Defect-engineered black tetragonal-tungsten-bronze ferroelectric crystal for full spectrum absorption and broadband photoelectronic conversion.

Wang, Yaqian; Liu, Ruirui; Ma, Tian-Ci; Wu, Yabo; Lu, Dazhi; Zhang, Mao-Hua; Liang, Fei; Yu, Haohai et al. · Nat Commun · 2025

basic_science · Level V

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Abstract

Ferroelectric crystals have emerged as promising candidates for exotic optoelectronic platforms. However, the wide bandgaps of transparent ferroelectric crystals restrict their ultraviolet optical activity, hindering broadband photoelectric conversion. Herein, a hierarchical defect engineering strategy is proposed for ferroelectric oxides to achieve full-spectrum optical absorption and boost broadband self-powered photodetection. Based on the transparent calcium barium niobate crystal, red Ce:CSBN is designed through the cooperative isovalent substitution of Sr<sup>2+</sup> and aliovalent substitution of Ce<sup>3+</sup>. Furthermore, a black Ce:CSBN crystal is fabricated via thermal reduction, which demonstrated ultra-broadband absorption from the ultraviolet to the mid-infrared range. This extended absorption capability is attributed to the judiciously modulated oxygen vacancies. Consequently, self-powered photodetection is realized in the 250-5000 nm range with a high responsivity of >1 mA/W, representing the widest responsive range among all-known ferroelectric detectors. More impressively, a reversible red-black transition is achieved by controlling oxygen vacancy concentration.