Crystallization‐Induced Phase Separation in Solution‐Processed Small Molecule Bulk Heterojunction Organic Solar Cells

The driving forces and processes associated with the development of phase separation upon thermal annealing are investigated in solution‐processed small molecule bulk heterojunction (BHJ) organic solar cells utilizing a diketopyrrolopyrrole‐based donor molecule and a fullerene acceptor (PCBM). In‐situ thermal annealing X‐ray scattering is used to monitor the development of thin film crystallization and phase separation and reveals that the development of blend phase separation strongly correlates with the nucleation of donor crystallites. Additionally, these morphological changes lead to dramatic increases in blend electron mobility and solar cell figures of merit. These results indicate that donor crystallization is the driving force for blend phase separation. It is hypothesized that donor crystallization from an as‐cast homogeneous donor:acceptor blend simultaneously produces donor‐rich domains, consisting largely of donor crystallites, and acceptor‐rich domains, formed from previously mixed regions of the film that have been enriched with acceptor during donor crystallization. Control of donor crystallization in solution‐processed small molecule BHJ solar cells employing PCBM is thus emphasized as an important strategy for the engineering of the nanoscale phase separated, bicontinuous morphology necessary for the fabrication of efficient BHJ photovoltaic devices.     

Efficient Large Area All-Small-Molecule Organic Solar Cells Fabricated by Slot-Die Coating with Nonhalogen Solvent

The commercialization of organic solar cells (OSCs) requires the use of roll-to-roll coating technology. However, it is generally believed that all-small-molecule (ASM) systems cannot form high-quality films in most film-fabrication technologies except for spin coating, mainly due to their strong crystallinity and low solution viscosity. Herein, it is found that the small molecule donor and acceptor system with strong intermolecular interaction can weaken the molecular self-aggregation during film formation. As a result, all-small-molecule organic solar cells (ASM-OSCs) are successfully fabricated using the green solvent tetrahydrofuran via spin coating as well as slot-die coating technology. Under the optimal conditions, the devices achieve power conversion efficiency (PCE) of 14.05% and 13.41% prepared by spin coating and slot-die coating, respectively. Moreover, a large-area device with an area of 1 cm² achieve a PCE of 10.65% by slot-die coating. The study of the device performance and the active layer morphology reveal a unique film optimization mechanism in ASM-OSCs. In the slot-die coating process, a high-quality film is formed due to the significantly suppressed crystallinity of the small molecule donor; with further thermal annealing, the crystallization-induced phase separation enables an optimized morphology. This study proves that high-performance ASM-OSCs can be fabricated by the industrial-compatible method.     

Effect of Trace Solvent on the Morphology of P3HT:PCBM Bulk Heterojunction Solar Cells

The performance of bulk‐heterojunction (BHJ) solar cells is strongly correlated with the nanoscale structure of the active layer. Various processing techniques have been explored to improve the nanoscale morphology of the BHJ layer, e.g., by varying the casting solvent, thermal annealing, solvent annealing, and solvent additives. This paper highlights the role of residual solvent in the “dried” BHJ layer, and the effect of residual solvents on PCBM diffusion and ultimately the stability of the morphology. We show that solvent is retained within the BHJ film despite prolonged heat treatment, leading to extensive phase separation, as demonstrated by the growth in the size and quantity of PCBM agglomerates. The addition of a small volume fraction of nitrobenzene to the casting solution inhibits the diffusion of PCBM in the dry film, resulting in smaller PCBM agglomerates, and improves the fill factor of the BHJ device to 0.61 without further tempering. The addition of nitrobenzene also increases the P3HT crystalline content, while increasing the onset temperature for melting of P3HT side chains and backbone. The melting temperature for PCBM is also higher with the nitrobenzene additive present.     

