Experimental evidence for mixed-valent Cr ions in half-metallic CrO2: Temperature-dependent XMCD study

By employing soft X-ray magnetic circular dichroism (XMCD) and soft X-ray absorption spectroscopy (XAS), we have investigated the temperature (T)-dependent valence and spin states of Cr ions in half-metallic ferromagnet CrO2 nanorod powder. The lineshape-analysis of both the Cr 2p XAS and XMCD spectra of CrO2 reveals that the Cr ions in bulk CrO2 have both Cr4+ (t(2g)(2)up arrow) and Cr3+ (t(2g)(3)up arrow) valence configurations. This work provides the direct experimental evidence for the Cr3+-Cr4+ mixed-valent states in bulk CrO2 (Cr3.8+), demonstrating that the half-metallic ferromagnetism in CrO2 originates from the double-exchange interaction. The T-dependent intensity variation of the Cr 2p XMCD spectrum agrees well with the bulk magnetization M(T) and the Curie temperature, indicating that the measured Cr 2p XMCD data represent the intrinsic bulk ferromagnetism in CrO2, and support the above finding of the XMCD lineshape analysis. (C) 2017 Elsevier B.V. All rights reserved.