Mn²⁺ as an “Optical Energy Shutter” to Regulate Red‐to‐NIR Luminescence in Rare Earth Doped Layered Quadruple Perovskites

Abstract

Metal halide perovskites (MHPs) have shown great application prospects in the field of optoelectronics owing to their superior optical and optoelectronic properties. Bandgap engineering and impurity doping are effective ways to achieve regulation of luminous properties in the visible light region. However, realizing efficient deep red and wide‐range tunable near‐infrared (NIR) emission remains a challenge. Here, a series of rare earth (RE3+) ions (RE = Nd, Dy, Ho, Er, Tm, Yb) doped Cs4Cd1−xMnxSb2Cl12 (0 ≤ x ≤ 1) quadruple perovskites are designed. An efficient tunable luminescence from red to NIR light is achieved based on the energy transfer (ET) from Mn2+ to RE3+ by building the Mn2+ energy bridge, which covers the NIR‐I (650–900 nm) and NIR‐II (900–1700 nm) regions. Moreover, the ET efficiency is availably influenced by the doping concentration of Mn2+. Interestingly, the energy bridge from Mn2+ to RE3+ is cut off because of the increased bandgap when Bi3+ is introduced into the RE3+‐doped Cs4Cd0.4Mn0.6Sb2−yBiyCl12 (0 ≤ y ≤ 2) lattice. Through bandgap engineering, the ET from Mn2+ to RE3+ resembles an “optical energy shutter” which quenches the NIR emission of RE3+ owing to the mismatched energy level but enhances the emission of Mn2+.

Realizing efficient broadband near-infrared emission and multimode photoluminescence switching via coordination structure modulation in Sb3+-doped 0D organic metal chlorides

“…In parallel, rare earth ion (Yb 3+ , Er 3+ , Nd 3+ ) doped lead halide perovskites have also made remarkable progress in NIR emission, and an eruptive PLQY of nearly 200% has been obtained via a picosecond quantum-cutting process. [16][17][18][19] Nevertheless, rare earth ions generally exhibit sharp emission bands, severely limiting the desired applications in three-dimensional (3D) sensing and food inspection. 3,20,21 In recent years, the broadband NIR emission stemming from the 4 T 2 -4 A 2 transition of Cr 3+ ions in the weak crystal field has been observed.…”

Excitation-dependent efficient photoluminescence in an organic–inorganic (C4H12N)2HfCl6 perovskite induced by antimony doping

“…Chemical doping is an effective strategy for tailoring the electronic and optical properties of metal halides. 15–21 For example, antimony (Sb 3+ ) ions with ns 2 electronic configurations can be used to confer superb light-emitting properties to materials, typically including efficient broadband STE emission. 22–27 For these halide perovskite materials, excitons are absolutely confined in isolated polyhedrons with strong quantum confinement, ultimately producing only a single STE emission at room temperature and no emission of high-energy free excitons (FEs).…”

Lanthanide Doping into All-Inorganic Heterometallic Halide Layered Double Perovskite Nanocrystals for Multimodal Visible and Near-Infrared Emission

“…Reported examples include the incorporation of Ln 3+ ions (such as Yb 3+ , Er 3+ , and Tb 3+ ) within Cs 2 M­(I)­M­(III)­Cl 6 (M­(I): Na + , Ag + ; M­(III): Bi 3+ , In 3+ ) double perovskite NCs, resulting in enhanced optical properties in the NIR range. , Co-doping Ln 3+ (e.g., Tb 3+ , Er 3+ , Sm 3+ , Nd 3+ ) with main group trivalent metal cations (e.g., Bi 3+ , Sb 3+ ) in Cs 2 AgInCl 6 double perovskite NCs has also been demonstrated. − Compared to double perovskites, LDPs possess a unique 2D layered “sandwiched” crystal structure that remains largely unexplored with regard to the Ln 3+ doping positions and energy transfer mechanisms . Despite few trials of doping Ln 3+ ions into bulk-scale LDPs, − the incorporation of Ln 3+ dopants in nanoscale LDP materials, enabling multimodal visible/NIR emissions, has yet to be presented. Therefore, there is a significant knowledge gap in our understanding of how Ln 3+ doping affects electronic and crystal structures and the intricate energy transfer mechanisms within Ln 3+ -doped LDP NCs.…”