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Here, in this work, an alcohol-soluble, low-temperature processable and relatively thickness insensitive electron-transporting layer (ETL) comprising a planar coronene derivative, CDIN, was exploited to effectively enhance the photovoltaic performance of various inverted organic photovoltaics (OPVs). Besides the decent charge-transporting property, such CDIN ETL was manifested to facilitate the face-on orientation of atop bulk-heterojunction (BHJ) layers as evidenced by GIWAXS analysis, which might benefit from its discotic geometry endowed with strong face-on π–π stacking in solid-states and better compatibility to the constituent organic photoactive components. Consequently, an enhancement of over 9% in PCE can be achieved in the state-of-the-art fullerene-based OPVsmore » to yield a PCE of 11.2% while over 13% enhancement can be realized in the representative non-fullerene OPVs to yield a PCE of 9%.« less

To realize commercialization of perovskie solar cell (PVSC) technology, it is essential to reduce the device costs while maintaining high power conversion efficiencies (PCEs). So far, the high cost of the most commonly used hole selective material, 2,2′,7,7′‐Tetrakis (N,N‐di‐p‐methoxyphenylamino)‐9,9′‐spirobifluorene (spiro‐OMeTAD), for high‐PCE PVSCs presents a significant obstacle for device cost reduction. In this work, the synthesis and characterization of a new spiro‐OMeTAD derivative hole selective material, 2,6,14‐tris(5′‐(N,N‐bis(4‐methoxyphenyl)aminophenol‐4‐yl)‐3,4‐ethylenedioxythiophen‐2‐yl)‐triptycene (TET) is reported. TET features a three‐dimensional structure consisting of a triptycene core and triarylamine arms linked by 3,4‐ethylenedioxythiophene, facilitating efficient hole transport. Planar PVSCs using TET hole selective layers (HSLs) achieved highmore » fill factors of over 81% and steady‐state efficiencies of up to 18.6%, comparable with that (19.0%) of PVSC using spiro‐OMeTAD HSL. Importantly, the hereby reported efficient PVSCs can be produced with very thin TET HSLs (about 30 nm). Considering the lower laboratory synthesis and purification cost ($123 vs. $500 g ⁻¹ ) and thinner HSL (30 vs. 200 nm), the cost for TET on a unit area of one device is 25 times lower than that for high‐purity spiro‐OMeTAD. The device with TET HSL shows good stability under continuous illumination. Therefore, this work makes a significant step forward toward the commercialization of the emerging PVSC technology.« less