The bulk anomalous photovoltaic (BAPV) effect of acentric materials refers to a distinct concept from traditional semiconductor-based devices, of which the above-bandgap photovoltage hints at a promise for solar-energy conversion. However, it is still a challenge to exploit new BAPV-active systems due to the lacking of knowledge on the structural origin of this concept. BAPV effects in single crystals of a 2D lead-free double perovskite, (BBA)2 CsAgBiBr7 (1, BBA = 4-bromobenzylammonium), tailored by mixing aromatic and alkali cations in the confined architecture to form electric polarization are acquired here. Strikingly, BAPV effects manifested by above-bandgap photovoltage (VOC ) show unique attributes of directional anisotropy and positive dependence on electrode spacing. The driving source stems from orientations of the polar aromatic spacer and Cs+ ion drift, being different from the known built-in asymmetry photovoltaic heterojunctions. As the first demonstration of the BAPV effect in the double perovskites, the results will enrich the family of environmentally green BAPV-active candidates and further facilitate their new optoelectronic application.
Keywords: bulk anomalous photovoltaic; double perovskite; electric polarization; ion displacement.
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