High‐Performance Pseudoplanar Heterojunction Ternary Organic Solar Cells with Nonfullerene Alloyed Acceptor

The vast majority of ternary organic solar cells are obtained by simply fabricating bulk heterojunction (BHJ) active layers. Due to the inappropriate distribution of donors and acceptors in the vertical direction, a new method by fabricating pseudoplanar heterojunction (PPHJ) ternary organic solar cells is proposed to better modulate the morphology of active layer. The pseudoplanar heterojunction ternary organic solar cells (P‐ternary) are fabricated by a sequential solution treatment technique, in which the donor and acceptor mixture blends are sequentially spin‐coated. As a consequence, a higher power conversion efficiency (PCE) of 14.2% is achieved with a V_oc of 0.79 V, J_sc of 25.6 mA cm^?2, and fill factor (FF) of 69.8% compared with the ternary BHJ system of 13.8%. At the same time, the alloyed acceptor is likely formed between two the acceptors through a series of in‐depth explorations. This work suggests that nonfullerene alloyed acceptor may have great potential to realize effective P‐ternary organic solar cells.     

Molecular Orientation Unified Nonfullerene Acceptor Enabling 14% Efficiency As‐Cast Organic Solar Cells

Molecular orientation and π–π stacking of nonfullerene acceptors (NFAs) determine its domain size and purity in bulk‐heterojunction blends with a polymer donor. Two novel NFAs featuring an indacenobis(dithieno[3,2‐b:2?,3?‐d]pyrrol) core with meta‐ or para‐alkoxyphenyl sidechains are designed and denoted as m‐INPOIC or p‐INPOIC , respectively. The impact of the alkoxyl group positioning on molecular orientation and photovoltaic performance of NFAs is revealed through a comparison study with the counterpart ( INPIC‐4F ) bearing para‐alkylphenyl sidechains. With inward constriction toward the conjugated backbone, m‐INPOIC presents predominant face‐on orientation to promote charge transport. The as‐cast organic solar cells (OSCs) by blending m‐INPOIC and PBDB‐T as active layers exhibit a power conversion efficiency (PCE) of 12.1%. By introducing PC₇₁BM as the solid processing‐aid, the ternary OSCs are further optimized to deliver an impressive PCE of 14.0%, which is among the highest PCEs for as‐cast single‐junction OSCs reported in literature to date. More attractively, PBDB‐T: m‐INPOIC :PC₇₁BM based OSCs exhibit over 11% PCEs even with an active layer thickness over 300 nm. And the devices can retain over 95% of PCE after storage for 20 days. The outstanding tolerance to film thickness and outstanding stability of the as‐cast devices make m‐INPOIC a promising candidate NFA for large‐scale solution‐processable OSCs.     

Fused Cyclopentadithienothiophene Acceptor Enables Ultrahigh Short‐Circuit Current and High Efficiency >11% in As‐Cast Organic Solar Cells

A new method to synthesize an electron‐rich building block cyclopentadithienothiophene (9H‐thieno‐[3,2‐b]thieno[2″,3″:4′,5′]thieno[2′,3′:3,4]cyclopenta[1,2‐d]thiophene, CDTT) via a facile aromatic extension strategy is reported. By combining CDTT with 1,1‐dicyanomethylene‐3‐indanone endgroups, a promising nonfullerene small molecule acceptor (CDTTIC) is prepared. As‐cast, single‐junction nonfullerene organic solar cells based on PFBDB‐T: CDTTIC blends exhibit very high short‐circuit currents up to 26.2 mA cm^?2 in combination with power conversion efficiencies over 11% without any additional processing treatments. The high photocurrent results from the near‐infrared absorption of the CDTTIC acceptor and the well‐intermixed blend morphology of polymer donor PFBDB‐T and CDTTIC. This work demonstrates a useful fused ring extension strategy and promising solar cell results, indicating the great potential of the CDTT derivatives as electron‐rich building blocks for constructing high‐performance small molecule acceptors in organic solar cells.     

