Synthesis,properties, and field effect transistor characteristics of new thiophene‐[1,2,5]thiadiazolo[3,4‐g]quinoxaline‐thiophene‐based conjugated polymers

Four new conjugated copolymers based on the moiety of bis(4‐hexylthiophen‐2‐yl)‐6,7‐diheptyl‐[1,2,5]thiadiazolo[3,4‐g]quinoxaline (BTHTQ) were synthesized and characterized, including poly(6,7‐diheptyl‐4,9‐bis(4‐hexylthiophen‐2‐yl)‐[1,2,5]thiadiazolo[3,4‐g]quinoxaline) (PBTHTQ), poly‐(6,7‐diheptyl‐4,9‐bis(4‐hexylthiophen‐2‐yl)‐[1,2,5]thiadiazolo‐[3,4‐g]quinoxaline‐alt‐2,5‐thiophene) (PTTHTQ), poly(6,7‐diheptyl‐4,9‐bis(4‐hexylthiophen‐2‐yl) [1,2,5]‐thiadiazolo‐[3,4‐g]quinoxaline‐alt‐9,9‐dioctyl‐2,7‐fluore‐ne) (PFBTHTQ), and poly(6,7‐diheptyl‐4,9‐bis(4‐hexylthiophen‐2‐yl)‐[1,2,5]thiadiazolo[3,4‐g]quinoxaline‐alt‐1,4‐bis(decyloxy)phenylene) (PPBTHTQ). The λ_max of PBTHTQ, PTTHTQ, PFBTHTQ, and PPBTHTP thin films was shown at 780, 876, 734, and 710 nm, respectively, with the corresponding optical band gaps (E) of 1.31, 1.05, 1.40, and 1.43 eV. The relatively small band gaps of the synthesized polymers suggested the significance of intramolecular charge transfer between the donor and TQ moiety. The estimated hole mobilities of PBTHTQ, PTTHTQ, and PFBTHTQ‐based field effect transistor devices using CHCl₃ solvent were 8.5 × 10^?5, 8.5 × 10^?4, and 2.8 × 10^?5 cm² V^?1 s^?1, respectively, but significantly enhanced to 1.6 × 10^?4, 3.8 × 10^?3, and 1.5 × 10^?4 cm² V^?1 s^?1 using high boiling point solvent of chlorobenzene (CB). The higher hole mobility of PTTHTQ than the other two copolymers was attributed from its smaller band gap or ordered morphology [wormlike (chloroform) or needle‐like (CB)]. The characteristics of small band gap and high mobility suggest the potential applications of the BTHTQ‐based conjugated copolymers in electronic and optoelectronic devices. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6305–6316, 2008     

Specific interaction between fluorine atoms and thiol groups accounting for higher domain purity and photostability in narrowband BHJ systems

In order to explore the role of fluorine atoms on photostability as well as morphology control of active layer in the presence of 1,4‐butanedithiol (BT), the four polymers with or without fluorine atoms in the backbones including polythieno[3,4‐b]thiophene/benzodithiophene, poly[(4,8‐bis‐(2‐ethylhexyloxy)‐benzo(1,2‐b:4,5‐b9)dithiophene)‐2,6‐diyl‐alt‐(4‐(2‐ethylhexanoyl)‐thieno[3,4‐b]thiophene‐)‐2‐6‐diyl)], poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b;4,5‐b′]dithiophene‐2,6‐diyl‐alt‐(4‐(2‐ethylhexyl)‐3‐fluorothieno[3,4‐b]thiophene‐)‐2‐carboxylate‐2‐6‐diyl)], and poly[4,8‐bis‐(2‐ethyl‐hexyl‐thiophene‐5‐yl)‐benzo[1,2‐b:4,5‐b0]dithiophene‐2,6‐diyl]‐alt‐[2‐(20‐ethyl‐hexanoyl)‐thieno [3,4‐b]thiophen‐4,6‐diyl] were selected for comparison. It is found that the specimens containing fluorine atoms in polymer backbones showed of higher stability after illumination for 1 h in the presence of BT additive, contributing to the higher domain purity. The specific interaction between fluorine atoms and thiol groups was demonstrated by the appearance of novel absorption peak at 2663.1 cm^?1, in addition to the broadening of peak at 2556.2 cm^?1 ascribing to S? H stretching vibration as confirmed by Fourier transform infrared (FTIR) spectroscopy. The finding may guide the accurate use of thiols as effective solvent additive in morphology and stability optimization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 941–951     

