Single‐Junction Binary‐Blend Nonfullerene Polymer Solar Cells with 12.1% Efficiency

A new fluorinated nonfullerene acceptor, ITIC‐Th1, has been designed and synthesized by introducing fluorine (F) atoms onto the end‐capping group 1,1‐dicyanomethylene‐3‐indanone (IC). On the one hand, incorporation of F would improve intramolecular interaction, enhance the push–pull effect between the donor unit indacenodithieno[3,2‐b]thiophene and the acceptor unit IC due to electron‐withdrawing effect of F, and finally adjust energy levels and reduce bandgap, which is beneficial to light harvesting and enhancing short‐circuit current density (J _SC). On the other hand, incorporation of F would improve intermolecular interactions through C? F···S, C? F···H, and C? F···π noncovalent interactions and enhance electron mobility, which is beneficial to enhancing J _SC and fill factor. Indeed, the results show that fluorinated ITIC‐Th1 exhibits redshifted absorption, smaller optical bandgap, and higher electron mobility than the nonfluorinated ITIC‐Th. Furthermore, nonfullerene organic solar cells (OSCs) based on fluorinated ITIC‐Th1 electron acceptor and a wide‐bandgap polymer donor FTAZ based on benzodithiophene and benzotriazole exhibit power conversion efficiency (PCE) as high as 12.1%, significantly higher than that of nonfluorinated ITIC‐Th (8.88%). The PCE of 12.1% is the highest in fullerene and nonfullerene‐based single‐junction binary‐blend OSCs. Moreover, the OSCs based on FTAZ:ITIC‐Th1 show much better efficiency and better stability than the control devices based on FTAZ:PC₇₁BM (PCE = 5.22%).     

High‐Performance Organic Bulk‐Heterojunction Solar Cells Based on Multiple‐Donor or Multiple‐Acceptor Components

Organic solar cells (OSCs) based on bulk heterojunction structures are promising candidates for next‐generation solar cells. However, the narrow absorption bandwidth of organic semiconductors is a critical issue resulting in insufficient usage of the energy from the solar spectrum, and as a result, it hinders performance. Devices based on multiple‐donor or multiple‐acceptor components with complementary absorption spectra provide a solution to address this issue. OSCs based on multiple‐donor or multiple‐acceptor systems have achieved power conversion efficiencies over 12%. Moreover, the introduction of an additional component can further facilitate charge transfer and reduce charge recombination through cascade energy structure and optimized morphology. This progress report provides an overview of the recent progress in OSCs based on multiple‐donor (polymer/polymer, polymer/dye, and polymer/small molecule) or multiple‐acceptor (fullerene/fullerene, fullerene/nonfullerene, and nonfullerene/nonfullerene) components.     

Recent Progress in Molecular Design of Fused Ring Electron Acceptors for Organic Solar Cells

The quest for sustainable energy sources has led to accelerated growth in research of organic solar cells (OSCs). A solution‐processed bulk‐heterojunction (BHJ) OSC generally contains a donor and expensive fullerene acceptors (FAs). The last 20 years have been devoted by the OSC community to developing donor materials, specifically low bandgap polymers, to complement FAs in BHJs. The current improvement from ≈2.5% in 2013 to 17.3% in 2018 in OSC performance is primarily credited to novel nonfullerene acceptors (NFA), especially fused ring electron acceptors (FREAs). FREAs offer unique advantages over FAs, like broad absorption of solar radiation, and they can be extensively chemically manipulated to tune optoelectronic and morphological properties. Herein, the current status in FREA‐based OSCs is summarized, such as design strategies for both wide and narrow bandgap FREAs for BHJ, all‐small‐molecule OSCs, semi‐transparent OSC, ternary, and tandem solar cells. The photovoltaics parameters for FREAs are summarized and discussed. The focus is on the various FREA structures and their role in optical and morphological tuning. Besides, the advantages and drawbacks of both FAs and NFAs are discussed. Finally, an outlook in the field of FREA‐OSCs for future material design and challenges ahead is provided.     