Balancing Intermolecular Interactions between Acceptors and Donor/Acceptor for Efficient Organic Photovoltaics

Promoted by uninterrupted materials and device innovation, organic solar cells have achieved impressive development. However, the complicated intermolecular interactions inside active layers are less understood. Herein, the intermolecular interactions are studied from the dual perspectives of acceptor/acceptor (A/A) and donor/acceptor (D/A), and how these interactions synergistically control the final efficiencies. Three small molecular acceptors (SMAs) are designed with different end-caps, which manipulate the crystallinity and electrostatic potential (ESP) distributions of acceptors, and accordingly, the A/A and D/A intermolecular interactions. The results show that SMA LA17 with low A/A interactions exhibits inferior performance around 12%, owing to its strong D/A interaction with donor PM6, which shapes too miscible morphology and increases charge recombination. Instead, LA16 with strong A/A interactions and moderate D/A interactions delivers improved bulk-heterojunction (BHJ) networks, and therefore, enhances charge transport and diminishes geminate or trap-assisted charge recombination. Consequently, PM6:LA16 records the competitive efficiency of up to 13.74% among the three systems. Therefore, this study deepens the synergistic or balancing effect of the D/A and A/A interactions on BHJ blends for efficient organic solar cells.     

Synthesis and photovoltaic properties of D–A–D type small molecules containing diketopyrrolopyrrole (DPP) acceptor central unit with different donor terminal units

Two D–A–D small molecules TDPP (FP)2 and TDPP (BuP)2 coded as CSDPP2 and CSDPP4 respectively were synthesized having same diketopyrrolopyrrole (DPP) as core acceptor and difluoro-phenyl (FP) and dibutyloxy phenyl (BuP) as different end donor units with broad absorption and suitable energy levels. We have used these small molecules as donor components along with the PC₇₀BM as electron acceptor for the preparation of bulk heterojunction (BHJ) active layer in small molecule (SM) organic photovoltaics (OPV) test cells. The optimal power conversion efficiencies obtained with CSDPP2 and CSDPP4 are 2.26% and 3.23% when the BHJ active layer was cast from CF solvent. The PCE has been further enhanced up to 3.03% and 4.65% for CSDPP2 and CSDPP4 when the BHJ active layer was cast from CN/CF solvent. The enhancement in PCE has been explained in terms of change in crystallinity and nanoscale morphology and more balanced charge transport resulting from increased hole mobility.     

Isomeric Small Molecule Donor with Terminal Branching Position Directly Attached to the Backbone Enables Efficient All-Small-Molecule Organic Solar Cells with Excellent Stability

All-small-molecule organic solar cells (ASM-OSCs) are challenging for their inadequate efficiency and device stability due to their more susceptive morphology. Herein, a family of isomeric small molecule donors (SMDs) is synthesized based on the benzodithiophene–terthiophene core with linear, 1st carbon, and 2nd carbon position branched butyl-based rhodanine for ASM-OSCs, respectively. The single crystal of thiophene-substituted model T-s-Bu forms a more compact intermolecular packing with herringbone structure than slip-layered packing-based T-n-Bu and T-i-Bu . SM-i-Bu and SM-s-Bu show slightly blue-shifted absorption and deepened HOMO levels in the neat film compared to SM-n-Bu . SM-s-Bu:BO-4Cl blend films have distinct face-on packing orientations and suitable fibrous phase separation along with more apparent microcrystals. Finally, SM-s-Bu : BO-4Cl -based device yields an improved power conversion efficiency of 16.06% compared to 15.12% and 8.22% for SM-n-Bu : BO-4Cl and SM-i-Bu : BO-4Cl , which is one of the top-ranked results for BTR-series SMDs in binary ASM-OSCs. More importantly, the excellent storage stability with a T₈₀ lifetime of over 1700 h and decent thermal stability is realized in SM-s-Bu : BO-4Cl . This work highlights that the isomeric terminal alkyl with a branching point directly connected to the backbone for SMDs is a promising strategy for improving the crystal packing and film morphology and achieving highly efficient and stable ASM-OSCs.     

