Design Principles of Large Cation Incorporation in Halide Perovskites

Perovskites have stood out as excellent photoactive materials with high efficiencies and stabilities, achieved via cation mixing techniques. Overcoming challenges to the stabilization of Perovskite solar cells calls for the development of design principles of large cation incorporation in halide perovskite to accelerate the discovery of optimal stable compositions. Large fluorinated organic cations incorporation is an attractive method for enhancing the intrinsic stability of halide perovskites due to their high dipole moment and moisture-resistant nature. However, a fluorinated cation has a larger ionic size than its non-fluorinated counterpart, falling within the upper boundary of the mixed-cation incorporation. Here, we report on the intrinsic stability of mixed Methylammonium (MA) lead halides at different concentrations of large cation incorporation, namely, ehtylammonium (EA; [CH3CH2NH3]+) and 2-fluoroethylammonium (FEA; [CH2FCH2NH3]+). Density functional theory (DFT) calculations of the enthalpy of the mixing and analysis of the perovskite structural features enable us to narrow down the compositional search domain for EA and FEA cations around concentrations that preserve the perovskite structure while pointing towards the maximal stability. This work paves the way to developing design principles of a large cation mixture guided by data analysis of DFT data. Finally, we present the automated search of the minimum enthalpy of mixing by implementing Bayesian optimization over the compositional search domain. We introduce and validate an automated workflow designed to accelerate the compositional search, enabling researchers to cut down the computational expense and bias to search for optimal compositions.

Demagistrisite, the Missing Link in a Polysomatic Series from Lawsonite to Orientite

Demagistrisite, ideally BaCa2Mn3+4(Si3O10)(Si2O7)(OH)4·3H2O, is a new mineral found at the Cerchiara mine (eastern Liguria, La Spezia province, Italy). The ore consists of rhythmic interlaying of braunite-bearing metasediments (5–15 cm thick) and hematite-rich cherts. Demagistrisite occurs in association with cerchiaraite-(Mn), namansilite, noelbensonite, orientite, richterite, ruizite, and saponite in matrix consisting of braunite, calcite, cryptomelane, orthoclase, and quartz. Demagistrisite crystals occur as tightly intergrown blades or as millimeter-sized prisms and needles with square cross-section, typically with irregular terminations, and rarely terminated by a low-angle pyramid. The mineral is orange brown to red brown, streak is beige, and luster is vitreous, translucent to transparent. Fracture is irregular. In thin section, it is orange brown. The mineral is optically biaxial (–) with α 1.805(5), β 1.825(5), γ 1.8305(5) (white light); 2Vmeas 58(5)°, 2Vcalc 54.7°; optical orientation X = c, Y = b, Z = a. Dispersion is very strong, r > v. Pleochroism is strong with X orange yellow, Y red brown, Z red brown; X << Z < Y. It is unreactive in concentrated HCl at room temperature. Thirteen chemical analyses by WDS-EMPA gave the following empirical formula (based on 24 O apfu): (Ba0.69Ca1.25Mn2+0.70Sr0.21Na0.12Mg0.02)Σ2.99(Mn3+3.97Al0.03)Σ4(Si3O10)(Si2O7)(OH)3.87·3.13H2O. The mineral is orthorhombic, space group Amm2, with unit-cell parameters a 16.312(8), b 6.176(4), c 9.075(6) Å, V 914.2(10) Å3, and Z = 2. The seven strongest X-ray powder diffraction lines are [d Å (I%; hkl)]: 16.21 (49; 100), 4.86 (44; 111), 4.34 (56; 102,211), 2.871 (54; 220), 2.731 (100; 511,013), 2.671 (74; 320,113,502), and 2.426 (51; 222,313,611). The crystal structure (R1 = 0.0572 for 1485 reflections with I > 2σI) is based on straight edge-sharing chains of Mn3+-centered octahedra extending along [010], which are bridged by disilicate (Si2O7) and trisilicate (Si3O10) groups, yielding a framework. Cavities within this framework contain two large cation sites. The structure of demagistrisite can be considered transitional between the structures of orientite and noelbensonite. Demagistrisite is named in honor of Leandro de Magistris (1906–1990).

Combination of large cation and coordinating additive improves carrier transport properties in quasi-2D perovskite solar cells

Two-dimensional perovskite materials have attracted considerable attention in the photovoltaic community, primarily due to their superior environmental stability. It mainly originates from the presence of bulky organic spacer cations that...

Ferroelectricity, ionic conductivity and structural paths for large cation migration in Ca10.5−xPbx(VO4)7 single crystals, x = 1.9, 3.5, 4.9

Crystal structure, thermal, ionic conductivity of large cations (Ca and Pb), dielectric and non-linear optical properties were investigated for Ca10.5−xPbx(VO4)7 single crystals (x = 1.9, 3.5, 4.9).