Naphthalenothiophene imide-based polymer exhibiting over 17% efficiency

•NTI is synthesized for a new family of polymer donors•The strategy introducing thiophene can significantly enhance the PCE NTI-polymer•PNTB-2T-based binary and ternary devices exhibit efficiencies 16.72% 17.35% With emergence highly efficient non-fullerene electron acceptors, there was demand to develop donors match these narrow band-gap molecules. Designing novel electron-deficient monomers that could effectively lower polymer’s HOMO level fine-tune physical properties vital donor evolution. Herein, we developed monomer naphthalenothiophene imide (NTI) NTI-based donors—PNTB PNTB-2T. Polymer chain modification strategy, which works by inserting extra thiophenes, enhanced efficiency 3.81% PNTB:Y6 PNTB-2T:Y6 device, eventually PNTB-2T:Y6:PC71BM device. PNTB-2T-based also excellent batch-to-batch reproducibility in photovoltaic performance distinguishes them from other high-performance donors. This work provides insights into renovation organic solar cells. 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Based above consideration, (4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)bis(trimethylstannane) ((4,8-bis(5-(2-butyloctyl)-4-fluorothiophen-2-yl)benzo[1,2-b:4,5-b']di-thiophene-2,6-diyl)bis (thiophene-5,2-diyl))-bis(trimethylstannane). Although has more each repeating PNTB, (−5.60 eV PNTB; −5.52 PNTB-2T). polymers’ resulting exhibiting stacking, packing, transport. After blending Y6, Voc 0.872 V, four batches varying weight (Mn: 47.16–114.61 KDa) polydispersity index (PDI: 2.69–2.87) best parallel experiments. indicate construction next-generation especially upcoming large-scale industrial production simply Suzuki coupling reaction between compounds 1 3,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophene (Scheme 1). 2016, Marcin al., reported synthesis NMI-pyrrole hybrid bears some kind similarity chemical structure NTI.43Zhylitskaya Cybińska Chmielewski Lis Stępień Bandgap engineering pi-extended pyrroles. modular approach chromophores multi-redox activity.J. 138: 11390-11398Crossref 8 step reactions starting material acenaphthene construct π-extended porphyrins, optical It noted did find any similar been type 3 Stille NTI-2Br 2-(tributylstannyl)-4-ethylhexylthiophene, followed bromination. (Figures 1A 1B ) prepared 4 5, respectively, Pd2(dba)3 catalyst. PNTB-2T, longer alkyl (butyloctyl) benzo[1,2-b:4,5-b']dithiophene (BDT) solubility ethylhexyl insoluble even refluxing chlorobenzene, makes processing impracticable. show good commonly solvent chloroform, chlorobenzene. gel permeation chromatography (GPC) measurement performed 150°C trichlorobenzene eluent. (PDI) three five presented Figures S1–S8. Thermogravimetric analysis (TGA) indicates thermal decomposition temperature (5% loss) 438°C 389°C (Figure S9), meet requirements fabrication. differential scanning calorimetry (DSC) shows no clear endothermic exothermic peak S10) scan range 40°C–300°C.Figure 1The structures, levels, polymersShow full caption(A B) (B).(C D) top view calculated geometries (C) (D).(E) Schematic Y6.(F) Absorption spectra chloroform solution, as-cast film.View Large Image Figure ViewerDownload Hi-res image Download (PPT) (A (B). (C (D). (E) Y6. (F) film. To investigate polymer-conjugated backbone planarity polymers, geometry density theory (DFT) Gaussian package B3LYP/6–31G∗. long replaced methyl group, calculation. shown 1C 1D. exhibits all atoms core same plane. steric hindrance exists bay area, dihedral angle 35.6° 32.4° respectively. group affects 22.1° 26.8° observed 3-methylthiophene thiophene/BDT PNTB. From seen leads large long-range torsion consistent distance 4.04 Å grazing-incidence wide-angle X-ray scattering (GIWAXS) measurement. Compared relatively better core. favors verified GIWAXS data. orbitals DFT B3LYP/6–31G∗ summarized S11. delocalized whole mainly localized extension onto chain. determined cyclic voltammetry (CV) ferrocene (−4.80 standard reference S12). ELUMO −3.53 −3.43 onset reduction potentials, EHOMO −5.60 5.52 oxidation (Table values −5.45 fluoride 4,8-bis(5-(2ethyl hexyl)thiophen-2-yl)benzo[1,2-b:4,5-b]dithiophene (BDTT) unit, obviously photovoltaics (OPV) devices.14Liu Scholar,27Zhang Scholar,32Chao slightly elevated due units. ΔEHOMO offset 0.05 0.13 eV, enough drive exciton dissociation blend films according systems.44Yao Cui Qian Ponseca Jr., C.S. Honarfar Gao al.14.7% electrostatic difference.J. 7743-7750Crossref (227) UV-vis concentration 1.5 × 10−5 g ml−1 measured recorded, 1F. maximum 511 nm, red shifted 48 559 nm. cast peaks 541 566 nm film 30 7 coefficient 6.9 104 9.8 cm−1 S13 Table 1. (450–650 nm) complements 600–900 harvesting. conventional configuration ITO/PEDOT:PSS/PNTB PNTB-2T:Y6/PNDIT-F3N/Ag fabricated employing acceptor. OPV under simulated illumination 100 mW cm−2 AM 1.5G nitrogen atmosphere. J-V curves, EQE spectra, parameters 2A 2B 2. layer thickness around spin-casted solution. Solar optimization donor/acceptor ratio tested. little amount additive annealing 110°C proved devices. 1:1.5 D:A mass ratio, 13 mg concentration, 0.5% DIO (volume ratio), annealed gave highest 3.81%; 0.899 V; Jsc 8.68 mA cm−2; FF