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

References 32

[1]	N. Brahme, A. Gupta, D.P. Bisen, R.S. Kher, S.J. Dhoble,Phys. Proc. 29, 97(2012)
[2]	J.C. Wang, C.T. Lin, C.H. Huang, C.S. Lai, C.H. Liao,Microelectron. Reliab. 52, 1627(2012)
[3]	G. Mialon, S. Turkcan, A. Alexandrou, T. Gacoin, J.P. Boilot, J. Phys. Chem. C 113, 18699 (2009)
[4]	G. Kim, N. Lee, K.B. Kim, B.K. Kim, H. Chang, S.J. Song, J.Y. Park, Int. J. Hydrog. Energy 38, 1571 (2013)
[5]	T. Miki, T. Ogawa, M. Haneda, N. Kakuta, A. Ueno, S. Tateishi, S. Matsuura, M. Sato, J. Phys. Chem. 94, 6464(1990)
[6]	S. Tsunekawa, T. Fukuda, A. Kasuya, J. Appl. Phys. 87, 1318(2000)
[7]	J.H. Cho, M. Bass, S. Babu, J.M. Dowding, W.T. Self, S. Seal, J. Lumin. 132, 743(2012)
[8]	G. Jose, G. Jose, V. Thomas, C. Joseph, M.A. Ittyachen, N.V. Unnikrishnan, J. Flouresc. 14, 733(2004)
[9]	G. Jose, C. Joseph, M.A. Ittyachen, N.V. Unnikrishnan,Opt. Mater. 29, 1495(2007)
[10]	V. Thomas, A. Elizebeth, H. Thomas, G. Jose, N.V. Unnikrishnan, C. Joseph, M.A. Ittyachen, J. Optoelectron. Adv. Mater. 7, 2687(2005)
[11]	R. Ghosh, D. Basaka, S. Fujihara, J. Appl. Phys. 96, 2689(2004)
[12]	H. Yahiro, K. Eguchi, H. Arai,Solid State Ion. 36, 71(1989)
[13]	Z. Fan, P.C. Chang, J.G. Lu, E.C. Walter, R.M. Penner, C.H. Lin, H.P. Lee,Appl. Phys. Lett. 85, 6128(2004)
[14]	S. Babu, A. Schulte, S. Seal,Appl. Phys. Lett. 92, 123112(2008)
[15]	N.S. Kumar, K.V. Bangera, G.K. Shivakumar,Superlattices Microstruct. 75, 303(2014)
[16]	F.H. Chung, D.K. Smith, Industrial Applications of X-ray Diffraction (Marcel Dekker Inc, NewYork, 2000)
[17]	A. Khorsand Zak, W.H.A. Majid, M.E. Abrishami, R. Yousef, Solid State Sci. 13, 251(2011)
[18]	A. Kumar, S. Babu, A.S. Karakoti, A. Schulte, S. Seal, Langmuir 25, 10998 (2009)
[19]	R. Tholkappiyan, K. Vishista, Phys. B 448, 177 (2014)
[20]	S.A. Safaan, A.M. Abo El Ata, M.S. El Messeery, J. Magn. Magn. Mater. 302, 362(2006)
[21]	M. Mogensen, N.M. Sammes, G.A. Tompsett,Solid State Ion. 129, 63(2000)
[22]	L.P. Zhu, G.H. Liao, N.C. Bing, L.L. Wang, H.Y. Xie,J. Solid State Chem. 184, 2405(2011)
[23]	G. Vimal, P.M. Kamal, P.R. Biju, C. Joseph, N.V. Unnikrishnan, M.A. Ittyachen, Spectrochim. Acta A 122, 624 (2014)
[24]	J.P. Hos, P.G. McCormick, Scr. Mater. 48, 85(2003)
[25]	N. Sutradhar, A. Sinhamahapatra, S. Pahari, M. Jayachandran, B. Subramanian, H.C. Bajaj, A.B. Panda, J. Phys. Chem. C 115, 7628 (2011)
[26]	C. Joseph, M.A. Ittyachen, K.S. Raju,Bull. Mater. Sci. 20, 37(1997)
[27]	I. Petrov, B. Soptrajanov, Spectrochim. Acta A 31, 309 (1975)
[28]	M.M. Natile, G. Boccaletti, A. Glisenti,Chem. Mater. 17, 6272(2005)
[29]	G. Vimal, K.P. Mani, P.R. Biju, C. Joseph, N.V. Unnikrishnan, M.A. Ittyachen, Appl. Nanosci. (2014). doi:10.1007/s13204-014-0375-5
[30]	L. Li, S. Zhang, J. Phys. Chem. B 110, 21438 (2006)
[31]	G. Lakshminarayana, H. Yang, Y. Teng, J. Qiu, J. Lumin. 129, 59(2009)
[32]	G. Blasse, B.C. Grabmaier, Luminescent Materials (Springer, Berlin, 1994)