Dithieno[3,2‐b:2′,3′‐d]pyrrol Fused Nonfullerene Acceptors Enabling Over 13% Efficiency for Organic Solar Cells

A new electron‐rich central building block, 5,5,12,12‐tetrakis(4‐hexylphenyl)‐indacenobis‐(dithieno[3,2‐b:2′,3′‐d]pyrrol) (INP), and two derivative nonfullerene acceptors (INPIC and INPIC‐4F) are designed and synthesized. The two molecules reveal broad (600–900 nm) and strong absorption due to the satisfactory electron‐donating ability of INP. Compared with its counterpart INPIC, fluorinated nonfullerene acceptor INPIC‐4F exhibits a stronger near‐infrared absorption with a narrower optical bandgap of 1.39 eV, an improved crystallinity with higher electron mobility, and down‐shifted highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels. Organic solar cells (OSCs) based on INPIC‐4F exhibit a high power conversion efficiency (PCE) of 13.13% and a relatively low energy loss of 0.54 eV, which is among the highest efficiencies reported for binary OSCs in the literature. The results demonstrate the great potential of the new INP as an electron‐donating building block for constructing high‐performance nonfullerene acceptors for OSCs.     

16.67% Rigid and 14.06% Flexible Organic Solar Cells Enabled by Ternary Heterojunction Strategy

Ternary heterojunction strategies appear to be an efficient approach to improve the efficiency of organic solar cells (OSCs) through harvesting more sunlight. Ternary OSCs are fabricated by employing wide bandgap polymer donor (PM6), narrow bandgap nonfullerene acceptor (Y6), and PC₇₁BM as the third component to tune the light absorption and morphologies of the blend films. A record power conversion efficiency (PCE) of 16.67% (certified as 16.0%) on rigid substrate is achieved in an optimized PM6:Y6:PC₇₁BM blend ratio of 1:1:0.2. The introduction of PC₇₁BM endows the blend with enhanced absorption in the range of 300–500 nm and optimises interpenetrating morphologies to promote photogenerated charge dissociation and extraction. More importantly, a PCE of 14.06% for flexible ITO‐free ternary OSCs is obtained based on this ternary heterojunction system, which is the highest PCE reported for flexible state‐of‐the‐art OSCs. A very promising ternary heterojunction strategy to develop highly efficient rigid and flexible OSCs is presented.     

Naphthodithiophene‐Based Nonfullerene Acceptor for High‐Performance Organic Photovoltaics: Effect of Extended Conjugation

Naphtho[1,2‐b:5,6‐b′]dithiophene is extended to a fused octacyclic building block, which is end capped by strong electron‐withdrawing 2‐(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene)malononitrile to yield a fused‐ring electron acceptor (IOIC2) for organic solar cells (OSCs). Relative to naphthalene‐based IHIC2, naphthodithiophene‐based IOIC2 with a larger π‐conjugation and a stronger electron‐donating core shows a higher lowest unoccupied molecular orbital energy level (IOIC2: ?3.78 eV vs IHIC2: ?3.86 eV), broader absorption with a smaller optical bandgap (IOIC2: 1.55 eV vs IHIC2: 1.66 eV), and a higher electron mobility (IOIC2: 1.0 × 10^?3 cm² V^?1 s^?1 vs IHIC2: 5.0 × 10^?4 cm² V^?1 s^?1). Thus, IOIC2‐based OSCs show higher values in open‐circuit voltage, short‐circuit current density, fill factor, and thereby much higher power conversion efficiency (PCE) values than those of the IHIC2‐based counterpart. In particular, as‐cast OSCs based on FTAZ: IOIC2 yield PCEs of up to 11.2%, higher than that of the control devices based on FTAZ: IHIC2 (7.45%). Furthermore, by using 0.2% 1,8‐diiodooctane as the processing additive, a PCE of 12.3% is achieved from the FTAZ:IOIC2 ‐ based devices, higher than that of the FTAZ:IHIC2 ‐ based devices (7.31%). These results indicate that incorporating extended conjugation into the electron‐donating fused‐ring units in nonfullerene acceptors is a promising strategy for designing high‐performance electron acceptors.     

