers in solution polymerization of two non-emissive monomers. These scalable terpolymers were suitable for sensing and high-performance exclusion of Cu(II), logic-function, and bioimaging. The structures of terpolymers, fluorescent monomers, aggregation-induced enhanced emissions, bioimaging abilities, and the superadsorption were understood using 1H/ 13C NMR, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, ultraviolet-visible spectroscopy, atomic absorption spectroscopy, thermogravimetric analysis, high-resolution transmission electron microscopy, dynamic light scattering, electron paramagnetic resonance spectroscopy, solid-state fluorescence, fluorescence imaging, and fluorescence lifetime, along with isotherms, kinetics, and thermodynamic studies. The geometries and electronic structures of fluorophores and absorption-emission properties of terpolymers were examined using density functional theory, time-dependent DFT, and natural transition orbital analyses. For 1, 2, and 5, the limit of detection values were 1.03 × 10?7, 1.65 × 10?7, and 1.77 × 10?7 M, respectively. The maximum adsorption capacities were 1575.21, 1433.70, and 1472.21 mg g?1 for 1, 2, and 5, respectively.
关键词： aliphatic,aggregation-induced enhanced emissions,light-emitting,logic-gates,superadsorption,Nonconventional,bioimaging,Cu(II)-sensors,DFT-TDDFT-NTO,terpolymers
更新于2025-09-11 14:15:04