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

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 10

References 32

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Chun-Hua Ma, Fu-Sheng Pan, Ding-Fei Zhang, Ai-Tao Tang, Zhi-Wen Lu. Effects of Sb Addition on Microstructural Evolution and Mechanical Properties of Mg-9Al-5Sn Alloy [J]. Acta Metallurgica Sinica (English Letters), 2021, 34(2): 278-288.
[2]	Ping Deng, En-Hou Han, Qunjia Peng, Chen Sun. Corrosion Behavior and Mechanism of Irradiated 304 Nuclear Grade Stainless Steel in High-Temperature Water [J]. Acta Metallurgica Sinica (English Letters), 2021, 34(2): 174-186.
[3]	L. B. Tong, J. H. Chu, D. N. Zou, Q. Sun, S. Kamado, H. G. Brokmeier, M. Y. Zheng. Simultaneously Enhanced Mechanical Properties and Damping Capacities of ZK60 Mg Alloys Processed by Multi-Directional Forging [J]. Acta Metallurgica Sinica (English Letters), 2021, 34(2): 265-277.
[4]	Meichen Liang, Hao Zhang, Lifeng Zhang, Peng Xue, Dingrui Ni, Weizhen Wang, Zongyi Ma, Hengqiang Ye, Zhiqing Yang. Evolution of Quasicrystals and Long-Period Stacking Ordered Structures During Severe Plastic Deformation and Mixing of Dissimilar Mg Alloys Upon Friction Stir Welding [J]. Acta Metallurgica Sinica (English Letters), 2021, 34(1): 12-24.
[5]	Jinglin Liu, Qi Song, Lihui Song, Shude Ji, Mingshen Li, Zhen Jia, Kang Yang. A Novel Friction Stir Spot Riveting of Al/Cu Dissimilar Materials [J]. Acta Metallurgica Sinica (English Letters), 2021, 34(1): 135-144.
[6]	Chao-Yue Zhao, Xian-Hua Chen, Peng Peng, Teng Tu, Andrej Atrens, Fu-Sheng Pan. Microstructures and Mechanical Properties of Mg-xAl-1Sn-0.3Mn (x = 1, 3, 5) Alloy Sheets [J]. Acta Metallurgica Sinica (English Letters), 2020, 33(9): 1217-1225.
[7]	Xudong Du, Feng Wang, Zhi Wang, Xingxing Li, Zheng Liu, Pingli Mao. Hot Tearing Susceptibility of AXJ530 Alloy Under Low-Frequency Alternating Magnetic Field [J]. Acta Metallurgica Sinica (English Letters), 2020, 33(9): 1259-1270.
[8]	Xiaohui Shi, Zuhan Cao, Zhiyuan Fan, Junwei Qiao. Texture Evolution Behavior and Its Triggered Mechanical Anisotropy of CP Ti During Severe Cold Rolling and Subsequent Annealing [J]. Acta Metallurgica Sinica (English Letters), 2020, 33(9): 1271-1282.
[9]	Dan-Yang Liu, Jin-Feng Li, Yong-Cheng Lin, Peng-Cheng Ma, Yong-Lai Chen, Xu-Hu Zhang, Rui-Feng Zhang. Cu/Li Ratio on the Microstructure Evolution and Corrosion Behaviors of Al-xCu-yLi-Mg Alloys [J]. Acta Metallurgica Sinica (English Letters), 2020, 33(9): 1201-1216.
[10]	Yuan Yu, Peiying Shi, Kai Feng, Jiongjie Liu, Jun Cheng, Zhuhui Qiao, Jun Yang, Jinshan Li, Weimin Liu. Effects of Ti and Cu on the Microstructure Evolution of AlCoCrFeNi High-Entropy Alloy During Heat Treatment [J]. Acta Metallurgica Sinica (English Letters), 2020, 33(8): 1077-1090.
[11]	Hui Jiang, Tian-Dang Huang, Chao Su, Hong-Bin Zhang, Kai-Ming Han, Sheng-Xue Qin. Microstructure and Mechanical Behavior of CrFeNi₂V_0.5W_x (x = 0, 0.25) High-Entropy Alloys [J]. Acta Metallurgica Sinica (English Letters), 2020, 33(8): 1117-1123.
[12]	Ibrahim Ondicho, Bernard Alunda, Dicken Owino, Luke Otieno, Melody Chepkoech. Revealing a Transformation-Induced Plasticity (TRIP) Phenomenon in a Medium-Entropy Alloy [J]. Acta Metallurgica Sinica (English Letters), 2020, 33(8): 1159-1165.
[13]	Chengbo Yang, Jing Zhang, Meng Li, Xuejian Liu. Soft-Magnetic High-Entropy AlCoFeMnNi Alloys with Dual-Phase Microstructures Induced by Annealing [J]. Acta Metallurgica Sinica (English Letters), 2020, 33(8): 1124-1134.
[14]	Ren Li, Jing Ren, Guo-Jia Zhang, Jun-Yang He, Yi-Ping Lu, Tong-Min Wang, Ting-Ju Li. Novel (CoFe₂NiV_0.5Mo_0.2)_100-_xNb_x Eutectic High-Entropy Alloys with Excellent Combination of Mechanical and Corrosion Properties [J]. Acta Metallurgica Sinica (English Letters), 2020, 33(8): 1046-1056.
[15]	Qiuxin Nie, Hui Liang, Dongxu Qiao, Zhaoxin Qi, Zhiqiang Cao. Microstructures and Mechanical Properties of Multi-component Al_xCrFe₂Ni₂Mo_0.2 High-Entropy Alloys [J]. Acta Metallurgica Sinica (English Letters), 2020, 33(8): 1135-1144.