JOURNAL OF SHANDONG UNIVERSITY (ENGINEERING SCIENCE) ›› 2014, Vol. 44 ›› Issue (4): 84-89.doi: 10.6040/j.issn.1672-3961.9.2014.001

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First-principles study of electronic and optical properties of Mn-doped cubic ZrO2

ZHANG Yufen1, HOU Zhitao2, REN Hao1, ZHAO Shuai1, WANG Cheng1   

  1. 1. School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, Shandong, China;
    2. Cooperation Development Department, Shandong University, Jinan 250100, Shandong, China
  • Received:2014-03-25 Revised:2014-06-26 Published:2014-03-25

Abstract: First-principles calculations based on DFT+U were performed on electronic and optical properties of Mn-doped cubic ZrO2. When Zr was replaced by Mn in cubic ZrO2, the density of states spectra showed that a band gap reduction was observed and an obvious increase at the top of valence band could make the width of valence band broader by about ~5%. In the majority spin, the states near the Fermi level were attributed to Mn 3 d states with a strong admixture of O 2p states, which resulted in a half-metallic ferromagnetism behavior of the system and may be the reason to cause the band gap reduction. By Mn doping, it found that there was an obvious increase of refractive index, and there was also a new steep absorption peak at lower energy region around 2.8 eV, which could be used for photo absorption applications. The ferromagnetism in Mn-doped system was explained by Zener's double exchange mechanism for ferromagnetism as in other compounds, and the probable relations between electronic structure and optical properties were also found out.

Key words: DFT, electronic property, optical property, Mn doping, cubic ZrO2, ferromagnetism

CLC Number: 

