Self-healing and shape-memory polymers based on cellulose acetate matrix.

The creation of self-healing polymers with superior strength and stretchability from biodegradable materials is attracting increasing attention. In this study, we synthesized new biomass-derived cellulose acetate (CA) derivatives by ring-opening graft polymerization of δ-valerolactone followed by the introduction of ureidopyrimidinone (Upy) groups in the polymer side chains. Due to the semicrystalline aliphatic characteristics of the side chain poly(δ-valerolactone) (PVL) and quadruple hydrogen bonds formed by the Upy groups, the stretchability of the resulting polymers was significantly enhanced. Moreover, the shape memory ability and self-healing property (58.3% of self-healing efficiency) were successfully imparted to the polymer. This study demonstrates the great significance of using biomass sources to create self-healing polymers.

This paper describes the first successful demonstration of self-healing polymers with superior strength and stretchability from a biodegradable material, cellulose acetate (CA). We initially introduced the ureidopyrimidinone (Upy) groups in the side chains of CA. However, the resulting polymer was not soluble and processable. In order to solve this issue, a new strategy based on the ring-opening graft polymerization of δ-valerolactone followed by the introduction of ureidopyrimidinone (Upy) groups was adopted. Due to the semicrystalline aliphatic characteristics of the side chain poly(δ-valerolactone) (PVL), the resulting polymers were soluble and processable. In addition, the quadruple hydrogen bonds formed by the Upy groups enhanced the stretchability of the resulting polymers. Moreover, the shape memory ability and self-healing property were successfully achieved due to the presence of PVL and Upy. The developed new strategy can be applied to a variety of polymers including biomass-based polymers and materials.

Enhanced Photothermal Property of NDI-Based Conjugated Polymers by Copolymerization with a Thiadiazolobenzotriazole Unit.

Solar steam generation (SSG) is a promising photothermal technology to solve the global water storage issue. The potential of π-conjugated polymers as photothermal materials is significant, because their absorption range can be customized through molecular design. In this study, naphthalenediimide (NDI) and thiadiazolobenzotriazole (TBZ) were employed as bifunctional monomers to produce conjugated polymers. There are two types of polymers, P1 and P2. P1 is based on NDI, while P2 is a copolymer of NDI and TBZ in a ratio of 9:1. Both polymers had high molecular weights and sufficient thermal stability. UV-vis-near-infrared (NIR) absorption spectra revealed that both polymers have large extinction coefficients ascribed to the NDI and TBZ chromophores. Notably, the absorption spectrum of P2 exhibited a significant red shift compared to P1, resulting in a narrow optical bandgap and absorption in the NIR range. This result suggested that P2 has a higher light absorption than P1. Photoluminescence (PL) spectra were measured to elucidate the conversion of the absorbed light into thermal energy. It was found that P2 has a reduced fluorescence quantum yield as a result of the TBZ unit, signifying a proficient conversion of the photothermal energy. Based on the results, it appears that the P2 film has a greater photothermal property compared to that of the P1 film. The surface temperature of the P2 film reached approximately 50 °C under the investigated conditions. In addition, copolymer P2 exhibited an impressive SSG efficiency of 72.4% under 1 sun (1000 W/m2) irradiation. All the results suggested that narrow bandgap conjugated polymers containing the TBZ unit are highly effective materials for achieving optimal performance in SSGs.

PEDOT:PSS versus Polyaniline: A Comparative Study of Conducting Polymers for Organic Electrochemical Transistors.

Organic electrochemical transistors (OECTs) based on conducting polymers have attracted significant attention in the field of biosensors. PEDOT:PSS and polyaniline (PANI) are representative conducting polymers used for OECTs. While there are many studies on PEDOT:PSS, there are not so many reports on PANI-based OECTs, and a detailed study to compare these two polymers has been desired. In this study, we investigated the fabrication conditions to produce the best performance in the OECTs using the above-mentioned two types of conducting polymers. The two main parameters were film thickness and film surface roughness. For PEDOT:PSS, the optimal conditions for fabricating thin films were a spin-coating rate of 3000 rpm and a DI water immersion time of 18 h. For PANI, the optimal conditions were a spin-coating rate of 3000 rpm and DI water immersion time of 5 s, and adding dodecylbenzenesulfonic acid (DBSA) was found to provide better OECT performances. The OECT performances based on PEDOT:PSS were superior to those based on PANI in terms of conductivity and transconductance, but PANI showed excellence in terms of film thickness and surface smoothness, leading to the good reproducibility of OECT performances.

