Realizing Over 13% Efficiency in Green‐Solvent‐Processed Nonfullerene Organic Solar Cells Enabled by 1,3,4‐Thiadiazole‐Based Wide‐Bandgap Copolymers

Two novel wide‐bandgap copolymers, PBDT‐TDZ and PBDTS‐TDZ, are developed based on 1,3,4‐thiadiazole (TDZ) and benzo[1,2‐b:4,5‐b′]dithiophene (BDT) building blocks. These copolymers exhibit wide bandgaps over 2.07 eV and low‐lying highest occupied molecular orbital (HOMO) levels below −5.35 eV, which match well with the typical low‐bandgap acceptor of ITIC, resulting in a good complementary absorption from 300 to 900 nm and a low HOMO level offset (≤0.13 eV). Compared to PBDT‐TDZ, PBDTS‐TDZ with alkylthio side chains exhibits the stronger optical absorption, lower‐lying HOMO level, and higher crystallinity. By using a single green solvent of o‐xylene, PBDTS‐TDZ:ITIC devices exhibit a large open‐circuit voltage (V_oc) up to 1.10 eV and an extremely low energy loss (E_loss) of 0.48 eV. At the same time, the desirable high short‐circuit current density (J_sc) of 17.78 mA cm⁻² and fill factor of 65.4% are also obtained, giving rise to a high power conversion efficiency (PCE) of 12.80% without any additive and post‐treatment. When adopting a homotandem device architecture, the PCE is further improved to 13.35% (certified as 13.19%) with a much larger V_oc of 2.13 V, which is the best value for any type of homotandem organic solar cells reported so far.     

High‐Performance Nonfullerene Polymer Solar Cells based on Imide‐Functionalized Wide‐Bandgap Polymers

High‐performance nonfullerene polymer solar cells (PSCs) are developed by integrating the nonfullerene electron‐accepting material 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′]dithiophne) (ITIC) with a wide‐bandgap electron‐donating polymer PTzBI or PTzBI‐DT, which consists of an imide functionalized benzotriazole (TzBI) building block. Detailed investigations reveal that the extension of conjugation can affect the optical and electronic properties, molecular aggregation properties, charge separation in the bulk‐heterojunction films, and thus the overall photovoltaic performances. Single‐junction PSCs based on PTzBI:ITIC and PTzBI‐DT:ITIC exhibit remarkable power conversion efficiencies (PCEs) of 10.24% and 9.43%, respectively. To our knowledge, these PCEs are the highest efficiency values obtained based on electron‐donating conjugated polymers consisting of imide‐functionalized electron‐withdrawing building blocks. Of particular interest is that the resulting device based on PTzBI exhibits remarkable PCE of 7% with the thickness of active layer of 300 nm, which is among the highest values of nonfullerene PSCs utilizing thick photoactive layer. Additionally, the device based on PTzBI:ITIC exhibits prominent stability, for which the PCE remains as 9.34% after thermal annealing at 130 °C for 120 min. These findings demonstrate the great promise of using this series of wide‐bandgap conjugated polymers as electron‐donating materials for high‐performance nonfullerene solar cells toward high‐throughput roll‐to‐roll processing technology.     

Efficient Nonfullerene Polymer Solar Cells Enabled by a Novel Wide Bandgap Small Molecular Acceptor

A wide bandgap small molecular acceptor, SFBRCN, containing a 3D spirobifluorene core flaked with a 2,1,3‐benzothiadiazole (BT) and end‐capped with highly electron‐deficient (3‐ethylhexyl‐4‐oxothiazolidine‐2‐yl)dimalononitrile (RCN) units, has been successfully synthesized as a small molecular acceptor (SMA) for nonfullerene polymer solar cells (PSCs). This SMA exhibits a relatively wide optical bandgap of 2.03 eV, which provides a complementary absorption to commonly used low bandgap donor polymers, such as PTB7‐Th. The strong electron‐deficient BT and RCN units afford SFBRCN with a low‐lying LUMO (lowest unoccupied molecular orbital) level, while the 3D structured spirobifluorene core can effectively suppress the self‐aggregation tendency of the SMA, thus yielding a polymer:SMA blend with reasonably small domain size. As the results of such molecular design, SFBRCN enables nonfullerene PSCs with a high efficiency of 10.26%, which is the highest performance reported to date for a large bandgap nonfullerene SMA.     