High‐Efficiency All‐Small‐Molecule Organic Solar Cells Based on an Organic Molecule Donor with Alkylsilyl‐Thienyl Conjugated Side Chains

Two medium‐bandgap p‐type organic small molecules H21 and H22 with an alkylsily‐thienyl conjugated side chain on benzo[1,2‐b:4,5‐b′]dithiophene central units are synthesized and used as donors in all‐small‐molecule organic solar cells (SM‐OSCs) with a narrow‐bandgap n‐type small molecule 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) as the acceptor. In comparison to H21 with 3‐ethyl rhodanine as the terminal group, H22 with cyanoacetic acid esters as the terminal group shows blueshifted absorption, higher charge‐carrier mobility and better 3D charge pathway in blend films. The power conversion efficiency (PCE) of the SM‐OSCs based on H22:IDIC reaches 10.29% with a higher open‐circuit voltage of 0.942 V and a higher fill factor of 71.15%. The PCE of 10.29% is among the top efficiencies of nonfullerene SM‐OSCs reported in the literature to date.     

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.     

High Efficiency Nonfullerene Polymer Solar Cells with Thick Active Layer and Large Area

In this work, high‐efficiency nonfullerene polymer solar cells (PSCs) are developed based on a thiazolothiazole‐containing wide bandgap polymer PTZ1 as donor and a planar IDT‐based narrow bandgap small molecule with four side chains (IDIC) as acceptor. Through thermal annealing treatment, a power conversion efficiency (PCE) of up to 11.5% with an open circuit voltage (V _oc) of 0.92 V, a short‐circuit current density (J _sc) of 16.4 mA cm^?2, and a fill factor of 76.2% is achieved. Furthermore, the PSCs based on PTZ1:IDIC still exhibit a relatively high PCE of 9.6% with the active layer thickness of 210 nm and a superior PCE of 10.5% with the device area of up to 0.81 cm². These results indicate that PTZ1 is a promising polymer donor material for highly efficient fullerene‐free PSCs and large‐scale devices fabrication.     

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.     

An Unfused‐Core‐Based Nonfullerene Acceptor Enables High‐Efficiency Organic Solar Cells with Excellent Morphological Stability at High Temperatures

Most nonfullerene acceptors developed so far for high‐performance organic solar cells (OSCs) are designed in planar molecular geometry containing a fused‐ring core. In this work, a new nonfullerene acceptor of DF‐PCIC is synthesized with an unfused‐ring core containing two cyclopentadithiophene (CPDT) moieties and one 2,5‐difluorobenzene (DFB) group. A nearly planar geometry is realized through the F···H noncovalent interaction between CPDT and DFB for DF‐PCIC. After proper optimizations, the OSCs with DF‐PCIC as the acceptor and the polymer PBDB‐T as the donor yield the best power conversion efficiency (PCE) of 10.14% with a high fill factor of 0.72. To the best of our knowledge, this efficiency is among the highest values for the OSCs with nonfullerene acceptors owning unfused‐ring cores. Furthermore, no obvious morphological changes are observed for the thermally treated PBDB‐T:DF‐PCIC blended films, and the relevant devices can keep ≈70% of the original PCEs upon thermal treatment at 180 °C for 12 h. This tolerance of such a high temperature for so long time is rarely reported for fullerene‐free OSCs, which might be due to the unique unfused‐ring core of DF‐PCIC. Therefore, the work provides new idea for the design of new nonfullerene acceptors applicable in commercial OSCs in the future.     

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.     

Unique Energy Alignments of a Ternary Material System toward High‐Performance Organic Photovoltaics

Incorporating narrow‐bandgap near‐infrared absorbers as the third component in a donor/acceptor binary blend is a new strategy to improve the power conversion efficiency (PCE) of organic photovoltaics (OPV). However, there are two main restrictions: potential charge recombination in the narrow‐gap material and miscompatibility between each component. The optimized design is to employ a third component (structurally similar to the donor or acceptor) with a lowest unoccupied molecular orbital (LUMO) energy level similar to the acceptor and a highest occupied molecular orbital (HOMO) energy level similar to the donor. In this design, enhanced absorption of the active layer and enhanced charge transfer can be realized without breaking the optimized morphology of the active layer. Herein, in order to realize this design, two new narrow‐bandgap nonfullerene acceptors with suitable energy levels and chemical structures are designed, synthesized, and employed as the third component in the donor/acceptor binary blend, which boosts the PCE of OPV to 11.6%.     