Improved supercapacitor performances by adding carbonized C60-based nanospheres to PVA/TEMPO-cellulose hydrogel-based electrolyte.

With the emergence of the energy crisis and the development of flexible electronics, there is an urgent need to develop new reliable energy supply devices with good flexibility, stable energy storage, and efficient energy transfer. Porous carbon materials have been proven to enhance the efficiency of ion transport, as the nanospaces within them serve as pathways for mass transport. However, they have been mainly investigated in the electrodes of supercapacitors and batteries. To elucidate their function in the solid electrolytes, we introduced C60-based carbonized nanospheres into PVA/TEMPO-cellulose-based hydrogels by exploiting the electrostatic interaction between the carboxyl groups of TEMPO-cellulose and the carbonized nanospheres. The obtained hydrogels were further utilized as the solid electrolytes for the supercapacitors. Through a comprehensive investigation, we found that the carbonized nanospheres can act as physical crosslinking points and increase the maximum stress of the hydrogel from 0.12 to 0.31 MPa without affecting the maximum strain. In addition, the nanospaces of the carbonized nanospheres provided a pathway for ion transport, improving the capacitance of the supercapacitor from 344.83 to 369.18 mF cm-2 at 0.5 mA cm-2. The capacitance retention was also improved from 53% to 62% at 10 mA cm-2. Collectively, this study provides new insights into the application of carbonized materials to solid electrolytes.

Conjugated photothermal materials and structure design for solar steam generation.

With the development of solar steam generation (SSG) for clean water production, conjugated photothermal materials (PTMs) have attracted significant interest because of their advantages over metallic and inorganic PTMs in terms of high light absorption, designable molecular structures, flexible morphology, and solution processability. We review here the recent progress in solar steam generation devices based on conjugated organic materials. Conjugated organic materials are processed into fibers, membranes, and porous structures. Therefore, nanostructure design based on the concept of nanoarchitectonics is crucial to achieve high SSG efficiency. We discuss the considerations for designing SSG absorbers and describe commonly used conjugated organic materials and structural designs.

Click Synthesis of Triazole Polymers Based on Lignin-Derived Metabolic Intermediate and Their Strong Adhesive Properties to Cu Plate.

2-Pyrone-4,6-dicarboxylic acid (PDC) is a chemically stable metabolic intermediate of lignin that can be produced on a large scale by transforming bacteria. Novel biomass-based polymers based on PDC were synthesized by Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) and fully characterized by nuclear magnetic resonance, infrared spectroscopies, thermal analysis, and tensile lap shear strength measurements. The onset decomposition temperatures of these PDC-based polymers were all above 200 °C. In addition, the PDC-based polymers exhibited strong adhesive properties to various metal plates, with the highest adhesion to a copper plate of 5.73 MPa. Interestingly, this result was in contrast to our previous findings that PDC-based polymers weakly adhere to copper. Furthermore, when bifunctional alkyne and azide monomers were polymerized in situ under hot-press conditions for 1 h, the resulting PDC-based polymer displayed a similar adhesion to a copper plate of 4.18 MPa. The high affinity of the triazole ring to copper ions improved the adhesive ability and selectivity of the PDC-based polymers to copper while still maintaining the strong adhesive ability to other metals, which is conducive to enhancing the versatility of PDC-based polymers as adhesives.

Benzothiadiazole versus Thiazolobenzotriazole: A Structural Study of Electron Acceptors in Solution-Processable Organic Semiconductors.

Despite the rapid progress of organic electronics, developing high-performance n-type organic semiconductors is still challenging. Donor-acceptor (D-A) type conjugated structures have been an effective molecular design strategy to achieve chemically-stable semiconductors and the appropriate choice of the acceptor units determines the electronic properties and device performances. We have now synthesized two types of A1 -D-A2 -D-A1 type conjugated molecules, namely, NDI-BTT-NDI and NDI-TBZT-NDI, with different central acceptor units. In order to investigate the effects of the central acceptor units on the charge-transporting properties, organic field-effect transistors (OFETs) were fabricated. NDI-TBZT-NDI had shallower HOMO and deeper LUMO levels than NDI-BTT-NDI. Hence, the facilitated charge injection resulted in ambipolar transistor performances with the optimized hole and electron mobilities of 0.00134 and 0.151 cm2 V-1 s-1 , respectively. In contrast, NDI-BTT-NDI displayed only an n-channel OFET performance with the electron mobility of 0.0288 cm2 V-1 s-1 . In addition, the device based on NDI-TBZT-NDI showed a superior air stability to that based on NDI-BTT-NDI. The difference in these OFET performances was reasonably explained by the contact resistance and film morphology. Overall, this study demonstrated that the TBZ acceptor is a promising building block to create n-type organic semiconductors.