Single‐Junction Polymer Solar Cells with 16.35% Efficiency Enabled by a Platinum(II) Complexation Strategy

A new strategy of platinum(II) complexation is developed to regulate the crystallinity and molecular packing of polynitrogen heterocyclic polymers, optimize the morphology of the active blends, and improve the efficiency of the resulting nonfullerene polymer solar cells (NF‐PSCs). The newly designed s‐tetrazine (s‐TZ)‐containing copolymer of PSFTZ (4,8‐bis(5‐((2‐butyloctyl)thio)‐4‐fluorothiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐alt‐3,6‐bis(4‐octylthiophen‐2‐yl)‐1,2,4,5‐tetrazine) has a strong aggregation property, which results in serious phase separation and large domains when blending with Y6 ((2,2′‐((2Z,2′Z)‐((12,13‐bis(2‐ethylhexyl)‐3,9‐diundecyl‐12,13‐dihydro‐[1,2,5]thiadiazolo[3,4‐e]thieno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2‐g]thieno[2′,3′:4,5]thieno[3,2‐b]indole‐2,10‐diyl)bis(methanylylidene))bis(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))dimalononitrile)), and produces a power‐conversion efficiency (PCE) of 13.03%. By adding small amount of Pt(Ph)₂(DMSO)₂ (Ph, phenyl and DMSO, dimethyl sulfoxide), platinum(II) complexation would occur between Pt(Ph)₂(DMSO)₂ and PSFTZ. The bulky benzene ring on the platinum(II) complex increases the steric hindrance along the polymer main chain, inhibits the polymer aggregation strength, regulates the phase separation, optimizes the morphology, and thus improves the efficiency to 16.35% in the resulting devices. 16.35% is the highest efficiency for single‐junction PSCs reported so far.     

Highly Efficient Ternary‐Blend Polymer Solar Cells Enabled by a Nonfullerene Acceptor and Two Polymer Donors with a Broad Composition Tolerance

In this work, highly efficient ternary‐blend organic solar cells (TB‐OSCs) are reported based on a low‐bandgap copolymer of PTB7‐Th, a medium‐bandgap copolymer of PBDB‐T, and a wide‐bandgap small molecule of SFBRCN. The ternary‐blend layer exhibits a good complementary absorption in the range of 300–800 nm, in which PTB7‐Th and PBDB‐T have excellent miscibility with each other and a desirable phase separation with SFBRCN. In such devices, there exist multiple energy transfer pathways from PBDB‐T to PTB7‐Th, and from SFBRCN to the above two polymer donors. The hole‐back transfer from PTB7‐Th to PBDB‐T and multiple electron transfers between the acceptor and the donor materials are also observed for elevating the whole device performance. After systematically optimizing the weight ratio of PBDB‐T:PTB7‐Th:SFBRCN, a champion power conversion efficiency (PCE) of 12.27% is finally achieved with an open‐circuit voltage (V _oc) of 0.93 V, a short‐circuit current density (J _sc) of 17.86 mA cm^?2, and a fill factor of 73.9%, which is the highest value for the ternary OSCs reported so far. Importantly, the TB‐OSCs exhibit a broad composition tolerance with a high PCE over 10% throughout the whole blend ratios.     

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.     

A 3‐Fluoro‐4‐hexylthiophene‐Based Wide Bandgap Donor Polymer for 10.9% Efficiency Eco‐Friendly Nonfullerene Organic Solar Cells

