The Electronic and Optical Properties of Tetrahedral Doped Co1-xRexCr2O4 (Re = Li, Na, K, Rb) Spinel

doi:10.15541/jim20150030

Abstract

Abstract:

The structure parameters, electronic density of states, and optical properties of Re (Re = Li, Na, K and Rb) doped tetrahedral Co_(1-_x₎Re_xCr₂O₄(x=0.125) system were investigated by using plane-wave ultrasoft pseudopotential method with generalized gradient approximation. The obtained data indicate that monovalent ions doping results in a slight tetrahedral lattice distortion, leading to the stability of the system being reduced and the Rb doped system the most stable. The calculated electronic density of states demonstrates that the conduction bands of doping system are mainly dominated by Co-3d and Cr-3d electrons and the peak of Co-3d in conduction band shifts down when compared to the pure CoCr₂O₄. Moreover, the Fermi levels of the doping system get into the deeper valence band along with the doping concentration increases. Finally, the doped systems present a red shift phenomenon and a strong absorption in the low energy region according to the absorption spectral calculations, suggesting that doping system can greatly improve the absorption and photo catalytic efficiency of visible light for CoCr₂O₄.

Key words: CoCr2O4 spine, density functional theory, electronic structure, optical properties

CLC Number:

YANG Zhi-Huai, ZHANG Yun-Peng, ZHANG Mei-Guang, XU Qiang, ZHANG Ya-Ni, ZHANG Rong. The Electronic and Optical Properties of Tetrahedral Doped Co_1-_xRe_xCr₂O₄ (Re = Li, Na, K, Rb) Spinel[J]. Journal of Inorganic Materials, 2015, 30(8): 819-824.

Figures/Tables 8

Fig. 1 Crystal structure (a) and polyhedral view of CoCr2O4(b)The grey is octahedron, blue is the tetrahedron, and blue spheres represent Co, red spheres represent O, and purple spheres represent Cr As atoms

Table 1 Change of lattice constants and energies of pure CoCr2O4 and doping systems

Spcies	Latice/nm a=b=c	Difference ΔV/ %	Energy 10⁴/ eV	Space group
Pure	0.84465	0.0	-6.1828	FD-3M (227)
Li	0.84306	-0.5638	-5.9550	CS-3(8)
Na	0.84644	0.6365	-6.0664	CS-3(8)
K	0.84983	1.8510	-6.0138	CS-3(8)
Rb	0.85318	3.0643	-6.1441	CS-3(8)

Table 2 Change of bond of pure CoCr2O4 and doping systems

Spcies	Bond	Population	Spin	Length/nm
Pure	O-Cr	0.28	-0.01	0.20176
Pure	O-Co	0.36	-0.01	0.19940
Li	O-Li	0.0225	0.0075	0.20390
	O-Cr	0.2922	-0.0117	0.20129
	O-Co	0.3429	-0.0185	0.20000
Na	O-Na	0.0775	0.01	0.21740
	O-Cr	0.2952	-0.0031	0.20150
	O-Co	0.3461	-0.0076	0.20034
K	O-K	-0.2075	0.005	0.22993
	O-Cr	0.2974	-0.0117	0.20186
	O-Co	0.3503	-0.0165	0.20082
Rb	O-Rb	-0.0975	0.0025	0.23739
	O-Cr	0.2991	-0.0109	0.20215
	O-Co	0.35	-0.0171	0.20118

Fig. 2 Partial density of states (PDOS) of different doping Co(1-x)RexCr2O4 system(a) Pure; (b) Li doped; (c) Na doped; (d) K doped; (e) Rb doped; (f) Doping of various Re at low PDOS

Fig. 3 Dielectric function curves of pure CoCr2O4 and doped CoCr2O4 (a) The real parts ε1(ω); (b) The imaginary parts ε2(ω)

Fig. 4 Optical conductivity spectra of pure CoCr2O4 and doped CoCr2O4 (a) The real parts; (b) The imaginary parts

Fig. 6 Optical absorption curves of pure and doped CoCr2O4

Fig. 5 The codex refractive index of pure CoCr2O4 and doped CoCr2O4, (a) Refractive index n; (b) Extinction coefficient k

References 12

[1]	SICKAFUS K E, WILLS J M, GRIMES N W.Structure of spinel.J. Am. Ceram. Soc., 1999, 82(12): 3279-3292.
[2]	SUZUKI Y, VAN DOVER R B, GYORGY E M, et al. Structure and magnetic properties of epitaxial spinel ferrite thin films.Applied physics letters, 1996, 68(5): 714-716.
[3]	KAMENSKYI D, ENGELKAMP H, FISCHER T, et al. Observation of an intersublattice exchange magnon in CoCr2O4 and analysis of magnetic ordering. Physical Review B, 2013, 87(13): 134423-1-3.
[4]	HU DONG-SHENG, HAN AI-JUN, YE MING-QUAN, et al.Preparation and spectroscopy analysis of spinel CoCr2-xAlxO4 by low-temperature combustion synthesis.Journal of Inorganic Materials, 2011, 26(3): 285-289.
[5]	BUSHA A A, SHKURATOVA V Y, KAMENTSEVA K E, et al.Preparation and X-ray diffraction, dielectric, and Mössbauer characterization of Co1-xNix Cr2O4 Solid Solutions.Inorganic Materials. 2013, 49(3): 301-307.
[6]	XUE LI-MEI, CHEN BIN, ZHANG FENG-HUA.Prepared and photocatalytic properties of Na-doped CoCr2O4 spinel.Journal of Heilongjiang Institute of Science & Technology, 2012, 22(3): 256-258.
[7]	CHEN J, SHI W, ZHANG X, et al.Roles of Li+ and Zr4+ cations in the catalytic performances of Co1-xMxCr2O4 (M=Li,Zr; x=0-0.2) for methane combustion.Environmental Science & Technology, 2011, 45(19): 8491-8497.
[8]	YANG ZHI-HUAI, ZHANG YUN-PENG, ZHANG MEI-GUANG, et al.Effect of electronic structure and optical properties of spinel structure Co(1-x)NaxCr2O4 with Na+.Acta Optica Sinica, 2014, 34(11): 1102001.
[9]	SEGALL M D, PHILIP J D L, PROBERT M J, et al. First-principles simulation: ideas, illustrations and the CASTEP code.Journal of Physics: Condensed Matter, 2002, 14(11): 2717-2744.
[10]	PERDEW J P, BURKE K, ERNZERHOF M.Generalized gradient approximation made simple.Physical Review Letters, 1996, 77(18): 3865-3868.
[11]	VANDE RBILT D.Soft self-consistent pseudopotentials in a generalized eigenvalue formalism.Physical Review B, 1990, 41(11): 7892-7895.
[12]	HUANG KUN, HAN RU-QI.Solid-state Physics. Beijing: Higher Eduion Press (in chinese), 1988: 442-444.

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The Electronic and Optical Properties of Tetrahedral Doped Co_1-_xRe_xCr₂O₄ (Re = Li, Na, K, Rb) Spinel

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