Efficient Ternary Organic Solar Cells with Suppressed Nonradiative Recombination and Fine-Tuned Morphology via IT-4F as Guest Acceptor.

The large open circuit voltage (VOC) loss is currently one of the main obstacles to achieving efficient organic solar cells (OSCs). In this study, the ternary OSCs comprising PM6:BTP-eC9:IT-4F demonstrate a superior efficiency of 18.2 %. Notably, the utilization of the medium bandgap acceptor IT-4F as the third component results in an exceptionally low nonradiative recombination energy loss of 0.28 V. The desirable energy level cascade is formed among PM6, BTP-eC9, and IT-4F due to the low-lying HOMO and LUMO energy levels of IT-4F. More importantly, the VOC of PM6:BTP-eC9:IT-4F OSCs can reach as high as 0.86 V, which is higher than both binary OSCs without sacrificing JSC and FF. Besides, this strategy proved that IT-4F can not only broaden the absorption range but also work as a morphology modifier in PM6:BTP-eC9:IT-4F OSCs, and there also exists efficient energy transfer between BTP-eC9 and IT-4F. This result provides a promising way to suppress the nonradiative recombination energy loss and realize higher VOC than the two binary OSCs in ternary OSCs to obtain high power conversion efficiencies.

Reducing Interfacial Losses in Solution-Processed Integrated Perovskite-Organic Solar Cells.

Low bandgap organic semiconductors have been widely employed to broaden the light response range to utilize much more photons in the inverted perovskite solar cells (PSCs). However, the serious charge recombination at the heterointerface contact between perovskite and organic semiconductors usually leads to large energy loss and limits the device performance. In this work, a titanium chelate, bis(2,4-pentanedionato) titanium(IV) oxide (C10H14O5Ti), was directly used as an interlayer between the perovskite layer and organic bulk heterojunction layer for the first time. Impressively, it was found that C10H14O5Ti can not only increase the surface potential of perovskite films but also show a positive passivation effect toward the perovskite film surface. Drawing from the above function, a smoother perovskite active layer with a higher work function was realized upon the use of C10H14O5Ti. As a result, the C10H14O5Ti-modified integrated devices show lower interfacial loss and obtain the best power conversion efficiency (PCE) of up to 20.91% with a high voltage of 1.15 V. The research offers a promising strategy to minimize the interfacial loss for the preparation of high-performance perovskite solar cells.

Achieved 18.9% Efficiency by Fine-Tuning Non-Fullerene Acceptor Content to Simultaneously Increase the Short-Circuit Current and Fill Factor of Organic Solar Cells.

In this study, using PM6:L8-BO as the main system and non-fullerene acceptor IDIC as the third component, a series of ternary organic solar cells (TOSCs) are fabricated. The results reveal that IDIC plays a significant role in enhancing the performance of TOSCs by optimizing the morphology of blended films and forming interpenetrating nanostructure. The improved film morphology facilitates exciton dissociation and collection in TOSCs, which causes an increase in the short-circuit current density (JSC ) and fill factor (FF). Further, by optimizing the IDIC content, the power conversion efficiency (PCE) of TOSCs reaches 18.9%. Besides, the prepared TOSCs exhibit a JSC of 27.51 mA cm-2 and FF of 76.64%, which are much higher than those of PM6:L8-BO-based organic solar cells (OSCs). Furthermore, the addition of IDIC improves the long-term stability of the OSCs. Meanwhile, TOSCs with a large effective area of 1.00 cm2 have been prepared, which exhibit a PCE of 12.4%. These findings suggest that modifying the amount of the third component can be a useful strategy to construct hight-efficiency TOSCs with practical application potential.

Target Therapy for Buried Interface Enables Stable Perovskite Solar Cells with 25.05% Efficiency.

The buried interface in perovskite solar cells (PSCs) is pivotal for achieving high efficiency and stability. However, it is challenging to study and optimize the buried interface due to its non-exposed feature. Here, a facile and effective strategy is developed to modify the SnO2 /perovskite buried interface by passivating the buried defects in perovskite and modulating carrier dynamics via incorporating formamidine oxalate (FOA) in SnO2 nanoparticles. Both formamidinium and oxalate ions show a longitudinal gradient distribution in the SnO2 layer, mainly accumulating at the SnO2 /perovskite buried interface, which enables high-quality upper perovskite films, minimized defects, superior interface contacts, and matched energy levels between perovskite and SnO2 . Significantly, FOA can simultaneously reduce the oxygen vacancies and tin interstitial defects on the SnO2 surface and the FA+ /Pb2+ associated defects at the perovskite buried interface. Consequently, the FOA treatment significantly improves the efficiency of the PSCs from 22.40% to 25.05% and their storage- and photo-stability. This method provides an effective target therapy of buried interface in PSCs to achieve very high efficiency and stability.