Nonfullerene organic solar cells (NFOSCs) are attracting increasing academic and industrial interest due to their potential uses for flexible and lightweight products using low‐cost roll‐to‐roll technology. In this work, two wide bandgap (WBG) polymers, namely P(fTh‐BDT)‐C6 and P(fTh‐2DBDT)‐C6, are designed and synthesized using benzodithiophene (BDT) derivatives. Good oxidation stability and high solubility are achieved by simultaneously introducing fluorine and alkyl chains to a single thiophene (Th) unit. Solid P(fTh‐2DBDT)‐C6 films present WBG optical absorption, suitable frontier orbital levels, and strong π–π stacking effects. In addition, P(fTh‐2DBDT)‐C6 exhibits good solubility in both halogenated and nonhalogenated solvents, suggesting its suitability as donor polymer for NFOSCs. The P(fTh‐2DBDT)‐C6:3,9‐bis(2‐methylene‐(3‐(1,1‐dicyanomethylene)‐indanone))‐5,5,11,11‐tetrakis(5‐hexylthienyl)‐dithieno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene (ITIC‐Th) based device processed using chlorobenzene/1,8‐diiodooctane (CB/DIO) exhibits a remarkably high power conversion efficiency (PCE) of 11.1%. Moreover, P(fTh‐2DBDT)‐C6:ITIC‐Th reaches a high PCE of 10.9% when processed using eco‐friendly solvents, such as o‐xylene/diphenyl ether (DPE). The cell processed using CB/DIO maintains 100% efficiency after 1272 h, while that processed using o‐xylene/DPE presents a 101% increase in efficiency after 768 h and excellent long‐term stability. The results of this study demonstrate that simultaneous fluorination and alkylation are effective methods for designing donor polymers appropriate for high‐performance NFOSCs.     

High‐Performance As‐Cast Nonfullerene Polymer Solar Cells with Thicker Active Layer and Large Area Exceeding 11% Power Conversion Efficiency

In this work, a nonfullerene polymer solar cell (PSC) based on a wide bandgap polymer donor PM6 containing fluorinated thienyl benzodithiophene (BDT‐2F) unit and a narrow bandgap small molecule acceptor 2,2′‐((2Z,2′Z)‐((4,4,9,9‐tetrahexyl‐4,9‐dihydro‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐2,7‐diyl)bis(methanylylidene))bis(3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))dimalononitrile (IDIC) is developed. In addition to matched energy levels and complementary absorption spectrum with IDIC, PM6 possesses high crystallinity and strong π–π stacking alignment, which are favorable to charge carrier transport and hence suppress recombination in devices. As a result, the PM6:IDIC‐based PSCs without extra treatments show an outstanding power conversion efficiency (PCE) of 11.9%, which is the record value for the as‐cast PSC devices reported in the literature to date. Moreover, the device performances are insensitive to the active layer thickness (≈95–255 nm) and device area (0.20–0.81 cm²) with PCEs of over 11%. Besides, the PM6:IDIC‐based flexible PSCs with a large device area of 1.25 cm² exhibit a high PCE of 6.54%. These results indicate that the PM6:IDIC blend is a promising candidate for future roll‐to‐roll mass manufacturing and practical application of highly efficient PSCs.     

Enhanced π–π Interactions of Nonfullerene Acceptors by Volatilizable Solid Additives in Efficient Polymer Solar Cells

Fine‐tuning of the nanoscale morphologies of the active layers in polymer solar cells (PSCs) through various techniques plays a vital role in improving the photovoltaic performance. However, for emerging nonfullerene (NF) PSCs, the morphology optimization of the active‐layer films empirically follows the methods originally developed in fullerene‐based blends and lacks systematic studies. In this work, two solid additives with different volatilities, SA‐4 and SA‐7, are applied to investigate their influence on the morphologies and photovoltaic performances of NF‐PSCs. Although both solid additives effectively promote the molecular packing of the NF acceptors, due to the higher volatility of SA‐4, the devices processed with SA‐4 exhibit a power conversion efficiency of 13.5%, higher than that of the control devices, and the devices processed with SA‐7 exhibit poor performances. Through a series of detailed morphological analyses, it is found that the volatilization of SA‐4 after thermal annealing is beneficial for the self‐assembly packing of acceptors, while the residuals due to the incomplete volatilization of SA‐7 have a negative effect on the film morphology. The results delineate the feasibility of applying volatilizable solid additives and provide deeper insights into the working mechanism, establishing guidelines for further material design of solid additives.     

