Search

The structural rigidity of fused units in the polymer backbone, in addition to the resulting stabilizing effect of the quinoidal structure, and tunable electronic properties have played a key role in promoting highly-ordered π-stacking moieties, exhibiting promising charge carrier mobilities. The electron-deficient thiazole moiety shows high planarity and effective π–π stacking, which leads to the reduction in the energy levels of the highest occupied and lowest unoccupied molecular orbitals (HOMO/LUMO), and ideally enhances the electron charge mobility. Four heterocycle-based monomers BTzS, BTzSe, DTS, and DTG based on fused bithiazole and dithiophene units incorporated with sulfur, selenium, silicon, and germanium as the bridging atoms were synthesized and characterized. The monomers were copolymerized with the electron-rich alkylated thienylenevinylene (TV) unit to afford copolymers P1–P4. The thermal, optical, and electrochemical properties and crystallinity of the copolymers were thoroughly investigated. Extensive OFET device optimization using different solvents and annealing temperatures resulted in the best charge mobility of 0.09 cm2 V−1 s−1 for the electron-deficient bithiazole BTzS copolymer P1 and 0.36 cm2 V−1 s−1 for the DTS copolymer P3.

Conjugated polymers and small molecules (SMs) with fused electron-rich and electron-deficient building blocks are promising materials for low-cost organic electronic devices. Benzotrithiophene (BTT) is one such electron-rich hybrid building block composed of three fused thiophene moieties with an extended π-system that has been widely used to synthesize a variety of electronic materials. Additionally, BTT has a planar and sulfur-rich core with a number of distinct advantages, including structural diversity, tunable electro-optical properties and exceptional hole-transport behavior. So far, four BTT-based isomers have been synthesized on a gram scale from seven isomeric structures, three of which are symmetric (BTT1-3) and one of which is asymmetric (BTT5), for use in a variety of optoelectronic applications. However, no report summarizing the progress of BTT-based semiconductors for electronic applications is available. The current review presents an overview of the recent developments in BTT-based monomers, polymers and SMs, as well as their applications in energy harvesting. Additionally, recent advances on charge transport devices, most notably organic solar cells (OSCs), organic thin field-effect transistors (OTFTs), and perovskite solar cells (Pero-SCs) are also surveyed and summarized. It is anticipated that this comprehensive review will stimulate further research and development of future BTT-based electronic materials, particularly for low-cost and high-performance organic electronic devices.

We report the synthesis and characterization of four novel small bandgap copolymers incorporating the electron-deficient thieno[2,3-d:5,4-d′]bisthiazole and selenopheno[2,3-d:5,4-d′]bisthiazole building blocks with a series of electron-deficient diketopyrrolopyrole units. The four resultant copolymers were synthesized via palladium Stille cross-coupling reaction, and their optical, thermal stability, electrochemical, and field-effect charge transport properties were investigated. All copolymers showed low optical bandgaps (1.53–1.56 eV); in addition, X-ray diffraction on solution-cast films revealed that the selenium-containing copolymers exhibit higher crystallinity compared to their thiophene counterparts.

Stille polymerization was employed to synthesize a low-band-gap (LBG) conjugated main-chain polymer PBTH consisting of bithiazole, dithieno[3,2-b:2′,3′-d]pyrroles (DTP), and pendent melamine derivatives. Novel supramolecular polymer networks PBTH/C and PBTH/F were developed by mixing proper molar amounts of polymer PBTH (containing melamine pendants) to be hydrogen-bonded (H-bonded) with complementary uracil-based conjugated cross-linkers C and F (i.e., containing two symmetrical uracil moieties connected with carbazole and fluorene units through triple bonds). The formation of multiple H-bonds between polymer PBTH and cross-linkers C or F was confirmed by FT-IR measurements. In contrast to polymer PBTH , the supramolecular design with multiple H-bonds can enhance the photovoltaic properties of polymer solar cell (PSC) devices containing H-bonded polymer networks PBTH/C and PBTH/F by tuning their light harvesting capabilities, HOMO energy levels, and crystallinities. Initially, the power conversion efficiency (PCE) values of PSC devices containing supramolecular polymer networks PBTH/C and PBTH/F as electron donors and [6,6]-phenyl-C 71 -butyric acid methyl ester (PC 70 BM) as an electron acceptor (polymer:PC 70 BM = 1:1 w/w) are found to be 0.97 and 0.68%, respectively, in contrast to 0.52% for polymer PBTH . The highest PCE value of 1.56% with a short-circuit current densities ( J sc ) value of 7.16 mA/cm 2 , a open circuit voltages ( V oc ) value of 0.60 V, and a fill factor (FF) of 0.36 was further optimized in the PSC device containing a supramolecular polymer network PBTH/C as polymer:PC 70 BM = 1:2 w/w. These results indicate that supramolecular design is an effective route towards better photovoltaic properties of V oc , J sc , and PCE values in polymer solar cells.