Polymer solar cells based on quinoxaline and dialkylthienyl substituted benzodithiophene with enhanced open circuit voltage

A poly[benzodithiophene‐alt‐di‐2‐thienyl‐quinoxaline] series (PBDTDPQ‐EH, PBDTDPQ‐OD, and PBDTDPQ‐HDT) was synthesized via Stille coupling. Deep highest occupied molecular orbital (HOMO) levels were achieved by the introduction of 2‐decyl‐4‐hexyl‐thiophen‐yl (HDT) side chains. The introduction of the various side chains increased the molecular weight of the polymers, and the polymers dissolved well in common organic solvents at room temperature. The HOMO energy level (?5.20 to ?5.49 eV) decreased because of the 2D conjugated structure. X‐ray diffraction analysis showed that PBDTDPQ‐OD had a slightly edge‐on structure. In the case of PBDTDPQ‐HDT, however, the structure was amorphous due to the thiophene side chain, and the extent of π stacking increased. After fabricating bulk‐heterojunction‐type polymer solar cells, the OPV characteristics were evaluated. The values of open‐circuit voltage (V_oc), short‐circuit current (J_sc), fill factor, and power conversion efficiency (PCE) were 0.88 V, 7.9 mA cm^?2, 45.4%, and 3.2%, respectively. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1028–1036     

Synthesis and FET characterization of novel ambipolar and low‐bandgap naphthalene‐diimide‐based semiconducting polymers

A novel series of naphthalene‐diimide‐based semiconducting polymers ( P1–P4 ) containing benzodithiophene or dithienopyrrole were successfully synthesized for ambipolar semiconducting materials showing near infrared absorptions. The incorporation of a 3‐hexylthiophene (3HT) spacer extended the intramolecular charge‐transfer (ICT) peak from λ_onset = 739 nm ( P1 ) to 785 nm ( P3 ). Moreover, about 250 nm red‐shift of the ICT peaks was observed in P2 and P4 compared to P1 and P3 due to the increased high‐lying HOMO energy levels. The grazing incidence X‐ray scattering of the P3 and P4 films proved the slightly improved crystalline order in the π?π stacking direction, indicating that the planar backbone is probably due to the introduced 3HT. The P1–P4 ‐based field‐effect transistor showed n‐type dominant ambipolar characteristics. The P2 and P4 showed higher electron mobilities up to 1.5 × 10^?2 cm² V^?1 s^?1 than P1 and P3 , which might be influenced by the orientation of the polymer backbone and the intermolecular orbital overlap. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 359–367     

Phenacyl–Thiophene and Quinone Semiconductors Designed for Solution Processability and Air‐Stability in High Mobility n‐Channel Field‐Effect Transistors

Electron‐transporting organic semiconductors (n‐channel) for field‐effect transistors (FETs) that are processable in common organic solvents or exhibit air‐stable operation are rare. This investigation addresses both these challenges through rational molecular design and computational predictions of n‐channel FET air‐stability. A series of seven phenacyl–thiophene‐based materials are reported incorporating systematic variations in molecular structure and reduction potential. These compounds are as follows: 5,5′′′‐bis(perfluorophenylcarbonyl)‐2,2′:5′,‐ 2′′:5′′,2′′′‐quaterthiophene ( 1 ), 5,5′′′‐bis(phenacyl)‐2,2′:5′,2′′: 5′′,2′′′‐quaterthiophene ( 2 ), poly[5,5′′′‐(perfluorophenac‐2‐yl)‐4′,4′′‐dioctyl‐2,2′:5′,2′′:5′′,2′′′‐quaterthiophene) ( 3 ), 5,5′′′‐bis(perfluorophenacyl)‐4,4′′′‐dioctyl‐2,2′:5′,2′′:5′′,2′′′‐quaterthiophene ( 4 ), 2,7‐bis((5‐perfluorophenacyl)thiophen‐2‐yl)‐9,10‐phenanthrenequinone ( 5 ), 2,7‐bis[(5‐phenacyl)thiophen‐2‐yl]‐9,10‐phenanthrenequinone ( 6 ), and 2,7‐bis(thiophen‐2‐yl)‐9,10‐phenanthrenequinone, ( 7 ). Optical and electrochemical data reveal that phenacyl functionalization significantly depresses the LUMO energies, and introduction of the quinone fragment results in even greater LUMO stabilization. FET measurements reveal that the films of materials 1 , 3 , 5 , and 6 exhibit n‐channel activity. Notably, oligomer 1 exhibits one of the highest μ_e (up to ≈0.3 cm² V^?1 s^?1) values reported to date for a solution‐cast organic semiconductor; one of the first n‐channel polymers, 3 , exhibits μ_e≈10^?6 cm² V^?1 s^?1 in spin‐cast films (μ_e=0.02 cm² V^?1 s^?1 for drop‐cast 1 : 3 blend films); and rare air‐stable n‐channel material 5 exhibits n‐channel FET operation with μ_e=0.015 cm² V^?1 s^?1, while maintaining a large I_on:off=10⁶ for a period greater than one year in air. The crystal structures of 1 and 2 reveal close herringbone interplanar π‐stacking distances (3.50 and 3.43 Å, respectively), whereas the structure of the model quinone compound, 7 , exhibits 3.48 Å cofacial π‐stacking in a slipped, donor‐acceptor motif.     

