On the prospects of high-entropy organic A-site halide perovskites

High entropy is a hot topic in materials research due to several interesting and surprising phenomena, of which one crucial aspect is entropic stabilization. As well-known materials for optoelectronic and electrochemical applications, halide perovskites (HPs) suffer from instability issues and would benefit greatly from increased configurational entropy. Despite that, only a few literature reports have connected HPs with the concept of high-entropy materials. Furthermore, mixing A-site cations, especially organic ones, to achieve maximized configurational entropies has not been explored in detail either in experimental or computational works. Aiming to obtain high-entropy organic A-site HPs, we synthesized and characterized a system of penta-organic A-site cations HP of general formula GAxFAxEAxACxMA1-4xPbI3. Results on the structure and phase transitions show that single-phase solid solutions can be obtained for x values up to almost 0.08, resulting in one of the highest configurational entropies ever reported in A-site-only mixed HPs. The high-entropy HPs also showed band gaps of about 1.5 eV, decreased ionic transport, and remarkable stability compared to the unsubstituted composition. The results consolidate the potential of maximizing the configurational entropy as a design parameter in HPs. Maximizing entropy in halide perovskites may be possible through A-site substitution with multiple organic cations.