Polarization‐Modulated Photovoltaic Effect at the Morphotropic Phase Boundary in Ferroelectric Ceramics

Ferroelectric materials, which exhibit switchable polarization, are potential candidates for photovoltaic applications owing to their intriguing charge carrier separation mechanism associated with polarization and breaking of inversion symmetry. To overcome the low photocurrent of ferroelectrics, extensive efforts have focused on reducing their bandgaps to increase the optical absorption of the solar spectrum and thus the power conversion efficiency. Here, a new avenue of enhancing photovoltaic performance via engineering the polarization across a morphotropic phase boundary (MPB) is reported. Tetragonal compositions in the vicinity of the MPB in a PbTiO3-Bi(Ni1/2Ti1/2)O3 solid solution are shown to generate up to 3.6 kV cm−1 photoinduced electric field and 6.2 µA cm−2 short-circuit photocurrent, multiple times higher than its pseudocubic counterpart under the same illumination conditions with excellent polarization retention. This enhancement allows the investigation of the correlation between the polarization switching and photovoltaic switching, which enables a controllable multistate photocurrent. Combined with a bandgap of 2.2 eV, this material exhibits a sizable photoresponse over a broad spectral range. These findings provide a new approach to improve the photovoltaic performance of ferroelectric materials and can expand their potential applications in optoelectronic devices.