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We have employed variable-temperature scanning tunneling microscopy (STM) to follow the kinetics of reoxidation of a nonstoichiometric TiO2 (110) single-crystal surface. The surface is seen to grow during reoxidation between 573 and 1000 K and at pressures from 5A—10-8 to 2A—10-6 mbar O2. The reaction proceeds by combination of gas-phase O2 with mobile interstitial Ti3+ from the bulk. The surface is observed to grow new layers of TiO2 in a cyclic process, resulting in the formation of alternate layers of (1A—1) and cross-linked (1A—2). The growth rate was calculated by measuring the area of new material grown on consecutive STM images of the same area. The rate shows a linear dependence upon oxygen pressure, with an Arrhenius plot indicating an activation barrier of âˆ¼25Â±4 kJ mol-1 (0.25Â±0.04 eV/O2 molecule) for the surface reaction.

physical review. b, condensed matter

Measurement of the surface-growth kinetics of reduced<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mrow><mml:msub><mml:mrow><mml:mi mathvariant="normal">TiO</mml:mi></mml:mrow><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:mrow><mml:mn /><mml:mo>(</mml:mo><mml:mn>110</mml:mn><mml:mo>)</mml:mo><mml:mn /></mml:math>during reoxidation using time-resolved scanning tunneling microscopy

Measurement of the surface-growth kinetics of reducedTiO2(110)during reoxidation using time-resolved scanning tunneling microscopy