Solid Additive Enables Organic Solar Cells with Efficiency up to 18.6.

Additive strategies play a critical role in improving the performance of organic solar cells (OSCs). There are only a few reports on the application of solid additives for OSCs, which leaves a large space for further improvement of solid additives and further study on the relationship between material structure and property. PM6:BTP-eC9-based organic solar cells (OSCs) were prepared by using a small molecule BTA3 as a solid additive, and a high energy conversion efficiency of 18.65% is achieved. BTA3 has good compatibility with the acceptor component (BTP-eC9) and optimizes the morphology of the thin films. Moreover, the introduction of a small amount of BTA3 (5 wt %) effectively promotes exciton dissociation and charge transfer and suppresses charge recombination, and the relationship between the BTA3 content and the device parameter is deeply revealed. The use of BTA3 in the active layers is an attractive and effective strategy for high-performance OSCs.

Efficient and stable organic solar cells enabled by multicomponent photoactive layer based on one-pot polymerization.

Degradation of the kinetically trapped bulk heterojunction film morphology in organic solar cells (OSCs) remains a grand challenge for their practical application. Herein, we demonstrate highly thermally stable OSCs using multicomponent photoactive layer synthesized via a facile one-pot polymerization, which show the advantages of low synthetic cost and simplified device fabrication. The OSCs based on multicomponent photoactive layer deliver a high power conversion efficiency of 11.8% and exhibit excellent device stability for over 1000 h (>80% of their initial efficiency retention), realizing a balance between device efficiency and operational lifetime for OSCs. In-depth opto-electrical and morphological properties characterizations revealed that the dominant PM6-b-L15 block polymers with backbone entanglement and the small fraction of PM6 and L15 polymers synergistically contribute to the frozen fine-tuned film morphology and maintain well-balanced charge transport under long-time operation. These findings pave the way towards the development of low-cost and long-term stable OSCs.

Terminal Cyano-Functionalized Fused Bithiophene Imide Dimer-Based n-Type Small Molecular Semiconductors: Synthesis, Structure-Property Correlations, and Thermoelectric Performances.

n-Doped small molecular organic thermoelectric materials (OTMs) hold advantages of high Seebeck coefficient and better performance reproducibility over their polymeric analogues; however, high-performance n-type small molecular OTMs are severely lacking. We report here a class of small molecular OTMs based on terminal cyanation of a bithiophene imide-based ladder-type heteroarene BTI2. It was found that the cyanation could effectively lower the lowest unoccupied molecular orbital (LUMO) level from -2.90 eV (BTI2) to -4.14 eV (BTI2-4CN) and thus lead to significantly improved n-doping efficiency. Additionally, terminal cyano-functionalization can maintain the close packing and efficient intermolecular charge transfer between these cyanated molecules, thus yielding high electron mobilities of up to 0.40 cm2 V-1 s-1. Benefiting from its low LUMO-enabled efficient n-doping and high electron mobility, an encouraging n-type electrical conductivity of 0.43 S cm-1 and power factor (PF) of 6.34 µW m-1 K-2 were achieved for tetracyanated BTI2-4CN, significantly outperforming those of its noncynated BTI2 (<10-7 S cm-1, PF undetectable) and dicyanated BTI2-2CN (0.24 S cm-1, 1.78 µW m-1 K-2). These results suggest the great potential of the terminal cyanation strategy of ladder-type heteroarenes for developing high-performance small molecular OTMs.

Thermally Crosslinked Hole Conductor Enables Stable Inverted Perovskite Solar Cells with 23.9% Efficiency.

Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) represents the state-of-the-art hole transport material (HTM) in inverted perovskite solar cells (PSCs). However, unsatisfied surface properties of PTAA and high energy disorder in the bulk film hinder the further enhancement of device performance. Herein, a simple small molecule 10-(4-(3,6-dimethoxy-9H-carbazol-9-yl)phenyl)-3,7-bis(4-vinylphenyl)-10H-phenoxazine (MCz-VPOZ) is strategically developed for in situ fabrication of polymer hole conductor (CL-MCz) via a facile and low-temperature cross-linking technology. The resulting polymer CL-MCz offers high energy ordering and improved electrical conductivity, as well as appropriate energy-level alignment, enabling efficient charge carrier collection in the devices. Meanwhile, CL-MCz synchronously provides satisfied surface wettability and interfacial functionalization, facilitating the formation of high-quality perovskite films with fewer bulk iodine vacancies and suppressed carrier recombination. Significantly, the device with CL-MCz yields a champion efficiency of 23.9% along with an extremely low energy loss down to 0.41 eV, which represents the highest reported efficiency for non-PTAA-based polymer HTMs in inverted PSCs. Furthermore, the corresponding unencapsulated devices exhibit competitive shelf-life stability under various operational stressors up to 2500 h, reflecting high promises of CL-MCz in the scalable PSC application. This work underscores the promising potential of the cross-linking approach in preparing low-cost, stable, and efficient polymer HTMs toward reliable PSCs.

Green-Solvent-Processable Low-Cost Fluorinated Hole Contacts with Optimized Buried Interface for Highly Efficient Perovskite Solar Cells.

Solution-processed hole contact materials, as an indispensable component in perovskite solar cells (PSCs), have been widely studied with consistent progress achieved. One bottleneck for the commercialization of PSCs is the lack of hole contact materials with high performance, cost-effective preparation, and green-solvent processability. Therefore, the development of versatile hole contact materials is of great significance. Herein, we report two novel donor-acceptor (D-A)-type hole contact molecules (FMPA-BT-CA and 2FMPA-BT-CA) with low cost and alcohol-based processability by utilizing a fluorination strategy. We showed that the fluorine atoms lead to the lowered highest occupied molecular orbital (HOMO) energy levels and larger dipole moments for FMPA-BT-CA and 2FMPA-BT-CA. Moreover, fluorination also improves the buried interfacial interaction between hole contacts and perovskite. As a result, a remarkable power conversion efficiency (PCE) of 22.37% along with good light stability could be achieved for green-solvent-processed FMPA-BT-CA-based inverted PSC devices, demonstrating the great potential of environmentally compatible hole contacts for highly efficient PSCs.

Interfacial Passivation Engineering for Highly Efficient Perovskite Solar Cells with a Fill Factor over 83.

Charge carrier nonradiative recombination (NRR) caused by interface defects and nonoptimal energy level alignment is the primary factor restricting the performance improvement of perovskite solar cells (PSCs). Interfacial modification is a vital strategy to restrain NRR and enable high-performance PSCs. We report here two interfacial materials, PhI-TPA and BTZI-TPA, consisting of phthalimide and a 2,1,3-benzothiadiazole-5,6-dicarboxylicimide core, respectively. The difunctionalized BTZI-TPA with imide and thiadiazole shows higher hole mobility, better aligned energy levels, and stronger interaction with uncoordinated Pb2+ on the perovskite surface, suppressing NRR and carrier accumulation at the interface of perovskite/spiro-OMeTAD and yielding enhanced open-circuit voltage and fill factor. Consequently, the PSC based on BTZI-TPA delivers a high efficiency of 24.06% with an excellent fill factor of 83.10%, superior to that (21.47%) of the reference cell without an interfacial layer, and 21.45% efficiency for the device with a scaled-up area (1.00 cm2). These results underscore the potential of imide and thiadiazole groups in developing interfacial layers with strong passivation capability, effective charge transport property, and fine-tuned energetics for stable and efficient PSCs.

Intramolecular Noncovalent Interaction-Enabled Dopant-Free Hole-Transporting Materials for High-Performance Inverted Perovskite Solar Cells.

Intramolecular noncovalent interactions (INIs) have served as a powerful strategy for accessing organic semiconductors with enhanced charge transport properties. Herein, we apply the INI strategy for developing dopant-free hole-transporting materials (HTMs) by constructing two small-molecular HTMs featuring an INI-integrated backbone for high-performance perovskite solar cells (PVSCs). Upon incorporating noncovalent S⋅⋅⋅O interaction into their simple-structured backbones, the resulting HTMs, BTORA and BTORCNA, showed self-planarized backbones, tuned energy levels, enhanced thermal properties, appropriate film morphology, and effective defect passivation. More importantly, the high film crystallinity enables the materials with substantial hole mobilities, thus rendering them as promising dopant-free HTMs. Consequently, the BTORCNA-based inverted PVSCs delivered a power conversion efficiency of 21.10 % with encouraging long-term device stability, outperforming the devices based on BTRA without S⋅⋅⋅O interaction (18.40 %). This work offers a practical approach to designing charge transporting layers with high intrinsic mobilities for high-performance PVSCs.