Deciphering the Role of Side-Chain Engineering and Solvent Vapor Annealing for Binary All-Small-Molecule Organic Solar Cells

Fibrous interpenetrating network structure morphology is extremely crucial for all-small-molecule organic solar cells (ASM-OSCs) in achieving high power conversion efficiency (PCE). Rational molecular design and suitable posttreatment to the film are feasible methods to accomplish this goal. Herein, two small molecule donors, namely T4 and T6, with different substituents on their selenophene conjugated units, alkyl for T4 while trialkylsilyl for T6, are developed. Both as cast devices obtain poor PCEs (≈4.5%) when blending these two donors with N3 due to the oversize phase separation. Satisfactorily, the PCEs are dramatically increased after CS₂ annealing, which mainly originates from the favorable reorganization of donor and acceptor in the active layer, ultimately improving the phase separation and vertical electronic properties. As a result, the device based on trialkylsilyl-substituted T6 acquires a remarkable PCE of 16.03%, much higher than that of the blends of alkyl-substituted T4 and N3 (12.61%). The enhanced PCE of the T6-based device is attributed to the deeper HOMO energy levels, more obvious fibrous interpenetrating networks, and stronger molecular interaction between T6 and N3, as compared with T4-based ones. This study indicates that precise molecular design and the proper posttreatment process can be a brilliant approach for realizing highly efficient ASM-OSCs.     

Dual-Additive-Driven Morphology Optimization for Solvent-Annealing-Free All-Small-Molecule Organic Solar Cells

All-small-molecule organic solar cells (ASM-OSCs), which consist of small-molecule donors and acceptors, have recently been studied extensively to eliminate the batch-to-batch variation from polymer-based donor or acceptor. On the other hand, the control of their active layer morphology is more challenging due to the similar chemical structure and miscibility of small-molecule donor and small-molecule accepter. Hence, this study develops a dual-additive-driven morphology optimization method for ASM-OSCs based on BTR-Cl:Y6. One solid additive – 1,4-diiodobenzene (DIB) and one liquid additive – diiodomethane (DIM) are selected, making use of their distinct interaction mechanisms with Y6 and BTR-Cl. It is found that DIB can form a eutectic phase with Y6, which can increase the intermolecular interactions and modulate the acceptor phase separation, while the simultaneous volatilization of DIM suppresses the over-aggregation of BTR-Cl during the film casting process. As a result of the synergistic morphology tuning, the optimized device delivers a power conversion efficiency (PCE) as high as 15.2%, among the highest PCE reported to date for binary ASM-OSCs without solvent annealing treatment. This work demonstrates the potential of morphology tuning via the incorporation of dual additives into ASM-OSCs, enabling them to achieve comparable efficiencies to those of conventional polymer/small-molecule based OSCs.     

Solution Processable Fluorenyl Hexa‐peri‐hexabenzocoronenes in Organic Field‐Effect Transistors and Solar Cells

The organization of organic semiconductor molecules in the active layer of organic electronic devices has important consequences to overall device performance. This is due to the fact that molecular organization directly affects charge carrier mobility of the material. Organic field‐effect transistor (OFET) performance is driven by high charge carrier mobility while bulk heterojunction (BHJ) solar cells require balanced hole and electron transport. By investigating the properties and device performance of three structural variations of the fluorenyl hexa‐peri‐hexabenzocoronene (FHBC) material, the importance of molecular organization to device performance was highlighted. It is clear from ¹H NMR and 2D wide‐angle X‐ray scattering (2D WAXS) experiments that the sterically demanding 9,9‐dioctylfluorene groups are preventing π–π intermolecular contact in the hexakis‐substituted FHBC 4 . For bis‐substituted FHBC compounds 5 and 6 , π–π intermolecular contact was observed in solution and hexagonal columnar ordering was observed in solid state. Furthermore, in atomic force microscopy (AFM) experiments, nanoscale phase separation was observed in thin films of FHBC and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC₆₁BM) blends. The differences in molecular and bulk structural features were found to correlate with OFET and BHJ solar cell performance. Poor OFET and BHJ solar cells devices were obtained for FHBC compound 4 while compounds 5 and 6 gave excellent devices. In particular, the field‐effect mobility of FHBC 6 , deposited by spin‐casting, reached 2.8 × 10^?3 cm² V^?1 s and a power conversion efficiency of 1.5% was recorded for the BHJ solar cell containing FHBC 6 and PC₆₁BM.     

