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Transparent ferroelectrics, with promising prospects in transparent optoelectronic devices, have unique advantages in self-powered photodetection. The self-powered photodetectors based on the photovoltaic effect have quicker responses and higher stability compared with those based on the pyroelectric effect. However, the ferroelectric ceramics previously applied are always opaque and have no infrared light-stimulated photovoltaic effect. Thus, it would be very meaningful to design photodetectors based on infrared light-stimulated photovoltaic effect and/or transparent ferroelectric ceramics. In this work, highly optical transparent pristine lead lanthanum zirconate titanate (PLZT) and band gap-engineered Ni-doped PLZT ceramics with excellent piezoelectric/ferroelectric properties were prepared by hot-pressing sintering. Stable and excellent photovoltaic performance was obtained for pristine PLZT and band gap-engineered PLZT. The value of short-circuit current density is at least 2 orders of magnitude larger than those in PLZT reported in previous works. The transparent PLZT and Ni-doped PLZT ferroelectric ceramics are applied as self-powered photodetectors for the first time for 405 nm and near-infrared light, respectively. The devices based on PLZT under 405 nm light exhibit high detectivity (7.15 × 107 Jones) and quick response (9.5 ms for rise and 11.5 ms for decay), and those devices based on Ni-doped PLZT, under near-infrared light filtered from AM 1.5 G simulated sunlight, also exhibit high detectivity (6.86 × 107 Jones) and short response time (8.5 ms), both presenting great potential for future transparent photodetectors.

Defect-engineered perovskite oxides that exhibit ferroelectric and photovoltaic properties are promising multifunctional materials. Though introducing gap states by transition metal doping on the perovskite B-site can obtain low bandgap (i.e., 1.1-3.8 eV), the electrically leaky perovskite oxides generally lose piezoelectricity mainly due to oxygen vacancies. Therefore, the development of highly piezoelectric ferroelectric semiconductor remains challenging. Here, inspired by point-defect-mediated large piezoelectricity in ferroelectrics especially at the morphotropic phase boundary (MPB) region, an efficient strategy is proposed by judiciously introducing the gap states at the MPB where defect-induced local polar heterogeneities are thermodynamically coupled with the host polarization to simultaneously achieve high piezoelectricity and low bandgap. A concrete example, Ni2+ -mediated (1-x)Na0.5 Bi0.5 TiO3 -xBa(Ti0.5 Ni0.5 )O3-δ (x = 0.02-0.08) composition is presented, which can show excellent piezoelectricity and unprecedented visible/near-infrared light absorption with a lowest ever bandgap ≈0.9 eV at room temperature. In particular, the MPB composition x = 0.05 shows the best ferroelectricity/piezoelectricity (d33 = 151 pC N-1 , Pr = 31.2 μC cm-2 ) and a largely enhanced photocurrent density approximately two orders of magnitude higher compared with classic ferroelectric (Pb,La)(Zr,Ti)O3 . This research provides a new paradigm for designing highly piezoelectric and visible/near-infrared photoresponsive perovskite oxides for solar energy conversion, near-infrared detection, and other multifunctional applications.