Design of Cyanovinylene‐Containing Polymer Acceptors with Large Dipole Moment Change for Efficient Charge Generation in High‐Performance All‐Polymer Solar Cells

Designing polymers that facilitate exciton dissociation and charge transport is critical for the production of highly efficient all‐polymer solar cells (all‐PSCs). Here, the development of a new class of high‐performance naphthalenediimide (NDI)‐based polymers with large dipole moment change (Δµ_ge) and delocalized lowest unoccupied molecular orbital (LUMO) as electron acceptors for all‐PSCs is reported. A series of NDI‐based copolymers incorporating electron‐withdrawing cyanovinylene groups into the backbone (PNDITCVT‐R) is designed and synthesized with 2‐hexyldecyl (R = HD) and 2‐octyldodecyl (R = OD) side chains. Density functional theory calculations reveal an enhancement in Δµ_ge and delocalization of the LUMO upon the incorporation of cyanovinylene groups. All‐PSCs fabricated from these new NDI‐based polymer acceptors exhibit outstanding power conversion efficiencies (7.4%) and high fill factors (65%), which is attributed to efficient exciton dissociation, well‐balanced charge transport, and suppressed monomolecular recombination. Morphological studies by grazing X‐ray scattering and resonant soft X‐ray scattering measurements show the blend films containing polymer donor and PNDITCVT‐R acceptors to exhibit favorable face‐on orientation and well‐mixed morphology with small domain spacing (30–40 nm).     

Effect of Molecular Orientation of Donor Polymers on Charge Generation and Photovoltaic Properties in Bulk Heterojunction All‐Polymer Solar Cells

All‐polymer solar cells (all‐PSCs) utilizing p‐type polymers as electron‐donors and n ‐typepolymers as electron‐acceptors have attracted a great deal of attention, and their efficiencies have been improved considerably. Here, five polymer donors with different molecular orientations are synthesized by random copolymerization of 5‐fluoro‐2,1,3‐benzothiadiazole with different relative amounts of 2,2′‐bithiophene (2T) and dithieno[3,2‐b;2′,3′‐d]thiophene (DTT). Solar cells are prepared by blending the polymer donors with a naphthalene diimide‐based polymer acceptor (PNDI) or a [6,6]‐phenyl C₇₁‐butyric acid methyl ester (PC₇₁BM) acceptor and their morphologies and crystallinity as well as optoelectronic, charge‐transport and photovoltaic properties are studied. Interestingly, charge generation in the solar cells is found to show higher dependence on the crystal orientation of the donor polymer for the PNDI‐based all‐PSCs than for the conventional PC₇₁BM‐based PSCs. As the population of face‐on‐oriented crystallites of the donor increased in PNDI‐based PSC, the short‐circuit current density (J_SC) and external quantum efficiency of the devices are found to significantly improve. Consequently, device efficiency was enhanced of all‐PSC from 3.11% to 6.01%. The study reveals that producing the same crystal orientation between the polymer donor and acceptor (face‐on/face‐on) is important in all‐PSCs because they provide efficient charge transfer at the donor/acceptor interface.     

Designing 1,5‐Naphthyridine‐2,6‐dione‐Based Conjugated Polymers for Higher Crystallinity and Enhanced Light Absorption to Achieve 9.63% Efficiency Polymer Solar Cells

