title: Surface electronic structure transitions at high temperature on perovskite oxides: the case of strained La0.8Sr0.2CoO3 thin films.
abstract: In-depth probing of the surface electronic structure on solid oxide fuel cell (SOFC) cathodes, considering the effects of high temperature, oxygen pressure, and material strain state, is essential toward advancing our understanding of the oxygen reduction activity on them. Here, we report the surface structure, chemical state, and electronic structure of a model transition metal perovskite oxide system, strained La(0.8)Sr(0.2)CoO(3) (LSC) thin films, as a function of temperature up to 450 °C in oxygen partial pressure of 10(-3) mbar. Both the tensile and the compressively strained LSC film surfaces transition from a semiconducting state with an energy gap of 0.8-1.5 eV at room temperature to a metallic-like state with no energy gap at 200-300 °C, as identified by in situ scanning tunneling spectroscopy. The tensile strained LSC surface exhibits a more enhanced electronic density of states (DOS) near the Fermi level following this transition, indicating a more highly active surface for electron transfer in oxygen reduction. The transition to the metallic-like state and the relatively more enhanced DOS on the tensile strained LSC at elevated temperatures result from the formation of oxygen vacancy defects, as supported by both our X-ray photoelectron spectroscopy measurements and density functional theory calculations. The reversibility of the semiconducting-to-metallic transitions of the electronic structure discovered here, coupled to the strain state and temperature, underscores the necessity of in situ investigations on SOFC cathode material surfaces.
authors.affiliation: Laboratory for Electrochemical Interfaces, Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Zhuhua
authors.initials: Z
authors.lastname: Cai
authors.forename: Yener
authors.initials: Y
authors.lastname: Kuru
authors.forename: Jeong Woo
authors.initials: JW
authors.lastname: Han
authors.forename: Yan
authors.initials: Y
authors.lastname: Chen
authors.forename: Bilge
authors.initials: B
authors.lastname: Yildiz
mesh_terms: D003035:Cobalt / Q000737:chemistry; D004583:Electrons; D007811:Lanthanum / Q000737:chemistry; D008567:Membranes, Artificial; D015394:Molecular Structure; D010087:Oxides / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D013324:Strontium / Q000737:chemistry; D013499:Surface Properties; D013696:Temperature
chemical_list: D008567:Membranes, Artificial; D010087:Oxides; D003035:Cobalt; D007811:Lanthanum; D010100:Oxygen; D013324:Strontium