Two random (Zn(II)-based P1-P2) and two alternating (Ru(II)-based P3-P4) metallo-copolymers containing bis-terpyridyl ligands with various central donor (i.e., fluorene or carbazole) and acceptor (i.e., benzothiadiazole) moieties were synthesized. The effects of electron donor-acceptor interactions with metal (Zn(II) and Ru(II)) ions on their thermal, optical, and electrochemical properties were investigated. Because of the strong ICT transitions between donor and acceptor ligands in both Zn(II)- and Ru(II)-based metallo-coplymers and MLCT transitions in Ru(II)-based metallo-coplymers, the absorption spectra covered a broad range of 260-750 nm with the band gaps of 1.57-1.77 eV. In addition, the introduction of Ru(II)-based metallo-coplymer P4 mixed with PC(60)BM as an active layer of the BHJ solar cell device exhibited the highest PCE value up to 0.90%.

A conjugated main-chain copolymer (PBT) consisting of bithiazole, dithieno[3,2-b:2′,3′-d]pyrroles (DTP), and pendent melamine units was synthesized by Stille polymerization, which can be hydrogen-bonded (H-bonded) with proper molar amounts of bi-functional π-conjugated crosslinker F (i.e., two uracil motifs covalently attached to a fluorene core through triple bonds symmetrically) to develop a novel supramolecular polymer network (PBT/F). The effects of multiple H-bonds on light harvesting capabilities, HOMO levels, and photovoltaic properties of polymer PBT and H-bonded polymer network PBT/F are investigated. The formation of supramolecular polymer network (PBT/F) between PBT and F was confirmed by FTIR and XRD measurements. Because of the stronger light absorption, lower HOMO level, and higher crystallinity of H-bonded polymer network PBT/F, the solar cell device containing PBT/F showed better photovoltaic properties than that containing polymer PBT. The preliminary results show that the solar cell device containing 1:1 weight ratio of PBT/F and [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) offers the best power conversion efficiency (PCE) value of 0.86% with a short-circuit current density (Jsc) of 4.97 mA/cm2, an open circuit voltage (Voc) of 0.55 V, and a fill factor (FF) of 31.5%. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Five conjugated LBG polymers P1–P5 consisting of a DTP unit as an electron donor and various bithiazole units as electron acceptors are designed and synthesized for photovoltaic applications. The effects of the electron-deficient bithiazole derivatives on the thermal, optical, electrochemical, and photovoltaic properties are investigated. The molecular structures are confirmed and characterized. The resulting polymers have high thermal stabilities and broad absorption bands with low optical bandgaps. The hole and electron mobilities are calculated. PSC devices are fabricated utilizing the polymers as electron donors and PCBM as an electron acceptor. The PSC device with an active layer of P4:PCBM (1:1 by weight) exhibits the best power-conversion efficiency.

Two b-cyano-thiophenevinylene-based polymers containing cyclopentadithiophene (CPDT-CN) and dithienosilole (DTS-CN) units were synthesized via Stille coupling reaction with Pd(PPh3)4 as a catalyst. The effects of the bridged atoms (C and Si) and cyano-vinylene groups on their thermal, optical, electrochemical, charge transporting, and photovoltaic proper- ties were investigated. Both polymers possessed the highest occupied molecular orbital (HOMO) levels of about � 5.30 eV and the lowest unoccupied molecular orbital (LUMO) levels of about � 3.60 eV, and covered broad absorption ranges with narrow optical band gaps (ca. 1.6 eV). The bulk heterojunction polymer solar cell (PSC) devices containing an active layer of