Alkoxy‐Functionalized Thienyl‐Vinylene Polymers for Field‐Effect Transistors and All‐Polymer Solar Cells

π‐conjugated polymers based on the electron‐neutral alkoxy‐functionalized thienyl‐vinylene (TVTOEt) building‐block co‐polymerized, with either BDT (benzodithiophene) or T2 (dithiophene) donor blocks, or NDI (naphthalenediimide) as an acceptor block, are synthesized and characterized. The effect of BDT and NDI substituents (alkyl vs alkoxy or linear vs branched) on the polymer performance in organic thin film transistors (OTFTs) and all‐polymer organic photovoltaic (OPV) cells is reported. Co‐monomer selection and backbone functionalization substantially modifies the polymer MO energies, thin film morphology, and charge transport properties, as indicated by electrochemistry, optical spectroscopy, X‐ray diffraction, AFM, DFT calculations, and TFT response. When polymer P7 is used as an OPV acceptor with PTB7 as a donor, the corresponding blend yields TFTs with ambipolar mobilities of μ_e = 5.1 × 10^?3 cm² V^–1 s^–1 and μ_h = 3.9 × 10^?3 cm² V^–1 s^–1 in ambient, among the highest mobilities reported to date for all‐polymer bulk heterojunction TFTs, and all‐polymer solar cells with a power conversion efficiency (PCE) of 1.70%, the highest reported PCE to date for an NDI‐polymer acceptor system. The stable transport characteristics in ambient and promising solar cell performance make NDI‐type materials promising acceptors for all‐polymer solar cell applications.     

Synthesis,Morphology, and Properties of Poly(3‐hexylthiophene)‐block‐Poly(vinylphenyl oxadiazole) Donor–Acceptor Rod–Coil Block Copolymers and Their Memory Device Applications

Novel donor–acceptor rod–coil diblock copolymers of regioregular poly(3‐hexylthiophene) ( P3HT )‐block‐poly(2‐phenyl‐5‐(4‐vinylphenyl)‐1,3,4‐oxadiaz‐ole) ( POXD ) are successfully synthesized by the combination of a modified Grignard metathesis reaction ( GRIM ) and atom transfer radical polymerization ( ATRP ). The effects of the block ratios of the P3HT donor and POXD pendant acceptor blocks on the morphology, field effect transistor mobility, and memory device characteristics are explored. The TEM, SAXS, WAXS, and AFM results suggest that the coil block fraction significantly affects the chain packing of the P3HT block and depresses its crystallinity. The optical absorption spectra indicate that the intramolecular charge transfer between the main chain P3HT donor and the side chain POXD acceptor is relatively weak and the level of order of P3HT chains is reduced by the incorporation of the POXD acceptor. The field effect transistor (FET) hole mobility of the system exhibits a similar trend on the optical properties, which are also decreased with the reduced ordered P3HT crystallinity. The low‐lying highest occupied molecular orbital (HOMO) energy level (–6.08 eV) of POXD is employed as charge trap for the electrical switching memory devices. P3HT‐ b ‐POXD exhibits a non‐volatile bistable memory or insulator behavior depending on the P3HT / POXD block ratio and the resulting morphology. The ITO/ P3HT₄₄ ‐b‐ POXD₁₈ /Al memory device shows a non‐volatile switching characteristic with negative differential resistance (NDR) effect due to the charge trapped POXD block. These experimental results provide the new strategies for the design of donor‐acceptor rod‐coil block copolymers for controlling morphology and physical properties as well as advanced memory device applications.     

