Abstract

Photo‐ferroelectric single crystals and highly oriented thin‐films have been extensively researched recently, with increasing photovoltaic energy conversion efficiency (from 0.5% up to 8.1%) achieved. Rare attention has been paid to polycrystalline ceramics, potentially due to their negligible efficiency. However, ceramics offer simple and cost‐effective fabrication routes and stable performance compared to single crystals and thin‐films. Therefore, a significantly increased efficiency of photo‐ferroelectric ceramics contributes toward widened application areas for photo‐ferroelectrics, e.g., multisource energy harvesting. Here, all‐optical domain control under illumination, visible‐range light‐tunable photodiode/transistor phenomena and optoelectrically tunable photovoltaic properties are demonstrated, using a recently discovered photo‐ferroelectric ceramic (K_0.49Na_0.49Ba_0.02)(Nb_0.99Ni_0.01)O_2.995. For this monolithic material, tuning of the electric conductivity independent of the ferroelectricity is achieved, which previously could only be achieved in organic phase‐separate blends. Guided by these discoveries, a boost of five orders of magnitude in the photovoltaic output power and energy conversion efficiency is achieved via optical and electrical control of ferroelectric domains in an energy‐harvesting circuit. These results provide a potentially supplementary approach and knowledge for other photo‐ferroelectrics to further boost their efficiency for energy‐efficient circuitry designs and enable the development of a wide range of optoelectronic devices.