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001014684 1001_ $$0P:(DE-Juel1)142194$$aRodenbücher, Christian$$b0$$eCorresponding author
001014684 245__ $$aAn Operando Study of the Thermal Reduction of BaTiO3 Crystals: The Nature of the Insulator–Metal Transition of the Surface Layer
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001014684 520__ $$aThe insulator-to-metal transition upon the thermal reduction of perovskites is a well-known yet not completely understood phenomenon. By combining different surface-sensitive analysis techniques, we analyze the electronic transport properties, electronic structure, and chemical composition during the annealing and cooling of high-quality BaTiO3 single crystals under ultra-high-vacuum conditions. Our results reveal that dislocations in the surface layer of the crystal play a decisive role as they serve as easy reduction sites. In this way, conducting filaments evolve and allow for turning a macroscopic crystal into a state of metallic conductivity upon reduction, although only an extremely small amount of oxygen is released. After annealing at high temperatures, a valence change of the Ti ions in the surface layer occurs, which becomes pronounced upon the quenching of the crystal. This shows that the reduction-induced insulator-to-metal transition is a highly dynamic non-equilibrium process in which resegregation effects in the surface layer take place. Upon cooling to the ferroelectric phase, the metallicity can be preserved, creating a “ferroelectric metal.” Through a nanoscale analysis of the local conductivity and piezoelectricity, we submit that this phenomenon is not a bulk effect but originates from the simultaneous existence of dislocation-based metallic filaments and piezoelectrically active areas, which are spatially separated.
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001014684 7001_ $$0P:(DE-Juel1)130545$$aBihlmayer, Gustav$$b1
001014684 7001_ $$0P:(DE-Juel1)140525$$aKorte, Carsten$$b2
001014684 7001_ $$0P:(DE-HGF)0$$aRytz, Daniel$$b3
001014684 7001_ $$0P:(DE-HGF)0$$aSzade, Jacek$$b4
001014684 7001_ $$0P:(DE-HGF)0$$aSzot, Kristof$$b5
001014684 773__ $$0PERI:(DE-600)2661516-2$$a10.3390/cryst13081278$$gVol. 13, no. 8, p. 1278 -$$n8$$p1278 -$$tCrystals$$v13$$x2073-4352$$y2023
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001014684 9101_ $$0I:(DE-HGF)0$$6P:(DE-HGF)0$$a  A. Chełkowski Institute of Physics, University of Silesia, 41-500 Chorzów, Poland$$b4
001014684 9101_ $$0I:(DE-HGF)0$$6P:(DE-HGF)0$$a  A. Chełkowski Institute of Physics, University of Silesia, 41-500 Chorzów, Poland$$b5
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