As‐Cast Ternary Organic Solar Cells Based on an Asymmetric Side‐Chains Featured Acceptor with Reduced Voltage Loss and 14.0% Efficiency

A new small‐molecule nonfullerene acceptor based on the benzo[1,2‐b:4,5‐b′]dithiophene (BDT) fused central core with asymmetrical alkoxy and thienyl side chains, namely TOBDT , is designed and synthesized. The alkoxy unit helps narrow the bandgap, and thienyl side chain helps enhance the intermolecular interaction. As a result, TOBDT is suitable to match the deep‐lying highest occupied molecular orbital (HOMO) of polymer donor PM6 . Then, a strong crystalline acceptor IDIC is introduced as the third component to fabricate as‐cast nonfullerene ternary devices to achieve absorption and morphology control. Addition of IDIC not only mixes well with TOBDT but modulates the morphology of the blend film, which helps to balance the charge transport properties and reduce the photovoltage loss of ternary devices. All these contribute to synergetic improvement of J_sc, V_oc, and fill factor parameters, leading to a power conversion efficiency of 14.0% for the as‐cast fullerene‐free ternary device.     

Enhancing the Charge Transport in Solution‐Processed Perylene Di‐imide Transistors via Thermal Annealing of Metastable Disordered Films

The introduction of side chains in π‐conjugated molecules is a design strategy widely exploited to increase molecular solubility thus improving the processability, while directly influencing the self‐assembly and consequently the electrical properties of thin films. Here, a multiscale structural analysis performed by X‐ray diffraction, X‐ray reflectivity, and atomic force microscopy on thin films of dicyanoperylene molecules decorated with either linear or branched side chains is reported. The substitution with asymmetric branched alkyl chains allows obtaining, upon thermal annealing, field‐effect transistors with enhanced transport properties with respect to linear alkyl chains. Branched chains induce molecular disorder during the film growth from solution, effectively favouring 2D morphology. Post‐deposition thermal annealing leads to a structural transition towards the bulk‐phase for molecules with branched chains, still preserving the 2D morphology and allowing efficient charge transport between crystalline domains. Conversely, molecules with linear chains self‐assemble into 3D islands exhibiting the bulk‐phase structure. Upon thermal annealing, these 3D islands keep their size constant and no major changes are observed in the organic field effect transistor characteristics. These findings demonstrate that the disorder generated by the asymmetric branched chains when the molecule is physisorbed in thin film can be instrumental for enhancing charge transport via thermal annealing.     

Influence of side chain symmetry on the performance of poly(2,5-dialkoxy-p-phenylenevinylene): fullerene blend solar cells

We report on studies of poly-(2,5-dihexyloxy-p-phenylenevinylene) (PDHeOPV), a symmetric side-chain polymer, as a potential new donor material for polymer:fullerene blend solar cells. We study the surface morphology of blend films of PDHeOPV with PCBM, the transport properties of the blend films, and the performance of photovoltaic devices made from such blend films, all as a function of PCBM content. In each case, results are compared with those obtained using the asymmetric side chain polymer, poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV), in order to investigate the influence of polymer side chain symmetry on solar cell performance. AFM images show that large PCBM aggregates appear at lower PCBM content (50 wt.% PCBM) for PDHeOPV:PCBM than for MDMO-PPV:PCBM (67 wt.% PCBM) blend films. Time-of-Flight (ToF) mobility measurements show that charge mobilities depend more weakly on PCBM content in PDHeOPV:PCBM than in MDMO:PPV:PCBM, with the result that at high PCBM content the mobilities in PDHeOPV:PCBM are significantly lower than in MDMO:PPV:PCBM blend films, despite the higher mobilities in pristine PDHeOPV compared to pristine MDMO-PPV. Photovoltaic devices show significantly lower power conversion efficiency (～0.93%) for PDHeOPV:PCBM (80 wt.% PCBM) blend films than for MDMO-PPV:PCBM (2.2% at 80 wt.% PCBM) blends. This is attributed to the relatively poor transport properties of the PDHeOPV:PCBM blend, which limit the optimum thickness of the photoactive layer in PDHeOPV:PCBM blend devices. The behaviour is tentatively attributed to a higher tendency for the symmetric side-chain polymer chains to aggregate, resulting in poorer interaction with the fullerene and poorer network formation for charge transport.     

