Symmetric-breaking strategy has broadly applied in organic photovoltaic material design while a comprehensive understanding of the effects of two dimension (2D) asymmetric side chains in all-small-molecule organic solar cells (ASM-OSCs)...

Over 17% efficiency all-small-molecule organic solar cells based on an organic molecular donor employing 2D side chain symmetric-breaking strategy

The morphology plays a key role in determining the charge generation and collection process, thus impacting the performances of organic solar cells (OSCs). The limited selection pool of additives to optimize the morphology of OSCs, especially for the emerging layer‐by‐layer (LbL) OSCs, impeding the improvements of photovoltaic performances. Herein, a new method of using conjugated polymers as the additives to optimize the morphology for improving the photovoltaic performances of LbL‐OSCs is reported. Four polymers of PH, PS, PF, and PCl are developed with different side chains. These polymers exhibit poor performances as donor materials and additives in the BHJ devices, due to the unsuitable energy level alignment and unfavorable molecular interactions. By contrast, they can be served as efficient additives to optimize the PM6 fibril matrix for facilitating the penetration of BTP‐eC9 and forming an intertwined D/A bicontinuous network with a vertical segregation. Such morphology is optimized by side chain engineering, which enables the progressive improvement of the charge separation and collection. As a result, adding a small amount of PCl as the additive, the optimized morphology contributes to a champion PCE of 19.10% with a high FF of 80.5%.

19.10% Efficiency and 80.5% Fill Factor Layer‐by‐Layer Organic Solar Cells Realized by 4‐Bis(2‐Thienyl)Pyrrole‐2,5‐Dione Based Polymer Additives for Inducing Vertical Segregation Morphology

Raising the lowest unoccupied molecular orbital (LUMO) energy level of Y‐type non‐fullerene acceptors can increase the open‐circuit voltage (Voc) and thus the photovoltaic performance of the current top performing polymer solar cells (PSCs). One of the viable routes is demonstrated by the successful Y6 derivative of L8‐BO with the branched alkyl chains at the outer side. This will introduce steric hindrance and reduce intermolecular aggregation, thus open up the bandgap and raise the LUMO energy level. To take further advantages of the steric hindrance influence on optoelectronic properties of Y6 derivatives, two Y‐type non‐fullerene acceptors of BTP‐Cy‐4F and BTP‐Cy‐4Cl are designed and synthesized by adopting outer branched side chains and inner cyclohexane side chains. An outstanding Voc of 0.937 V is achieved in the D18:BTP‐Cy‐4F binary blend devices along with a power conversion efficiency (PCE) of 18.52%. With the addition of BTP‐eC9 to extend the absorption spectral coverage, a remarkable PCE of 19.36% is realized finally in the related ternary blend devices, which is one of the highest values for single‐junction PSCs at present. The results illustrate the great potential of cyclohexane side chains in constructing high‐performance non‐fullerene acceptors and their PSCs.

Y‐Type Non‐Fullerene Acceptors with Outer Branched Side Chains and Inner Cyclohexane Side Chains for 19.36% Efficiency Polymer Solar Cells

Organic semiconducting materials with fluorine or chlorine substitution are commonly designed to prepare efficient polymer solar cells (PSCs) through finely modulating the energy levels and absorption spectra. Herein, two small molecular acceptors with fluorine substitution L8‐BO or chlorine substitution eC9‐2Cl are selected to prepare ternary PSCs with PM6 as polymer donor. The optimal ternary PSCs exhibit a power conversion efficiency of 18.66%, benefiting from the simultaneously increased open‐circuit voltage (VOC) of 0.89 V, short‐circuit current density (JSC) of 26.63 mA cm−2, and fill factor of 78.74% when the content of chlorine substitution eC9‐2Cl is about 20 wt% in acceptors. Fluorinated and chlorinated substitutions can improve the VOC or JSC of the corresponding binary PSCs, which can be recombined into efficient ternary PSCs through optimizing their content in acceptors. Chlorinated materials have special crystalline conditions due to the specific features of the chlorine atoms with large atomic radius and the empty 3d orbits compared to the corresponding fluorinated materials. Adding an appropriate amount of the chlorine substitution eC9‐2Cl further enhances the crystallization and intermolecular interaction of the ternary PSCs, which is beneficial for charge transport in the active layer and for device performance improvement.

18.66% Efficiency of Polymer Solar Cells Employing Two Nonfullerene Acceptors with Fluorine or Chlorine Substitution

18.2%-efficient ternary all-polymer organic solar cells with improved stability enabled by a chlorinated guest polymer acceptor

A record power conversion efficiency (PCE) of over 19% is realized in planar‐mixed heterojunction (PMHJ) organic solar cells (OSCs) by adopting the asymmetric selenium substitution strategy in making a pseudosymmetric electron acceptor, BS3TSe‐4F. The combined molecular asymmetry with more polarizable selenium substitution increases the dielectric constant of the D18/BS3TSe‐4F blend, helping lower the exciton binding energy. On the other hand, dimer packing in BS3TSe‐4F is facilitated to enable free charge generation, helping more efficient exciton dissociation and lowering the radiative recombination loss (ΔE2) of OSCs. As a result, PMHJ OSCs based on D18/BS3TSe‐4F achieve a PCE of 18.48%. By incorporating another mid‐bandgap acceptor Y6‐O into D18/BS3TSe‐4F to form a ternary PMHJ, a higher open‐circuit voltage (VOC) can be achieved to realize an impressive PCE of 19.03%. The findings of using pseudosymmetric electron acceptors in enhancing device efficiency provides an effective way to develop highly efficient acceptor materials for OSCs.