An Electron Acceptor with Broad Visible–NIR Absorption and Unique Solid State Packing for As‐Cast High Performance Binary Organic Solar Cells

A novel acceptor–donor–acceptor (A–D–A) type electron acceptor 6TIC‐4F with terthieno[3,2‐b]thiophene (6T) as the core unit is rationally designed and synthesized, which exhibits an extraordinarily narrow bandgap (≈1.24 eV) and strong absorption between 650 and 1000 nm. X‐ray crystallographic analysis reveals that it has unique intermolecular π–π stacking. The solar cells based on the as‐cast poly[(2,6‐(4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)‐benzo[1,2‐b:4,5‐b′]dithiophene))‐alt‐(5,5‐(1′,3′‐di‐2‐thienyl‐5′,7′‐bis(2‐ethylhexyl)benzo[1′,2′‐c:4′,5′‐c′]dithiophene‐4,8‐dione))]) (PBDB‐T): 6TIC‐4F binary blends exhibit an excellent power conversion efficiency (PCE) of 11.14% with a high J_SC of 23.00 mA cm^?2, and a high fill factor of 0.67, which represents one of the best PCE values for low bandgap (E_g < 1.3 eV)–based organic solar cells.     

Conformation Locking on Fused‐Ring Electron Acceptor for High‐Performance Nonfullerene Organic Solar Cells

In this work, sidechain engineering on conjugated fused‐ring acceptors for conformation locking is demonstrated as an effective molecular design strategy for high‐performance nonfullerene organic solar cells (OSCs). A novel nonfullerene acceptor (ITC6‐IC) is designed and developed by introducing long alkyl chains into the terminal electron‐donating building blocks. ITC6‐IC has achieved definite conformation with a planar structure and better solubility in common organic solvents. The weak electron‐donating hexyl upshifts the lowest unoccupied molecular orbital level of ITC6‐IC, resulting in a higher V_OC in comparison to the widely used ITIC. The OSCs based on PBDB‐T:ITC6‐IC reveal a promising power conversion efficiency of 11.61% and an expected high V_OC of 0.97 V. The weaker π–π stacking induced by steric hindrance affords ITC6‐IC with enhanced compatibility with polymer donors. The blend film treated with suitable thermal annealing exhibits a fibril crystallization feature with a good bicontinuous network morphology. The results indicate that the molecular design approach of ITC6‐IC can be inspirational for future development of nonfullerene acceptors for high efficiency OSCs.     

Mechanistic Investigation into Dynamic Function of Third Component Incorporated in Ternary Near‐Infrared Nonfullerene Organic Solar Cells

Organic solar cells (OSCs) consisting of an ultralow‐bandgap nonfullerene acceptor (NFA) with an optical absorption edge that extends to the near‐infrared (NIR) region are of vital interest to semitransparent and tandem devices. However, huge energy‐loss related to inefficient charge dissociation hinders their further development. The critical issues of charge separation as exemplified in NIR‐NFA OSCs based on the paradigm blend of PTB7–Th donor (D) and IEICO–4F acceptor (A) are revealed here. These studies corroborate efficient charge transfer between D and A, accompanied by geminate recombination of photo‐excited charge carriers. Two key factors restricting charge separation are unveiled as the connection discontinuity of individual phases in the blend and long‐lived interfacial charge‐transfer states (CTS). By incorporation of a third‐component of benchmark ITIC or PC₇₁BM with various molar ratios, these two issues are well‐resolved accordingly, yet in distinctly influencing mechanisms. ITIC molecules modulate film morphology to create more continuous paths for charge transportation, whereas PC₇₁BM diminishes CTS and enhances electron transfer at the D/A interfaces. Consequently, the optimal untreated ternary OSCs comprising 0.3 wt% ITIC and 0.1 wt% PC₇₁BM in the blend deliver higher J_SC values of 21.9 and 25.4 mA cm^‐2, and hence increased PCE of 10.2% and 10.6%, respectively.     

