Solid State Ionics, Vol.315, 98-101, 2018
Optical absorption and redox kinetics of YBa2Cu3O7 (- delta) thin films studied by optical in-situ spectroscopy
Optical absorption and redox kinetics of YBa2Cu3O7 (-) (delta) thin films in oxidizing (O-2) and reducing (Ar/H-2) atmospheres were studied at temperatures from 200 degrees C to 500 degrees C by means of in situ UV-vis-NIR optical spectroscopy. The optical spectra in oxidizing atmospheres are characterized by optical absorption of oxygen holes, O- (O-I'), e.g., at about 450 nm at 200 degrees C, whereas those in reducing atmospheres are dominated by a band at about 600 nm due to electron hopping between Cu-ions. The fast redox processes of oxygen incorporation into and oxygen release from YBCO thin films induced by sudden changes in the ambient atmosphere between 02 and Ar/H-2 are found to be controlled by surface exchange reaction. The oxygen surface exchange coefficients, k(delta), determined from optical absorption relaxation experiments are about 4.96 x 10(-7) m/s for the oxidation process and about 4.85 x 10(-9) m/s for the reduction process at 500 degrees C. The temperature dependence of k(delta) yields an activation energy of about 0.3 eV for both oxidation and reduction processes in the studied temperature range. In addition, the rapid oxidation processes can be explained in terms of a high concentration of electrons in the reduced state of YBCO thin films, facilitating electron-transfer steps at the surface of YBCO film for oxygen exchange.