Highly crystalline conjugated polymers represent a key material for producing high‐performance thick‐active‐layer polymer solar cells (PSCs). However, despite their potential, a limited number of crystalline polymers are used in PSCs because of the lack of highly coplanar acceptor building blocks and insufficient light absorptivity (α < 10⁵) of most donor (D)–acceptor (A)‐type polymers. This study reports a series of novel 3,7‐di(thiophen‐2‐yl)‐1,5‐naphthyridine‐2,6‐dione (NTDT) acceptor‐based conjugated polymers, PNTDT‐2T, PNTDT‐TT, and PNTDT‐2F2T, synthesized with 2,2′‐bithiophene (2T), thieno[3,2‐b]thiophene (TT), and 3,3′‐difluoro‐2,2′‐bithiophene (2F2T) donor units, respectively. PNTDT‐2F2T exhibits superior polymer crystallinity and a much higher absorption coefficient than those of PNTDT‐2T or PNTDT‐TT because of adequate matching between highly coplanar A (NTDT) and D (2F2T) building blocks. A bulk heterojunction solar cell based on PNTDT‐2F2T exhibits a power conversion efficiency of up to 9.63%, with a high short circuit current of 18.80 mA cm^?2 and fill factor of 0.70, when a thick active layer (>200 nm) is used, without postfabrication hot processing. The findings demonstrate that the polymer crystallinity and absorption coefficient can be effectively controlled by selecting appropriate D and A building blocks, and that NTDT is a novel and versatile A building block for highly efficient thick‐active‐layer PSCs.     

8.0% Efficient All‐Polymer Solar Cells with High Photovoltage of 1.1 V and Internal Quantum Efficiency near Unity

In very recent years, growing efforts have been devoted to the development of all‐polymer solar cells (all‐PSCs). One of the advantages of all‐PSCs over the fullerene‐based PSCs is the versatile design of both donor and acceptor polymers which allows the optimization of energy levels to maximize the open‐circuit voltage (V_oc). However, there is no successful example of all‐PSCs with both high V_oc over 1 V and high power conversion efficiency (PCE) up to 8% reported so far. In this work, a combination of a donor polymer poly[4,8‐bis(5‐(2‐octylthio)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl‐alt‐(5‐(2‐ethylhexyl)‐4H‐thieno[3,4‐c]pyrrole‐4,6(5H)‐dione)‐1,3‐diyl] (PBDTS‐TPD) with a low‐lying highest occupied molecular orbital level and an acceptor polymer poly[[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐thiophene‐2,5‐diyl] (PNDI‐T) with a high‐lying lowest unoccupied molecular orbital level is used, realizing high‐performance all‐PSCs with simultaneously high V_oc of 1.1 V and high PCE of 8.0%, and surpassing the performance of the corresponding PC₇₁BM‐based PSCs. The PBDTS‐TPD:PNDI‐T all‐PSCs achieve a maximum internal quantum efficiency of 95% at 450 nm, which reveals that almost all the absorbed photons can be converted into free charges and collected by electrodes. This work demonstrates the advantages of all‐PSCs by incorporating proper donor and acceptor polymers to boost both V_oc and PCEs.     

Photoactive Blend Morphology Engineering through Systematically Tuning Aggregation in All‐Polymer Solar Cells

Polymer aggregation plays a critical role in the miscibility of materials and the performance of all‐polymer solar cells (APSCs). However, many aspects of how polymer texturing and aggregation affect photoactive blend film microstructure and photovoltaic performance are poorly understood. Here the effects of aggregation in donor–acceptor blends are studied, in which the number‐average molecular weights (M_ns) of both an amorphous donor polymer, poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b;4,5‐b′]dithiophene‐2,6‐diyl‐alt‐(4‐(2‐ethylhexyl)‐3‐fluorothieno[3,4‐b]thiophene‐)‐2‐carboxylate‐2‐6‐diyl)] ( PBDTT‐FTTE ) and a semicrystalline acceptor polymer, poly{[N,N′‐bis(2‐octyldodecyl)naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} ( P(NDI2OD‐T2) ) are systematically varied. The photovoltaic performance is correlated with active layer microstructural and optoelectronic data acquired by in‐depth transmission electron microscopy, grazing incidence wide‐angle X‐ray scattering, thermal analysis, and optical spectroscopic measurements. Coarse‐grained modeling provides insight into the effects of polymer aggregation on the blend morphology. Notably, the computed average distance between the donor and the acceptor polymers correlates well with solar cell photovoltaic metrics such as short‐circuit current density (J_sc) and represents a useful index for understanding/predicting active layer blend material intermixing trends. Importantly, these results demonstrate that for polymers with different texturing tendencies (amorphous/semicrystalline), the key for optimal APSC performance, photovoltaic blend morphology can be controlled via both donor and acceptor polymer aggregation.     