Effects of substituted side‐chain position on donor–acceptor conjugated copolymers

The optical properties and electrical properties of a series of low‐band‐gap conjugated copolymers, in which alkyl side chains were substituted at various positions, were investigated using donor–acceptor conjugated copolymers consisting of a cyclopentadithiophene derivative and dithienyl‐benzothiadiazole. With substituted side chains, the intrinsic properties of the copolymers were significantly altered by perturbations of the intramolecular charge transfer. The absorption of poly[2, 6‐(4,4‐bis(2‐octyl)‐4H‐cyclopenta‐[2,1‐b:3,4‐b′]dithiophene)‐alt‐4, 7‐bis(4‐octyl‐thiophene‐2‐yl)benzo‐2,1,3‐thiadiazole] [ PCPDT‐ttOTBTOT ( P2 )], which assumed a tail–tail configuration, tended to blue shift relative to the absorption of poly[2,6‐(4,4‐bis(2‐octyl)‐4H‐cyclopenta‐[2,1‐b:3,4‐b′]dithiophene)‐alt‐4,7‐bis (thiophene‐2‐yl)benzo‐2,1,3‐thiadiazole] [ PCPDT‐TBTT ( P1 )]. The absorption of poly[2,6‐(4,4‐bis(2‐octyl)‐4H‐cyclopenta‐[2,1‐b:3, 4‐b′]dithiophene)‐alt‐4,7‐bis(3‐octyl‐thiophene‐2‐yl)benzo‐2,1,3‐thiadiazole] [ PCPDT‐hhOTBTOT ( P3 )], which assumed a head–head configuration, was blue shifted relative to that of P2 . The electrical transport properties of field‐effect transistors were sensitive to the side chain position. The field‐effect mobility in P2 (μ₂ = 1.8 × 10^?3 cm²/V s) was slightly lower than that in P1 (μ₁ = 4.9 × 10^?3 cm²/V s). However, the mobility of P3 was very low (μ₃ = 3.8 × 10^?6 cm²/V s). Photoexcitation spectroscopy showed that the charge generation efficiency (shown in transient absorption spectra) and polaron pair mobility in P1 and P2 were higher than in P3 , yielding P1 and P2 device performances that were better than the performance of devices based on P3 . © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

High‐performance amorphous donor–acceptor conjugated polymers containing x‐shaped anthracene‐based monomer and 2,5‐bis(2‐octyldodecyl)pyrrolo[3,4‐c]pyrrole‐1,4(2H,5H)‐dione for organic thin‐film transistors

