Core-Shell Structure and Luminescence of SrMoO4:Eu3+ (10%) Phosphors

doi:10.1016/j.jmst.2016.04.018

Abstract

Abstract:

SrMoO₄:Eu³⁺ (10%) phosphors were produced via hydrothermal synthesis and co-precipitation. We systematically analyzed how the morphology and luminescence properties of the phosphors were affected by the synthesis conditions, including the pH of the precursor solution, stirring speed, and post-sintering temperature. The samples synthesized at pH = 8 and 9 were spindle-like rods with a core-shell structure. When the stirring speed increased to V_s = 150 r/min, the core-shell structure disappeared. Photoluminescence measurements indicated that the SrMoO₄:Eu³⁺ samples under ultraviolet radiation produced strong red emission centered at 616 nm. The luminescence properties were greatly affected by the pH, stirring during hydrothermal reaction, and use of post-annealing. The related mechansim is discussed.

Key words: SrMoO₄, Core-shell structure, Eu3+-doped, Luminescence

Zhu Yanan,Zheng Ganhong,Dai Zhenxiang,Zhang Lingyun,Mu Jingjing. Core-Shell Structure and Luminescence of SrMoO₄:Eu³⁺ (10%) Phosphors[J]. J. Mater. Sci. Technol., 2016, 32(12): 1361-1371.

Figures/Tables 20

Table 1. Summary of the experimental conditions

Samples	Preparation methods	pH value	Stirring speed, V_s (r/min)	Sintering temperature
S1	Co-precipitation	8	—	—
S2	Co-precipitation	9	—	—
S3	Hydrothermal	8	0	—
S4	Hydrothermal	9	0	—
S5	Hydrothermal	6	0	—
S6	Hydrothermal	7	0	—
S7	Hydrothermal	6	100	—
S8	Hydrothermal	7	100	—
S9	Hydrothermal	8	100	—
S10	Hydrothermal	9	100	—
S11	Hydrothermal	8	50	—
S12	Hydrothermal	8	150	—
S13	Hydrothermal	8	0	200 °C
S14	Hydrothermal	8	0	300 °C
S15	Hydrothermal	8	0	500 °C

Fig. 1. XRD patterns for S1 (Co-precipitation method) and S3 (hydrothermal method) samples (a), and for S13 (pH = 8, hydrothermal method, sintering 200 °C), S14 (pH = 8, hydrothermal method, sintering300 °C) and S15 (pH = 8, hydrothermal method, sintering 500 °C) samples (b).

Fig. 2. Crystal structure of SrMoO4.

Fig. 3. SEM and TEM images of the SrMoO4:Eu samples (S1-4) prepared via the co-precipitation (S1 (a, c), S2 (b, d)) and hydorthermal method (S3 (e, f), S4 (g, h)).

Scheme 1. Schematic illustration for the possible formation mechanism of SrMoO4 with various SEM morphologies under different experimental methods and conditions.

Scheme 2. Schematic illustration for the possible formation mechanism of SrMoO4 core-shell structure under hydrothermal preparation.

Fig. 4. SEM images of S3 (a, e) (pH = 8, hydrothermal method), S4 (b, f) (pH = 9, hydrothermal method), S5 (c, g) (pH = 6, hydrothermal method), and S6 (d, h) (pH = 7, hydrothermal method) samples.

Fig. 5. SEM images of S7 (a) (pH = 6, hydrothermal method, stirring speed Vs = 100 r/min), S8 (b) (pH = 7, hydrothermal method, stirring speed Vs = 100 r/min), S9 (c) (pH = 8, hydrothermal method, stirring speed Vs = 100 r/min), and S10 (d) (pH = 9, hydrothermal method, stirring speed Vs = 100 r/min) samples.

Fig. 6. SEM images of S3 (a, e) (pH = 8, hydrothermal method, stirring speed Vs = 0), S11 (b, f) (pH = 8, hydrothermal method, stirring speed Vs = 50 r/min), S9(c, g) (pH = 8, hydrothermal method, stirring speed Vs = 100 r/min), and S12 (d, h) (pH = 8, hydrothermal method, stirring speed Vs = 150 r/min) samples.

Fig. 7. TEM (a) and HRTEM (b) images for S9 (pH = 8, hydrothermal method, stirring speed Vs = 100 r/min) sample.

Fig. 8. Excitation spectra for monitoring the emission at λem = 616 nm of S2 (Co-precipitation method) sample.

Fig. 9. Emission spectrum of S2 (Co-precipitation method) and S4 (hydrothermal method) samples under (a) λex = 215 and (b) 396 nm excitation.

Scheme 3. VO43--Eu3+ energy transfer and Eu3+ emission process.

Fig. 10. Excitation spectra for monitoring the emission at λem = 616 nm of S3 (pH = 8, hydrothermal method), S4 (pH = 9, hydrothermal method), S5 (pH = 6, hydrothermal method), and S6 (pH = 7, hydrothermal method) samples.

Fig. 11. Emission spectra for S3 (pH = 8, hydrothermal method), S4 (pH = 9, hydrothermal method), S5 (pH = 6, hydrothermal method), and S6 (pH = 7, hydrothermal method) samples under 396 nm excitation.

Fig. 12. Excitation spectra for monitoring the emission at λem = 616 nm (a) and emission spectra under 396 nm excitation for S3 (pH = 8, hydrothermal method, stirring speed Vs = 0), S11 (pH = 8, hydrothermal method, stirring speed Vs = 50 r/min), S9 (pH = 8, hydrothermal method, stirring speed Vs = 100 r/min), and S12 (pH = 8, hydrothermal method, stirring speed Vs = 100 r/min) samples.

Table 2. R/O Ratios and CIE coordinates for samples at different stirring speeds

Samples at different stirring speeds (r/min)	R/O	CIE (x,y)
0	4.7557	(0.59,0.34)
50	4.3247	(0.64,0.33)
100	3.9965	(0.64,0.32)
150	3.9743	(0.65,0.33)

Fig. 13. Variation of emission intensities around 592, 616, 625, and 700 nm for stirring speeds of 0, 50, 100 and 150 r/min) samples under 396 nm excitation.

Fig. 14. Emission spectra for S3 (pH = 8, hydrothermal method, no-sintering), S13 (pH = 8, hydrothermal method, sintering 200 °C), S14 (pH = 8, hydrothermal method, sintering 300 °C) and S15 (pH = 8, hydrothermal method, sintering 500 °C) samples under 396 nm excitation.

Fig. 15. FT-IR spectra of the S1 (co-precipitation method), S5 (hydrothermal method pH = 6), S9 (hydrothermal method pH = 6, stirring speed Vs = 100 r/min), S10 (hydrothermal method pH = 9, stirring speed Vs = 100 r/min), and S15 (hydrothermal method pH = 8, stirring speed Vs = 0, sintering 500 °C) samples.

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Core-Shell Structure and Luminescence of SrMoO₄:Eu³⁺ (10%) Phosphors

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