A Zero‐Dimensional Organic Seesaw‐Shaped Tin Bromide with Highly Efficient Strongly Stokes‐Shifted Deep‐Red Emission

Abstract

The synthesis and characterization is reported of (C NH ) SnBr , a novel organic metal halide hybrid with a zero-dimensional (0D) structure, in which individual seesaw-shaped tin (II) bromide anions (SnBr ) are co-crystallized with 1-butyl-1-methylpyrrolidinium cations (C NH ). Upon photoexcitation, the bulk crystals exhibit a highly efficient broadband deep-red emission peaked at 695 nm, with a large Stokes shift of 332 nm and a high quantum efficiency of around 46 %. The unique photophysical properties of this hybrid material are attributed to two major factors: 1) the 0D structure allowing the bulk crystals to exhibit the intrinsic properties of individual SnBr species, and 2) the seesaw structure enabling a pronounced excited state structural deformation as confirmed by density functional theory (DFT) calculations.

A Lead‐Free All‐Inorganic Metal Halide with Near‐Unity Green Luminescence

“…Thermogravimetric analysis (Figure S8, Supporting Information) was also performed to verify the stability of β‐Cs 3 Cu 2 Cl 5 , showing that the all‐inorganic compound possesses excellent thermal stability and will not decompose until 550 °C which is much higher than that of 0D organic–inorganic metal halide hybrids. [ 17,33 ] No obvious change of the powder XRD patterns after one week exposure to ambient conditions was observed (Figure S9, Supporting Information). Moreover, β‐Cs 3 Cu 2 Cl 5 is photostable under continuous high power mercury lamp irradiation (300 mW cm −2 , Figure 4b), further highlighting its advantage for light‐emitting applications.…”

“…Recently low‐dimensional lead‐free metal halides have been reported to exhibit highly efficient emission via facile solution processing. [ 12–21 ] In particular for yellow and blue light‐emission, the photoluminescence quantum yield (PLQY) has reached near‐unity in some zero‐dimensional (0D) Sn‐based and Cu‐based halide compounds. [ 19,22–26 ] However, to our knowledge, for another one of the three primary colors of light, the PLQY of the reported lead‐free green‐light emitting metal halides, especially all‐inorganic semiconductors, is far behind the performance of lead halide perovskites.…”

Bismuth doped lead-free two-dimensional tin based halide perovskite single crystals

“…In addition, despite the superior properties of lead halide perovskites, the toxicity of Pb hinders their commercial potential. Thus, increasing attention has been focused on environmentally-friendly lead-free alternatives, in particular for Sn which comes from the same Group of periodic table with Pb [9,[19][20][21][22][23][24][25][26][27] .…”

From Distortion to Disconnection: Linear Alkyl Diammonium Cations Tune Structure and Photoluminescence of Lead Bromide Perovskites

“…[ 13 ] The organic–inorganic hybrid halide perovskites can be built to 0D, 1D, 2D, and 3D structures at molecular level, by choosing specific metal halides and organic ligands. [ 14–16 ] Different from the narrow and small Stokes shifted emissions of typical 3D perovskites, 0D, 1D, and corrugated 2D organic–inorganic hybrid perovskites achieved large Stokes shifted broadband emission attributing to reorganization of exciton or quantum self‐trapping. [ 17–19 ] Further, the low‐dimensional perovskites have more flexible structure tunability than the 3D organic–inorganic hybrid perovskites by replacing abundant A‐site cations.…”