Achieving 19% Power Conversion Efficiency in Planar‐Mixed Heterojunction Organic Solar Cells Using a Pseudosymmetric Electron Acceptor

Organic photovoltaics (OPVs) have progressed steadily through three stages of photoactive materials development: (i) use of poly(3-hexylthiophene) and fullerene-based acceptors (FAs) for optimizing bulk heterojunctions; (ii) development of new donors to better match with FAs; (iii) development of non-fullerene acceptors (NFAs). The development and application of NFAs with an A-D-A configuration (where A = acceptor and D = donor) has enabled devices to have efficient charge generation and small energy losses (Eloss < 0.6 eV), resulting in substantially higher power conversion efficiencies (PCEs) than FA-based devices. The discovery of Y6-type acceptors (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) with an A-DA' D-A configuration has further propelled the PCEs to go beyond 15% due to smaller Eloss values (∼0.5 eV) and higher external quantum efficiencies. Subsequently, the PCEs of Y6-series single-junction devices have increased to >19% and may soon approach 20%. This review provides an update of recent progress of OPV in the following aspects: developments of novel NFAs and donors, understanding of the structure-property relationships and underlying mechanisms of state-of-the-art OPVs, and tasks underpinning the commercialization of OPVs, such as device stability, module development, potential applications, and high-throughput manufacturing. Finally, an outlook and prospects section summarizes the remaining challenges for the further development of OPV technology.

Renewed Prospects for Organic Photovoltaics.

Self-assembled monolayers (SAMs) have been widely employed as an effective way to modify the interfaces of electronic/optoelectronic devices. To achieve a good control of the growth and molecular functionality of SAMs, we develop a co-assembled monolayer (co-SAM) for obtaining efficient hole selection and suppressed recombination at the hole selective interface in inverted perovskite solar cells (PSCs). By engineering the position of methoxy substituents, an aligned energy level and favorable dipole moment can be obtained in our newly synthesized SAM, ((2,7-dimethoxy-9H-carbazol-9-yl) methyl) phosphonic acid (DC-PA). An alkyl ammonium containing SAM is co-assembled to further optimize the surface functionalization and interaction with perovskite layer on top. A champion device with an excellent power conversion efficiency (PCE) of 23.59% and improved device stability are achieved. This work demonstrates the advantage of using co-SAM in improving performance and stability of PSCs.

Co-assembled Monolayers as Hole -se lective Contact for High-Performance Inverted Perovskite Solar Cells with Optimized Recombination Loss and Long-Term Stability.

A major challenge hindering the further development of all‐polymer solar cells (all‐PSCs) employing polymerized small‐molecule acceptors is the relatively low fill factor (FF) due to the difficulty in controlling the active‐layer morphology. The issues typically arise from oversized phase separation resulting from the thermodynamically unfavorable mixing between two macromolecular species, and disordered molecular orientation/packing of highly anisotropic polymer chains. Herein, a facile top‐down controlling strategy to engineer the morphology of all‐polymer blends is developed by leveraging the layer‐by‐layer (LBL) deposition. Optimal intermixing of polymer components can be achieved in the two‐step process by tuning the bottom‐layer polymer swelling during top‐layer deposition. Consequently, both the molecular orientation/packing of the bottom layer and the molecular ordering of the top layer can be optimized with a suitable top‐layer processing solvent. A favorable morphology with gradient vertical composition distribution for efficient charge transport and extraction is therefore realized, affording a high all‐PSC efficiency of 17.0% with a FF of 76.1%. The derived devices also possess excellent long‐term thermal stability and can retain >90% of their initial efficiencies after being annealed at 65 °C for 1300 h. These results validate the distinct advantages of employing an LBL processing protocol to fabricate high‐performance all‐PSCs.

Feng Xiao Qi

Papers

Achieving 19% Power Conversion Efficiency in Planar‐Mixed Heterojunction Organic Solar Cells Using a Pseudosymmetric Electron Acceptor

Renewed Prospects for Organic Photovoltaics.

Co-assembled Monolayers as Hole -se lective Contact for High-Performance Inverted Perovskite Solar Cells with Optimized Recombination Loss and Long-Term Stability.

A Top‐Down Strategy to Engineer ActiveLayer Morphology for Highly Efficient and Stable All‐Polymer Solar Cells

Non-Fullerene Acceptor Doped Block Copolymer for Efficient and Stable Organic Solar Cells