Visible to Near‐Infrared Photodetection Based on Ternary Organic Heterojunctions

Organic semiconductors have attracted tremendous attention in the past few years, thanks to their excellent flexibility, solution‐processability, low‐cost, chemical versatility, etc. Particularly, organic solar cells based on ternary heterojunctions have shown remarkable device performance, with the recent development of nonfullerene acceptor materials. These novel materials are also promising for photodetection. However, there are several key limits facing organic photodetectors, such as relatively large bandgaps, poor charge transport, and stability. In this work, a novel nonfullerene acceptor—CO_i8DFIC—is introduced, blended with a fullerene derivative and a donor to form ternary heterojunctions. After optimization, photodiodes based on such ternary blends exhibit compelling performance metrics, including low dark current, decent responsivity, large linear dynamic range, fast response, and excellent stability. This device performance is actually on a par with the established silicon technology, suggesting great potential for photodetection and imaging.     

Fine-Tuning Alkyl Chains on Quinoxaline Nonfullerene Acceptors Enables High-Efficiency Ternary Organic Solar Cells with Optimizing Molecular Stacking and Reducing Energy Loss

Material design of guest acceptor is always a big challenge for improving the efficiency of ternary organic solar cells (OSCs). Here, a pair of isomeric nonfullerene acceptors based on quinoxaline core, Qx–p-C₇H₈O and Qx–m-C₇H₈O, is designed and synthesized. By moving the alkoxy chain attached on side phenyl from meta-position to para-position, both π–π stacking distance and crystallinity are enhanced simultaneously. They obtain the uplifted lowest unoccupied molecular orbital level. Compared to Qx–m-C₇H₈O, Qx–p-C₇H₈O exhibits wider absorption spectrum and higher extinction coefficient. Using D18-Cl:N3 as host materials, the addition of guest acceptor Qx–p-C₇H₈O significantly improves the power conversion efficiency (PCE) from 17.61% to 18.49% because of higher open-circuit voltage (0.875 V) and short-circuit current density (27.85 mA cm⁻²). This can be attributed to the faster exciton dissociation, more balanced carrier mobility, fine fiber morphology, and lower energy loss in the ternary devices. However, Qx–m-C₇H₈O-based ternary device achieves relatively low PCE of 17.17% because this device shows extremely low electron mobility. The results indicate that molecular stacking, film morphology, etc., can be effectively modulated by fine-tuning the side chains of guest materials, which may be an effective design rule for further improving the PCE of OSCs.     

Donor–Acceptor Poly(3‐hexylthiophene)‐block‐Pendent Poly(isoindigo) with Dual Roles of Charge Transporting and Storage Layer for High‐Performance Transistor‐Type Memory Applications

Field‐effect transistor memories usually require one additional charge storage layer between the gate contact and organic semiconductor channel. To avoid such complication, new donor–acceptor rod–coil diblock copolymers (P3HT₄₄‐b‐Piso_n) of poly(3‐hexylthiophene) (P3HT)‐block‐poly(pendent isoindigo) (Piso) are designed, which exhibit high performance transistor memory characteristics without additional charge storage layer. The P3HT and Piso blocks are acted as the charge transporting and storage elements, respectively. The prepared P3HT₄₄‐b‐Piso_n can be self‐assembled into fibrillar‐like nanostructures after the thermal annealing process, confirmed by atomic force microscopy and grazing‐incidence X‐ray diffraction. The lowest‐unoccupied molecular orbital levels of the studied polymers are significantly lowered as the block length of Piso increases, leading to a stronger electron affinity as well as charge storage capability. The field‐effect transistors (FETs) fabricated from P3HT₄₄‐b‐Piso_n possess p‐type mobilities up to 4.56 × 10^?2 cm² V^?1 s^?1, similar to that of the regioregular P3HT. More interestingly, the FET memory devices fabricated from P3HT₄₄‐b‐Piso_n exhibit a memory window ranging from 26 to 79 V by manipulating the block length of Piso, and showed stable long‐term data endurance. The results suggest that the FET characteristics and data storage capability can be effectively tuned simultaneously through donor/acceptor ratio and thin film morphology in the block copolymer system.     