High‐Performance and Stable All‐Polymer Solar Cells Using Donor and Acceptor Polymers with Complementary Absorption

To explore the advantages of emerging all‐polymer solar cells (all‐PSCs), growing efforts have been devoted to developing matched donor and acceptor polymers to outperform fullerene‐based PSCs. In this work, a detailed characterization and comparison of all‐PSCs using a set of donor and acceptor polymers with both conventional and inverted device structures is performed. A simple method to quantify the actual composition and light harvesting contributions from the individual donor and acceptor is described. Detailed study on the exciton dissociation and charge recombination is carried out by a set of measurements to understand the photocurrent loss. It is unraveled that fine‐tuned crystallinity of the acceptor, matched donor and acceptor with complementary absorption and desired energy levels, and device architecture engineering can synergistically boost the performance of all‐PSCs. As expected, the PBDTTS‐FTAZ:PNDI‐T10 all‐PSC attains a high and stable power conversion efficiency of 6.9% without obvious efficiency decay in 60 d. This work demonstrates that PNDI‐T10 can be a potential alternative acceptor polymer to the widely used acceptor N2200 for high‐performance and stable all‐PSCs.     

Medium Bandgap Polymer Donor Based on Bi(trialkylsilylthienyl‐benzo[1,2‐b:4,5‐b′]‐difuran) for High Performance Nonfullerene Polymer Solar Cells

A new 2D‐conjugated medium bandgap donor–acceptor copolymer, J81 , based on benzodifuran with trialkylsilyl thiophene side chains as donor unit and fluorobenzothiazole as acceptor, is synthesized and successfully used in nonfullerene polymer solar cells (PSCs) with low bandgap n‐type organic semiconductor (n‐OS) 3,9‐bis(2‐methylene‐ (3‐(1,1‐dicyanomethylene)‐indanone)‐5,5,11,11‐tetrakis(4‐ hexylphenyl)‐dithieno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]‐ dithiophene (ITIC) and m ‐ITIC as acceptor. J81 possesses a lower‐lying highest occupied molecular orbital (HOMO) energy level of ?5.43 eV and medium bandgap of 1.93 eV with complementary absorption in the visible–near infrared region with the n‐OS acceptor. The PSCs based on J81 :ITIC and J81 :m ‐ITIC yield high power conversion efficiency of 10.60% and 11.05%, respectively, with high V _oc of 0.95–0.96 V benefit from the lower‐lying HOMO energy level of J81 donor. The work indicates that J81 is another promising polymer donor for the nonfullerene PSCs.     

Effect of Alkylsilyl Side‐Chain Structure on Photovoltaic Properties of Conjugated Polymer Donors

Side‐chain engineering is an important strategy for optimizing photovoltaic properties of organic photovoltaic materials. In this work, the effect of alkylsilyl side‐chain structure on the photovoltaic properties of medium bandgap conjugated polymer donors is studied by synthesizing four new polymers J70 , J72 , J73 , and J74 on the basis of highly efficient polymer donor J71 by changing alkyl substituents of the alkylsilyl side chains of the polymers. And the photovoltaic properties of the five polymers are studied by fabricating polymer solar cells (PSCs) with the polymers as donor and an n‐type organic semiconductor (n‐OS) m‐ITIC as acceptor. It is found that the shorter and linear alkylsilyl side chain could afford ordered molecular packing, stronger absorption coefficient, higher charge carrier mobility, thus results in higher J_sc and fill factor values in the corresponding PSCs. While the polymers with longer or branched alkyl substituents in the trialkylsilyl group show lower‐lying highest occupied molecular orbital energy levels which leads to higher V_oc of the PSCs. The PSCs based on J70 :m‐ITIC and J71 :m‐ITIC achieve power conversion efficiency (PCE) of 11.62 and 12.05%, respectively, which are among the top values of the PSCs reported in the literatures so far.     

