Lattice doping of lanthanide ions in Cs2ZrCl6 nanocrystals enabling phase transition and tunable photoluminescence

• Published in: Materials horizons Vol. 11; no. 21; pp. 5341 - 5351
• Main Authors: Liu, Yachong, Yun, Rui, Yang, Huanxin, Sun, Wenda, Li, Yue, Lu, Haolin, Zhang, Libing, Li, Xiyan
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 28.10.2024
• Subjects: Broadband; Dopants; Energy transfer; Excitation; Excitons; Lead free; Nanocrystals; Optoelectronics; Perovskites; Phase transitions; Photoelectric effect; Photoelectricity; Photoluminescence; Terbium
• ISSN: 2051-6347; 2051-6355; 2051-6355
• DOI: 10.1039/d4mh00723a

Dopants can endow lead-free perovskite nanocrystals with novel photoelectric properties. However, understanding the effect of dopants on the structure and energy transfer of lead-free perovskite nanocrystals remains limited. In this work, we synthesize zero-dimensional Cs2ZrCl6 nanocrystals with a blue light quantum yield of up to 75.6% by an improved hot-injection method. And we introduce trace amounts of lanthanide ions (Ln3+) (<∼8%) in the lattice of nanocrystals and establish an effective energy transfer channel from self-trapped excitons (STEs) to various Ln3+ ions (Tb3+, Eu3+, Dy3+, Sm3+, and Pr3+), which can achieve tunable photoluminescence between red, green and blue. Interestingly, with increasing Ln3+ concentrations (>∼10%), the phase transition from the cubic phase Cs2ZrCl6:Ln3+ to the monoclinic phase Cs3LnCl6:Zr4+ occurred, while Zr4+ ions began to act as dopants. And a new energy transfer channel from dopant [ZrCl6]2− to host Ln3+ ions was established in the Cs3LnCl6 host accompanied by enhanced broadband photoluminescence excitation (PLE) and photoluminescence (PL). In particular, the photoluminescence quantum yield (PLQY) of Tb3+ ions increases from 0.77% to 54% upon the phase transition (under 276 nm excitation). Our study provides new insights into the effects of dopants on the structure of perovskite nanocrystals and is beneficial to the design of a variety of light-emitting materials for optoelectronic applications.