Unraveling the mechanochemical synthesis and luminescence in MnII-based two-dimensional hybrid perovskite (C4H9NH3)2PbCl4

Abstract

The mechanochemical route is a facile and fast way and has received much attention for developing versatile advanced functional materials. Herein, we reported a mechanochemical synthesis for incorporating divalent manganese ions (Mn II ) into a two-dimensional (2D) hybrid perovskite (C 4 H 9 NH 3 ) 2 PbCl 4 . The mild external stimuli originating from the grinding at room temperature enabled the formation of Mn II -doped 2D hybrid perovskites, and rapidly changed the luminescence characteristics. The photoluminescence analyses show that the violet and orange emissions are attributed to (C 4 H 9 NH 3 ) 2 Pb 1-x Mn x Cl 4 band-edge emission and the T 1 → 6 A 1 transition of Mn 2+ resulting from an efficient energy transfer process, respectively. Site preference and distribution of the doped Mn 2+ cations on the locations of Pb 2+ were analyzed. The formation energy calculated by the density functional theory (DFT) indicates that the Mn 2+ ions can rapidly enter the crystal lattice due to the unique 2D crystal structure of the hybrid perovskite. Such a case of mechanochemical synthesis for the 2D hybrid perovskite motivates many novel emerging materials and the related applications.

Mn2+‐Doped Metal Halide Perovskites: Structure, Photoluminescence, and Application

“…Xia's group reported the Mn 2+ ‐doped (C 4 H 9 NH 3 ) 2 PbCl 4 system, which indicates that the (C 4 H 9 NH 3 ) 2 PbCl 4 :Mn 2+ can be synthesized using mechanical grinding at room temperature. [ 171 ] It is noteworthy that annealing after grinding is vital for successfully introducing Mn 2+ ions into 2D layered perovskites. The band‐edge blue‐light emission in Mn 2+ ‐doped (But) 2 PbBr 4 retains a dominant and the only weak orange‐light emission of Mn 2+ ions is obtained at room temperature.…”

Synthesis of Gram‐Scale Ultrastable Mn‐Doped 2D Perovskites for Light‐Emitting Diodes

“…Then, through mechanical grinding and thermal annealing, Mn ions are successfully introduced into 2D perovskites (C 4 H 9 NH 3 ) 2 PbBr 4 ) to obtain final products. Xia and co‐workers [ 23,24 ] have also reported different kinds of Mn‐doped 2D perovskites by using similar synthetic methods. Bi and co‐workers [ 25 ] and Pradhan and co‐workers [ 26 ] simplified the complicated solid‐state grinding method into high‐temperature solution‐based synthesis and prepared layered L 2 PbX 4 (X = Cl, Br, or I) with Mn(II) doped.…”

Enhanced nonlinear optical functionality in birefringence and refractive index dispersion of the deep-ultraviolet fluorooxoborates

“…A promising DUV NLO material should achieve a subtle balance of the correlated criteria. In view of the structure-property relationship, fundamental building units (FBUs) form the 'backbone' of inorganic materials, which, combining their microscopic functionality and arrangement information, greatly influence or even determine their performances [14][15][16][17][18][19][20]. For NLO systems, a superior FBU with optimized spatial arrangement, namely a functional module, featured by large HOMO-LUMO (the highest occupied molecular orbital and the lowest unoccupied molecular orbital) gap, apparent polarizability anisotropy (δ) and high hyperpolarizability, will bring benefits to crystals for band gaps, SHG responses, birefringences.…”