Efficient Semitransparent Solar Cells with High NIR Responsiveness Enabled by a Small‐Bandgap Electron Acceptor

Inspired by the remarkable promotion of power conversion efficiency (PCE), commercial applications of organic photovoltaics (OPVs) can be foreseen in near future. One of the most promising applications is semitransparent (ST) solar cells that can be utilized in value‐added applications such as energy‐harvesting windows. However, the single‐junction STOPVs utilizing fullerene acceptors show relatively low PCEs of 4%–6% due to the limited sunlight absorption because it is a dilemma that more photons need to be harvested in UV–vis–near‐infrared (NIR) region to generate high photocurrent, which leads to the significant reduction of device transparency. This study describes the development of a new small‐bandgap electron‐acceptor material ATT‐2, which shows a strong NIR absorption between 600 and 940 nm with an E _g^opt of 1.32 eV. By combining with PTB7‐Th, the as‐cast OPVs yield PCEs of up to 9.58% with a fill factor of 0.63, an open‐circuit voltage of 0.73 V, and a very high short‐circuit current of 20.75 mA cm^?2. Owing to the favorable complementary absorption of low‐bangap PTB7‐Th and small‐bandgap ATT‐2 in NIR region, the proof‐of‐concept STOPVs show the highest PCE of 7.7% so far reported for single‐junction STOPVs with a high transparency of 37%.     

P3HT‐Based Polymer Solar Cells with 8.25% Efficiency Enabled by a Matched Molecular Acceptor and Smart Green‐Solvent Processing Technology

A novel molecular acceptor of TrBTIC (2,7,12‐tris((2‐(3‐oxo‐2,3‐dihydroinden‐1‐ylidene)malononitrile‐7‐benzothiadiazole‐2‐)truxene) is designed by attaching the 2‐(3‐oxo‐2,3‐dihydroinden‐1‐ylidene)malononitrile‐benzothiadiazole (BTIC) electron‐deficient unit to an electron‐rich truxene core. TrBTIC has excellent solubility in common solvents and features good energy level matching with poly(3‐hexylthiophene) (P3HT). Interestingly, P3HT can be readily dissolved in warm 1,2,4‐trimethylbenzene (TMB), a green solvent, but crystallizes slowly with long‐term aging in TMB at room temperature. A prephase separation can thus occur before active blend film deposition, and the separation degree can be easily controlled by varying the aging time. After 40 min of aging, the resulting active blend has the most appropriate phase separation with uniform nanowires, which forms favorable interpenetrating networks for exciton dissociation and charge transport. As a result, the device performance is improved from 6.62% to 8.25%. Excitingly, 8.25% is a new record for P3HT‐based solar cells. The study not only provides an efficient nonfullerene acceptor for matching P3HT donors but also develops a promising processing technology to realize high‐performance P3HT‐based polymer solar cells with an efficiency over 8%.     

Highly Efficient,Stable, and Ductile Ternary Nonfullerene Organic Solar Cells from a Two‐Donor Polymer Blend

Organic solar cells (OSCs) are one of the most promising cost‐effective options for utilizing solar energy, and, while the field of OSCs has progressed rapidly in device performance in the past few years, the stability of nonfullerene OSCs has received less attention. Developing devices with both high performance and long‐term stability remains challenging, particularly if the material choice is restricted by roll‐to‐roll and benign solvent processing requirements and desirable mechanical durability. Building upon the ink (toluene:FTAZ:IT‐M) that broke the 10% benchmark when blade‐coated in air, a second donor material (PBDB‐T) is introduced to stabilize and enhance performance with power conversion efficiency over 13% while keeping toluene as the solvent. More importantly, the ternary OSCs exhibit excellent thermal stability and storage stability while retaining high ductility. The excellent performance and stability are mainly attributed to the inhibition of the crystallization of nonfullerene small‐molecular acceptors (SMAs) by introducing a stiff donor that also shows low miscibility with the nonfullerene SMA and a slightly higher highest occupied molecular orbital (HOMO) than the host polymer. The study indicates that improved stability and performance can be achieved in a synergistic way without significant embrittlement, which will accelerate the future development and application of nonfullerene OSCs.