Four novel symmetrical organic dyes (S1–S4) configured with acceptor–donor–acceptor (A–D–A) structures containing electron donating fluorene (S1 and S2) and N-alkyl dithieno[3,2-b:2′,3′-d]pyrrole (DTP) (S3 and S4) cores terminated with two anchoring cyanoacrylic acids (as electron acceptors) were synthesized and applied to dye-sensitized solar cells (DSSCs). The DSSC device based on S2 dye showed the best photovoltaic performance among S1–S4 dyes: a maximum monochromatic incident photon-to-current conversion efficiency (IPCE) of 76%, a short circuit current (JSC) of 12.27 mA/cm2, an open circuit voltage (VOC) of 0.61 V, a fill factor (FF) of 0.63, and an overall power conversion efficiency (η) of 4.73%. Besides, the utilization of chenodoxycholic acid (CDCA) as a co-adsorbent in the DSSC device based on S3 dye showed a significant improvement in its η value (from 3.70% to 4.31%), which is attributed to the suppression of dye aggregation on TiO2 surface and thus to increase the JSC value eventually.

A series of novel hydrogen-bonded (H-bonded) cross-linking polymers were generated by complexing various proton-donor (H-donor) solar cell dyes containing 3,6- and 2,7-functionalized electron-donating carbazole cores bearing symmetrical thiophene linkers and cyanoacrylic acid termini with a proton-acceptor (H-acceptor) side-chain homopolymer carrying pyridyl pendants (with 1/2 M ratio of H-donor/H-acceptor). The supramolecular H-bonded structures between H-donor dyes and the H-acceptor side-chain polymer were confirmed by FTIR measurements. The effects of the supramolecular architecture on optical, electrochemical, and organic photovoltaic (OPV) properties were investigated. From DFT (density functional theory) calculations, the optimized geometries of organic dyes reflected that the carbazole cores of H-donor dyes were coplanar with the conjugated thiophenes and cyanoacrylic acids, which is essential for strong conjugations across the donor-acceptor units in D1–D4 dyes. Under 100 mW/cm2 of AM 1.5 white-light illumination, bulk heterojunction (BHJ) OPV cell devices containing an active layer of H-bonded polymers (PDFTP/D1–D4) as an electron donor blended with [6,6]-phenyl C61-butyric acid methyl ester (PCBM) as an electron acceptor in a weight ratio of 1:1 were explored. From the preliminary investigations, the OPV device containing 1:1 weight ratio of H-bonded polymer PDFTP/D2 and PCBM showed the best power conversion efficiency (PCE) value of 0.31% with a short-circuit current (Jsc) of 1.9 mA/cm2, an open-circuit voltage (Voc) of 0.55 V, and a fill factor (FF) of 29%, which has a higher PCE value than the corresponding H-donor D2 dye (PCE = 0.15%) or H-acceptor PDFTP homopolymer (PCE = 0.02%) blended with PCBM in 1:1 weight ratio.

A series of novel low-bandgap triphenylamine- based conjugated polymers (PCAZCN, PPTZCN, and PDTPCN) consisting of different electron-rich donor main chains (N-alkyl- 2,7-carbazole, phenothiazine, and cyclopentadithinopyrol, respectively) as well as cyano- and dicyano-vinyl electron- acceptor pendants were synthesized and developed for poly- mer solar cell applications. The polymers covered broad absorption spectra of 400-800 nm with narrow optical band- gaps ranging 1.66-1.72 eV. The highest occupied molecular or- bital and lowest unoccupied molecular orbital levels of the polymers measured by cyclic voltammetry were found in the range of � 5.12 to � 5.32 V and � 3.45 to � 3.55 eV, respectively. Under 100 mW/cm 2 of AM 1.5 white-light illumination, bulk heterojunction photovoltaic devices composing of an active

