Citation: Huang Qingming, Yu Han, Zhang Xinqi, Cao Wenbing, Yu Jianchang. Upconversion Performance Enhancement of NaYF₄:Yb/Tm by Codoping Hf⁴⁺ as Energy Migrator[J]. Acta Chimica Sinica, ;2015, 74(2): 191-198. doi: 10.6023/A15040257 shu

Upconversion Performance Enhancement of NaYF₄:Yb/Tm by Codoping Hf⁴⁺ as Energy Migrator

Huang Qingming ^a,b ,
Yu Han ^a ,
Zhang Xinqi ^b ,
Cao Wenbing ^a ,
Yu Jianchang ^a,*,,

a.
College of Materials Science and Engineering, Fuzhou University, Fuzhou, Fujian 350108
b.
Instrumentation Analysis and Research Center, Fuzhou University, Fuzhou, Fujian 350002

Corresponding author: Yu Jianchang, jcyu@fzu.edu.cn
Received Date: 14 April 2015

Fund Project: the Natural Science Fund of Fujian Province No. 2013J05027

Figures(6)

In this paper we report the infrared to visible upconversion(UC) luminescence properties of Hf⁴⁺ and Zr⁴⁺ codoped NaYF₄:Yb³⁺/Tm³⁺. Samples were synthesised by hydrothermal method. Concentration of Tm³⁺ and Yb³⁺ ions were fixed to be 2 mol% and 5 mol% for all samples, respectively. NaY_0.93-xYb_0.05Tm_0.02F₄ was tridoped with 0, 2, 4, 6, 8 mol% Hf⁴⁺ or Zr⁴⁺ and corresponding samples were named as Hf0, Hf2, Hf4, Hf6, Hf8 and Zr0, Zr2, Zr4, Zr6, Zr8, respectively. In a typical procedure, trivalent nitrate stock solutions of 0.2 mol/L were prepared at first by dissolving the corresponding metal oxide in concentrated nitric acid or hydrofluoric acid at elevated temperatures. And then, a certain mole percentage of trivalent nitrate solutions were added into 20 mL 0.04 mmol EDTA aqueous solution. After vigorous stirring for 30 min, 25 mL ethanol solution containing 0.2 mmol NaF, 0.2 mmol NH₄HF₂ and corresponding stoichiometric amount Hf⁴⁺ or Zr⁴⁺ were dropwise added into the solution, and then pH value of solution was adjusted to 3.0 by addition 1 mol/L HF, and stirring continued for 30 min. Then the emulsion mixture was moved to PTFE-lined high pressure pot and incubated in oven at 180℃ for 12 h. The final products were collected, washed several times with water and ethanol alternately, and gathered by centrifugation, and then dried in oven at 60℃. Crystal microstructure, morphology and UC luminescence properties of samples were investigated by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and upconversion photoluminescence spectra. Results revealed the bond distance of F₁-Y and F₂-Y become close with the rising of Hf⁴⁺ or Zr⁴⁺ codoped concentration, indicating crystal field asymmetry of rare earth ions were tuned effectively by Hf⁴⁺ or Zr⁴⁺ codoping. Electron hypersensitive transition was promoted, and the intensity of 802 nm emission was enhanced obviously. Hf⁴⁺ ion was a better dopant than Zr⁴⁺, for the extranuclear electronic structure of Hf⁴⁺ was the same with rare earth ions, and Hf⁴⁺ ion was involved in UC process as a migrator to improve Tm³⁺ upper state levels'population. UC luminescence of Hf⁴⁺ codoped sample were enhanced obviously, especially the shortwave emissions. The reported work establishes the understanding of Hf⁴⁺ as a migrator for Tm³⁺ ions upconversion luminescence, which may be helpful for design and synthesis of high-performance upconversion materials.
- upconversion,
- hafnium doping,
- crystal field,
- energy migration
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Upconversion Performance Enhancement of NaYF4:Yb/Tm by Codoping Hf4+ as Energy Migrator

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Upconversion Performance Enhancement of NaYF₄:Yb/Tm by Codoping Hf⁴⁺ as Energy Migrator