Multi-Selenophene Incorporated Thiazole Imide-Based n-Type Polymers for High-Performance Organic Thermoelectrics.

Developing polymers with high electrical conductivity (σ) after n-doping is a great challenge for the advance of the field of organic thermoelectrics (OTEs). Herein, we report a series of thiazole imide-based n-type polymers by gradually increasing selenophene content in polymeric backbone. Thanks to the strong intramolecular noncovalent N⋅⋅⋅S interaction and enhanced intermolecular Se⋅⋅⋅Se interaction, with the increase of selenophene content, the polymers show gradually lowered LUMOs, more planar backbone, and improved film crystallinity versus the selenophene-free analogue. Consequently, polymer PDTzSI-Se with the highest selenophene content achieves a champion σ of 164.0 S cm-1 and a power factor of 49.0 µW m-1 K-2 in the series when applied in OTEs after n-doping. The σ value is the highest one for n-type donor-acceptor OTE materials reported to date. Our work indicates that selenophene substitution is a powerful strategy for developing high-performance n-type OTE materials and selenophene incorporated thiazole imides offer an excellent platform in enabling n-type polymers with high backbone coplanarity, deep-lying LUMO and enhanced mobility/conductivity.

High-Performance n-Type Organic Thermoelectrics with Exceptional Conductivity by Polymer-Dopant Matching.

Achieving high electrical conductivity (σ) and power factor (PF) simultaneously remains a significant challenge for n-type organic themoelectrics (OTEs). Herein, we demonstrate the state-of-the-art OTEs performance through blending a fused bithiophene imide dimer-based polymer f-BTI2g-SVSCN and its selenophene-substituted analogue f-BSeI2g-SVSCN with a julolidine-functionalized benzimidazoline n-dopant JLBI, vis-à-vis when blended with commercially available n-dopants TAM and N-DMBI. The advantages of introducing a more lipophilic julolidine group into the dopant structure of JLBI are evidenced by the enhanced OTEs performance that JLBI-doped films show when compared to those doped with N-DMBI or TAM. In fact, thanks to the enhanced intermolecular interactions and the lower-lying LUMO level enabled by the increase of selenophene content in polymer backbone, JLBI-doped films of f-BSeI2g-SVSCN exhibit a unprecedent σ of 206 S cm-1 and a PF of 114 µW m-1 K-2. Interestingly, σ can be further enhanced up to 326 S cm-1 by using TAM dopant as a consequence of its favorable diffusion behavior into densely packed crystalline domains. These values are the highest to date for solution-processed molecularly n-doped polymers, demonstrating the effectiveness of the polymer-dopant matching approach carried out in this work.

Fused Bithiophene Imide Dimer-Based n-Type Polymers for High-Performance Organic Electrochemical Transistors.

The development of n-type organic electrochemical transistors (OECTs) lags far behind their p-type counterparts. In order to address this dilemma, we report here two new fused bithiophene imide dimer (f-BTI2)-based n-type polymers with a branched methyl end-capped glycol side chain, which exhibit good solubility, low-lying LUMO energy levels, favorable polymer chain orientation, and efficient ion transport property, thus yielding a remarkable OECT electron mobility (µe ) of up to ≈10-2  cm2 V-1 s-1 and volumetric capacitance (C*) as high as 443 F cm-3 , simultaneously. As a result, the f-BTI2TEG-FT-based OECTs deliver a record-high maximum geometry-normalized transconductance of 4.60 S cm-1 and a maximum µC* product of 15.2 F cm-1 V-1 s-1 . The µC* figure of merit is more than one order of magnitude higher than that of the state-of-the-art n-type OECTs. The emergence of f-BTI2TEG-FT brings a new paradigm for developing high-performance n-type polymers for low-power OECT applications.

Fused Bithiophene Imide Oligomer and Diketopyrrolopyrrole Copolymers for n-Type Thin-Film Transistors.

Diketopyrrolopyrrole (DPP)-based copolymers have received considerable attention as promising semiconducting materials for high-performance organic thin-film transistors (OTFTs). However, these polymers typically exhibit p-type or ambipolar charge-transporting characteristics in OTFTs due to their high-lying highest occupied molecular orbital (HOMO) energy levels. In this work, a new series of DPP-based n-type polymers have been developed by incorporating fused bithiophene imide oligomers (BTIn) into DPP polymers. The resulting copolymers BTIn-DPP show narrow band gaps as low as 1.27 eV and gradually down-shifted frontier molecular orbital energy levels upon the increment of imide group number. Benefiting from the coplanar backbone conformation, well-delocalized π-system, and favorable polymer chain packing, the optimal polymer in the series shows promising n-type charge transport with an electron mobility up to 0.48 cm2 V-1 s-1 in OTFTs, which is among the highest values for the DPP-based n-type polymers reported to date. The results demonstrate that incorporating fused bithiophene imide oligomers into polymers can serve as a promising strategy for constructing high-performance n-type polymeric semiconductors.