Tuning Ambipolarity of the Conjugated Polymer Channel Layers of Floating-Gate Free Transistors: From Volatile Memories to Artificial Synapses.

Three-terminal synaptic transistor has drawn significant research interests for neuromorphic computation due to its advantage of facile device integrability. Lately, bulk-heterojunction-based synaptic transistors with bipolar modulation are proposed to exempt the use of an additional floating gate. However, the actual correlation between the channel's ambipolarity, memory characteristic, and synaptic behavior for a floating-gate free transistor has not been investigated yet. Herein, by studying five diketopyrrolopyrrole-benzotriazole dual-acceptor random conjugated polymers, a clear correlation among the hole/electron ratio, the memory retention characteristic, and the synaptic behavior for the polymer channel layer in a floating-gate free transistor is described. It reveals that the polymers with balanced ambipolarity possess better charge trapping capabilities and larger memory windows; however, the high ambipolarity results in higher volatility of the memory characteristics, namely poor memory retention capability. In contrast, the polymer with a reduced ambipolarity possesses an enhanced memory retention capability despite showing a reduced memory window. It is further manifested that this enhanced charge retention capability enables the device to present artificial synaptic characteristics. The results highlight the importance of the channel's ambipolarity of floating-gate free transistors on the resultant volatile memory characteristics and synaptic behaviors.

A Route to Conjugated Monomers and Polymers Incorporating 2,5-Connected Oxazole in the Backbone.

Joining of imidazole, pyrimidine, and oxazole to other conjugated core units was explored in pursuit of yielding monomers to synthesize organic semiconducting polymers. Regioregular oxazole-flanked thiophene, benzothiadiazole, naphthalene diimide (NDI), and thienopyrroledione (TPD) were successfully isolated via stannylation of oxazole and the Stille coupling of brominated core units (overall yields ranging from ca. 40 to 60%). From subsequent direct arylation polymerization, NDI/oxazole/TPD-containing regioisomeric polymers were obtained with optical and electrochemical orbital energetics in the semiconducting regime.

Energy-Level Manipulation in Novel Indacenodithiophene-Based Donor-Acceptor Polymers for Near-Infrared Organic Photodetectors.

Organic photodetectors (OPDs) are promising candidates for next-generation digital imaging and wearable sensors due to their low cost, tuneable optoelectrical properties combined with high-level performance, and solution-processed fabrication techniques. However, OPD detection is often limited to shorter wavelengths, whereas photodetection in the near-infrared (NIR) region is increasingly being required for wearable electronics and medical device applications. NIR sensing suffers from low responsivity and high dark currents. A common approach to enhance NIR photon detection is lowering the optical band gap via donor-acceptor (D-A) molecular engineering. Herein, we present the synthesis of two novel indacenodithiophene (IDT)-based D-A conjugated polymers, namely, PDPPy-IT and PSNT-IT via palladium-catalyzed Stille coupling reactions. These novel polymers exhibit optical band gaps of 1.81 and 1.27 eV for PDPPy-IT and PSNT-IT, respectively, with highly desirable visible and NIR light detection through energy-level manipulation. Moreover, excellent materials' solubility and thin-film processability allow easy incorporation of these polymers as an active layer into OPDs for light detection. In the case of PSNT-IT devices, a photodetection up to 1000 nm is demonstrated with a peak sensitivity centered at 875 nm, whereas PDPPy-IT devices are efficient in detecting the visible spectrum with the highest sensitivity at 660 nm. Overall, both OPDs exhibit spectral responsivities up to 0.11 A W-1 and dark currents in the nA cm-2 range. With linear dynamic ranges exceeding 140 dB and fast response times recorded below 100 µs, the use of novel IDT-based polymers in OPDs shows great potential for wearable optoelectronics.

Organic J-Aggregate Nanodots with Enhanced Light Absorption and Near-Unity Fluorescence Quantum Yield.

