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Volume 31 Issue 4
Apr.  2024

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Ilan Riess, Neutral and metallic vs. charged and semiconducting surface layer in acceptor doped CeO2, Int. J. Miner. Metall. Mater., 31(2024), No. 4, pp. 795-802. https://doi.org/10.1007/s12613-023-2789-0
Cite this article as:
Ilan Riess, Neutral and metallic vs. charged and semiconducting surface layer in acceptor doped CeO2, Int. J. Miner. Metall. Mater., 31(2024), No. 4, pp. 795-802. https://doi.org/10.1007/s12613-023-2789-0
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研究论文

受体掺杂CeO2中的中性和金属与带电和半导电表面层


  • 通讯作者:

    Ilan Riess    E-mail: riess@tecchnion.ac.il

  • 受体掺杂的CeO2的单分子体表面层可以变成中性的和金属的或者带电的和半导电的,这在具有两种不同掺杂剂类型并在不同氧压下操作的受主掺杂二氧化铈中表面缺陷浓度的氧压依赖性的理论分析中揭示。最近公布的含有固定价掺杂剂Sm3+的高度还原Sm0.2Ce0.8O1.9–x(SDC)的实验数据与在较温和条件下还原可变价掺杂剂Pr4+/Pr3+的Pr0.1Ce0.9O2–x(PCO)的实验结果非常不同。这些实验结果的理论分析与SDC和PCO的实验结果非常吻合。这导致了以下预测:SDC的高度还原表面是金属和中性的,金属表面电子态密度为gs = 0.9 × 1038 J–1·m–2(1.4 × 1015 eV–1·cm–2),电子有效质量为meff,s = 3.3me,还原表面的相图具有α (fcc)散装结构。在PCO中,预计在表面和本体之间形成双层,表面带负电且半导电。PCO的表面在高于本体中的氧压力下保持高的Pr3+缺陷浓度以及相对高的氧空位浓度。综述了受主掺杂CeO2的金属表面层和半导体表面层之间存在差异的原因,以及解决这一问题的关键理论考虑因素。为此,我们利用了受主掺杂二氧化铈的实验数据和理论分析。
  • Research Article

    Neutral and metallic vs. charged and semiconducting surface layer in acceptor doped CeO2

    + Author Affiliations
    • The monomolecular surface layer of acceptor doped CeO2 may become neutral and metallic or charged and semiconducting. This is revealed in the theoretical analysis of the oxygen pressure dependence of the surface defects concentration in acceptor doped ceria with two different dopant types and operated under different oxygen pressures. Recently published experimental data for highly reduced Sm0.2Ce0.8O1.9–x (SDC) containing a fixed valence dopant Sm3+ are very different from those published for Pr0.1Ce0.9O2–x (PCO) with the variable valence dopant Pr4+/Pr3+ being reduced under milder conditions. The theoretical analysis of these experimental results fits very well the experimental results of SDC and PCO. It leads to the following predictions: the highly reduced surface of SDC is metallic and neutral, the metallic surface electron density of state is gs = 0.9 × 1038 J–1·m–2 (1.4 × 1015 eV–1·cm–2), the electron effective mass is meff,s = 3.3me, and the phase diagram of the reduced surface has the α (fcc) structure as in the bulk. In PCO a double layer is predicted to be formed between the surface and the bulk with the surface being negatively charged and semiconducting. The surface of PCO maintains high Pr3+ defect concentration as well as relative high oxygen vacancy concentration at oxygen pressures higher than in the bulk. The reasons for the difference between a metallic and semiconducting surface layer of acceptor doped CeO2 are reviewed, as well as the key theoretical considerations applied in coping with this problem. For that we make use of the experimental data and theoretical analysis available for acceptor doped ceria.
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    • [1]
      I. Riess, Point defect concentrations in surface layers of binary oxides, Solid State Ionics, 329(2019), p. 95. doi: 10.1016/j.ssi.2018.10.007
      [2]
      W.C. Chueh, A.H. McDaniel, M.E. Grass, et al., Highly enhanced concentration and stability of reactive Ce3+ on doped CeO2 surface revealed in operando, Chem. Mater., 24(2012), No. 10, p. 1876. doi: 10.1021/cm300574v
      [3]
      Q.Y. Lu, G. Vardar, M. Jansen, et al., Surface defect chemistry and electronic structure of Pr0.1Ce0.9O2– δ revealed in operando, Chem. Mater., 30(2018), No. 8, p. 2600. doi: 10.1021/acs.chemmater.7b05129
      [4]
      I. Riess, Analysis of point defect concentrations in highly reduced, monomolecular surface layer of doped ceria, Solid State Ionics, 373(2021), art. No. 115791. doi: 10.1016/j.ssi.2021.115791
      [5]
      I. Riess, Analysis of the unique dependence on oxygen pressure of Pr3+ concentration in the surface of Pr doped ceria, Solid State Ionics, 380(2022), art. No. 115899. doi: 10.1016/j.ssi.2022.115899
      [6]
      J. Jamnik, J. Maier, and S. Pejovnik, Interfaces in solid ionic conductors: Equilibrium and small signal picture, Solid State Ionics, 75(1995), p. 51. doi: 10.1016/0167-2738(94)00184-T
      [7]
      N.W. Ashcropt and N.D. Mermin, Solid State Physics, Cengage Learning, Stamford, 1976, p. 626.
      [8]
      J.T. Devreese and F.M. Peeters, Electron–phonon interaction in two-dimensional systems: Polaron effects and screening, [in] J.T. Devreese and F.M. Peeters, The Physics of the Two-dimensional Electron Gas, Springer, Berlin, 1987, p. 131.
      [9]
      R. Schmitt, A. Nenning, O. Kraynis, et al., A review of defect structure and chemistry in ceria and its solid solutions, Chem. Soc. Rev., 49(2020), No. 2, p. 554. doi: 10.1039/C9CS00588A
      [10]
      K. Barnham and D.D. Vvedensky, Low-dimensional Semiconductor Structures : Fundamentals and Device Applications, Cambridge University Press, New York, 2001, p. 58.
      [11]
      J.A. López-Villanueva, F. Gámiz, I. Melchor, and J.A. Jiménez-Tejada, Density of states of a two-dimensional electron gas including nonparabolicity, J. Appl. Phys., 75(1994), No. 8, p. 4267. doi: 10.1063/1.355967
      [12]
      M. Ricken, J. Nölting, and I. Riess, Specific heat and phase diagram of nonstoichiometric ceria (CeO2− x ), J. Solid State Chem., 54(1984), No. 1, p. 89. doi: 10.1016/0022-4596(84)90135-X
      [13]
      N. Stelzer, J. Nölting, and I. Riess, Phase diagram of nonstoichiometric 10mol% Gd2O3-doped cerium oxide determined from specific heat measurements, J. Solid State Chem., 117(1995), No. 2, p. 392. doi: 10.1006/jssc.1995.1290
      [14]
      J. Maier, Physical Chemistry of Ionic Materials : Ions and Electrons in Solids, John Wiley & Sons, New York, 2004, p. 217.
      [15]
      C. Chatzichristodoulou and P.V. Hendriksen, Oxygen nonstoichiometry and defect chemistry modeling of Ce0.8Pr0.2O2– δ , J. Electrochem. Soc., 157(2010), No. 4, art. No. B481. doi: 10.1149/1.3288241
      [16]
      H. Rickert, Electrochemistry of Solids : An Introduction, Springer-Verlag, Berlin, 1982, p. 119.
      [17]
      P.M. Morse, Thermal physics, 2nd Ed., Addison-Wesley, Massachusetts, 1969.

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