Design for highly piezoelectric and visible/near‐infrared photoresponsive perovskite oxides
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 (ie, 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 …
are promising multifunctional materials. Though introducing gap states by transition metal
doping on the perovskite B‐site can obtain low bandgap (ie, 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 …
Abstract
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)Na0.5Bi0.5TiO3‐xBa(Ti0.5Ni0.5)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.
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