Development of biocompatible fluorophores with small size, bright fluorescence, and narrow spectrum translate directly into major advances in fluorescence imaging and related techniques. Here, we discover that a small donor-acceptor-donor-type organic molecule consisting of a carbazole (Cz) donor and benzothiazole (BT) acceptor (CzBTCz) assembles into quasi-crystalline J-aggregates upon a formation of ultrasmall nanoparticles. The 3.5 nm CzBTCz Jdots show a narrow absorption spectrum (fwhm = 27 nm), near-unity fluorescence quantum yield (ϕfl = 0.95), and enhanced peak molar extinction coefficient. The superior spectroscopic characteristics of the CzBTCz Jdots result in two orders of magnitude brighter photoluminescence of the Jdots compared with semiconductor quantum dots, which enables continuous single-Jdots imaging over a 1 h period. Comparison with structurally similar CzBT nanoparticles demonstrates a critical role played by the shape of CzBTCz on the formation of the Jdots. Our findings open an avenue for the development of a new class of fluorescent nanoparticles based on J-aggregates.

Millimeter-Deep Detection of Single Shortwave-Infrared-Emitting Polymer Dots through Turbid Media.

Fluorescence imaging at longer wavelengths, especially in the shortwave-infrared (SWIR: 1000-1700 nm) region, leads to a substantial decrease in light attenuation, scattering, and background autofluorescence, thereby enabling enhanced penetration into biological tissues. The limited selection of fluorescent probes is a major bottleneck in SWIR fluorescence imaging. Here, we develop SWIR-emitting nanoparticles composed of donor-acceptor-type conjugated polymers. The bright SWIR fluorescence of the polymer dots (primarily attributable to their large absorption cross-section and high fluorescence saturation intensity (as high as 113 kW·cm-2)) enables the unprecedented detection of single particles as small as 14 nm through millimeter-thick turbid media. Unlike most SWIR-emitting nanomaterials, which have an excited-state lifetime in the range of microseconds to milliseconds, our polymer dots exhibit a subnanosecond excited-state lifetime. These characteristics enable us to demonstrate new time-gated single-particle imaging with a high signal-to-background ratio. These findings expand the range of potential applications of single-particle deep-tissue imaging.

Development of Block Copolymers with Poly(3-hexylthiophene) Segments as Compatibilizers in Non-Fullerene Organic Solar Cells.

Poly(3-hexylthiophene) (P3HT)-segment-based block copolymers have been reported to deliver an effective compatibilizer function in the P3HT:PC61BM bulk-heterojunction (BHJ) system to simultaneously improve performance and stability. However, as limited by the deficient optophysic properties of the P3HT:PC61BM system, the resultant power conversion efficiency (PCE) of compatibilizer-mediated devices is low despite the optimized chemical structures of the P3HT-segment-based block copolymers. To better shed light on such a compatibilizer effect, the compatibilizer function of the P3HT-segment-based block copolymers is herein investigated in the emerging non-fullerene acceptor (NFA)-based BHJ systems. A P3HT analogue, poly[(4,4'-bis(2-butyloctoxycarbonyl-[2,2'-bithiophene]-5,5-diyl)-alt-(2,2'-bithiophene-5,5'-diyl))] (PDCBT), is used as the polymer donor since it shares the same backbone as P3HT to afford good compatibility with the P3HT-segment-based block copolymers and it has been proven to deliver a higher PCE than P3HT in the NFA BHJ systems. The P3HT-segment-based block copolymers (P1-P4) are manifested to offer similar compatibilizer functions for the PDCBT-based NFA BHJ systems, and the importance of their structural design is also revealed. As a result, addition of P4 delivers the largest enhancement in PCE: from 5.30 to 7.11% for the PDCBT:ITIC blend and from 6.21 to 8.04% for the PDCBT:IT-M blend. Moreover, it can also enhance the device's thermal stability, which can maintain 77% of the initial PCE after annealing at 85 °C for 120 h (for the PDCBT:ITIC blend), outperforming the pristine binary device (66% preservation). More importantly, the entire compatibilizer-mediated device exhibits an improved Voc. Such reduced potential loss can be attributed to the improved interfacial compatibility between the photoactive components, the most important function of a compatibilizer.

Donor-Acceptor Effect of Carbazole-Based Conjugated Polymer Electrets on Photoresponsive Flash Organic Field-Effect Transistor Memories.