Smartly Optimizing Crystallinity,Compatibility, and Morphology for Polymer Solar Cells by Small Molecule Acceptor with Unique 2D-EDOT Side Chain

A desired morphology is essential for achieving efficient polymer solar cells. Donors and acceptors with appropriate crystallization can lead to a suitable phase-separated morphology for effective photocurrent generation process. Inspired by the success of Y6 acceptors and the 2D side chain engineering on popular polymer donors and small molecule acceptors, the usage of unique 2D 3,4-ethylene dioxythiophene (EDOT) side chains on Y6 to regulate its crystallinity, compatibility, and thus the related blend morphology is explored. In this study, two molecules of BTP-EDOT-4F and BTP-EDOT-4Cl with such unique 2D EDOT side chains are designed and synthesized. Due to the advantage of EDOT side chain, when these molecules are blended with PM6, the decent power conversion efficiencies (PCEs) of 16.78% and 15.87% are obtained. Furthermore, BTP-EDOT-4F is selected as the third component and added into PM6:L8-BO binary system to form ternary blends. The optimized crystallinity, compatibility, and morphology of such ternary blend are discovered in the presence of BTP-EDOT-4F, which enables efficient exciton dissociation and charge transport as well as decreased recombination, resulting in higher short circuit current density (J_sc) and fill factor. Finally, the outstanding PCE of 18.56% is achieved in ternary blends containing PM6, L8-BO, and BTP-EDOT-4F.     

Unconjugated Side‐Chain Engineering Enables Small Molecular Acceptors for Highly Efficient Non‐Fullerene Organic Solar Cells: Insights into the Fine‐Tuning of Acceptor Properties and Micromorphology

2D conjugated side‐chain engineering is an effective strategy that is widely utilized to construct benzodithiophene‐based polymers. Herein, an unconjugated side‐chain strategy to design fused‐benzodithiophene‐based non‐fullerene small molecule acceptors (SMAs) via vertical aromatic side‐chain engineering on the ladder‐type core is employed. Three SMAs named BTTIC‐Th, BTTIC‐TT, and BTTIC‐Ph with thiophene, thieno[3,2‐b]thiophene, and benzene, respectively, as side chains, are designed and synthesized. Three SMAs exhibit similar absorption ranges but different lowest unoccupied molecular orbital (LUMO) energy levels due to the different strength of the δ‐inductive effect between vertical aromatic side chains and their electron‐rich core. Organic solar cells based on PBDB‐T:BTTIC‐TT achieve a power conversion efficiency (PCE) of 13.44%, which is higher than the PCE of devices based on PBDB‐T:BTTIC‐Th (12.91%) and PBDB‐T:BTTIC‐Ph (9.14%). The difference in device performance is investigated by electrical and morphological characterizations. A large domain size and different types of π–π stacking are found in the bulk heterojunction layer of PBDB‐T:BTTIC‐Ph blend film, which are detrimental to exciton dissociation and charge transport. Overall, it is demonstrated that when designing unconjugated side chains, thieno[3,2‐b]thiophene is superior to thiophene and benzene through its dual roles of promoting the LUMO energy level and optimizing the morphology. These results shed light on the side‐chain engineering of high‐performance non‐fullerene SMAs.     

