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.     

Fused Tris(thienothiophene)‐Based Electron Acceptor with Strong Near‐Infrared Absorption for High‐Performance As‐Cast Solar Cells

A fused tris(thienothiophene) (3TT) building block is designed and synthesized with strong electron‐donating and molecular packing properties, where three thienothiophene units are condensed with two cyclopentadienyl rings. Based on 3TT, a fused octacylic electron acceptor (FOIC) is designed and synthesized, using strong electron‐withdrawing 2‐(5/6‐fluoro‐3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene)‐malononitrile as end groups. FOIC exhibits absorption in 600–950 nm region peaked at 836 nm with extinction coefficient of up to 2 × 10⁵m ^–1 cm^–1, low bandgap of 1.32 eV, and high electron mobility of 1.2 × 10^–3 cm² V^–1 s^–1. Compared with its counterpart ITIC3 based on indacenothienothiophene core, FOIC exhibits significantly upshifted highest occupied molecular orbital level, slightly downshifted lowest unoccupied molecular orbital level, significantly redshifted absorption, and higher mobility. The as‐cast organic solar cells (OSCs) based on blends of PTB7‐Th donor and FOIC acceptor without additional treatments exhibit power conversion efficiencies (PCEs) as high as 12.0%, which is much higher than that of PTB7‐Th: ITIC3 (8.09%). The as‐cast semitransparent OSCs based on the same blends show PCEs of up to 10.3% with an average visible transmittance of 37.4%.     

High‐Performance Additive‐/Post‐Treatment‐Free Nonfullerene Polymer Solar Cells via Tuning Molecular Weight of Conjugated Polymers

In recent years, rapid advances are achieved in polymer solar cells (PSCs) using nonfullerene small molecular acceptors. However, no research disclosing the influence of molecular weight (M_n) of conjugated polymer on the nonfullerene device performance is reported. In this work, a series of polymers with different M_ns are synthesized to systematically investigate the connection between M_n and performance of nonfullerene devices for the first time. It is found that the device performance improves substantially as the M_n increases from 12 to 38 kDa and a power conversion efficiency (PCE) as high as 10.5% is realized. It has to be noted this PCE is achieved without using any additives and post‐treatments, which is among the top efficiencies of additive‐ and post‐treatment‐free PSCs. Most importantly, the variation trend of the optimal active layer thickness and morphology is significantly different from the device with fullerene as acceptor. The findings clarify the effect of M_n on the performance of nonfullerene PSCs, which would benefit further efficiency improvement of nonfullerene PSCs.     

High‐Performance Long‐Term‐Stable Dopant‐Free Perovskite Solar Cells and Additive‐Free Organic Solar Cells by Employing Newly Designed Multirole π‐Conjugated Polymers

Perovskite solar cells (PSCs) and organic solar cells (OSCs) are promising renewable light‐harvesting technologies with high performance, but the utilization of hazardous dopants and high boiling additives is harmful to all forms of life and the environment. Herein, new multirole π‐conjugated polymers (P1–P3) are developed via a rational design approach through theoretical hindsight, further successfully subjecting them into dopant‐free PSCs as hole‐transporting materials and additive‐free OSCs as photoactive donors, respectively. Especially, P3‐based PSCs and OSCs not only show high power conversion efficiencies of 17.28% and 8.26%, but also display an excellent ambient stability up to 30 d (for PSCs only), owing to their inherent superior optoelectronic properties in their pristine form. Overall, the rational approach promises to support the development of environmentally and economically sustainable PSCs and OSCs.     

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.     

High‐Performance Inverted Planar Perovskite Solar Cells Enhanced by Thickness Tuning of New Dopant‐Free Hole Transporting Layer

A new hole transporting material (HTM) named DMZ is synthesized and employed as a dopant‐free HTM in inverted planar perovskite solar cells (PSCs). Systematic studies demonstrate that the thickness of the hole transporting layer can effectively enhance the morphology and crystallinity of the perovskite layer, leading to low series resistance and less defects in the crystal. As a result, the champion power conversion efficiency (PCE) of 18.61% with J_SC = 22.62 mA cm^?2, V_OC = 1.02 V, and FF = 81.05% (an average one is 17.62%) is achieved with a thickness of ≈13 nm of DMZ (2 mg mL^?1) under standard global AM 1.5 illumination, which is ≈1.5 times higher than that of devices based on poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonic acid) (PEDOT:PSS). More importantly, the devices based on DMZ exhibit a much better stability (90% of maximum PCE retained after more than 556 h in air (relative humidity ≈ 45%–50%) without any encapsulation) than that of devices based on PEDOT:PSS (only 36% of initial PCE retained after 77 h in same conditions). Therefore, the cost‐effective and facile material named DMZ offers an appealing alternative to PEDOT:PSS or polytriarylamine for highly efficient and stable inverted planar PSCs.