New diketopyrrolopyrrole (DPP)‐containing amorphous conjugated polymers, such as poly(3‐(5‐((9,10‐bis((4‐hexylphenyl)ethynyl)‐6‐(prop‐1‐ynyl)anthracen‐2‐yl)ethynyl) thiophen‐2‐yl)‐5‐(2‐hexyldecyl)‐2‐(2‐octyldodecyl)‐6‐(thiophen‐2‐yl)pyrrolo[3,4‐c]pyrrole‐1,4(2H,5H)‐dione) ( 4 ), and poly(3‐(5‐((2,6‐bis((4‐hexylphenyl)ethynyl)‐10‐(prop‐1‐ynyl)anthracen‐9‐yl)ethynyl)thiophen‐2‐yl)‐2,5‐bis(2‐octyldodecyl)‐6‐(thio phen‐2‐yl)pyrrolo[3,4‐c]pyrrole‐1,4(2H,5H)‐dione) ( 7 ), were successfully synthesized via Sonogashira coupling reactions under microwave conditions. Copolymer 7 , incorporating a DPP moiety at the 9,10‐position of the anthracene ring through a triple bond, showed a much lower bandgap energy (E_g = 1.81 eV) than copolymer 4 (E_g = 2.13 eV). Tuning of the molecular frontier orbital energies was achieved by only changing the anchoring position of dithiophenyl‐DPP from the 2,6‐ to the 9,10‐position in the anthracene ring. Because of the donor–acceptor (D–A) interaction and the two‐dimensional planar structure of the X‐shaped donor monomer, the resulting polymers showed good interchain π?π stacking in the thin‐film state, despite being amorphous polymers. When the newly synthesized polymer 7 was used as a semiconductor material in an organic thin‐film transistor, the best mobility of up to 0.12 cm² V^?1 s^?1 (I_on/off = ～ 4.4 × 10⁶) was observed, which is one of the highest values recorded for amorphous polymer films reported to date. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Field‐effect transistors based on PPV derivatives as a semiconducting layer

A series of modified thiophene groups containing PPV‐based semiconducting materials, poly[(2,5‐bis(octyloxy)‐1,4‐phenylenevinylene)‐alt‐(2,2′bithienylenevinylene)] ( PPBT ), poly[(2,5‐bis(octyloxy)‐1,4‐phenylenevinylene)‐alt‐(5,5‐thiostilylenevinylene)] ( PPTVT ), have been synthesized through a Horner coupling reaction. From the FTIR and ¹H NMR spectroscopy, the configuration of the vinylene groups in the polymers was all trans (E) geometry. The weight‐average molecular weights (M_w) of PPBT and PPTVT were found to be 11,700 and 11,800, with polydispersity indices of 2.51 and 2.53, respectively. PPBT and PPTVT thin films exhibit UV–visible absorption maxima at 538 and 558 nm, respectively, and the strong absorption shoulder peaks at 578 and 602 nm, respectively. Solution processed field‐effect transistors (FET) fabricated using all the polymers showed p‐type OTFT characteristics. The field‐effect mobility of the PPTVT was obtained up to 2.3 × 10^?3 cm² V^?1 s^?1, an on/off ratio of 1.0 × 10⁵ with ambient air stability. Studies of the atomic force microscopy (AFM) and X‐ray diffraction (XRD) analysis of the polymer thin films revealed that all the polymers were amorphous structure. The greater planarity and rigidity of PPTVT compared to PPBT results in elongation of conjugation length and better π–π stacking of polymer chains in amorphous region, which leads to improved FET performance. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 111–120, 2009     

Electro‐optical properties of electropolymerized poly(3‐hexylthiophene)/carbon nanotube composite thin films

3‐hexylthiophene was electropolymerized on a carbon nanotube (CNT)‐laden fluorine‐doped tin oxide substrate. Scanning electron microscopy and Raman spectroscopy revealed that the polymer was infused throughout the thickness of the 150‐nm thick CNT mat, resulting in a conducting composite film with a dense CNT network. The electropolymerized poly(3‐hexylthiophene) (e‐P3HT)/CNT composites exhibited photoluminescence intensity quenching by as much as 92% compared to the neat e‐P3HT, which provided evidence of charge transfer from the polymer phase to the CNT phase. Through‐film impedance and J‐V measurements of the composites gave a conductivity (σ) of 1.2 × 10^?10 S cm^?1 and zero‐field mobility (μ₀) of 8.5 × 10^?4 cm² V^?1 s^?1, both of which were higher than those of neat e‐P3HT films (σ = 9.9 × 10^?12 S cm^?1, μ₀ = 3 × 10^?5 cm² V^?1 s^?1). In electropolymerized samples, the thiophene rings were oriented in the (010) direction (thiophene rings parallel to substrate), which resulted in a broader optical absorbance than for spin coated samples, however, the lack of long‐range conjugation caused a blueshift in the absorbance maximum from 523 nm for unannealed regioregular P3HT (rr‐P3HT) to 470 nm for e‐P3HT. Raman spectroscopy revealed that π‐π stacking in e‐P3HT was comparable to that in rr‐P3HT and significantly higher than in regiorandom P3HT (ran‐P3HT) as shown by the principal Raman peak shift from 1444 to 1446 cm^?1 for e‐P3HT and rr‐P3HT to 1473 cm^?1 for ran‐P3HT. This work demonstrates that these polymer/CNT composites may have interesting properties for electro‐optical applications. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1269–1275, 2011     

