Ferroelasticity in Two-Dimensional Hybrid Ruddlesden-Popper Perovskites Mediated by Cross-Plane Intermolecular Coupling and Metastable Funnel-like Phases.

Ferroelasticity is a phenomenon in which a material exhibits two or more equally stable orientation variants and can be switched from one form to another under an applied stress. Recent works have demonstrated that two-dimensional layered organic-inorganic hybrid Ruddlesden-Popper perovskites can serve as ideal platforms for realizing ferroelasticity, however, the ferroelastic (FE) behavior of structures with a single octahedra layer such as (BA)2PbI4 [BA = CH3(CH2)3NH3+] has remained elusive. Herein, by using a combined first-principles and metadynamics approach, the FE behavior of (BA)2PbI4 under mechanical and thermal stresses is uncovered. FE switching is mediated by cross-plane intermolecular coupling, which could occur through multiple rotational modes, rendering the formation of FE domains and several metastable paraelastic (PE) phases. Such metastable phases are akin to wrinkled structures in other layered materials and can act as a "funnel" of hole carriers. Thermal excitation tends to flatten the kinetic barriers of the transition pathways between orientation variants, suggesting an enhanced concentration of metastable PE states at high temperatures, while halogen mixing with Br raises these barriers and conversely lowers the concentration of PE states. These findings reveal the rich structural diversity of (BA)2PbI4 domains, which can play a vital role in enhancing the optoelectronic properties of the perovskite and raise exciting prospects for mechanical switching, shape memory, and information processing.

Additive Molecules Adsorbed on Monolayer PbI2: Atomic Mechanism of Solvent Engineering for Perovskite Solar Cells.

Solvent engineering is highly essential for the upscaling synthesis of high-quality metal halide perovskite materials for solar cells. The complexity in the colloidal containing various residual species poses great difficulty in the design of the formula of the solvent. Knowledge of the energetics of the solvent-lead iodide (PbI2) adduct allows a quantitative evaluation of the coordination ability of the solvent. Herein, first-principles calculations are performed to explore the interaction of various organic solvents (Fa, AC, DMSO, DMF, GBL, THTO, NMP, and DPSO) with PbI2. Our study establishes the energetics hierarchy with an order of interaction as DPSO > THTO > NMP > DMSO > DMF > GBL. Different from the common notion of forming intimate solvent-Pb bonds, our calculations reveal that DMF and GBL cannot form direct solvent-Pb2+ bonding. Other solvent bases, such as DMSO, THTO, NMP, and DPSO, form direct solvent-Pb bonds, which penetrate through the top iodine plane and possess much stronger adsorption than DMF and GBL. A strong solvent-PbI2 adhesion (i.e., DPSO, NMP, and DMSO), associated with a high coordinating ability, explains low volatility, retarded precipitation of the perovskite solute, and tendency of a large grain size in the experiment. In contrast, weakly coupled solvent-PbI2 adducts (i.e., DMF) induces a fast evaporation of the solvent, accordingly a high nucleation density and small grains of perovskites are observed. For the first time, we reveal the promoted absorption above the iodine vacancy, which implies the need for pre-treatment of PbI2 like vacuum annealing to stabilize solvent-PbI2 adducts. Our work establishes a quantitative evaluation of the strength of the solvent-PbI2 adducts from the atomic scale perspective, which allows the selective engineering of the solvent for high-quality perovskite films.