The molecular structure of polymer electrets is crucial for creating diverse functionalities of organic field-effect transistor (OFET) devices. Herein, a conceptual framework has been applied in this study to design the highly photoresponsive carbazole-based copolymer electret materials for the application of photoresponsive OFET memory. As an electret layer, two 1,8-carbazole-based copolymers were utilized; the copoly(CT) consisted of carbazole as the donor group and thiophene as the π-spacer, whereas the copoly(CBT) was further introduced as an acceptor moiety, benzothiadiazole, for comparison. Both copolymers exhibited efficient visible-light absorption and photoluminescence quenching in the film state, indicating the formation of a considerable number of nonemissive excitons, one of the crucial factors for achieving photoinduced recovery behavior in OFET memories. Compared to copoly(CT) with the pure donor system, faster and more effective photoinduced recovery behavior was discovered in the copoly(CBT) with the conjugated donor-acceptor structure because of the coexistence of the conjugated donor and acceptor groups. Thus, the dissociation of the generated excitons facilitated the stimulating of the unique ambipolar trapping property, resulting in the high-density data storage devices with multilevel current states. In addition, the nonvolatile and durable characteristics demonstrated the feasibility in application of memory and photorecorders.

Impact of Incorporating Nitrogen Atoms in Naphthalenediimide-Based Polymer Acceptors on the Charge Generation, Device Performance, and Stability of All-Polymer Solar Cells.

Substitution of C atoms in a polymer backbone by N atoms allows for the facile tuning of the energy levels as well as the backbone conformation and packing structures of conjugated polymers. Herein, we report a series of three polymer acceptors (PAs) with N atoms introduced at different positions of the backbone and investigate how these N atoms affect the device performances of all-polymer solar cells (all-PSCs). The three PAs, namely, P(NDI2DT-BTT), P(NDI2DT-PTT), and P(NDI2DT-BTTz), are composed of naphthalenediimide (NDI)-based and benzothiadiazole (BT)-based derivatives (dithiophene-BT (BTT), dithiophene-thiadiazolepyridine (PTT), and dithiazole-BT (BTTz)). The PTT and BTTz units are synthesized by replacing the C atoms in BT and thiophene, respectively, with N atoms, which effectively tune the optical, electrochemical, and charge-transporting properties of the corresponding PAs. The all-PSCs using poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl))benzo[1,2-b:4,5-b']dithiophene)-co-(1,3-di(5-thiophene-2-yl)-5,7-bis(2-ethylhexyl)benzo[1,2-c:4,5-c']dithiophene-4,8-dione)] (PBDB-T) as a polymer donor and P(NDI2DT-PTT) as PA exhibit a significantly enhanced power conversion efficiency (PCE) of 6.95%, whereas the all-PSCs based on the other PAs show relatively lower PCEs (6.02% for PBDB-T:P(NDI2DT-BTT) and 1.43% for PBDB-T:P(NDI2DT-BTTz)). The high PCE of the PBDB-T:P(NDI2DT-PTT) device is due to the superior charge transfer and charge dissociation, resulting from the closely matched energy levels between PBDB-T and P(NDI2DT-PTT), as well as a more favorable bulk heterojunction morphology with improved miscibility. Importantly, the P(NDI2DT-PTT)-based all-PSC device shows improved air stability compared to the P(NDI2DT-BTT)-based device, which is most likely due to a decreased lowest unoccupied molecular orbital level of the PA. Our findings suggest that the incorporation of N atoms into the PAs is an effective strategy for improving the efficiency and stability of all-PSCs.

Significant Difference in Semiconducting Properties of Isomeric All-Acceptor Polymers Synthesized via Direct Arylation Polycondensation.

The direct arylation polycondensation (DArP) appeared as an efficient method for producing semiconducting polymers but often requires acceptor monomers with orienting or activating groups for the reactive carbon-hydrogen (C-H) bonds, which limits the choice of acceptor units. In this study, we describe a DArP for producing high-molecular-weight all-acceptor polymers composed of the acceptor monomers without any orienting or activating groups via a modified method using Pd/Cu co-catalysts. We thus obtained two isomeric all-acceptor polymers, P1 and P2, which have the same backbone and side-chains but different positions of the nitrogen atoms in the thiazole units. This subtle change significantly influences their optoelectronic, molecular packing, and charge-transport properties. P2 with a greater backbone torsion has favorable edge-on orientations and a high electron mobility µe of 2.55 cm2 V-1 s-1 . Moreover, P2-based transistors show an excellent shelf-storage stability in air even after the storage for 1 month.

Dual Imide-Functionalized Unit-Based Regioregular D-A1-D-A2 Polymers for Efficient Unipolar n-Channel Organic Transistors and All-Polymer Solar Cells.