Performance Optimization of Parallel‐Like Ternary Organic Solar Cells through Simultaneous Improvement in Charge Generation and Transport

Ternary organic photovoltaic (OPV) devices with multiple light‐absorbing active materials have emerged as an efficient strategy for realizing further improvements in the power conversion efficiency (PCE) without building complex multijunction structures. However, the third component often acts as recombination centers and, hence, the optimization of ternary blend morphology poses a major challenge to improving the PCE of these devices. In this work, the performance of OPVs is enhanced through the morphological modification of nonfullerene acceptor (NFA)‐containing binary active layers. This modification is achieved by incorporating fullerenes into the layers. The uniformly dispersed fullerenes are sufficiently continuous and successfully mediate the ordering of NFA without charge or energy transfer. Owing to the simultaneous improvement in the charge generation and extraction, the PCE (12.1%) of these parallel‐linked ternary devices is considerably higher than those of the corresponding binary devices (9.95% and 7.78%). Moreover, the additional energy loss of the ternary device is minimized, compared with that of the NFA‐based binary device, due to the judicious control of the effective donor:acceptor composition of the ternary blends.     

V‐Shaped Thiophene‐Based Oligomers with Improved Electroluminescence Properties

The synthesis via the Stille coupling of a new family of oligomers derived from benzo[b]thiophene is reported. Owing to their branched molecular structure lacking any symmetry element, these compounds display a low tendency to crystallization and better film‐forming properties than their linear counterparts. Spin‐coated films show photoluminescence efficiencies up to 50 %. Light‐emitting diodes with spin‐coated films as the active layers display markedly improved performance with respect to similar devices based on linear oligothiophenes, with luminance values up to more than 10 000 cd m^–2. Semiempirical PM3 and ZINDO/S calculations provide insight into the molecular geometries and electron distribution of the frontier orbitals of the new compounds. Cyclic voltammetry data indicates that the transformation of the thienyl sulfur of benzo[b]thiophene to the corresponding thienyl‐S,S‐dioxide leads an increase in electron affinity by 0.5–0.7 V, analogous to that of the corresponding linear oligomers.     

Naphtho[1,2‐c:5,6‐c′]bis[1,2,5]thiadiazole‐Containing π‐Conjugated Compound: Nonfullerene Electron Acceptor for Organic Photovoltaics

The development of nonfullerene acceptor materials applicable to organic photovoltaics (OPVs) has attracted considerable attention for the achievement of a high power conversion efficiency (PCE) in recent years. However, it is still challenging due to the insufficiency of both the variety of effective electron‐deficient units and certain guidelines for the design of such materials. This work focusses on naphtho[1,2‐c:5,6‐c′]bis[1,2,5]thiadiazole (NTz) as a key electron‐deficient unit. Therefore, a new electron‐accepting π‐conjugated compound (NTz‐Np), whose structure is based on the combination of NTz and the fluorene‐containing imide‐annelated terminal units (Np), is designed and synthesized. The NTz‐Np compound exhibits a narrow optical energy gap (1.73 eV), a proper energy level (?3.60 eV) of the lowest unoccupied molecular orbital, and moderate electron mobility (1.6 × 10^?5 cm² V^?1 s^?1), indicating that NTz‐Np has appropriate characteristics as an acceptor against poly(3‐hexylthiophene) (P3HT), a representative donor. OPV devices based on NTz‐Np under the blend with P3HT show high photovoltaic performance with a PCE of 2.81%, which is the highest class among the P3HT/nonfullerene‐based OPVs with the conventional device structure. This result indicates that NTz unit can be categorized as a potential electron‐deficient unit for the nonfullerene acceptors.     