Transition metal-catalysed molecular n-doping of organic semiconductors.

Chemical doping is a key process for investigating charge transport in organic semiconductors and improving certain (opto)electronic devices1-9. N(electron)-doping is fundamentally more challenging than p(hole)-doping and typically achieves a very low doping efficiency (η) of less than 10%1,10. An efficient molecular n-dopant should simultaneously exhibit a high reducing power and air stability for broad applicability1,5,6,9,11, which is very challenging. Here we show a general concept of catalysed n-doping of organic semiconductors using air-stable precursor-type molecular dopants. Incorporation of a transition metal (for example, Pt, Au, Pd) as vapour-deposited nanoparticles or solution-processable organometallic complexes (for example, Pd2(dba)3) catalyses the reaction, as assessed by experimental and theoretical evidence, enabling greatly increased η in a much shorter doping time and high electrical conductivities (above 100 S cm-1; ref. 12). This methodology has technological implications for realizing improved semiconductor devices and offers a broad exploration space of ternary systems comprising catalysts, molecular dopants and semiconductors, thus opening new opportunities in n-doping research and applications12, 13.

A Dual-Functional Conjugated Polymer as an Efficient Hole-Transporting Layer for High-Performance Inverted Perovskite Solar Cells.

Conductive polyelectrolytes such as P3CT-Na have been widely used as efficient hole-transporting layers (HTLs) in inverted perovskite solar cells (PSCs) due to their high hole mobility. However, the acid-base neutralization reaction is indispensable for preparing such polyelectrolytes and the varied content of cations usually leads to poor reproducibility of the device performance in PSCs. In this work, a commercially available polymer poly[3-(4-carboxybutyl)thiophene-2,5-diyl] (P3CT) was directly applied as an HTL in PSCs for the first time. Encouragingly, it was found that due to the dual functionality of carboxyl groups on side chains, a thin layer of P3CT can not only strongly anchor on ITO electrode and optimize its work function but also show an effective passivation effect toward perovskite active layer. Benefiting from such dual functionality, a uniform perovskite film with better quality was obtained on P3CT. As a result, the P3CT-based PSCs show much lower nonradiative recombination and achieve a champion power conversion efficiency (PCE) of 21.33% with a high fill factor (FF) of 83.6%. Impressively, as the device area is increased to 0.80 cm2, a PCE of 19.65% can still be obtained for the PSCs based on P3CT HTL. Our work provides important strategy for developing HTLs for high-performance PSCs.

A Narrow-Bandgap n-Type Polymer with an Acceptor-Acceptor Backbone Enabling Efficient All-Polymer Solar Cells.

Narrow-bandgap polymer semiconductors are essential for advancing the development of organic solar cells. Here, a new narrow-bandgap polymer acceptor L14, featuring an acceptor-acceptor (A-A) type backbone, is synthesized by copolymerizing a dibrominated fused-ring electron acceptor (FREA) with distannylated bithiophene imide. Combining the advantages of both the FREA and the A-A polymer, L14 not only shows a narrow bandgap and high absorption coefficient, but also low-lying frontier molecular orbital (FMO) levels. Such FMO levels yield improved electron transfer character, but unexpectedly, without sacrificing open-circuit voltage (Voc ), which is attributed to a small nonradiative recombination loss (Eloss,nr ) of 0.22 eV. Benefiting from the improved photocurrent along with the high fill factor and Voc , an excellent efficiency of 14.3% is achieved, which is among the highest values for all-polymer solar cells (all-PSCs). The results demonstrate the superiority of narrow-bandgap A-A type polymers for improving all-PSC performance and pave a way toward developing high-performance polymer acceptors for all-PSCs.

Teaching an Old Anchoring Group New Tricks: Enabling Low-Cost, Eco-Friendly Hole-Transporting Materials for Efficient and Stable Perovskite Solar Cells.

