Hybrid organic-inorganic halide perovskites with the prototype material of CH 3 NH 3 PbI 3 have recently attracted intense interest as low-cost and high-performance photovoltaic absorbers. Despite the high power conversion efficiency exceeding 20% achieved by their solar cells, two key issues -the poor device stabilities associated with their intrinsic material instability and the toxicity due to water soluble Pb 2+ -need to be resolved before large-scale commercialization. Here, we address these issues by exploiting the strategy of cation-transmutation to design stable inorganic Pb-free halide perovskites for solar cells. The idea is to convert two divalent Pb 2+ ions into one monovalent M + and one trivalent M 3+ ions, forming a rich class of quaternary halides in double-perovskite structure. We find through first-principles calculations this class of materials have good phase stability against decomposition and wide-range tunable optoelectronic properties. With photovoltaic-functionality-directed materials screening, we identify eleven optimal materials with intrinsic thermodynamic stability, suitable band gaps, small carrier effective masses, and low excitons binding energies as promising candidates to replace Pb-based photovoltaic absorbers in perovskite solar cells. The chemical trends of phase stabilities and electronic properties are also established for this class of materials, offering useful guidance for the development of perovskite solar cells fabricated with them.

Abstract:The long-term chemical instability and the presence of toxic Pb in otherwise stellar solar absorber APbX 3 made of organic molecules on the A site and halogens for X have hindered their large-scale commercialization. Previously explored ways to achieve

Practical application of hybrid Pb-based halide perovskites needs not only to fabricate high-quality film samples on a large scale but also to properly overcome the issues of Pb toxicity and materials instability. Finding new, stable, Pb-free perovskites currently attracts significant research interest. Among various strategies, hetero-substitution of Pb to form quaternary halide double perovskites represents a promising direction to keep the high structural (and likely electronic) dimensionality nature of perovskite lattice and meanwhile offers rich chemical compositions a degree of freedom for discovering new perovskite materials. We herein present a perspective that concisely reviews the progress of rational design of Pb-free halide double perovskites by both theoretical and experimental efforts as well as their current and potential applications in various optoelectronic categories. We also envision the future research directions to realize new materials by exploring broader chemical composition space and to better utilize existing materials by considering optoelectronic properties modulation.

The environmental toxicity of Pb in organic-inorganic hybrid perovskite solar cells remains an issue, which has triggered intense research on seeking alternative Pb-free perovskites for solar applications. Halide perovskites based on group-VA cations of Bi and Sb with the same lone-pair ns state as Pb are promising candidates. Herein, through a joint experimental and theoretical study, we demonstrate that Cl-incorporated methylammonium Sb halide perovskites (CHNH)SbClI show promise as efficient solar absorbers for Pb-free perovskite solar cells. Inclusion of methylammonium chloride into the precursor solutions suppresses the formation of the undesired zero-dimensional dimer phase and leads to the successful synthesis of high-quality perovskite films composed of the two-dimensional layered phase favored for photovoltaics. Solar cells based on the as-obtained (CHNH)SbClI films reach a record-high power conversion efficiency over 2%. This finding offers a new perspective for the development of nontoxic and low-cost Sb-based perovskite solar cells.

We investigate theoretically the effects of interaction between an optical dipole (semiconductor quantum dot or molecule) and metal nanoparticles. The calculated absorption spectra of hybrid structures demonstrate strong effects of interference coming from the exciton-plasmon coupling. In particular, the absorption spectra acquire characteristic asymmetric lineshapes and strong antiresonances. We present here an exact solution of the problem beyond the dipole approximation and find that the multipole treatment of the interaction is crucial for the understanding of stronglyinteracting exciton-plasmon nano-systems. Interestingly, the visibility of the exciton resonance becomes greatly enhanced for small inter-particle distances due to the interference phenomenon, multipole effects, and electromagnetic enhancement. We find that the destructive interference is particularly strong. Using our exact theory, we show that the interference effects can be observed experimentally even in the exciting systems at room temperature.