机械化学法制备Cs2NaHoCl6:Yb3+双钙钛矿及上转换发光性能研究

doi:10.15541/jim20250488

摘要/Abstract

摘要：

作为一类极具前景的发光材料, Cs₂NaHoCl₆在保持传统卤化铅钙钛矿优点的同时, 其稳定性更好, 且更易实现稀土离子掺杂, 在生物医学和固态照明等领域具有很好的应用前景。然而, 发展绿色无污染的批量合成方法仍然非常迫切。本研究通过机械化学法合成了Cs₂NaHoCl₆:Yb³⁺双钙钛矿材料, 该方法只需将金属氯化物简单研磨, 然后烘干即可。整个合成过程无需高温、高压或任何有毒溶剂, 产率近100%。980 nm激光激发下, Cs₂NaHoCl₆:Yb³⁺发出位于665 nm的红光发射和550 nm的绿光发射, 其分别对应于Ho³⁺离子的⁵F₅→⁵I₈和⁵S₂/⁵F₄→⁵I₈跃迁。随着Yb³⁺掺杂量增加, 发光增强, 在掺杂量为40%(摩尔百分数)时达到最强, 进一步增加Yb³⁺浓度到50%(摩尔百分数)时, 有杂相生成。在Cs₂NaHoCl₆:Yb³⁺样品中观察到反热猝灭上转换发光现象, 这可能和陷阱态的热激活与钝化有关。另一个可能的原因是温度升高导致Cs₂NaHoCl₆:Yb³⁺双钙钛矿表面-OH脱附, 进而造成表面猝灭效应减弱及上转换发光增强。本研究发展了一种绿色无污染的无铅双钙钛矿合成方法, 并在Cs₂NaHoCl₆:Yb³⁺双钙钛矿中观察到反热猝灭上转换发光, 为无铅双钙钛矿材料的大规模生产奠定基础。

关键词: 机械化学法, 双钙钛矿, Cs₂NaHoCl₆, 上转换发光

Abstract:

As one of highly promising luminescent materials, Cs₂NaHoCl₆:Yb³⁺ not only retains the advantages of traditional halide lead perovskite but also enables easier doping with rare earth ions, thus endowing it with richer luminescent properties. It has wide applications in the fields of biomedicine and solid-state lighting, etc. However, the development of green and pollution-free batch synthesis methods is still extremely urgent. In this study, Cs₂NaHoCl₆:Yb³⁺ was synthesized by the mechanochemical method, which only required grinding the metal chlorides and then drying them. High temperature or any toxic solvents are not needed throughout the entire synthesis process, and the yield is nearly 100%. Under the excitation of 980 nm laser, Cs₂NaHoCl₆:Yb³⁺ emitted red emission at 665 nm and green emission at 550 nm, corresponding to the ⁵F₅→⁵I₈ and ⁵S₂/⁵F₄→⁵I₈ transitions of Ho³⁺ ions. The upconversion intensity gradually increased with the increase of Yb³⁺ doping concentration and reached the strongest when 40% (in molar) Yb³⁺ ions were doped, and secondary phases appeared as Yb³⁺ content further increased to 50% (in molar). Furthermore, anti-thermal quenching upconversion luminescence was observed in the Cs₂NaHoCl₆:Yb³⁺ sample, which may be related to the thermal activation and passivation of trap states. Another possible reason is that the increased temperature leads to the desorption of -OH groups on the surface of Cs₂NaHoCl₆:Yb³⁺, thereby weakening the surface quenching effect and enhancing the upconversion intensity. This study develops a green and pollution-free method for synthesizing lead-free double perovskites, where anti-thermal quenching upconversion luminescence was also observed, laying the foundation for the large-scale production of halide perovskite materials.

Key words: mechanochemical method, double perovskite, Cs₂NaHoCl₆, upconversion luminescence

中图分类号:

TQ174

李霄, 陆净冰, 艾茜茜, 方鹤, 王梅梅, 刘敏. 机械化学法制备Cs₂NaHoCl₆:Yb³⁺双钙钛矿及上转换发光性能研究[J]. 无机材料学报, 2026, 41(9): 1303-1309.

LI Xiao, LU Jingbing, AI Xixi, FANG He, WANG Meimei, LIU Min. Cs₂NaHoCl₆:Yb³⁺ Double Perovskite: Mechanochemical Synthesis and Upconversion Luminescence Properties[J]. Journal of Inorganic Materials, 2026, 41(9): 1303-1309.

图/表 7

图1 CNHC:xYb3+ (x=2%~50%)的制备流程及结构表征

Fig. 1 Synthesis flowchart and structural characterizations of CNHC:xYb3+ (x=2%-50%) (a) Synthesis process; (b) XRD patterns; (c) SEM image and EDS elemental mappings of CNHC:40%Yb3+. Colorful figures are available on website

图2 大批量制备的CNHC:40%Yb3+的XRD谱图

Fig. 2 XRD pattern of CNHC:40%Yb3+ perovskites synthesized on a large scale

图3 980 nm 激发下CNHC:xYb3+的上转换发光性能

Fig. 3 Upconversion properties of CNHC:xYb3+ under 980 nm excitation Variations of (a) emission spectra, (b) corresponding emission intensity and R/G with Yb3+ contents. Colorful figures are available on website

图4 980 nm激发下CNHC:40%Yb3+的发光寿命图(λem=550 nm)

Fig. 4 Decay curves of CNHC:40%Yb3+ under 980 nm excitation (λem=550 nm)

图5 不同激发功率下CNHC:40%Yb3+的上转换发光性能

Fig. 5 Power-dependent upconversion properties of CNHC:40% Yb3+ under different excitation powers (a) Upconversion spectra; (b) R/G ratios; (c) lgI-lgP graphs. Colorful figures are available on website

图6 980 nm激发下CNHC:40%Yb3+的上转换发光机理图

Fig. 6 Upconversion mechanism of CNHC:40%Yb3+ under 980 nm excitation

图7 298~473 K下CNHC:40%Yb3+的上转换发光性能

Fig. 7 Upconversion properties of CNHC:40%Yb3+ at 298-473 K (a) Temperature-dependent upconversion spectra; (b) Contour map of the thermal evolution of upconversion spectra; (c) Corresponding histograms of integrated intensities. Colorful figures are available on website

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机械化学法制备Cs₂NaHoCl₆:Yb³⁺双钙钛矿及上转换发光性能研究

Cs₂NaHoCl₆:Yb³⁺ Double Perovskite: Mechanochemical Synthesis and Upconversion Luminescence Properties

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