Synthesis and characterization of new selenophene‐based conjugated polymers for organic photovoltaic cells

Three new polymers poly(3,4′′′‐didodecyl) hexaselenophene) (P6S), poly(5,5′‐bis(4,4′‐didodecyl‐2,2′‐biselenophene‐5‐yl)‐2,2′‐biselenophene) (HHP6S), and poly(5,5′‐bis(3′,4‐didodecyl‐2,2′‐biselenophene‐5‐yl)‐2,2′‐biselenophene) (TTP6S) that have the same selenophene‐based polymer backbone but different side chain patterns were designed and synthesized. The weight‐averaged molecular weights (M_w) of P6S, HHP6S, and TTP6S were found to be 19,100, 24,100, and 19,700 with polydispersity indices of 2.77, 1.48, and 1.41, respectively. The UV–visible absorption maxima of P6S, HHP6S, and TTP6S are at 524, 489, and 513 nm, respectively, in solution and at 569, 517, and 606 nm, respectively, in the film state. The polymers P6S, HHP6S, and TTP6S exhibit low band gaps of 1.74, 1.95, and 1.58 eV, respectively. The field‐effect mobilities of P6S, HHP6S, and TTP6S were measured to be 1.3 × 10^?4, 3.9 × 10^?6, and 3.2 × 10^?4 cm² V^?1 s^?1, respectively. A photovoltaic device with a TTP6S/[6,6]‐phenyl C₇₁‐butyric acid methyl ester (1:3, w/w) blend film active layer was found to exhibit an open circuit voltage (V_OC) of 0.71 V, a short circuit current (J_SC) of 5.72 mA cm^?2, a fill factor of 0.41, and a power conversion efficiency (PCE) of 1.67% under AM 1.5 G (100 mW cm^?2) illumination. TTP6S has the most planar backbone of the tested polymers, which results in strong π–π interchain interactions and strong aggregation, leading to broad absorption, high mobility, a low band gap, and the highest PCE. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Blue to light gray electrochromic polymers from dodecyl‐derivatized thiophene Bis‐substituted dibenzothiophene/dibenzofuran

3‐Dodecylthiophene end‐capped two monomers: 2,8‐bis‐(4‐dodecyl‐thiophen‐2‐yl)‐dibenzothiophene (DBT‐3DTh) and 2,8‐bis‐(4‐dodecyl‐thiophen‐2‐yl)‐dibenzofuran (DBF‐3DTh) were synthesized via Stille coupling reaction. Both monomers exhibited emission peaks at about 400 nm with fluorescence quantum yields ranging from 0.16 to 0.21. The corresponding electroactive polymers poly(2,8‐bis‐(4‐dodecyl‐thiophen‐2‐yl)‐dibenzothiophene) (PDBT‐3DTh) and poly(2,8‐bis‐(4‐dodecyl‐thiophen‐2‐yl)‐dibenzofuran) (PDBF‐3DTh) were obtained by electropolymerization method and displayed good electrochemical stability. Both polymers switched between light gray in the neutral state and blue in the oxidized state. Kinetic investigations showed that PDBT‐3DTh exhibited a maximum optical contrast (ΔT %) of 25.23% at 575 nm with the coloration efficiency (CE) of 196 cm² C^?1. However, the electrochromic properties of PDBF‐3DTh were inferior to PDBT‐3DTh. Further detailed discussions with EDOT and 3‐alkylthiophenes end‐capped DBT/DBF hybrid electrochromic polymers were comparatively studied. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1468–1478     

High‐performance field‐effect transistors based on furan‐containing diketopyrrolopyrrole copolymer under a mild annealing temperature