Surpassing 10% Efficiency Benchmark for Nonfullerene Organic Solar Cells by Scalable Coating in Air from Single Nonhalogenated Solvent

The commercialization of nonfullerene organic solar cells (OSCs) critically relies on the response under typical operating conditions (for instance, temperature and humidity) and the ability of scale‐up. Despite the rapid increase in power conversion efficiency (PCE) of spin‐coated devices fabricated in a protective atmosphere, the efficiencies of printed nonfullerene OSC devices by blade coating are still lower than 6%. This slow progress significantly limits the practical printing of high‐performance nonfullerene OSCs. Here, a new and relatively stable nonfullerene combination is introduced by pairing the nonfluorinated acceptor IT‐M with the polymeric donor FTAZ. Over 12% efficiency can be achieved in spin‐coated FTAZ:IT‐M devices using a single halogen‐free solvent. More importantly, chlorine‐free, blade coating of FTAZ:IT‐M in air is able to yield a PCE of nearly 11% despite a humidity of ≈50%. X‐ray scattering results reveal that large π–π coherence length, high degree of face‐on orientation with respect to the substrate, and small domain spacing of ≈20 nm are closely correlated with such high device performance. The material system and approach yield the highest reported performance for nonfullerene OSC devices by a coating technique approximating scalable fabrication methods and hold great promise for the development of low‐cost, low‐toxicity, and high‐efficiency OSCs by high‐throughput production.     

Over 14% Efficiency in Organic Solar Cells Enabled by Chlorinated Nonfullerene Small‐Molecule Acceptors

To make organic solar cells (OSCs) more competitive in the diverse photovoltaic cell technologies, it is very important to demonstrate that OSCs can achieve very good efficiencies and that their cost can be reduced. Here, a pair of nonfullerene small‐molecule acceptors, IT‐2Cl and IT‐4Cl, is designed and synthesized by introducing easy‐synthesis chlorine substituents onto the indacenodithieno[3,2‐b]thiophene units. The unique feature of the large dipole moment of the C? Cl bond enhances the intermolecular charge‐transfer effect between the donor–acceptor structures, and thus expands the absorption and down shifts the molecular energy levels. Meanwhile, the introduction of C? Cl also causes more pronounced molecular stacking, which also helps to expand the absorption spectrum. Both of the designed OSCs devices based on two acceptors can deliver a power conversion efficiency (PCE) greater than 13% when blended with a polymer donor with a low‐lying highest occupied molecular orbital level. In addition, since IT‐2Cl and IT‐4Cl have very good compatibility, a ternary OSC device integrating these two acceptors is also fabricated and obtains a PCE greater than 14%. Chlorination demonstrates effective ability in enhancing the device performance and facile synthesis route, which both deserve further exploitation in the modification of photovoltaic materials.     

Fused Hexacyclic Nonfullerene Acceptor with Strong Near‐Infrared Absorption for Semitransparent Organic Solar Cells with 9.77% Efficiency

A fused hexacyclic electron acceptor, IHIC, based on strong electron‐donating group dithienocyclopentathieno[3,2‐b ]thiophene flanked by strong electron‐withdrawing group 1,1‐dicyanomethylene‐3‐indanone, is designed, synthesized, and applied in semitransparent organic solar cells (ST‐OSCs). IHIC exhibits strong near‐infrared absorption with extinction coefficients of up to 1.6 × 10⁵m ^?1 cm^?1, a narrow optical bandgap of 1.38 eV, and a high electron mobility of 2.4 × 10^?3 cm² V^?1 s^?1. The ST‐OSCs based on blends of a narrow‐bandgap polymer donor PTB7‐Th and narrow‐bandgap IHIC acceptor exhibit a champion power conversion efficiency of 9.77% with an average visible transmittance of 36% and excellent device stability; this efficiency is much higher than any single‐junction and tandem ST‐OSCs reported in the literature.     

