Influences of Annealing Temperature and Doping Concentration on Microstructural and Optical Properties of CeO2:Sm3+ Nanocrystals

doi:10.1007/s40195-015-0258-0

Abstract

Abstract:

Nanocrystals of CeO₂ with different doping concentrations of Sm³⁺ were synthesized by a novel and cost-effective method. The crystal structure, morphology and particle size were systematically investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Effects of the annealing temperature and doping concentrations on the microstructural properties of the crystals were studied. X-ray diffraction analysis indicates that the cubic structure of the CeO₂ is not affected by the doping of Sm³⁺ up to a doping concentration of 20%. Different structural parameters such as lattice constant, surface area, bulk density and porosity of the crystal were determined and discussed. Microscopic images of the CeO₂:Sm³⁺ suggest that the thermal decomposition of oxalate precursor is a suitable synthesis pathway to produce uniform-sized microparticles and nanoparticles. The influences of annealing temperature and doping concentration of Sm³⁺ on the optical properties of the nanocrystals were also discussed. The photoluminescence excitation spectra reveal that the charge transfer band is redshifted with increasing annealing temperatures. Emission attains its maximum intensity for Sm³⁺ concentration of 1%, and higher concentrations lead to emission quenching.

Key words: Microstructure, Strain, Photoluminescence, CeO2:Sm3+, nanocrystal, Doping, concentration, Annealing, temperature

G. Vimal, Kamal P. Mani, P. R. Biju, Cyriac Joseph, N. V. Unnikrishnan, M. A. Ittyachen. Influences of Annealing Temperature and Doping Concentration on Microstructural and Optical Properties of CeO₂:Sm³⁺ Nanocrystals[J]. Acta Metallurgica Sinica (English Letters), 2015, 28(6): 758-765.

Figures/Tables 10

Fig. 1 X-ray diffractograms of the pure and Sm3+ (concentration in mol%)-doped CeO2 annealed at different temperatures: a 400 °C; b 600 °C; c 800 °C

Table 1 Crystalline size, lattice parameter, crystal volume and microstrain of pure and Sm3+-doped CeO2 annealed at 600 and 800 °C

Annealing temperature (°C)	Sm³⁺ concentration (mol%)	2θ (°)	a (Å)	Crystal volume (Å³)	Strain (10^-4)	Size from HW plot (nm)	Size from Scherrer equation (nm)
600	0	28.65	5.405	157.95	0.818	25	25
	0.5	28.65	5.405	157.95	1.01	24	23
	1	28.648	5.405	157.95	1.54	22	22
	1.5	28.638	5.405	157.95	2.25	25	24
	2	28.58	5.409	158.23	2.34	23	22
	5	28.60	5.413	158.63	2.91	23	21
	10	28.55	5.418	159.02	5.01	20	19
	20	28.45	5.427	159.92	5.46	18	16
800	0	28.75	5.40	157.57	0.285	70	63
	0.5	28.70	5.402	157.63	0.34	67	61
	1	28.68	5.402	157.63	0.495	69	63
	1.5	28.68	5.403	157.76	1.25	77	67
	2	28.67	5.404	157.85	1.57	72	59
	5	28.65	5.411	158.46	1.76	69	56
	10	28.60	5.419	159.14	2.39	46	37
	20	28.53	5.429	160.02	2.62	46	36

Fig. 2 Variations of lattice parameter and microstrain with Sm3+ concentration and annealing temperature

Fig. 3 XRD peak corresponds to the (111) plane CeO2 for different doping concentrations of Sm3+ and splitting of the peak of Sm3+ doping concentration of 20 mol% (inset)

Table 2 X-ray density, specific surface area, bulk density and porosity of pure and Sm3+-doped CeO2 annealed at 600 and 800 °C

Annealing Temperature (°C)	Sm³⁺ (%)	X-ray density (g/cm³)	Specific surface area (m²/gm)	Bulk density (g/cm³)	Porosity
600	0	7.24	33.2	5.77	0.20
	0.5	7.24	36	5.64	0.22
	1	7.24	37.7	5.20	0.28
	1.5	7.24	34.5	5.15	0.29
	2	7.23	37.7	5.10	0.30
	5	7.21	39.6	5.04	0.30
	10	7.20	43.9	4.89	0.32
	20	7.16	52.3	4.57	0.36
800	0	7.25	11.8	6.28	0.13
	0.5	7.25	12.3	6.2	0.14
	1	7.25	12	6.30	0.13
	1.5	7.25	10.8	6.25	0.14
	2	7.22	11.5	6.22	0.14
	5	7.22	12	6.2	0.14
	10	7.19	18.1	6.18	0.14
	20	7.15	18.2	5.6	0.22

Fig. 4 SEM images of the crystals: a CeO2 annealed at 400 °C; b CeO2 doped with 1 mol% Sm3+ annealed at 400 °C; c CeO2 annealed at 600 °C; d CeO2 doped with 1 mol% Sm3+ annealed at 600 °C; e CeO2 annealed at 800°C; f CeO2 doped with 1 mol% Sm3+ annealed at 800 °C

Fig. 5 TEM images of the crystals: a pure CeO2 annealed at 400 °C; b CeO2 doped with 1 mol% Sm3+ annealed at 400 °C; c HRTEM and SAED pattern of pure CeO2 annealed at 400 °C; d pure CeO2 annealed at 600 °C

Fig. 6 FTIR spectra of the 5 mol% Sm3+-doped CeO2 annealed at 400, 600 and 800 °C (inset is the enlarged view of the spectra)

Fig. 7 Excitation spectra of Sm3+-doped CeO2 annealed at 400, 600 and 800 °C

Fig. 8 Emission spectra of Sm3+-doped CeO2 annealed at 400, 600 and 800 °C

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Influences of Annealing Temperature and Doping Concentration on Microstructural and Optical Properties of CeO₂:Sm³⁺ Nanocrystals

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