A series of low-band-gap (LBG) donor-accepor con- jugated main-chain copolymers (P1-P4) containing planar 2,7- carbazole as electron donors and bithiazole units (4,4 0 -dihexyl- 2,2 0 -bithiazole and 4,4 0 -dihexyl-5,5 0 -di(thiophen-2-yl)-2,2 0 -bithia- zole) as electron acceptors were synthesized and studied for the applications in bulk heterojunction (BHJ) solar cells. The effects of electron deficient bithiazole units on the thermal, optical, electrochemical, and photovoltaic (PV) properties of these LBG copolymers were investigated. Absorption spectra revealed that polymers P1-P4 exhibited broad absorption bands in UV and visible regions from 300 to 600 nm with opti- cal band gaps in the range of 1.93-1.99 eV, which overlapped with the major region of the solar emission spectrum. More- over, carbazole-based polymers P1-P4 showed low values of the highest occupied molecular orbital (HOMO) levels, which provided good air stability and high open circuit voltages (Voc) in the PV applications. The BHJ PV devices were fabricated using polymers P1-P4 as electron donors and (6,6)-phenyl-C61- butyric acid methyl ester (PC61BM) or (6,6)-phenyl-C71-butyric acid methyl ester (PC71BM) as electron acceptors in different weight ratios. The PV device bearing an active layer of polymer blend P4:PC71BM (1:1.5 w/w) showed the best power conver- sion efficiency value of 1.01% with a short circuit current den- sity (Jsc) of 4.83 mA/cm 2 , a fill factor (FF) of 35%, and Voc ¼ 0.60 V under 100 mW/cm 2 of AM 1.5 white-light illumination.

A series of soluble donor-acceptor conjugated poly- mers comprising of phenothiazine donor and various benzodia- zole acceptors (i.e., benzothiadiazole, benzoselenodiazole, and benzoxadiazole) sandwiched between hexyl-thiophene linkers were designed, synthesized, and used for the fabrication of polymer solar cells (PSC). The effects of the benzodiazole acceptors on the thermal, optical, electrochemical, and photo- voltaic properties of these low-bandgap (LBG) polymers were investigated. These LBG polymers possessed large molecular weight (Mn) in the range of 3.85� 5.13 � 10 4 with high thermal decomposition temperatures, which demonstrated broad absorption in the region of 300� 750 nm with optical bandgaps of 1.80� 1.93 eV. Both the HOMO energy level (� 5.38 to � 5.47 eV) and LUMO energy level (� 3.47 to � 3.60 eV) of the LBG polymers were within the desirable range of ideal energy level. Under 100 mW/cm 2 of AM 1.5 white-light illumination, bulk heterojunction PSC devices containing an active layer of elec- tron donor polymers mixed with electron acceptor (6,6)-phe- nyl-C61-butyric acid methyl ester (PC61BM) or (6,6)-phenyl-C71- butyric acid methyl ester (PC71BM) in different weight ratios were investigated. The best performance of the PSC device was obtained by using polymer PP6DHTBT as an electron do- nor and PC71BM as an acceptor in the weight ratio of 1:4, and a power conversion efficiency value of 1.20%, an open-circuit voltage (Voc) value of 0.75 V, a short-circuit current (Jsc) value of 4.60 mA/cm 2 , and a fill factor (FF) value of 35.0% were achieved. V C 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4823-4834, 2010

In this study we used convergent syntheses to prepare two novel acceptor–donor–acceptor (A–D–A) small molecules (BT4OT, BT6OT), each containing an electron-rich benzotrithiophene (BT) unit as the core, flanked by octylthiophene units, and end-capped with electron-deficient cyanoacetate units. The number of octylthiophene units affected the optical, electrochemical, morphological, and photovoltaic properties of BT4OT and BT6OT. Moreover, BT4OT and BT6OT possess low-energy highest occupied molecular orbitals (HOMOs), providing them with good air stability and their bulk heterojunction (BHJ) photovoltaic devices with high open-circuit voltages (Voc). A solar cell device containing BT6OT and [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) in a 1:0.75 ratio (w/w) exhibited a power conversion efficiency (PCE) of 3.61% with a short-circuit current density (Jsc) of 7.39 mA cm−2, a value of Voc of 0.88 V, and a fill factor (FF) of 56.9%. After adding 0.25 vol% of 1-chloronaphthalene (CN) as a processing additive during the formation of the blend film of BT6OT:PC71BM (1:0.75, w/w), the PCE increased significantly to 5.05% with values of Jsc of 9.94 mA cm−2, Voc of 0.86 V, and FF of 59.1% as a result of suppressed nanophase molecular aggregation.