Stability of the Eu²⁺ Dopant in CsPbBr₃ Perovskites: A First-Principles Study

Abstract

We study the stability of the rare-earth dopant, Eu, in metal-halide perovskite CsPbBr3 with cubic and orthorhombic structures from first-principles calculations. In these perovskites, Eu is substitutionally doped on Pb sites because of their comparable ionic sizes which lead to only a small strain in the doped system. Accordingly, our results show that the cost of Eu doping is quite small compared to the values in other common hosts such as GaN. This makes these perovskites excellent candidates to develop rare-earth doped semiconducting materials for bright luminescence as it has also been observed recently in the case of thin films of CH3NH3Pb1–x Eu x I3, Eu-doped quantum dots of CsPbBr3, and nanocrystals of CsPbCl3 in addition to their outstanding properties for applications in solar cells.

Europium and Acetate Co‐doping Strategy for Developing Stable and Efficient CsPbI2Br Perovskite Solar Cells

“…More recently, By partially substitute Pb 2+ with Eu 3+ , a stable α‐phase CsPbI 2 Br perovskite was obtained at room temperature, showing a maximum PCE of 13.71% . All of these findings demonstrated that smaller Eu 3+ can be doped into the inorganic perovskites to improve their photovoltaic performance and stability …”

“…For this purpose, a series of doping strategies have been carried out by incorporating some smaller metal cations into the perovskite lattice to modulate photoelectronic properties and improve the phase stabilities of inorganic perovskite materials. For instance, some works proposed to partially substitute B‐site cations (Pb 2+ , 120 pm) with smaller lanthanide ions such as Ce 3+ (103 pm), Eu 3+ (95 pm), Sm 3+ (111 pm), Er 3+ (88 pm), and so on in the inorganic perovskites . It demonstrated that the addition of lanthanide ions can effectively improve the photovoltaic performance and stability of inorganic PSCs.…”

Effects of mixed-valence states of Eu-doped FAPbI3 perovskite crystals studied by first-principles calculation

“…35,36 The photovoltaic properties and the electronic structures of the lanthanide and actinide perovskite compounds were characterized by experimental results using first-principles calculation. [37][38][39] Rare-earth-based compounds have unique types of physical phenomena owing to their heavy-electron behaviours, such as their magnetic properties, fluorescence characteristics, superconductivity and photovoltaic application. [40][41][42][43] For example, the 4f orbitals of europium are blocked by the closed shell structure of 5s-5p 6 , making them less susceptible to crystal fields in the coordination structure.…”

Improving the Stability and Optoelectronic Properties of All Inorganic Less‐Pb Perovskites by B‐Site Doping for High‐Performance Inorganic Perovskite Solar Cells

“…Lanthanide ions have been widely investigated as the optically active dopants in CsPbX 3 inorganic perovskite nanocrystals, achieving high photoluminescence quantum yield (PLQY), multiple color emission, and quantum cutting effect for lighting and labeling applications. [114][115][116][117] Inspired by those exciting developments, most of the lanthanide ions, such as La 3þ , Ce 3þ , Sm 3þ , Eu 3þ , Tb 3þ , Ho 3þ , Er 3þ , and Yb 3þ , have been considered as the promising B-site dopants to improve the optoelectronic properties and the stability of inorganic CsPbX 3 perovskite crystal for solar cell application in the past 2 years. [118][119][120][121][122][123][124][125] Jena et al reported that the B-site doping of Eu could greatly enhance the stability of CsPbI 3 perovskite in ambient condition and reduce the nonradiative recombination within CsPbI 3 perovskite films.…”