Ultrahigh Photovoltage Generation with Lateral Gradient >5700 V cm ⁻¹ Enabled by an Asymmetric Nanograting Structure

Abstract The strategic design of periodic microstructures composing diverse components with contrasting physical properties unlocks emerging material functionalities. Here, a laterally polar nanograting surface, fabricated through scalable nanoimprint lithography and self‐aligned multi‐patterning, featuring asymmetrically connected photovoltaic‐active units with submicron periodicity, is presented. This asymmetric nanograting structure is enabled by upright, fin‐like nano‐walls that serve both as structural templates and conductive interconnects, allowing for the selective deposition of donor–acceptor heterojunctions to optimize photovoltaic efficiency while minimizing inactive areas. After deliberate optimization, such as transitioning from a spin‐coated donor–acceptor bulk heterojunction to a vacuum‐deposited bilayer one, the design achieves unprecedented photovoltage output, with peak values exceeding 5700 V cm ⁻¹ in the best‐performing architecture. This remarkably high‐voltage output opens avenues for applications in micro‐optoelectromechanical systems, facilitating in‐chip powering of functional dielectrics and ultra‐light electrostatic engines.