Layered Perovskite Doping with Eu³⁺ and β-diketonate Eu³⁺ Complex

Abstract

Metal halide perovskites are attracting great interest for the fabrication of light-emitting devices encompassing light-emitting diodes, lasers, and scintillators. As the field develops, perovskite doping emerges as a promising way to enrich the material functionalities and enhance the luminescence yield and tunability. While Mn +2 addition has been well explored, doping with lanthanides has received less attention, even though their intense and line-like luminescence is interesting for a wide range of applications. In this work, we study the doping of NMA 2 PbBr 4 layered perovskites with Eu 3+ and Eu 3+ tetrakis β-diketonate complex. By exploiting the antenna effect of the naphthalene-based functional cation (NMA = 1-naphtylmethylammonium), direct sensitization of Eu 3+ is obtained; nevertheless, it is not very efficient due to the non-optimal energy level alignment with the resonance acceptor level of the lanthanide. Protection of Eu 3+ in the form of tetrakis β-diketonate complex grants a more ideal coordination geometry and energetic landscape for the energy transfer to europium in the perovskite matrix, allowing for a nearly 30-fold improvement in luminescence yield. This work sets the basis for new synthetic strategies for the design of functional perovskite/lanthanide host–guest systems with improved luminescence properties.

Strain Modulation for High Brightness Blue Luminescence of Pr3+-Doped Perovskite Nanocrystals via Siloxane Passivation

“…In this work, no emission lines associated with the Pr 3+ ion are observed. However, carrier transfer to lanthanide can be exploited for the design of advanced optoelectronic materials for high purity lanthanide emission by doping with alternative lanthanide ions or an advisable molecular design . These materials can be further developed by virtue of crystal field modulation, which is very likely effective in the Pr-ExMP-PeNC system in case excited carriers are transferred to the dopant.…”

Emerging doping strategies in two-dimensional hybrid perovskite semiconductors for cutting edge optoelectronics applications

“…Eu 3+ doping introduced ve sharp emission bands peaking at 576, 589, 611, 648, and 697 nm characteristic of the Eu 3+ intra-congurational transitions 5 D 0 / 7 F J (J ¼ 0-4) which appeared overlapped with the triplet emission. 88 The presence of all ve Eu 3+ transitions indicated strong deviations from the inversion symmetry due to strong octahedral distortion, the spatial arrangement of the nearest neighbors (e.g., organic cations), and the symmetry group of the crystal lattice. 88 The role of the NMA triplet was to sensitize the lanthanide material since Eu 3+ transitions were not observed in Eu doped BA 2 PbCl x Br 4Àx and PEA 2 PbCl x Br 4Àx systems where the organic cation does not have an accessible triplet level.…”

“…85 88 The europium chelate doping was achieved by initially synthesizing the tetrakis bdiketonate complex Eu(tta) 4 P(Ph) 4 [Eu(L)], then the prepared complex was added to the spin coating solution to form the doped system NMA 2 PbBr 4 :Eu(L). 88 In both cases, the XRD diffraction peaks shied towards smaller angles indicating increase in interplanar spacing, which was explained by partial incorporation of chlorine in NMA 2 PbBr 4 :Eu and lattice expansion for NMA 2 PbBr 4 :Eu(L) due to the formation of an intercalation compound. The diffraction peak intensity decreased in NMA 2 PbBr 4 :Eu(L), indicating the reduction in crystallinity due to the introduction of the bulky Eu complex (Fig.…”

“…D 0 / 7 F 2 PbBr 4 :Eu(L) and NMA 2 PbCl 2 Br 2 :Eu(L). The Eu complex doped 2D perovskite showed narrower emission and PL QYs of 9 and 13% for NMA 2 PbBr 4 :Eu(L) and NMA 2 PbCl 2 -Br 2 :Eu(L), respectively, which were $30-fold enhanced compared to that of EuCl 3 doped NMA 2 PbBr 4 perovskite 88. …”

Phase Regulation of CsPb2Br5/CsPbBr3 Perovskite Nanocrystals by Doping with Divalent Cations: Implications for Optoelectronic Devices with Enhanced Stability and Reduced Toxicity

“…In addition, rare earth ion (such as Eu 3+ and Sm 3+ ) doping is also widely used and a large number of high-performance perovskite luminescent materials have been obtained. However, due to the small reserves and high price of rare earth metals, their further application is limited. , Recently, some research showed that CsPb 2 Br 5 NCs have excellent water stability compared with CsPbBr 3 NCs. For example, Yao and his co-workers constructed the dual-phase CsPbBr 3 /CsPb 2 Br 5 NCs with high PLQY by reducing the trap density.…”