Tuning Energy Levels without Negatively Affecting Morphology: A Promising Approach to Achieving Optimal Energetic Match and Efficient Nonfullerene Polymer Solar Cells

One advantage of nonfullerene polymer solar cells (PSCs) is that they can yield high open‐circuit voltage (V_OC) despite their relatively low optical bandgaps. To maximize the V_OC of PSCs, it is important to fine‐tune the energy level offset between the donor and acceptor materials, but in a way not negatively affecting the morphology of the donor:acceptor (D:A) blends. Here, an effective material design rationale based on a family of D–A1–D–A2 terthiophene (T3) donor polymers is reported, which allows for the effective tuning of energy levels but without any negative impacts on the morphology of the blend. Based on a T3 donor unit combined with difluorobenzothiadiazole (ffBT) and difluorobenzoxadiazole (ffBX) acceptor units, three donor polymers are developed with highly similar morphological properties. This is particularly surprising considering that the corresponding quaterthiophene polymers based on ffBT and ffBX exhibit dramatic differences in their solubility and morphological properties. With the fine‐tuning of energy levels, the T3 polymers yield nonfullerene PSCs with a high efficiency of 9.0% for one case and with a remarkably low energy loss (0.53 V) for another polymer. This work will facilitate the development of efficient nonfullerene PSCs with optimal energy levels and favorable morphology properties.     

Green‐Solvent‐Processed All‐Polymer Solar Cells Containing a Perylene Diimide‐Based Acceptor with an Efficiency over 6.5%

To realize high power conversion efficiencies (PCEs) in green‐solvent‐processed all‐polymer solar cells (All‐PSCs), a long alkyl chain modified perylene diimide (PDI)‐based polymer acceptor PPDIODT with superior solubility in nonhalogenated solvents is synthesized. A properly matched PBDT‐TS1 is selected as the polymer donor due to the red‐shifted light absorption and low‐lying energy level in order to achieve the complementary absorption spectrum and matched energy level between polymer donor and polymer acceptor. By utilizing anisole as the processing solvent, an optimal efficiency of 5.43% is realized in PBDT‐TS1/PPDIODT‐based All‐PSC with conventional configuration, which is comparable with that of All‐PSCs processed by the widely used binary solvent. Due to the utilization of an inverted device configuration, the PCE is further increased to over 6.5% efficiency. Notably, the best‐performing PCE of 6.58% is the highest value for All‐PSCs employing PDI‐based polymer acceptors and green‐solvent‐processed All‐PSCs. The excellent photovoltaic performance is mainly attributed to a favorable vertical phase distribution, a higher exciton dissociation efficiency (P_diss) in the blend film, and a higher electrode carrier collection efficiency. Overall, the combination of rational molecular designing, material selection, and device engineering will motivate the efficiency breakthrough in green‐solvent‐processed All‐PSCs.     

Efficient Ternary Polymer Solar Cells with Two Well‐Compatible Donors and One Ultranarrow Bandgap Nonfullerene Acceptor

Nonfullerene polymer solar cells (PSCs) are fabricated by using one wide bandgap donor PBDB‐T and one ultranarrow bandgap acceptor IEICO‐4F as the active layers. One medium bandgap donor PTB7‐Th is selected as the third component due to the similar highest occupied molecular orbital level compared to that of PBDB‐T and their complementary absorption spectra. The champion power conversion efficiency (PCE) of PSCs is increased from 10.25% to 11.62% via incorporating 20 wt% PTB7‐Th in donors, with enhanced short‐circuit current (J_SC) of 24.14 mA cm^?2 and fill factor (FF) of 65.03%. The 11.62% PCE should be the highest value for ternary nonfullerene PSCs. The main contribution of PTB7‐Th can be summarized as the improved photon harvesting and enhanced exciton utilization of PBDB‐T due to the efficient energy transfer from PBDB‐T to PTB7‐Th. Meanwhile, PTB7‐Th can also act as a regulator to adjust PBDB‐T molecular arrangement for optimizing charge transport, resulting in the enhanced FF of ternary PSCs. This experimental result may provide new insight for developing high‐performance ternary nonfullerene PSCs by selecting two well‐compatible donors with different bandgap and one ultranarrow bandgap acceptor.     

