Transmission X-ray microscopy is employed to detect nanoscale valence changes in resistive switching SrTiO3 thin film devices. By recording Ti L-edge spectra of samples in different resistive states, we could show that some spots with slightly distorted structure and a small reduction to Ti3+ are already present in the virgin films. In the ON-state, these spots are further reduced to Ti3+ to different degrees while the remaining film persists in the Ti4+ configuration. These observations are consistent with a self-accelerating reduction within pre-reduced extended growth defects
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