Perovskites with d-block metals for solar energy applications

Abstract

Pb²⁺ halide organic–inorganic perovskites are excellent semiconductors for use in solar energy applications, but at the expense of robustness and environmental compatibility. Tin (Sn), which sits just above lead in the periodic table, forms pure (or mixed with lead) perovskites when at the 2+ or 4+ oxidation state. It can act as a promising alternative; however, there are still some serious concerns regarding its suitability. This presents a major challenge; viable metal cations have to be identified. A good number of elements, originating from a large range of d-block metal ions, with adequate oxidation states, moderate toxicity, and relative abundance, seem ideal for this purpose. In this review, we present the most characteristic perovskites (conventional perovskites, layered, or double perovskites) that can be formed with the help of these metals. We focus on d-block metal ions with stable oxidation states, such as Ag⁺ or Ti⁴⁺, which have exhibited satisfactory photovoltaic properties until now. Further, we highlight the results involving compounds other than halide perovskites, such as oxides, chalcogenides, and nitrides (as well as oxyhalides, oxysulfides, and oxynitrides); a few of them are ferroelectric (based on Ti⁴⁺, Zr⁴⁺, Fe³⁺, and Cr³⁺) and can yield a photovoltage that exceeds the bandgap of the material. Finally, we present the critical challenges that currently limit the efficiency of these systems and propose prospects for future directions.