Polymer Solar Cells with 90% External Quantum Efficiency Featuring an Ideal Light‐ and Charge‐Manipulation Layer

Rapid progress in the power conversion efficiency (PCE) of polymer solar cells (PSEs) is beneficial from the factors that match the irradiated solar spectrum, maximize incident light absorption, and reduce photogenerated charge recombination. To optimize the device efficiency, a nanopatterned ZnO:Al 2 O 3 composite film is presented as an efficient light‐ and charge‐manipulation layer (LCML). The Al 2 O 3 shells on the ZnO nanoparticles offer the passivation effect that allows optimal electron collection by suppressing charge‐recombination loss. Both the increased refractive index and the patterned deterministic aperiodic nanostructure in the ZnO:Al 2 O 3 LCML cause broadband light harvesting. Highly efficient single‐junction PSCs for different binary blends are obtained with a peak external quantum efficiency of up to 90%, showing certified PCEs of 9.69% and 13.03% for a fullerene blend of PTB7:PC 71 BM and a nonfullerene blend, FTAZ:IDIC, respectively. Because of the substantial increase in efficiency, this method unlocks the full potential of the ZnO:Al 2 O 3 LCML toward future photovoltaic applications.