Two furan‐flanked polymers poly{3,6‐difuran‐2‐yl‐2,5‐di(2‐octyldodecyl)‐pyrrolo[3,4‐c]pyrrole‐1,4‐dione‐alt‐thienylenevinylene} (PDVFs), with a highly π‐extended diketopyrrolopyrrole backbone, are developed for solution‐processed high‐performance polymer field‐effect transistors (FETs). Atomic force microscopy and grazing incidence X‐ray scattering analyses indicate that PDVF‐8 and PDVF‐10 films exhibit a similar nodular morphology with the ultrasmall lamellar distances of 16.84 and 18.98 Å, respectively. When compared with the reported polymers with the same alkyl substitutes, this is the smallest d‐spacing value observed to date. This closed lamellar crystallinity facilitates charge carrier transport. Therefore, polymer thin‐film transistors fabricated from as‐spun PDVF‐8 films exhibit a high hole mobility exceeding 1.0 cm² V^?1 s^?1 with a current on/off ratio above 10⁶. After annealing treatment at 100 °C in air, the highest hole mobility of PDVF‐8‐based FETs was significantly improved to 1.90 cm² V^?1 s^?1, which is among the highest values of the reported FET devices fabricated from polymer thin films based on this mild annealing temperature. In contrast, long alkyl‐substituted PDVF‐10 exhibited a relatively low hole mobility of 1.65 cm² V^?1 s^?1 mainly resulting from low molecular weight. This work demonstrated that PDVFs would be promising semiconductors for developing cost‐effective and large‐scale production of flexible organic electronics. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1970–1977     

Synthesis and characterization of copolymers based on cyclopenta[c]thiophene and bithiazole and their transistor properties

Two new copolymers, P1 and P2 , containing 5,5‐bis(dodecyloxymethyl)?5,6‐dihydro‐4H‐cyclopenta[c]thiophene (DCPT) or DCPT‐based thiophene trimer (as donor) and 4,4′‐dibutyl‐2,2′‐bithiazole (BTz, as weak acceptor) have been synthesized. To reduce the steric hindrance and enhance the conjugation, the thiophene spacers have been incorporated between DCPT and BTz in P2 , which play an important role in maintaining the side chain ordering and π‐stacking interactions. Both the polymers showed π‐stacking with similar distances (～0.37 nm) but with larger extent in P2 . Combination of DCPT with BTz has resulted in low lying HOMO levels for the resulting polymers with significant improvement in oxidative stability. P1 and P2 showed p‐type mobility of 0.03 and 0.052 cm² V^?1 s^?1 with current on/off ratio (I_on/I_off) in the order of 10⁴ and 10³, respectively. These differences in characteristics may be attributed to the variation in donor (D)–acceptor (A) property, supramolecular ordering, extent of π‐stacking, and film microstructure. The polymers were further characterized by GPC, TGA, DSC, PXRD, cyclic voltammetry, and atomic force microscopy. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4481–4488     

Photovoltaic performance enhancement using fluorene‐based copolymers containing pyrene units

A set of novel conjugated polyfluorene co‐ polymers, poly[(9,9′‐didecylfluorene‐2,7‐diyl)‐co‐(4,7′‐di‐2‐thienyl‐ 2′,1′,3′‐benzothiadiazole‐5,5‐diyl)‐co‐(pyrene‐1,6‐diyl)], are synthesized via Pd(II)‐mediated polymerization from 2,7‐bis(4′,4′,5′, 5′‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)‐9,9′‐di‐n‐decylfluorene, 4, 7‐di(2‐bromothien‐5‐yl)‐2,1,3‐benzothiadiazole, and 1,6‐dibromopyrene with a variety of monomer molar ratios. The field‐effect carrier mobilities and optical, electrochemical, and photovoltaic properties of the copolymers are systematically investigated. The hole mobilities of the copolymers are found to be in the range 7.0 × 10^?5 ? 8.0 × 10^?4 cm² V^?1 s^?1 and the on/off ratios were 8 × 10³ ? 7 × 10⁴. Conventional polymer solar cells (PSCs) with the configuration ITO/PEDOT:PSS/polymer:PC₇₁BM/LiF/Al are fabricated. Under optimized conditions, the polymers display power conversion efficiencies (PCEs) for the PSCs in the range 1.99–3.37% under AM 1.5 illumination (100 mW cm^?2). Among the four copolymers, P2, containing a 2.5 mol % pyrene component incorporated into poly[9,9′‐didecylfluorene‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)] (PFDTBT) displays a PCE of 3.37% with a short circuit current of 9.15 mA cm^?2, an open circuit voltage of 0.86 V, and a fill factor of 0.43, under AM 1.5 illumination (100 mW cm^?2). © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Successive stepwise evolution of host layer‐stacking framework upon the intercalation of mobile vapor guests within side‐chain layers

