Browse > Article
http://dx.doi.org/10.5757/ASCT.2016.25.1.19

Electronic Structure of Ce-doped ZrO2 Film: Study of DFT Calculation and Photoelectron Spectroscopy  

Jeong, Kwang Sik (Institute of Physics and Applied Physics, Yonsei University)
Song, Jinho (Institute of Physics and Applied Physics, Yonsei University)
Lim, Donghyuck (Institute of Physics and Applied Physics, Yonsei University)
Kim, Hyungsub (School of Materials Science and Engineering, Sungkyunkwan University)
Cho, Mann-Ho (Institute of Physics and Applied Physics, Yonsei University)
Publication Information
Applied Science and Convergence Technology / v.25, no.1, 2016 , pp. 19-24 More about this Journal
Abstract
In this study, we evaluated the change of electronic structure during redox process in cerium-doped $ZrO_2$ grown by sol gel method. By sol-gel method, we could obtain cerium-doped $ZrO_2$ in high oxygen partial pressure and low temperature. After post annealing process in nitrogen ambient, the film is deoxidized. We used spectroscopic and theoretical methods to analysis change of electronic structure. X-ray absorption spectroscopy (XAS) for O K1-edge and Density Functional Theory (DFT) calculation using VASP code were performed to verify the electronic structure of the film. Also, high resolution x-ray photoelectron spectroscopy (HRXPS) for Ce 3d was carried out to confirm chemical bond of cerium doped $ZrO_2$. Through the investigation of the electronic structure, we verified as followings. (1) During reduction process, binding energy of oxygen is increase. Simultaneously, oxidation state of cerium was change to 4+ to 3+. (2) Cerium 4+ and cerium 3+ states were generated at different energy level. (3) Absorption states in O K edge were mainly originated by Ce 4+ $f_0$ and Ce 3+, while occupied states in valance band were mainly originated from Ce 4+ $f_2$.
Keywords
Electronic structure; Ce-doped $ZrO_2$; DFT Calculation; XPS; XAS;
Citations & Related Records
연도 인용수 순위
  • Reference
1 Kaapar J, Fornasiero P, and Graziani M. Use of CeO2-based oxides in the three-way catalysis. Catal Today. 50(2) 285-98 (1999).
2 Hasegawa Y, Imanaka N, and Adachi G-y. Cerium ion conducting solid electrolyte. J Solid State Chem. 171(1-2) 387-90.   DOI
3 Skorodumova NV, Simak SI, and Lundqvist BI, Abrikosov IA, Johansson B. Quantum Origin of the Oxygen Storage Capability of Ceria. Phys Rev Lett. 89(16) 166601 (2002).   DOI
4 Suda A, Sobukawa H, Suzuki T, Kandori T, Ukyo Y, and Sugiura M. Store and Release of Oxygen of Ceria-Zirconia Solid Solution Synthesized by Solid Phase Reaction at Near Room Temperature. J Ceram Soc Jpn. 109(1267) 177-80 (2001).   DOI
5 Sugiura M. Oxygen Storage Materials for Automotive Catalysts: Ceria-Zirconia Solid Solutions. Catal Surv Asia. 7(1) 77-87 (2003).   DOI
6 Mamontov E, Egami T, Brezny R, Koranne M, and Tyagi S. Lattice Defects and Oxygen Storage Capacity of Nanocrystalline Ceria and Ceria-Zirconia. The Journal of Physical Chemistry B. 104(47) 11110-6 (2000).   DOI
7 Lee MS, An C-H, Park K, Choi J-Y, and Kim H. Effect of Y, Gd, Dy, and Ce Doping on the Microstructural and Electrical Properties of Sol-Gel-Deposited $ZrO_2$ Film. J Electrochem Soc. 158(6) G133-G6 (2011).   DOI
8 De Groot F and Kotani A. Core level spectroscopy of solids: CRC press; 2008.
9 Kresse G and Hafner J. Ab initio molecular dynamics for openshell transition metals. Phys Rev B Condens Matter. 48(17) 13115- 8 (1993).   DOI
10 Perdew JP, Burke K, and Ernzerhof M. Generalized Gradient Approximation Made Simple. Phys Rev Lett. 77(18) 3865-8 (1996).   DOI
11 Gutowski M, Jaffe JE, Liu C-L, Stoker M, Hegde RI, Rai RS, et al. Thermodynamic Stability of High-K Dielectric Metal Oxides $ZrO_2$ and HfO2 in Contact with Si and SiO2. MRS Online Proceedings Library. 716 null-null (2002).
12 Jeong KS, Song J, Lim D, Lee MS, Kim H, and Cho M-H. Structural evolution and defect control of yttrium-doped $ZrO_2$ films grown by a sol-gel method. Appl Surf Sci. 320 128-37 (2014).   DOI
13 Machida M, Kawano T, Eto M, Zhang D, and Ikeue K. Ln Dependence of the Large-Capacity Oxygen Storage/Release Property of Ln Oxysulfate/Oxysulfide Systems. Chem Mater. 19(4) 954-60 (2007).   DOI
14 Beche E, Charvin P, Perarnau D, Abanades S, and Flamant G. Ce 3d XPS investigation of cerium oxides and mixed cerium oxide (CexTiyOz). Surf Interface Anal. 40(3-4) 264-7 (2008).   DOI
15 Romeo M, Bak K, El Fallah J, Le Normand F, and Hilaire L. XPS Study of the reduction of cerium dioxide. Surf Interface Anal. 20(6) 508-12 (1993).   DOI
16 Burns RG. Mineralogical applications of crystal field theory: Cambridge University Press; 1993.