Probing phase transition in VO2 with the novel observation of low-frequency collective spin excitation

VO2 is well known for its first order, reversible, metal-to-insulator transition (MIT) along with a simultaneous structural phase transition (SPT) from a high-temperature metallic rutile tetragonal (R) to an insulating low-temperature monoclinic (M1) phase via two other insulating metastable phases of monoclinic M2 and triclinic T. At the same time, VO2 gains tremendous attention because of the half-a-century-old controversy over its origin, whether electron-electron correlation or electron-phonon coupling trigger the phase transition. In this regard, V1-xMgxO2 samples were grown in stable phases of VO2 (M1, M2, and T) by controlled doping of Mg. We have observed a new collective mode in the low-frequency Raman spectra of all three insulating M1, M2 and T phases. We identify this mode with the breather (singlet spin excitation) mode about a spin-Pierls dimerized one dimensional spin 1/2 Heisenberg chain. The measured frequencies of these collective modes are phenomenologically consistent with the superexchange coupling strength between V spin 1/2 moments in all three phases. The significant deviation of Stokes to anti-Stokes intensity ratio of this low-frequency Raman mode from the usual thermal factor exp(h?/KBT) for phonons, and the orthogonal dependency of the phonon and spinon vibration in the polarized Raman study confirm its origin as spin excitations. The shift in the frequency of spin-wave and simultaneous increase in the transition temperature in the absence of any structural change confirms that SPT does not prompt MIT in VO2. On the other hand, the presence of spin-wave confirms the perturbation due to spin-Peierls dimerization leading to SPT. Thus, the observation of spin-excitations resulting from 1-D Heisenberg spin-1/2 chain can finally resolve the years-long debate in VO2 and can be extended to oxide-based multiferroics, which are useful for various potential device applications.