For the ordered phases of hairy‐rod semiconductive poly(2,5‐bis(3‐tetradecylthiophene‐2‐yl)thieno[3,2‐b]thiophene) (PBTTT) sandwiched in between crystalline platelets of hexamethylbenzene, the successive stepwise evolution of layer‐stacking framework upon guest intercalation has been studied in this research. The direct consequence of the guest intercalation into side‐chain layers is evaluated to cause the lateral shift of thiophene backbones along π–π stacking, resulting in stepwise shift of ultraviolet absorption wavelength. The thermal motions of vapor guests within disordering side‐chain layers subsequently cause progressive expansion of host stacking framework. With the increase in side‐chain length, thicker layers of disordering side chains in liquid crystals (LCs) accommodate additional vapor guests and larger amplitudes of thermal motions of guests, hence promoting the level of reversible d‐spacing change. The mixing between mobile vapor guests and aliphatic side chains is clarified as the mechanism of guest intercalation, which rationalizes successive guest intercalation during heating and the contribution of disordering side‐chain layers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1448–1456     

Development of a new conjugated polymer containing dialkoxynaphthalene for efficient polymer solar cells and organic thin film transistors

A new semiconducting polymer, poly((5,5‐E‐α‐((2‐thienyl)methylene)‐2‐thiopheneacetonitrile)‐alt‐2,6‐[(1,5‐didecyloxy)naphthalene])) (PBTADN), an alternating copolymer of 2,3‐bis‐(thiophene‐2‐yl)‐acrylronitrile and didecyloxy naphthalene, is synthesized and used as an active material for organic thin film transistors (OTFTs) and organic solar cells. The incorporation of 2,3‐bis‐(thiophene‐2‐yl)‐acrylronitrile as an electron deficient group and didecyloxy naphthalene as an electron rich group resulted in a relatively low bandgap, high charge carrier mobility, and finally good photovoltaic performances of PBTADN solar cells. Because of the excellent miscibility of PBTADN and PC₇₁BM, as confirmed by Grazing Incident X‐ray Scattering (GIXS) measurements and Transmission Electron Microscopy (TEM), homogeneous film morphology was achieved. The maximum power conversion efficiency of the PBTADN:PC₇₁BM solar cell reached 2.9% with a V_oc of 0.88 V, a short circuit current density (J_sc) of 5.6 mA/cm², and a fill factor of 59.1%. The solution processed thin film transistor with PBTADN revealed a highest saturation mobility of 0.025 cm²/Vs with an on/off ratio of 10⁴. The molecular weight dependence of the morphology, charge carrier mobility, and finally the photovoltaic performances were also studied and it was found that high molecular weight PBTADN has better self assembly characteristics, showing enhanced performance. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and characterization of a novel polymer based on anthracene moiety for organic thin film transistor

We have designed and synthesized a new polymer, which could be used in the organic thin film transistor (OTFT). Poly[2,6‐bis(3′‐dodecythiophene‐2′‐yl)anthracene] (PDTAn), which is composed with anthracene moiety and dodecyl alkyl thiophene, was synthesized by oxidative polymerization using iron (III) chloride. The mole ratio of FeCl₃ and monomer (4.2:1), keeping low temperature during the initiation reaction, amount of solvent, and dropping order were very important for oxidative polymerization without crosslinking. The molecular weight of the polymer (M_w) was measured to be 40,000 with 2.85 of polydispersity index by GPC. The physical and optical properties of the polymer were characterized by differential scanning calorimetry (DSC), cyclic voltammetry (CV), and optical absorption and photoluminescence (PL) spectroscopy. A field‐effect mobility of 1.1 × 10^?4 cm² V^?1 S^?1, a current on/off ratio of 10⁵, and the V_th at ?15.2 V had been obtained for OTFTs using this polymer semiconductor by solution coating. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5115–5122, 2008     

