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.     

Stable and Efficient Organo‐Metal Halide Hybrid Perovskite Solar Cells via π‐Conjugated Lewis Base Polymer Induced Trap Passivation and Charge Extraction

High‐quality pinhole‐free perovskite film with optimal crystalline morphology is critical for achieving high‐efficiency and high‐stability perovskite solar cells (PSCs). In this study, a p‐type π‐conjugated polymer 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) is introduced into chlorobenzene to form a facile and effective template‐agent during the anti‐solvent process of perovskite film formation. The π‐conjugated polymer PBDB‐T is found to trigger a heterogeneous nucleation over the perovskite precursor film and passivate the trap states of the mixed perovskite film through the formation of Lewis adducts between lead and oxygen atom in PBDB‐T. The p‐type semiconducting and hydrophobic PBDB‐T polymer fills in the perovskite grain boundaries to improve charge transfer for better conductivity and prevent moisture invasion into the perovskite active layers. Consequently, the PSCs with PBDB‐T modified anti‐solvent processing leads to a high‐efficiency close to 20%, and the devices show excellent stability, retaining about 90% of the initial power conversion efficiency after 150 d storage in dry air.     

Nonfullerene Tandem Organic Solar Cells with High Performance of 14.11%

Fabricating solar cells with tandem structure is an efficient way to broaden the photon response range without further increasing the thermalization loss in the system. In this work, a tandem organic solar cell (TOSC) based on highly efficient nonfullerene acceptors (NFAs) with series connection type is demonstrated. To meet the different demands of front and rear sub‐cells, two NFAs named F‐M and NOBDT with a whole absorption range from 300 to 900 nm are designed, when blended with wide bandgap polymer 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) and narrow bandgap polymer PTB7‐Th, respectively, the PBDB‐T: F‐M system exhibits a high V_oc of 0.98 V and the PTB7‐Th: NOBDT system shows a remarkable J_sc of 19.16 mA cm^?2, which demonstrate their potential in the TOSCs. With the guidance of optical simulation, by systematically optimizing the thickness of each layer in the TOSC, an outstanding power conversion efficiency of 14.11%, with a V_oc of 1.71 V, a J_sc of 11.72 mA cm^?2, and a satisfactory fill factor of 0.70 is achieved; this result is one of the top efficiencies reported to date in the field of organic solar cells.     

A Tandem Organic Solar Cell with PCE of 14.52% Employing Subcells with the Same Polymer Donor and Two Absorption Complementary Acceptors

The tandem structure is an efficient way to simultaneously tackle absorption and thermalization losses of the single junction solar cells. In this work, a high‐performance tandem organic solar cell (OSC) using two subcells with the same donor 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) and two acceptors, F‐M and 2,9‐bis(2‐methylene‐(3(1,1‐dicyanomethylene)benz[f ]indanone))7,12‐dihydro‐(4,4,10,10‐tetrakis(4‐hexylphenyl)‐5,11‐diocthylthieno[3′,2′:4,5]cyclopenta[1,2‐b]thieno[2″,3″:3′,4′]cyclopenta[1′,2′:4,5]thieno[2,3‐f][1]benzothiophene (NNBDT), with complementary absorptions is demonstrated. The two subcells show high V_oc with value of 0.99 V for the front cell and 0.86 V for the rear cell, which is the prerequisite for obtaining high V_oc of their series‐connected tandem device. Although there is much absorption overlap for the subcells, a decent J_sc of the tandem cell is still obtained owing to the complementary absorption of the two acceptors in a wide range. With systematic device optimizations, a best power conversion efficiency of 14.52% is achieved for the tandem device, with a high V_oc of 1.82 V, a notable FF of 74.7%, and a decent J_sc of 10.68 mA cm^?2. This work demonstrates a promising strategy of fabricating high‐efficiency tandem OSCs through elaborate selection of the active layer materials in each subcell and tradeoff of the V_oc and J_sc of the tandem cells.     

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.     

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.     

Over 14% Efficiency in Polymer Solar Cells Enabled by a Chlorinated Polymer Donor

Fluorine‐contained polymers, which have been widely used in highly efficient polymer solar cells (PSCs), are rather costly due to their complicated synthesis and low yields in the preparation of components. Here, the feasibility of replacing the critical fluorine substituents in high‐performance photovoltaic polymer donors with chlorine is demonstrated, and two polymeric donors, PBDB‐T‐2F and PBDB‐T‐2Cl, are synthesized and compared in parallel. The synthesis of PBDB‐T‐2Cl is much simpler than that of PBDB‐T‐2F. The two polymers have very similar optoelectronic and morphological properties, except the chlorinated polymer possess lower molecular energy levels than the fluorinated one. As a result, the PBDB‐T‐2Cl‐based PSCs exhibit higher open circuit voltage (V_oc) than the PBDB‐T‐2F‐based devices, leading to an outstanding power conversion efficiency of over 14%. This work establishes a more economical design paradigm of replacing fluorine with chlorine for preparing highly efficient polymer donors.     

A Twisted Thieno[3,4‐b]thiophene‐Based Electron Acceptor Featuring a 14‐π‐Electron Indenoindene Core for High‐Performance Organic Photovoltaics

With an indenoindene core, a new thieno[3,4‐b ]thiophene‐based small‐molecule electron acceptor, 2,2′‐((2Z,2′Z)‐((6,6′‐(5,5,10,10‐tetrakis(2‐ethylhexyl)‐5,10‐dihydroindeno[2,1‐a]indene‐2,7‐diyl)bis(2‐octylthieno[3,4‐b]thiophene‐6,4‐diyl))bis(methanylylidene))bis(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))dimalononitrile ( NITI ), is successfully designed and synthesized. Compared with 12‐π‐electron fluorene, a carbon‐bridged biphenylene with an axial symmetry, indenoindene, a carbon‐bridged E ‐stilbene with a centrosymmetry, shows elongated π‐conjugation with 14 π‐electrons and one more sp³ carbon bridge, which may increase the tunability of electronic structure and film morphology. Despite its twisted molecular framework, NITI shows a low optical bandgap of 1.49 eV in thin film and a high molar extinction coefficient of 1.90 × 10⁵m ^?1 cm^?1 in solution. By matching NITI with a large‐bandgap polymer donor, an extraordinary power conversion efficiency of 12.74% is achieved, which is among the best performance so far reported for fullerene‐free organic photovoltaics and is inspiring for the design of new electron acceptors.     

Toward Efficient Polymer Solar Cells Processed by a Solution‐Processed Layer‐By‐Layer Approach

The solution‐processed layer‐by‐layer (LBL) method has potential to achieve high‐performance polymer solar cells (PSCs) due to its advantage of enriching donors near the anode and acceptors near the cathode. However, power conversion efficiencies (PCEs) of the LBL‐PSCs are still significantly lower than those of conventional one‐step‐processed PSCs (OS‐PSCs). A method to solve the critical problems in LBL‐PSCs is reported here. By employing a specific mixed solvent (o‐dichlorobenzene [o‐DCB]/tetrahydrofuran) to spin‐coat the small‐molecular acceptor IT‐4F onto a layer of the newly designed polymer donor (PBDB‐TFS1), appropriate interdiffusion between the PBDB‐TFS1 and the IT‐4F can critically be controlled, and then an ideal phase separation of the active layer and large donor/acceptor interface area can be realized with a certain amount of o‐DCB. The PSCs based on the LBL method exhibit PCEs as high as 13.0%, higher than that of the counterpart (11.8%) made by the conventional OS solution method. This preliminary work reveals that the LBL method is a promising approach to the promotion of the photovoltaic performance of polymer solar cells.     

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.