The demand for the development of more promising n-type semiconducting polymers with excellent electron mobilities and air stabilities is growing fast. In this study, we designed and synthesized a series of new dual imide-functionalized derivative-based regioregular D-A1-D-A2 copolymers with different side chains (namely, PNT-R, R = 2-decyltetradecyl (DT), 2-octadecyldodecyl (OD), and 2-hexyldecyl (HD)). These new polymers PNT-R showed strong electron affinities with deep lowest unoccupied molecular orbital (LUMO) levels down to -4.01 eV, indicating that they are promising electron-transporting materials. To optimize the electron mobility, side-chain engineering was adopted. Thus, the effects of the side-chain length on their optoelectronic and charge-transport properties as well as the performances of all-polymer solar cells (all-PSCs) were systematically investigated. Shortening the side-chain length significantly expanded the absorption range, deepened the LUMO energy level, strengthened the molecular packing properties, and developed more crystalline microstructures in the solid state, as evidenced by the ultraviolet-visible absorption spectra, cyclic voltammetry, synchrotron two-dimensional grazing-incidence wide-angle X-ray scattering, and atomic force microscopy measurements. Consequently, the highest electron mobility of 1.05 cm2 V-1 s-1 was achieved in PNT-HD-based organic thin-film transistors (OTFTs). Also, PNT-R polymers were successfully applied as electron acceptors in all-PSCs. In good agreement with the OTFT results, the highest power conversion efficiency of 6.62% was obtained for the PNT-HD-blend film due to its excellent short-circuit current ( Jsc) value (12.07 mA cm-2), which was much higher than that of the PNT-DT- and PNT-OD-based all-PSCs (7.67 and 10.19 mA cm-2, respectively). By further investigating the dependence of the Jsc and open-circuit voltage ( Voc) on the illuminated light intensity ( P), the high Jsc value of the PNT-HD-based device was found to originate from its highly suppressed mono- and bimolecular recombination as well as efficient exciton dissociation and charge transfer at the donor-acceptor interfaces. Overall, this study provides insights into the naphthalenediimide-based regioregular D-A1-D-A2 copolymers used in all-PSCs and offers important design guidelines for future development of n-type semiconducting polymers.

Poly(dithiazolfluorene- alt-selenadiazolobenzotriazole)-Based Blue-Light Photodetector and Its Application in Visible-Light Communication.

Conjugated polymers have attracted broad interest from synthetic chemists and device developers in optoelectronic fields. In this study, we report a blue-light organic photodetector (OPD) based on our low-band and ambipolar PSeN polymer. Besides high stability, the device has excellent color-selective property in the visible-light region. At the bias of -3 V, the ratio of the external quantum efficiency (EQE) in blue to red is more than 10:1. Meanwhile, the device also shows very low dark current density of ∼21 nA/cm2 and high EQE more than 100% for blue light at the bias of -3 V. Then, the mechanism of the high EQE in single-sensitive layer structure devices is analyzed by considering the activation energy of traps and carrier injection. Furthermore, for portable purposes, a flexible blue-light OPD is designed. This OPD shows a great orthogonal light response to blue and orange contents in a white light source and will be a potential candidate in a two-channel visible-light communication system.

Significant Improvement of Unipolar n-Type Transistor Performances by Manipulating the Coplanar Backbone Conformation of Electron-Deficient Polymers via Hydrogen Bonding.

The development of high-performance unipolar n-type semiconducting polymers still remains a significant challenge. Only a few examples exhibit a unipolar electron mobility over 5 cm2 V-1 s-1. In this study, a series of new poly(benzothiadiazole-naphthalenediimide) derivatives with a high unipolar electron mobility (µe) up to 7.16 cm2 V-1 s-1 in thin-film transistors are reported. The dramatically increased µe is achieved by finely optimizing the coplanar backbone conformation through the introduction of vinylene bridges, which can form intramolecular hydrogen bonds with the neighboring fluorine and oxygen atoms. The hydrogen-bonding functionalities are fused to the backbone to ensure a much more planar conformation of the conjugated π-system, as demonstrated by the density functional theory (DFT)-based calculations. The theoretical prediction is in good agreement with the experimental results. As the coplanarity is promoted by the hydrogen bonding, the thin-film crystallinity and molecular packing strength are also improved, which is evidenced by the synchrotron two-dimensional grazing-incidence wide-angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM) measurements. Notably, the GIWAXS measurements reveal an extremely short π-π stacking distance of 3.40 Å. Overall, this study marks a significant advance in the unipolar n-type semiconducting polymers and offers a general approach for further increasing the electron mobility of semiconducting polymers in organic electronics.