Efficient Exciton to Dopant Energy Transfer in Mn²⁺-Doped (C₄H₉NH₃)₂PbBr₄ Two-Dimensional (2D) Layered Perovskites

Abstract

Three-dimensional ABX 3 perovskite material has attracted immense interest and applications in optoelectronic devices, because of their enabling properties. Recently, Mn 2+ doping directly into APbCl 3 -type three-dimensional (3D) nanocrystals, manifesting host-to-dopant energy transfer, have been reported for LED display applications. Strongly bound excitons in the doped system can enhance the dopant-carrier exchange interactions, leading to efficient energy transfer. Here, we report the simple and scalable synthesis of Mn 2+doped (C 4 H 9 NH 3 ) 2 PbBr 4 two-dimensional (2D) layered perovskites. The Mn 2+ -doped 2D perovskite shows enhanced energy transfer efficiency from the strongly bound excitons of the host material to the d electrons of Mn 2+ ions, resulting in intense orange-yellow emission, which is due to spin-forbidden internal transition ( 4 T 1 → 6 A 1 ) with the highest quantum yield (Mn 2+ ) of 37%. Because of this high quantum yield, stability in ambient atmosphere, and simplicity and scalability of the synthetic procedure, Mn 2+ -doped 2D perovskites could be beneficial as color-converting phosphor material and as energy downshift coating for perovskite solar cells. The newly developed Mn 2+ -doped 2D perovskites can be a suitable material to tune dopant-exciton exchange interactions to further explore their magneto-optoelectronic properties.

Doped Lead Halide White Phosphors for Very High Efficiency and Ultra‐High Color Rendering

“…Doping activators such as Mn 2+ ,Tb 3+ ,Eu 2+ ,orCe 3+ have been reported to generate broadband photoluminescence in hybrid lead halides. [14,[27][28][29][30][31][32] Of particular interest, Mn 2+ can be used to dope most of the hybrid lead halides by substituting the metal element. [14,31,33] This ion is commonly used to improve the photoluminescence quantum yield (PLQY) or/ and the stability of perovskite lattices.…”

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

“…The PXRD patterns reflect only the crystal planes due to distinct preferred orientation, as shown in Fig. 2a, which also reveals the layered structure [14,15]. The preferred orientations were eliminated by the introduction of amorphous glass.…”

“…This layered structure is packed by one or more sheets of cornershared PbX 6 octahedra and bilayers of organic cations alternating along the c axis [3]. The excitons within the octahedral planes are isolated by the organic layers which act as a dielectric spacer forming confining layers, leading to high oscillator strengths, high exciton binding energies, and fast radiative decay rates [8,9,13,14]. These features are highly beneficial to the applications in the field of lighting and displays.…”

“…Up to now, the analogous series have been extensively explored for solar cells and photodetectors [7,8,[15][16]. Despite some research on the intrinsic optical performance of 2D perovskites, such as (C 6 H 11 NH 3 ) 2 PbBr 4 [17], (C 6 H 13 N 3 )PbBr 4 [18], (CH 3 CH 2 NH 3 ) 4 Pb 3 Br 10-x Cl x [12], and others [1, 9,13,19], little attention has been paid to the luminescence properties of 2D layered hybrid perovskite doped with [14]. Doping Mn 2+ ions in low-dimensional semiconductor materials in quantum confinement regime provides fascinating optical properties, due to the interaction of the quantum confined charge carriers of the host with the dopant ions [20][21][22].…”

Effects of transition metals incorporated into perovskite crystals on the electronic structures and magnetic properties by first-principles calculation

“…The photo-induced magnetic mechanisms were based on the electronic structure with intermixing hybrization of the localized 3 d orbital on the transition metal and itinerant carriers on 6 p orbital of Pb and 5 p orbital of I atoms as functions of magnetic interaction and the size of the Fermi surface. The slight perturbation of the ligand field of the 3 d orbital on the transition metal in the perovskite crystal will cause a change of the photo-induced magnetic properties [23]. For instant, the electronic and magnetic properties of cerium manganese oxide (CeMnO 3 ) with the Mn-3 d and Ce-4 d electrons were investigated as referred by Ref.…”