High-Performance n-Type Polymeric Mixed Ionic-Electronic Conductors: The Impacts of Halogen Functionalization.

Developing high-performance n-type polymer mixed ionic-electronic conductors (PMIECs) is a grand challenge, which largely determines their applications in vaious organic electronic devices, such as organic electrochemical transistors (OECTs) and organic thermoelectrics (OTEs). Herein, two halogen-functionalized PMIECs f-BTI2g-TVTF and f-BTI2g-TVTCl built from fused bithiophene imide dimer (f-BTI2) as the acceptor unit and halogenated thienylene-vinylene-thienylene (TVT) as the donor co-unit are reported. Compared to the control polymer f-BTI2g-TVT, the fluorinated f-BTI2g-TVTF shows lower-positioned lowest unoccupied molecular orbital (LUMO), improved charge transport property, and greater ion uptake capacity. Consequently, f-BTI2g-TVTF delivers a state-of-the-art µC* of 90.2 F cm-1 V-1 s-1 with a remarkable electron mobility of 0.41 cm2 V-1 s-1 in OECTs and an excellent power factor of 64.2 µW m-1 K-2 in OTEs. An OECT-based inverter amplifier is further demonstrated with voltage gain up to 148 V V-1 , which is among the highest values for OECT inverters. Such results shed light on the impacts of halogen atoms on developing high-performing n-type PMIECs.

Selenophene Substitution Enabled High-Performance n-Type Polymeric Mixed Ionic-Electronic Conductors for Organic Electrochemical Transistors and Glucose Sensors.

High-performance n-type polymeric mixed ionic-electronic conductors (PMIECs) are essential for realizing organic electrochemical transistors (OECTs)-based low-power complementary circuits and biosensors, but their development still remains a great challenge. Herein, by devising two novel n-type polymers (f-BTI2g-SVSCN and f-BSeI2g-SVSCN) containing varying selenophene contents together with their thiophene-based counterpart as the control, it is demonstrated that gradually increasing selenophene loading in polymer backbones can simultaneously yield lowered lowest unoccupied molecular orbital levels, boosted charge-transport properties, and improved ion-uptake capabilities. Therefore, a remarkable volumetric capacitance (C*) of 387.2 F cm-3 and a state-of-the-art OECT electron mobility (µe,OECT ) of 0.48 cm2 V-1 s-1 are synchronously achieved for f-BSeI2g-SVSCN having the highest selenophene content, yielding an unprecedented geometry-normalized transconductance (gm,norm ) of 71.4 S cm-1 and record figure of merit (µC*) value of 191.2 F cm-1 V-1 s-1 for n-type OECTs. Thanks to such excellent performance of f-BSeI2g-SVSCN-based OECTs, a glucose sensor with a remarkably low detection limit of 10 nMm and decent selectivity is further implemented, demonstrating the power of selenophene substitution strategy in enabling high-performance n-type PMIECs for biosensing applications.

Cyano-Functionalized Fused Bithiophene Imide Dimer-Based n-Type Polymers for High-Performance Organic Thermoelectrics.

Doped n-type polymers usually exhibit low electrical conductivities and thermoelectric power factors (PFs), restricting the development of high-performance p-n-junction-based organic thermoelectrics (OTEs). Herein, the design and synthesis of a new cyano-functionalized fused bithiophene imide dimer (f-BTI2), CNI2, is reported, which synergistically combines the advantages of both cyano and imide functionalities, thus leading to substantially higher electron deficiency than the parent f-BTI2. On the basis of this novel building block, a series of n-type donor-acceptor and acceptor-acceptor polymers are successfully synthesized, all of which show good solubility, deep-lying frontier molecular orbital levels, and favorable polymer chain orientation. Among them, the acceptor-acceptor polymer PCNI2-BTI delivers an excellent electrical conductivity up to 150.2 S cm-1 and a highest PF of 110.3 µW m-1  K-2 in n-type OTEs, attributed to the optimized polymer electronic properties and film morphology with improved molecular packing and higher crystallinity assisted by solution-shearing technology. The PF value is the record of n-type polymers for OTEs to date. This work demonstrates a facile approach to designing high-performance n-type polymers and fabricating high-quality films for OTE applications.