  • O48
[1] KENDALL K, WILLIAMS D S. Catalysts for butane reforming in zirconia fuel cells[J].Platinum Metals Rev, 1998, 42(4):164-167.
[2] UTT K, LANGE S, JRVEKLG M, et al. Structure and optical properties of Sm-doped ZrO2 microrolls[J]. Optical Materials, 2010, 32(8):823826.
[3] HOWARD C J, HILL R J, REICHERT B E. Structures of ZrO2 polymorphs at room temperature by high-resolution neutron powder diffraction[J]. Acta Cryst, 1988, B44:116-120.
[4] TEUFER G. The crystal structure of tetragonal ZrO2[J]. Acta Cryst, 1962, 15:1187.
[5] STEFANIC G, MUSIC S, GAJOVIC A. A comparative study of the influence of milling media on the structural and microstructural changes in monoclinic ZrO2[J]. J Eur Ceram Soc, 2007, 27(2):1001-1016.
[6] KHAN M S, ISLAM M S, BATES D R. Cation doping and oxygen diffusion in zirconia: a combined atomistic simulation and molecular dynamics study[J]. J Mater Chem, 1998, 8 (10): 2299-2307.
[7] XIA X, OLDMAN R J, CATLOW C R A. Oxygen adsorption and dissociation on yttria stabilized zirconia surfaces[J]. J Mater Chem, 2012, 22(17):8594-8612.
[8] CAO X Q, VASSEN R, STOEVER D. Ceramic materials for thermal barrier coatings[J]. J Eur Ceram Soc, 2004, 24(1):1-10.
[9] CONRADSON S D, DEGUELDRE C A, ESPINOSA-FALLER F J, et al. Complex behavior in quaternary zirconias for inert matrix fuel: what do these materials look like at the nanometer scale[J]. Progr Nucl Energy, 2001, 38(3-4):221-230.
[10] PEACOCK P W, ROBERTSON J. Bonding, energies, and band offsets of Si-ZrO2 and HfO2 gate oxide interfaces[J]. Phys Rev Lett, 2004, 92(5):057601.
[11] JIA X, YANG W, QIN M, et al. Structure and magnetism in Mn-doped zirconia: density-functional theory studies[J]. J Magn Magn Mater, 2009, 321(15):2354-2358.
[12] OSTANIN S, ERNST A, SANDRATSKII L M, et al. Mn-stabilized zirconia: from imitation diamonds to a new potential high-Tc ferromagnetic spintronics material[J]. Phys Rev Lett, 2007, 98(1):016101.
[13] ARCHER T, PEMMARAJU C DAS, SANVITO S. Magnetic properties of ZrO2 diluted magnetic semiconductors[J]. J Magn Magn Mater, 2007, 316:e188.
[14] JOHNSON M. Spintronics[J]. J Phys Chem B, 2005, 109(30):14278-14291.
[15] ZUTIC I, FABIAN J, SARMA S DAS. Spintronics: fundamentals and applications[J]. Rev Mod Phys, 2004, 76(2):323-410.
[16] TAGUCHI A, INOUE S, AKAMARU S, et al.Phase transition and electrochemical capacitance of mechanically treated manganese oxides[J]. J Alloys Compd, 2006, 414 (1-2):137-141.
[17] SINGHAL R K, DHAWAN M S, GAUR S K, et al.Room temperature ferromagnetism in Mn-doped dilute ZnO semiconductor: an electronic structure study using X-ray photoemission[J]. J Alloys Compd, 2009, 477 (1-2):379-385.
[18] PATEL S K S, GAJBHIYE N S, DATE S K. Ferromagnetism of Mn-doped TiO2 nanorods synthesized by hydrothermal method[J]. J Alloys Compd, 2011, 509(S):427-430.
[19] YANG Y L, FAN X L, LIU C, et al. First principles study of structural and electronic properties of cubic phase of ZrO2 and HfO2[J]. Physica B, 2014, 434(1):7-13.
[20] KOHN W, SHAM L J. Self-consistent equations including exchange and correlation effects[J]. Phys Rev, 1965, 140: A1133.
[21] PAYNE M C, TETER M P, ALLAN D C, et al.Iterative minimization techniques for ab initio total-energy calculations: molecular dynamics and conjugate gradients[J]. Rev Mod Phys, 1992, 64(4):1045-1097.
[22] VANDERBILT D. Soft self-consistent pseudopotentials in a generalized eigenvalue formalism[J]. Phys Rev B, 1990, 41(11):7892-7895.
[23] PERDEW J P, BURKE K, ERNZERHOF M. Generalized gradient approximation made simple[J]. Phys Rev Lett, 1996, 77(18):3865-3868.
[24] MONKHORST H J, PACK J D. Special points for Brillouin-zone integrations[J]. Phys Rev B, 1976, 13(12):5188-5192.
[25] POLAK E. Computational Methods in Optimization[M]. New York: Academic, 1971.
[26] LIU Q J, LIU Z T, FENG L P, et al. First-principles study of structural, optical and elastic properties of cubic HfO2[J]. Physica B, 2009, 404(20):3614-3619.
[27] FABRIS S, VICARIO G, BALDUCCI G, et al. Electronic and atomistic structures of clean and reduced ceria surfaces[J]. J Phys Chem B, 2005, 109(48):22860-22867.
[28] ZHANG Y, JI V, XU K W. The detailed geometrical and electronic structures of monoclinic zirconia[J]. Journal of Physics and Chemistry of Solids, 2013, 74(3):518-523.
[29] CEN W, LIU Y, WU Z, et al. A theoretic insight into the catalytic activity promotion of CeO2 surfaces by Mn doping[J]. Phys Chem Chem Phys, 2012, 14(16):5769-5777.
[30] IGAWA N, ISHII Y, NAGASAKI T, et al. Crystal structure of metastable tetragonal zirconia by neutron powder diffraction study[J]. J Am Ceram Soc, 1993, 76(10):2673-2676.
[31] SAINI H S, SINGH M, RESHAK A H, et al.Emergence of half metallicity in Cr-doped GaP dilute magnetic semiconductor compound within solubility limit[J]. J Alloys Compd, 2012, 536(1-2):214-218.
[32] SATO K, BERGQVIST L, KUDRNOVSKY J, et al.First-principles theory of dilute magnetic semiconductors[J]. Rev Mod Phys, 2010, 82(2):1633.
[33] MO S D, OUYANG L, CHING W Y, et al. Interesting physical properties of the new spinel phase of Si3N4 and C3N4[J]. Phys Rev Lett, 1999, 83(24):5046-5049.
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