Initial Engineering and Outdoor Stability Assessment of “Gray/Black” Fullerene-Free Organic Photovoltaics Based on Only Two Complementary Absorbing Materials: A Tetrabenzotriazacorrole and a Subphthalocyanine

[Image: see text] Broad absorption is a desired characteristic of materials employed in the photoactive layers of organic photovoltaic (OPV) devices. Here, we have identified tetrabenzotriazacorroles (Tbcs) as complementary absorbing chromophores and electron donors to the promising nonfullerene acceptors boron subphthalocyanines (BsubPcs). These two materials, which can be utilized as donor–acceptor pairs within fullerene-free OPVs, yield spectral coverage over the entire visible range of 300–750 nm. Oxy phosphorus Tbc derivative (POTbc) was employed as an electron donor and paired initially with multiple BsubPc derivatives having a distribution of highest occupied molecular orbital/lowest unoccupied molecular orbital energy levels in planar heterojunction OPVs. These devices were “gray/black” due to the broad absorption across the visible spectrum. Upon screening, the partially halogenated chloro hexachloro BsubPc (Cl–Cl(6)BsubPc) showed the greatest promise for coupling with POTbc. The thickness ratio and total thickness of the active layer were then probed in order to identify the optical and electrical limitations on the POTbc/Cl–Cl(6)BsubPc-based OPV device. A maximum power conversion efficiency (PCE) of 2.13% was achieved at 60 nm total thickness of the active layer and 1 to 3 (POTbc to Cl–Cl(6)BsubPc) thickness ratio. Outdoor stability of the champion device was evaluated using protocols established by International Summits on OPV Stability and was found to be on par with an α-sexithiophene/Cl–Cl(6)BsubPc baseline OPV.