Cyano-Functionalized n-Type Polymer with High Electron Mobility for High-Performance Organic Electrochemical Transistors.

n-Type organic mixed ionic-electronic conductors (OMIECs) with high electron mobility are scarce and highly challenging to develop. As a result, the figure-of-merit (µC*) of n-type organic electrochemical transistors (OECTs) lags far behind the p-type analogs, restraining the development of OECT-based low-power complementary circuits and biosensors. Here, two n-type donor-acceptor (D-A) polymers based on fused bithiophene imide dimer f-BTI2 as the acceptor unit and thienylene-vinylene-thienylene (TVT) as the donor co-unit are reported. The cyanation of TVT enables polymer f-BTI2g-TVTCN with simultaneously enhanced ion-uptake ability, film structural order, and charge-transport property. As a result, it is able to obtain a high volumetric capacitance (C*) of 170 ± 22 F cm-3 and a record OECT electron mobility (µe,OECT ) of 0.24 cm2 V-1 s-1 for f-BTI2g-TVTCN, subsequently achieving a state-of-the-art µC* of 41.3 F cm-1 V-1 s-1 and geometry-normalized transconductance (gm,norm ) of 12.8 S cm-1 in n-type accumulation-mode OECTs. In contrast, only a moderate µC* of 1.50 F cm-1 V-1 s-1 is measured for the non-cyanated polymer f-BTI2g-TVT. These remarkable results demonstrate the great power of cyano functionalization of polymer semiconductors in developing n-type OMIECs with substantial electron mobility in aqueous environment for high-performance n-type OECTs.

Fluorine-Substituted Dithienylbenzodiimide-Based n-Type Polymer Semiconductors for Organic Thin-Film Transistors.

Imide functionalization is one of the most effective approaches to develop electron-deficient building blocks for constructing n-type organic semiconductors. Driven by the attractive properties of imide-functionalized dithienylbenzodiimide (TBDI) and the promising device performance of TBDI-based polymers, a novel acceptor with increased electron affinity, fluorinated dithienylbenzodiimide (TFBDI), was designed with the hydrogen replaced by fluorine on the benzene core, and the synthetic challenges associated with this highly electron-deficient fluorinated imide building block are successfully overcome. TFBDI showed suppressed frontier molecular orbital energy levels as compared with TBDI. Copolymerizing this new electron-withdrawing TBDI with various donor co-units afforded a series of n-type polymer semiconductors TFBDI-T, TFBDI-Se, and TFBDI-BSe. All these TFBDI-based polymers exhibited a lower-lying lowest unoccupied molecular orbital (LUMO) energy level than the polymer analogue without fluorine. When applied in organic thin-film transistors, three polymers showed unipolar electron transport with large on-current/off-current ratios (Ion/Ioff) of 105-107. Among them, the selenophene-based polymer TFBDI-Se with the deepest-positioned LUMO and optimal chain stacking exhibited the highest electron mobility of 0.30 cm2 V-1 s-1. This result demonstrates that the new TFBDI is a highly attractive electron-deficient unit for enabling n-type polymer semiconductors, and the fluorination of imide-functionalized arenes offers an effective approach to develop more electron-deficient building blocks in organic electronics.

Thiazole Imide-Based All-Acceptor Homopolymer: Achieving High-Performance Unipolar Electron Transport in Organic Thin-Film Transistors.

High-performance unipolar n-type polymer semiconductors are critical for advancing the field of organic electronics, which relies on the design and synthesis of new electron-deficient building blocks with good solubilizing capability, favorable geometry, and optimized electrical properties. Herein, two novel imide-functionalized thiazoles, 5,5'-bithiazole-4,4'-dicarboxyimide (BTzI) and 2,2'-bithiazolothienyl-4,4',10,10'-tetracarboxydiimide (DTzTI), are successfully synthesized. Single crystal analysis and physicochemical study reveal that DTzTI is an excellent building block for constructing all-acceptor homopolymers, and the resulting polymer poly(2,2'-bithiazolothienyl-4,4',10,10'-tetracarboxydiimide) (PDTzTI) exhibits unipolar n-type transport with a remarkable electron mobility (µe ) of 1.61 cm2 V-1 s-1 , low off-currents (Ioff ) of 10-10 -10-11 A, and substantial current on/off ratios (Ion /Ioff ) of 107 -108 in organic thin-film transistors. The all-acceptor homopolymer shows distinctive advantages over prevailing n-type donor-acceptor copolymers, which suffer from ambipolar transport with high Ioff s > 10-8 A and small Ion /Ioff s < 105 . The results demonstrate that the all-acceptor approach is superior to the donor-acceptor one, which results in unipolar electron transport with more ideal transistor performance characteristics.