As a key component in perovskite solar cells (PVSCs), hole-transporting materials (HTMs) have been extensively explored and studied. Aiming to meet the requirements for future commercialization of PVSCs, HTMs which can enable excellent device performance with low cost and eco-friendly processability are urgently needed but rarely reported. In this work, a traditional anchoring group (2-cyanoacrylic acid) widely used in molecules for dye-sensitized solar cells is incorporated into donor-acceptor-type HTMs to afford MPA-BT-CA, which enables effective regulation of the frontier molecular orbital energy levels, interfacial modification of an ITO electrode, efficient defect passivation toward the perovskite layer, and more importantly alcohol solubility. Consequently, inverted PVSCs with this low-cost HTM exhibit excellent device performance with a remarkable power conversion efficiency (PCE) of 21.24% and good long-term stability in ambient conditions. More encouragingly, when processing MPA-BT-CA films with the green solvent ethanol, the corresponding PVSCs also deliver a substantial PCE as high as 20.52% with negligible hysteresis. Such molecular design of anchoring group-based materials represents great progress for developing efficient HTMs which combine the advantages of low cost, eco-friendly processability, and high performance. We believe that such design strategy will pave a new path for the exploration of highly efficient HTMs applicable to commercialization of PVSCs.

Ultranarrow Bandgap Naphthalenediimide-Dialkylbifuran-Based Copolymers with High-Performance Organic Thin-Film Transistors and All-Polymer Solar Cells.

A new polymer acceptor poly{(N,N'-bis(2-ethylhexyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl)-alt-5,5-(3,3'-didodecyl-2,2'-bifuran)} (NDI-BFR) made from naphthalenediimide (NDI) and furan-derived head-to-head-linked 3,3'-dialkyl-2,2'-bifuran (BFR) units is reported in this study. Compared to the benchmark polymer poly(naphthalenediimide-alt-bithiophene) (N2200), NDI-BFR exhibits a larger bathochromic shift of absorption maxima (842 nm) with a much higher absorption coefficient (7.2 × 104 m-1 cm-1 ), leading to an ultranarrow optical bandgap of 1.26 eV. Such properties ensure good harvesting of solar light from visible to the near-infrared region in solar cells. Density functional theory calculation reveals that the polymer acceptor NDI-BFR possesses a higher degree of backbone planarity versus the polymer N2200. The polymer NDI-BFR exhibits a decent electron mobility of 0.45 cm2 V-1 s-1 in organic thin-film transistors (OTFTs), and NDI-BFR-based all-polymer solar cells (all-PSCs) achieve a power conversion efficiency (PCE) of 4.39% with a very small energy loss of 0.45 eV by using the environmentally friendly solvent 1,2,4-trimethylbenzene. These results demonstrate that incorporating head-to-head-linked BFR units in the polymer backbone can lead to increased planarity of the polymer backbone, reduced optical bandgap, and improved light absorbing. The study offers useful guidelines for constructing n-type polymers with narrow optical bandgaps.

A New Wide Bandgap Donor Polymer for Efficient Nonfullerene Organic Solar Cells with a Large Open-Circuit Voltage.

Significant progress has been made in nonfullerene small molecule acceptors (NF-SMAs) that leads to a consistent increase of power conversion efficiency (PCE) of nonfullerene organic solar cells (NF-OSCs). To achieve better compatibility with high-performance NF-SMAs, the direction of molecular design for donor polymers is toward wide bandgap (WBG), tailored properties, and preferentially ecofriendly processability for device fabrication. Here, a weak acceptor unit, methyl 2,5-dibromo-4-fluorothiophene-3-carboxylate (FE-T), is synthesized and copolymerized with benzo[1,2-b:4,5-b']dithiophene (BDT) to afford a series of nonhalogenated solvent processable WBG polymers P1-P3 with a distinct side chain on FE-T. The incorporation of FE-T leads to polymers with a deep highest occupied molecular orbital (HOMO) level of -5.60-5.70 eV, a complementary absorption to NF-SMAs, and a planar molecular conformation. When combined with the narrow bandgap acceptor ITIC-Th, the solar cell based on P1 with the shortest methyl chain on FE-T achieves a PCE of 11.39% with a large V oc of 1.01 V and a J sc of 17.89 mA cm-2. Moreover, a PCE of 12.11% is attained for ternary cells based on WBG P1, narrow bandgap PTB7-Th, and acceptor IEICO-4F. These results demonstrate that the new FE-T is a highly promising acceptor unit to construct WBG polymers for efficient NF-OSCs.