Self‐Organization of Polymer Additive,Poly(2‐vinylpyridine) via One‐Step Solution Processing to Enhance the Efficiency and Stability of Polymer Solar Cells

Interfaces between the photoactive layers and electrodes play critical roles in controlling the performance of optoelectronic devices. Herein, a novel nonconjugated polymer additive (nPA), poly(2‐vinylpyridine) (P2VP), is reported for modifying the interfaces between the bulk‐heterojunction (BHJ) and cathode/metal oxide (MO) layers. The P2VP nPA enables remarkably enhanced power conversion efficiencies (PCEs) and ambient stability in different types of polymer solar cells (PSCs). Importantly, interfacial engineering can be achieved during deposition of the P2VP nPA‐containing BHJ active layer via simple, one‐step solution processing. The P2VP nPA has much higher surface energy than the BHJ active components and stronger interaction with the surface of MO, which affords spontaneous vertical phase separation from the BHJ layer on the MO surface by one‐step solution processing. The self‐assembled P2VP layer substantially reduces the work function and surface defect density of MO, thereby minimizing the charge‐extraction barrier and increasing the PCEs of the PSCs significantly, i.e., PTB7‐Th:PC₇₁BM (10.53%→11.14%), PTB7:PC₇₁BM (7.37%→8.67%), and PTB7‐Th:P(NDI2HD‐T) all‐PSCs (5.52%→6.14%). In addition, the lifetimes of the PSCs are greatly improved by the use of the P2VP nPA.     

Roll‐to‐Roll Printed Large‐Area All‐Polymer Solar Cells with 5% Efficiency Based on a Low Crystallinity Conjugated Polymer Blend

The challenge of continuous printing in high‐efficiency large‐area organic solar cells is a key limiting factor for their widespread adoption. A materials design concept for achieving large‐area, solution‐coated all‐polymer bulk heterojunction solar cells with stable phase separation morphology between the donor and acceptor is presented. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity, and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, the results show that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers. This methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small‐scale solution shearing coater to a large‐scale continuous roll‐to‐roll (R2R) printer. Large‐area all‐polymer solar cells are continuously roll‐to‐roll slot die printed with power conversion efficiencies of 5%, with combined cell area up to 10 cm². This is among the highest efficiencies realized with R2R‐coated active layer organic materials on flexible substrate.     

Efficiency Enhancement of Polymer Solar Cells Based on Poly(3‐hexylthiophene)/Indene‐C70 Bisadduct via Methylthiophene Additive

Photovoltaic performance of polymer solar cells based on poly(3‐hexylthiophene) (P3HT) as the donor and indene‐C₇₀ bisadduct (IC₇₀BA) as the acceptor is improved by adding 3 vol% 3‐methylthiophene (MT) or 3‐hexylthiophene (HT) as processing additives. The results of UV‐vis absorption spectroscopy, X‐ray diffraction analysis and atomic force microscopy indicate that with the MT or HT processing additive, the active layer of the blend of P3HT/IC₇₀BA showed strengthened absorbance, enhanced crystallinity and improved film morphology. The power conversion efficiency (PCE) of the PSCs was improved from 5.80% for the device without the additive to 6.35% for the device with HT additive and to 6.69% with MT additive. The PCE of 6.69% is the top value reported so far for the PSCs based on P3HT.     

