Wide range zero-thermal-quenching ultralong phosphorescence from zero-dimensional metal halide hybrids

Abstract

Materials with ultralong phosphorescence have wide-ranging application prospects in biological imaging, light-emitting devices, and anti-counterfeiting. Usually, molecular phosphorescence is significantly quenched with increasing temperature, rendering it difficult to achieve high-efficiency and ultralong room temperature phosphorescence. Herein, we spearhead this challenging effort to design thermal-quenching resistant phosphorescent materials based on an effective intermediate energy buffer and energy transfer route. Co-crystallized assembly of zero-dimensional metal halide organic-inorganic hybrids enables ultralong room temperature phosphorescence of (Ph4P)2Cd2Br6 that maintains luminescent stability across a wide temperature range from 100 to 320 K (ΔT = 220 °C) with the room temperature phosphorescence quantum yield of 62.79% and lifetime of 37.85 ms, which exceeds those of other state-of-the-art systems. Therefore, this work not only describes a design for thermal-quenching-resistant luminescent materials with high efficiency, but also demonstrates an effective way to obtain intelligent systems with long-lasting room temperature phosphorescence for optical storage and logic compilation applications.

Sb3+‐Doping in Cesium Zinc Halides Single Crystals Enabling High‐Efficiency Near‐Infrared Emission

“…As a new generation of luminescent materials, emerging metal halide perovskites/perovskite derivatives with unique photoluminescence (PL) properties have attracted growing research interests. [ 14–23 ] Many of high‐efficiency blue, green, yellow, red, and even single‐phase white emitting metal halides have been explored, in which the PL wavelength covering the entire visible light region can be controlled by assembling alkali metal cations or organic cations with different metal halide species. [ 24,25 ] Meanwhile, thanks to the low‐temperature solution processable characteristic and the great adjustability of emission, metal halides have also been considered as a promising next‐generation NIR light sources.…”

Boosting Wide‐Range Tunable Long‐Afterglow in 1D Metal–Organic Halide Micro/Nanocrystals for Space/Time‐Resolved Information Photonics

“…Connection of adjacent independent complex units via the π-π interactions of protonated 4HP ligands and hydrogen bonding interactions (N-H•••X) favors dense stacking, which somewhat impedes nonradiative decays and quenching by oxygen (Figure 1; Figure S3 and Table S3, Supporting Information). [40][41][42] The large steric hindrance imparted by two ZnCl 2 units connected to the binuclear complexes causes the distance of the two neighboring 4HP rings in binuclear complexes to be larger than that in mononuclear systems. [43] Moreover, the dihedral angles for binuclear complexes ZnCl 2 -B and ZnBr 2 -B are 10.08° and 4.74°, respectively, whereas those for mononuclear ZnCl 2 -G and ZnBr 2 -G are both 0°.…”

Tuning Organic Room‐Temperature Phosphorescence through the Confinement Effect of Inorganic Micro/Nanostructures

“…Because of the larger tolerance of organic phosphors (such as tetraphenylphosphorous) and looser organic molecular accumulation alleviating the TTA process, 0D hybrid OIMHs can achieve high phosphorescent quantum yields of up to 63%. [ 26 ] The hybrid materials also provide an excellent platform for controlling the luminescent properties of inorganic metal halides. White and tunable emissions covering the whole visible spectrum can be realized by controlling the topological structures of metal halide‐emitting centers and changing the types of metal ions and halogens.…”

“…[ 52 ] Yan and coworkers used tetraphenylphosphorous units as organic phosphors combined with metal halide tetrahedral clusters and obtained a series of new 0D hybrid OIMHs, (Ph 4 P) 2 Cd 2 X 6 and (Ph 4 P) 2 CdX 4 (X = Br or Cl), through cocrystal assembly. [ 26 ] They found that the thermally activated delayed fluorescence (TADF) bands of organic phosphor could serve as energy buffer layers to compensate for the phosphorescence loss with the increase in temperature ( Figure ). As a result, this provided a new method to realize the zero‐temperature quenching of visible emissions over a wide range from 100 to 320 K. Furthermore, (Ph 4 P) 2 Cd 2 Br 6 showed a high phosphorescent quantum yield of 63%, which was a new record for the reported OIMHs with RTP (Table 1, Entry 21).…”

“…Finally, the phosphors are uniformly dispersed in the inorganic micro/nanosized framework, preventing aggregation‐caused quenching (ACQ), and single‐molecule phosphorescence can be obtained. At present, RTP with a high quantum yield (Φ > 56%) [ 25,26 ] and long organic afterglow with a lifetime greater than 22 s can be achieved by selecting a suitable inorganic framework. [ 27 ]…”