Rational Tuning of Molecular Interaction and Energy Level Alignment Enables High‐Performance Organic Photovoltaics

The performance of organic photovoltaics (OPVs) has rapidly improved over the past years. Recent work in material design has primarily focused on developing near‐infrared nonfullerene acceptors with broadening absorption that pair with commercialized donor polymers; in the meanwhile, the influence of the morphology of the blend film and the energy level alignment on the efficiency of charge separation needs to be synthetically considered. Herein, the selection rule of the donor/acceptor blend is demonstrated by rationally considering the molecular interaction and energy level alignment, and highly efficient OPV devices using both‐fluorinated or both‐nonfluorinated donor/acceptor blends are realized. With the enlarged absorption, ideal morphology, and efficient charge transfer, the devices based on the PBDB‐T‐F/Y1‐4F blend and PBDB‐T‐F/Y6 exhibit champion power conversion efficiencies as high as 14.8% and 15.9%, respectively.     

Two Well‐Miscible Acceptors Work as One for Efficient Fullerene‐Free Organic Solar Cells

High‐performance ternary organic solar cells are fabricated by using a wide‐bandgap polymer donor (bithienyl‐benzodithiophene‐alt‐fluorobenzotriazole copolymer, J52) and two well‐miscible nonfullerene acceptors, methyl‐modified nonfullerene acceptor (IT‐M) and 2,2′‐((2Z ,2′Z )‐((5,5′‐(4,4,9,9‐tetrakis(4‐hexylphenyl)‐4,9‐dihydros‐indaceno[1,2‐b :5,6‐b ′]dithiophene‐2,7‐diyl)bis(4‐((2‐ethylhexyl)oxy)thiophene‐5,2‐diyl))bis(methanylylidene))bis(3‐oxo‐2,3‐dihydro‐1H ‐indene‐2,1‐diylidene))dimalononitrile (IEICO). The two acceptors with complementary absorption spectra and similar lowest unoccupied molecular orbital levels show excellent compatibility in the blend due to their very similar chemical structures. Consequently, the obtained ternary organic solar cells (OSC) exhibits a high efficiency of 11.1%, with an enhanced short‐circuit current density of 19.7 mA cm^?2 and a fill factor of 0.668. In this ternary system, broadened absorption, similar output voltages, and compatible morphology are achieved simultaneously, demonstrating a promising strategy to further improve the performance of ternary OSCs.     

Black Phosphorous Quantum Dots Sandwiched Organic Solar Cells

Black phosphorous quantum dots (BPQDs) possess ambipolar charge transport, high mobility, and a tunable direct bandgap. Here, liquid‐exfoliated BPQDs are used as interlayers to modify both the electron transport layer and hole transport layer in organic solar cells (OSCs). The incorporation of BPQDs is beneficial to the formation of a cascade band structure and electron/hole transfer and extraction. The power conversion efficiency of the BPQDs‐incorporated OSC based on PTB7‐Th:FOIC blend is enhanced from 11.8% to 13.1%. In addition, power conversion efficiency enhancement is also achieved for other nonfullerene and fullerene‐based devices, demonstrating the universality of this interlayer methodology.     

Efficient Semitransparent Organic Solar Cells with Tunable Color enabled by an Ultralow‐Bandgap Nonfullerene Acceptor

Semitransparent organic solar cells (OSCs) show attractive potential in power‐generating windows. However, the development of semitransparent OSCs is lagging behind opaque OSCs. Here, an ultralow‐bandgap nonfullerene acceptor, “IEICO‐4Cl”, is designed and synthesized, whose absorption spectrum is mainly located in the near‐infrared region. When IEICO‐4Cl is blended with different polymer donors (J52, PBDB‐T, and PTB7‐Th), the colors of the blend films can be tuned from purple to blue to cyan, respectively. Traditional OSCs with a nontransparent Al electrode fabricated by J52:IEICO‐4Cl, PBDB‐T:IEICO‐4Cl, and PTB7‐Th:IEICO‐4Cl yield power conversion efficiencies (PCE) of 9.65 ± 0.33%, 9.43 ± 0.13%, and 10.0 ± 0.2%, respectively. By using 15 nm Au as the electrode, semitransparent OSCs based on these three blends also show PCEs of 6.37%, 6.24%, and 6.97% with high average visible transmittance (AVT) of 35.1%, 35.7%, and 33.5%, respectively. Furthermore, via changing the thickness of Au in the OSCs, the relationship between the transmittance and efficiency is studied in detail, and an impressive PCE of 8.38% with an AVT of 25.7% is obtained, which is an outstanding value in the semitransparent OSCs.