A Facile Method to Fine‐Tune Polymer Aggregation Properties and Blend Morphology of Polymer Solar Cells Using Donor Polymers with Randomly Distributed Alkyl Chains

The device performance of polymer solar cells (PSCs) is strongly dependent on the blend morphology. One of the strategies for improving PSC performance is side‐chain engineering, which plays an important role in controlling the aggregation properties of the polymers and thus the domain crystallinity/purity of the donor–acceptor blends. In particular, for a family of high‐performance donor polymers with strong temperature‐dependent aggregation properties, the device performances are very sensitive to the size of alkyl chains, and the best device performance can only be achieved with an optimized odd‐numbered alkyl chain. However, the synthetic route of odd‐numbered alkyl chains is costly and complicated, which makes it difficult for large‐scale synthesis. Here, this study presents a facile method to optimize the aggregation properties and blend morphology by employing donor polymers with a mixture of two even‐numbered, randomly distributed alkyl chains. In a model polymer system, this study suggests that the structural and electronic properties of the random polymers comprising a mixture of 2‐octyldodecyl and 2‐decyltetradecyl alkyl chains can be systematically tuned by varying the mixing ratio, and a high power conversion efficiency (11.1%) can be achieved. This approach promotes the scalability of donor polymers and thus facilitates the commercialization of PSCs.     

Polymer Blend Solar Cells Based on a High‐Mobility Naphthalenediimide‐Based Polymer Acceptor: Device Physics,Photophysics and Morphology

A high electron mobility polymer, poly{[N,N’‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5’‐(2,2’‐bithiophene) (P(NDI2OD‐T2)) is investigated for use as an electron acceptor in all‐polymer blends. Despite the high bulk electron mobility, near‐infrared absorption band and compatible energy levels, bulk heterojunction devices fabricated with poly(3‐hexylthiophene) (P3HT) as the electron donor exhibit power conversion efficiencies of only 0.2%. In order to understand this disappointing photovoltaic performance, systematic investigations of the photophysics, device physics and morphology of this system are performed. Ultra‐fast transient absorption spectroscopy reveals a two‐stage decay process with an initial rapid loss of photoinduced polarons, followed by a second slower decay. This second slower decay is similar to what is observed for efficient P3HT:PCBM ([6,6]‐phenyl C₆₁‐butyric acid methyl ester) blends, however the initial fast decay that is absent in P3HT:PCBM blends suggests rapid, geminate recombination of charge pairs shortly after charge transfer. X‐ray microscopy reveals coarse phase separation of P3HT:P(NDI2OD‐T2) blends with domains of size 0.2 to 1 micrometer. P3HT photoluminescence, however, is still found to be efficiently quenched indicating intermixing within these mesoscale domains. This hierarchy of phase separation is consistent with the transient absorption, whereby localized confinement of charges on isolated chains in the matrix of the other polymer hinders the separation of interfacial electron‐hole pairs. These results indicate that local, interfacial processes are the key factor determining the overall efficiency of this system and highlight the need for improved morphological control in order for the potential benefit of high‐mobility electron accepting polymers to be realized.     

Layer‐by‐Layer Solution‐Processed Low‐Bandgap Polymer‐PC61BM Solar Cells with High Efficiency

Polymer solar cells (PSCs) are fabricated without solvent additives using a low‐bandgap polymer, PBDTTT‐C‐T, as the donor and [6,6]‐phenyl‐C61‐butyric‐acid‐methyl‐ester (PC₆₁BM) as the acceptor. Donor‐acceptor blend and layer‐by‐layer (LL) solution process are used to form active layers. Relative to the blend devices, the LL devices exhibit stronger absorption, better vertical phase separation, higher hole and electron mobilities, and better charge extraction at correct electrodes. As a result, after thermal annealing the LL devices exhibit an average power conversion efficiency (PCE) of 6.86%, which is much higher than that of the blend devices (4.31%). The best PCE of the LL devices is 7.13%, which is the highest reported for LL processed PSCs and among the highest reported for PC₆₁BM‐based single‐junction PSCs.     