Charge Transportation and Chirality in Liquid Crystalline Helical Network Phases of Achiral BTBT-Derived Polycatenar Molecules

First examples of multichain (polycatenar) compounds, based on the π-conjugated [1]benzothieno[3,2-b]benzothiophene unit are designed, synthesized, and their soft self-assembly and charge carrier mobility are investigated. These compounds, terminated by the new fan-shaped 2-brominated 3,4,5-trialkoxybenzoate moiety, form bicontinuous cubic liquid crystalline (LC) phases with helical network structure over extremely wide temperature ranges (>200 K), including ambient temperature. Compounds with short chains show an achiral cubic phase with the double network, which upon increasing the chain length, is at first replaced by a tetragonal 3D phase and then by a mirror symmetry is broken triple network cubic phase. In the networks, the capability of bypassing defects provides enhanced charge carrier mobility compared to imperfectly aligned columnar phases, and the charge transportation is non-dispersive, as only rarely observed for LC materials. At the transition to a semicrystalline helical network phase, the conductivity is further enhanced by almost one order of magnitude. In addition, a mirror symmetry broken isotropic liquid phase is formed beside the 3D phases, which upon chain elongation is removed and replaced by a hexagonal columnar LC phase.     

Side‐Chain Engineering on Dopant‐Free Hole‐Transporting Polymers toward Highly Efficient Perovskite Solar Cells (20.19%)

A variety of dopant‐free hole‐transporting materials (HTMs) is developed to serve as alternatives to the typical dopant‐treated ones; however, their photovoltaic performance still falls far behind. In this work, the side chain of a polymeric HTM is engineered by partially introducing diethylene glycol (DEG) groups in order to simultaneously optimize the properties of both the bulk of the HTM layer and the HTM/perovskite interface. The intermolecular π–π stacking interaction in the HTM layer is unexpectedly weakened after the incorporation of DEG groups, whereas the lamellar packing interaction is strengthened. A doubled hole mobility is obtained when 3% of the DEG groups replace the original alkyl side chains, and a champion power conversion efficiency (PCE) of 20.19% (certified: 20.10%) is then achieved, which is the first report of values over 20% for dopant‐free organic HTMs. The device maintains 92.25% of its initial PCE after storing at ambient atmosphere for 30 d, which should be due to the enhanced hydrophobicity of the HTM film.     

Revealing the effect of donor/acceptor intermolecular arrangement on organic solar cells performance based on two-dimensional conjugated small molecule as electron donor

A series of solution processed organic solar cells (OSCs) were fabricated with a two-dimensional conjugated small molecule SMPV1 as electron donor and fullerene derivatives PC₇₁BM or ICBA as electron acceptor. The champion power conversion efficiency (PCE) of OSCs arrives to 7.05% for the cells with PC₇₁BM as electron acceptor. A relatively large open circuit voltage (V_OC) of 1.15 V is obtained from cells using ICBA as electron acceptor with an acceptable PCE of 2.54%. The fill factor (FF) of OSCs is 72% or 61% for the cells with PC₇₁BM or ICBA as electron acceptor, which is relatively high value for small molecule OSCs. The relatively low performance of OSCs with ICBA as electron acceptor indicates that ICBA cannot play positive role in photoelectric conversion processes, which is very similar to the phenomenon observed from the OSCs with high efficient narrow band gap polymers other than P3HT as electron donor, the underlying reason is still in debate. The SMPV1 has strong self-assemble ability to form an ordered two dimensional lamellar structure, which provides an effective platform to investigate the effect of electron acceptor chemical structure on the performance of OSCs. Experimental results exhibit that ICBA molecules may prefer to vertical cross-intercalation among side chains of SMPV1, PC₇₁BM molecules may have better miscibility with SMPV1 in the active layer. The different donor/acceptor (D/A) intermolecular arrangement strongly influences photon harvesting, exciton dissociation and charge carrier transport, which may provide a new sight on performance improvement of OSCs by adjusting D/A intermolecular arrangements.     

