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Halide perovskites are promising semiconductor materials for optoelectronics.One of their unique features is the synthesis, that could be performed by thecrystallization from the solution. This method is fast, but practicallycouldn't be optimized due to the strongly non-equilibrium conditions of crystalgrowth. Another quality limitation is the typical incorporation of organicsolvent molecules into crystals when perovskite crystallization is performedfrom solution with organic solvent. Here we report an alternative method ofperovskite single crystal growth based on the counterdiffusion of reagents inthe gel medium. This counterdiffusion-in-gel crystallization (CGC) method isbased on the difference of solubility between perovskites and lead halide inthe corresponding halide acid, HX. The difference of solubility betweenperovskites and lead halide leads to the formation of perovskite singlecrystals of sufficiently large size with an excellent optical quality atconstant room temperature. Particularly, here we report the growth of MAPbI3and MAPbBr3 halide perovskite single crystals (MA = CH3NH3+) by thecounterdiffusion of the organic-solvent-free reagents in the U-tube filled withthe silica gel. Their photoluminescence spectra recorded at 4 K demonstrate theexcitonic resonances with the full width < 2.5 meV, which proves theirexcellent optical quality. The proposed method can be used in fabrication ofhigh-quality halide perovskite single crystals for both fundamental research,and for applications where the absence of defects is a critical requirement.

Counterdiffusion-in-gel growth of high optical and crystal quality MAPbX3 (MA = CH3NH3+, X = I-, Br-) lead-halide perovskite single crystals