Side‐Chain Impact on Molecular Orientation of Organic Semiconductor Acceptors: High Performance Nonfullerene Polymer Solar Cells with Thick Active Layer over 400 nm

A new n‐type organic semiconductor (n‐OS) acceptor IDTPC with n‐hexyl side chains is developed. Compared to side chains with 4‐hexylphenyl counterparts (IDTCN), such a design endows the acceptor of IDTPC with higher electron mobility, more ordered face‐on molecular packing, and lower band gap. Therefore, the IDTPC‐based polymer solar cells (PSCs) with a newly developed wide bandgap polymer PTQ10 as donor exhibit the maximum power conversion efficiency (PCE) of 12.2%, a near 65% improvement in PCE relative to the IDTCN‐based control device. Most importantly, the IDTPC‐based device is insensitive to the thickness of the active layer from 70 to 505 nm, which still gives a PCE of 10.0% with the active‐layer thickness of 400 nm. To the best of the authors' knowledge, a PCE of 10.0% is the highest value for the nonfullerene PSCs with an active layer thicker than 400 nm. These results reveal that the blend of PTQ10 and IDTPC exhibits great potential for highly efficient nonfullerene PSCs and large‐area device fabrication.     

Improvement of Photovoltaic Performance of Polymer Solar Cells by Rational Molecular Optimization of Organic Molecule Acceptors

Two n‐type organic semiconductor (n‐OS) small molecules m‐ITIC‐2F and m‐ITIC‐4F with fluorinated 2‐(2,3‐dihydro‐3‐oxo‐1H‐inden‐1‐ylidene)propanedinitrile (IC) terminal moieties are prepared, for the application as an acceptor in polymer solar cells (PSCs), to further improve the photovoltaic performance of the n‐OS acceptor 3,9‐bis(2‐methylene‐(3‐(1,1‐dicyanomethylene) indanone) ‐5,5,11,11‐tetrakis(3‐hexylphenyl)‐dithieno[2,3‐d:2′,3′‐d′]‐sindaceno[1,2‐b:5,6‐b′]‐dithiophene (m‐ITIC). Compared to m‐ITIC, these two new acceptors show redshifted absorption, higher molecular packing order, and improved electron mobilities. The power conversion efficiencies (PCE) of the as‐cast PSCs with m‐ITIC‐2F or m‐ITIC‐4F as an acceptor and a low‐cost donor–acceptor (D–A) copolymer PTQ10 as a donor reach 11.57% and 11.64%, respectively, which are among the highest efficiency for the as‐cast PSCs so far. Furthermore, after thermal annealing treatment, improved molecular packing and enhanced phase separation are observed, and the higher PCE of 12.53% is achieved for both PSCs based on the two acceptors. The respective and unique advantage with the intrinsic high degree of order, molecular packing, and electron mobilities of these two acceptors will be suitable to match with different p‐type organic semiconductor donors for higher PCE values, which provide a great potential for the PSCs commercialization in the near future. These results indicate that rational molecular structure optimization is of great importance to further improve photovoltaic properties of the photovoltaic materials.     

All‐Polymer Solar Cells with over 12% Efficiency and a Small Voltage Loss Enabled by a Polymer Acceptor Based on an Extended Fused Ring Core

Although the field of all‐polymer solar cells (all‐PSCs) has seen rapid progress in device efficiencies during the past few years, there are limited choices of polymer acceptors that exhibit strong absorption in the near‐IR region and achieve high open‐circuit voltage (V_OC) at the same time. In this paper, an all‐PSC device is demonstrated with a 12.06% efficiency based on a new polymer acceptor (named PT‐IDTTIC) that exhibits strong absorption (maximum absorption coefficient: 2.41 × 10⁵ cm^?1) and a narrow optical bandgap (1.49 eV). Compared to previously reported polymer acceptors such as those based on the indacenodithiophene (IDT) core, the indacenodithienothiophene (IDTT) core has further extended fused ring, providing the polymer with extended absorption into the near‐IR region and also increases the electron mobility of the polymer. By blending PT‐IDTTIC with the donor polymer, PM6, a high‐efficiency all‐PSC is achieved with a small voltage loss of 0.52 V, without sacrificing J_SC and FF, which demonstrates the great potential of high‐performance all‐PSCs.