A Narrow-Bandgap n-Type Polymer Semiconductor Enabling Efficient All-Polymer Solar Cells.

Currently, n-type acceptors in high-performance all-polymer solar cells (all-PSCs) are dominated by imide-functionalized polymers, which typically show medium bandgap. Herein, a novel narrow-bandgap polymer, poly(5,6-dicyano-2,1,3-benzothiadiazole-alt-indacenodithiophene) (DCNBT-IDT), based on dicyanobenzothiadiazole without an imide group is reported. The strong electron-withdrawing cyano functionality enables DCNBT-IDT with n-type character and, more importantly, alleviates the steric hindrance associated with typical imide groups. Compared to the benchmark poly(naphthalene diimide-alt-bithiophene) (N2200), DCNBT-IDT shows a narrower bandgap (1.43 eV) with a much higher absorption coefficient (6.15 × 104 cm-1 ). Such properties are elusive for polymer acceptors to date, eradicating the drawbacks inherited in N2200 and other high-performance polymer acceptors. When blended with a wide-bandgap polymer donor, the DCNBT-IDT-based all-PSCs achieve a remarkable power conversion efficiency of 8.32% with a small energy loss of 0.53 eV and a photoresponse of up to 870 nm. Such efficiency greatly outperforms those of N2200 (6.13%) and the naphthalene diimide (NDI)-based analog NDI-IDT (2.19%). This work breaks the long-standing bottlenecks limiting materials innovation of n-type polymers, which paves a new avenue for developing polymer acceptors with improved optoelectronic properties and heralds a brighter future of all-PSCs.

Boosting Efficiency and Stability of Organic Solar Cells Using Ultralow-Cost BiOCl Nanoplates as Hole Transporting Layers.

A novel nanomaterial, bismuth oxychloride nanoplates (BiOCl NPs), was first applied in organic solar cells (OSCs) as hole transporting layers (HTLs). It is worth noting that the BiOCl NPs can be facilely synthesized at ∼1/200 of the cost of the commercial PEDOT:PSS and well dissolved in green solvents. Different from the PEDOT:PSS interlayer, the deposition of BiOCl HTL is free of post-treatment at elevated temperature, which reduces device fabrication complexity. To demonstrate the universality of BiOCl in improving photovoltaic performance, OSCs containing various representative active layers were investigated. The power conversion efficiencies (PCEs) of the P3HT:PC61BM, PTB7-Th:PC71BM, and PM6:Y6-based OSCs with the BiOCl HTL boosted from 3.62, 8.78, and 15.63 to 4.24, 9.92, and 16.11%, respectively, compared to the PEDOT:PSS-based ones. It was found that the superior performances of the BiOCl-based OSCs are mainly attributed to the sufficient oxygen vacancies and improved interfacial contact. Moreover, the BiOCl-based OSCs show a much better stability than the cells with the PEDOT:PSS interfacial layer.

Backbone Coplanarity Tuning of 1,4-Di(3-alkoxy-2-thienyl)-2,5-difluorophenylene-Based Wide Bandgap Polymers for Efficient Organic Solar Cells Processed from Nonhalogenated Solvent.

Halogenated solvents are prevailingly used in the fabrication of nonfullerene organic solar cells (NF-OSCs) at the current stage, imposing significant restraints on their practical applications. By copolymerizing phthalimide or thieno[3,4-c]pyrrole-4,6-dione (TPD) with 1,4-di(3-alkoxy-2-thienyl)-2,5-difluorophenylene (DOTFP), which features intramolecular noncovalent interactions, the backbone planarity of the resulting DOTFP-based polymers can be effectively tuned, yielding distinct solubilities, aggregation characters, and chain packing properties. Polymer DOTFP-PhI with a more twisted backbone showed a lower degree of aggregation in solution but an increased film crystallinity than polymer DOTFP-TPD. An organic thin-film transistor and NF-OSC based on DOTFP-PhI, processed with a nonhalogenated solvent, exhibited a high hole mobility up to 1.20 cm2 V-1 s-1 and a promising power conversion efficiency up to 10.65%, respectively. The results demonstrate that DOTFP is a promising building block for constructing wide bandgap polymers and backbone coplanarity tuning is an effective strategy to develop high-performance organic semiconductors processable with a nonhalogenated solvent.