Pyrene‐cored covalent organic polymers by thiophene‐based isomers,their gas adsorption,and photophysical properties

Two new pyrene‐cored covalent organic polymers (COPs), CK‐COP‐1 and CK‐COP‐2 , were synthesized via the one‐step polymerization of two thiophene‐based isomers, 1,3,6,8‐tetra(thiophene‐2‐yl) pyrene ( L₁ ) and 1,3,6,8‐tetra(thiophene‐3‐yl) pyrene ( L₂ ). The resulting pyrene‐cored COPs exhibit rather different surface areas of 54 m² g^?1 and 615 m²g^?1 for CK‐COP‐1 and CK‐COP‐2 , respectively. The CO₂ uptake capacities of CK‐COP‐1 and CK‐COP‐2 also show different values of 2.85 and 9.73 wt % at 273 K, respectively. Furthermore, CK‐COP‐2 offers not only a larger CO₂ adsorption capacity but also a better CO₂/CH₄ selectivity at 273 K compared with CK‐COP‐1 . CK‐COP‐1 and CK‐COP‐2 also exhibit considerable differences in their photophysical property. The different structure and properties of CK‐COPs could be attributed to the isomer effect of their corresponding thiophene‐based monomers. © 2017 Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 2383–2389     

High performance semiconducting polymers containing bis(bithiophenyl dithienothiophene)‐based repeating groups for organic thin film transistors

New dithienothiophene‐containing conjugated polymers, such as poly(2,6‐bis(2‐thiophenyl‐3‐dodecylthiophene‐2‐yl)dithieno[3,2‐b;2′,3′‐d]thiophene, 4 and poly(2,6‐bis (2‐thiophenyl‐4‐dodecylthiophene‐2‐yl)dithieno[3,2‐b;2′,3′‐d]thiophene, 8 have been successfully synthesized via Stille coupling reactions using dodecyl‐substituted thiophene‐based monomers, bistributyltin dithienothiophene, and bistributyltin bithiophene; these polymers have been fully characterized. The main difference between the two polymers is the substitution position of the dodecyl side chains in the repeating group. Grazing‐incidence X‐ray diffraction (GI‐XRD) gave clear evidence of edge‐on orientation of polycrystallites to the substrate. The semiconducting properties of the two polymers have been evaluated in organic thin film transistors (OTFTs). The two conjugated polymers 4 and 8 exhibit fairly high hole carrier mobilities as high as μ_ave = 0.05 cm²/Vs (I_ON/OFF = 3.42 × 10⁴) and μ_ave = 0.01 cm²/Vs, (I_ON/OFF = 1.3 × 10⁵), respectively, after thermal annealing process. The solvent annealed films underwent reorganization of the molecules to induce higher crystallinity. Well‐defined atomic force microscopy (AFM) topography supported a significant improvement in TFT device performance. The hole carrier mobilities of the solvent annealed films are comparable to those obtained for a thermally annealed sample, and were one‐order higher than those obtained with a pristine sample. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

ipso‐Arylative Ring‐Opening Polymerization as a Route to Electron‐Deficient Conjugated Polymers

ipso‐Arylative ring‐opening polymerization of 2‐bromo‐8‐aryl‐8H‐indeno[2,1‐b]thiophen‐8‐ol monomers proceeds to M_n up to 9 kg mol^?1 with conversion of the monomer diarylcarbinol groups to pendent conjugated aroylphenyl side chains (2‐benzoylphenyl or 2‐(4‐hexylbenzoyl)phenyl), which influence the optical and electronic properties of the resulting polythiophenes. Poly(3‐(2‐(4‐hexylbenzoyl)phenyl)thiophene) was found to have lower frontier orbital energy levels (HOMO/LUMO=?5.9/?4.0 eV) than poly(3‐hexylthiophene) owing to the electron‐withdrawing ability of the aryl ketone side chains. The electron mobility (ca. 2×10^?3 cm² V^?1 s^?1) for poly(3‐(2‐(4‐hexylbenzoyl)phenyl)thiophene) was found to be significantly higher than the hole mobility (ca. 8×10^?6 cm² V^?1 s^?1), which suggests such polymers are candidates for n‐type organic semiconductors. Density functional theory calculations suggest that backbone distortion resulting from side‐chain steric interactions could be a key factor influencing charge mobilities.