Additive‐Morphology Interplay and Loss Channels in “All‐Small‐Molecule” Bulk‐heterojunction (BHJ) Solar Cells with the Nonfullerene Acceptor IDTTBM

Achieving efficient bulk‐heterojunction (BHJ) solar cells from blends of solution‐processable small‐molecule (SM) donors and acceptors is proved particularly challenging due to the complexity in obtaining a favorable donor–acceptor morphology. In this report, the BHJ device performance pattern of a set of analogous, well‐defined SM donors— DR3TBDTT ( DR3 ), SMPV1 , and BTR —used in conjunction with the SM acceptor IDTTBM is examined. Examinations show that the nonfullerene “All‐SM” BHJ solar cells made with DR3 and IDTTBM can achieve power conversion efficiencies (PCEs) of up to ≈4.5% (avg. 4.0%) when the solution‐processing additive 1,8‐diiodooctane (DIO, 0.8% v/v) is used in the blend solutions. The figures of merit of optimized DR3:IDTTBM solar cells contrast with those of “as‐cast” BHJ devices from which only modest PCEs <1% can be achieved. Combining electron energy loss spectrum analyses in scanning transmission electron microscopy mode, carrier transport measurements via “metal‐insulator‐semiconductor carrier extraction” methods, and systematic recombination examinations by light‐dependence and transient photocurrent analyses, it is shown that DIO plays a determining role—establishing a favorable lengthscale for the phase‐separated SM donor–acceptor network and, in turn, improving the balance in hole/electron mobilities and the carrier collection efficiencies overall.     

Chemically Recyclable Conjugated Polymer and One-Shot Preparation of Thermally Stable and Efficient Bulk-Heterojunction from Recycled Monomer

Recyclable conjugated polymers are important for realizing eco-friendly electronics with advantages of solution processability and flexibility. A recyclable conjugated polymer, PY-TIP is developed, of which a key monomer is successfully extracted via a mild depolymerization process and is reused for the synthesis of novel conjugated polymers. One-shot preparation of polymer acceptor and its bulk-heterojunction (BHJ) is demonstrated from the recycled monomer, Y5-TA, for the first time and the resulting BHJ film shows optimal nanoscale morphology for efficient charge generation and transport. As a result, the solar cells prepared using the BHJ film show a higher efficiency of 13.08% and much improved thermal and mechanical stability compared with those based on the small molecular acceptor. These results are important in that the various polymers can be prepared from the recycled monomer in a solid state without organic solvents and purification step and this strategy is effective for improving the thermal and mechanical stability of the BHJ film as well as achieving high photovoltaic performance. PY-TIP is exemplary in that it can reproduce its monomer which can be used to synthesize conjugated polymers with novel chemical structures and physical properties. This work provides a design guideline for developing recyclable conjugated polymers with dynamic covalent bonds.     

Enhancing Field‐Effect Mobility of Conjugated Polymers Through Rational Design of Branched Side Chains

The design of polymer semiconductors possessing effective π–π intermolecular interactions coupled with good solution processability remains a challenge. Structure‐property relationships associated with side chain structure, π–π intermolecular interactions, polymer solubility, and charge carrier transport are reported for a donor–acceptor(1)‐donor–acceptor(2) polymer: 5‐Decylheptadecyl (5‐DH), 2‐tetradecyl (2‐DT), and linear n‐octadecyl (OD) chains are substituted onto a polymer backbone consisting of terthiophene units (T) between two different electron acceptors, benzothiadiazole (B), and diketopyrrolopyrrole (D), pTBTD, to afford pTBTD‐5DH, pTBTD‐2DT, and pTBTD‐OD, respectively. In the 5‐DH side chain, the branching position is remote from the polymer backbone, whereas it is proximal in 2‐DT. This study demonstrates that incorporation of branched side chains where the branching position is remote from the polymer backbone merges the advantages of improved solubility from branched units with effective π–π intermolecular interactions normally associated with linear chains on conjugated polymers. pTBTD‐5DH exhibits superior qualities with respect to the degree of polymerization, solution processability, π–π interchain stacking, and charge carrier transport relative to the other analogs. pTBTD‐5DH exhibits a field‐effect hole mobility of up to 2.95 cm² V^–1 s^–1, a factor of 3–7 times that achieved with pBDT6‐DT and pBDT6‐OD.