A Cross‐Linkable Donor Polymer as the Underlying Layer to Tune the Active Layer Morphology of Polymer Solar Cells

For polymer solar cells (PSCs) with conventional configuration, the vertical composition profile of donor:acceptor in active layer is detrimental for charge carrier transporting/collection and leads to decreased device performance. A cross‐linkable donor polymer as the underlying morphology‐inducing layer (MIL) to tune the vertical composition distribution of donor:acceptor in the active layer for improved PSC device performance is reported. With poly(thieno[3,4‐b]‐thiophene/benzodithiophene):[6,6]‐phenyl C₇₁‐butyric acid methyl ester (PTB7:PC₇₁BM) as the active layer, the MIL material, PTB7‐TV , is developed by attaching cross‐linkable vinyl groups to the side chain of PTB7. PSC device with PTB7‐TV layer exhibits a power conversion efficiency (PCE) of 8.55% and short‐circuit current density (J_SC) of 15.75 mA cm^?2, in comparison to PCE of 7.41% and J_SC of 13.73 mA cm^?2 of the controlled device. The enhanced device performance is ascribed to the much improved vertical composition profile and reduced phase separation domain size in the active layer. These results demonstrate that cross‐linked MIL is an effective strategy to improve photovoltaic performance of conventional PSC devices.     

Wide Bandgap Copolymers Based on Quinoxalino[6,5‐f].quinoxaline for Highly Efficient Nonfullerene Polymer Solar Cells

Two novel wide bandgap copolymers based on quinoxalino[6,5‐f]quinoxaline (NQx) acceptor block, PBDT–NQx and PBDTS–NQx, are successfully synthesized for efficient nonfullerene polymer solar cells (PSCs). The attached conjugated side chains on both benzodithiophene (BDT) and NQx endow the resulting copolymers with low‐lying highest occupied molecular orbital (HOMO) levels. The sulfur atom insertion further reduces the HOMO level of PBDTS–NQx to ?5.31 eV, contributing to a high open‐circuit voltage, V _oc, of 0.91 V. Conjugated n ‐octylthienyl side chains attached on the NQx skeletons also significantly improve the π–π* transitions and optical absorptions of the copolymers in the region of short wavelengths, which induce a good complementary absorption when blending with the low bandgap small molecular acceptor of 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. The wide absorption range makes the active blends absorb more photons, giving rise to a high short‐circuit current density, J _sc, value of 15.62 mA cm^?2. The sulfur atom insertion also enhances the crystallinity of PBDTS–NQx and presents its blend film with a favorable nanophase separation, resulting in improved J _sc and fill factor (FF) values with a high power conversion efficiency of 11.47%. This work not only provides a new fused ring acceptor block (NQx) for constructing high‐performance wide bandgap copolymers but also provides the NQx‐based copolymers for achieving highly efficient nonfullerene PSCs.     

Self‐Healing Materials via Reversible Crosslinking of Poly(ethylene oxide)‐Block‐Poly(furfuryl glycidyl ether) (PEO‐b‐PFGE) Block Copolymer Films

The application of well‐defined poly(furfuryl glycidyl ether) (PFGE) homopolymers and poly(ethylene oxide)‐b‐poly(furfuryl glycidyl ether) (PEO‐b‐PFGE) block copolymers synthesized by living anionic polymerization as self‐healing materials is demonstrated. This is achieved by thermo‐reversible network formation via (retro) Diels‐Alder chemistry between the furan groups in the side‐chain of the PFGE segments and a bifunctional maleimide crosslinker within drop‐cast polymer films. The process is studied in detail by differential scanning calorimetry (DSC), depth‐sensing indentation, and profilometry. It is shown that such materials are capable of healing complex scratch patterns, also multiple times. Furthermore, microphase separation within PEO‐b‐PFGE block copolymer films is indicated by small angle X‐ray scattering (lamellar morphology with a domain spacing of approximately 19 nm), differential scanning calorimetry, and contact angle measurements.     

Fluorobenzotriazole (FTAZ)‐Based Polymer Donor Enables Organic Solar Cells Exceeding 12% Efficiency

The fluorobenzotriazole (FTAZ)‐based copolymer donors are promising candidates for nonfullerene polymer solar cells (PSCs), but suffer from relatively low photovoltaic performance due to their unsuitable energy levels and unfavorable morphology. Herein, three polymer donors, L24 , L68 , and L810 , based on a chlorinated‐thienyl benzodithiophene (BDT‐2Cl) unit and FTAZ with different branched alkyl side chain, are synthesized. Incorporation of a chlorine (Cl) atom into the BDT unit is found to distinctly optimize the molecular planarity, energy levels, and improve the polymerization activity. Impressively, subtle side chain length of FTAZ realizes a dramatic improvement in all the device parameters, as revealed by the short‐current density (J_sc) improved from 7.41 to 20.76 mA cm^?2, fill‐factor from 36.3 to 73.5%, and even the open‐circuit voltage (V_oc) from 0.495 to 0.790 V. The best power conversion efficiency (PCE) of 12.1% is obtained from the L810‐based device, which is one of the highest values reported for FTAZ‐based PSCs so far. Notably, the corresponding external quantum efficiency curve keeps a very prominent value up to 80% from 500 to 800 nm. The notable performance is discovered from the reduced energy loss, improved molecular face‐on orientation, the down‐shifted energy levels, and optimized absorption coefficient regulated by side‐chain engineering.     

Near‐Infrared Small Molecule Acceptor Enabled High‐Performance Nonfullerene Polymer Solar Cells with Over 13% Efficiency

One of the most promising approaches to achieve high‐performance polymer solar cells (PSCs) is to develop nonfullerene small molecule acceptors (SMAs) with an absorption extending to the near‐infrared (NIR) region. In this work, two novel SMAs, namely, BTTIC and BTOIC, are designed and synthesized, with optical bandgaps (E_g^opt) of 1.47 and 1.39 eV, respectively. Desipte the narrow E_g^opt, the PBDB‐T:BTTIC‐ and PBDB‐T:BTOIC‐based PSCs can maintain high V_OCs of over 0.90 and 0.86 V, respectively, with low energy losses (E_loss) < 0.6 eV. Meanwhile, due to the favorable morphology of the PBDB‐T:BTTIC blend, balanced carrier mobilities are achieved. The high external quantum efficiencies enable a high power conversion efficiency (PCE) up to 13.18% for the PBDB‐T:BTTIC‐based PSCs. In comparison, BTOIC shows an excessive crystallization propensity owing to its oxyalkyl side groups, which eventually leads to a relatively low PCE for the PBDB‐T:BTOIC‐based PSCs. Overall, this work provides insights into the design of novel NIR‐absorbing SMAs for nonfullerene PSCs.     

Ternary Polymer Solar Cells with High Efficiency of 14.24% by Integrating Two Well‐Complementary Nonfullerene Acceptors

Ternary polymer solar cells (PSCs) are one of the most promising device architectures that maintains the simplicity of single‐junction devices and provides an important platform to better tailor the multiple performance parameters of PSCs. Herein, a ternary PSC system is reported employing a wide bandgap polymeric donor (PBTA‐PS) and two small molecular nonfullerene acceptors (labeled as LA1 and 6TIC). LA1 and 6TIC keep not only well‐matched absorption profiles but also the rational crystallization properties. As a result, the optimal ternary PSC delivers a state of the art power conversion efficiency (PCE) of 14.24%, over 40% higher than the two binary devices, resulting from the prominently increased short‐circuit current density (J_sc) of 22.33 mA cm^?2, moderate open‐circuit voltage (V_oc) of 0.84 V, and a superior fill factor approaching 76%. Notably, the outstanding PCE of the ternary PSC ranks one of the best among the reported ternary solar cells. The greatly improved performance of ternary PSCs mainly derives from combining the complementary properties such as absorption and crystallinity. This work highlights the great importance of the rational design of matched acceptors toward highly efficient ternary PSCs.