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We summarize the current knowledge on crystal structures, synthesis, applications, and Raman spectroscopy of Wadsley phases of vanadium oxide, including VO2 (B), V6O13, V4O9, V3O7, and V2O5. While these oxides have garnered significant attention for potential energy storage applications and have been studied for decades, there remains inconsistency in data regarding their characteristic Raman spectra. To address this, we synthesized a series of Wadsley phases by physical vapor deposition of amorphous vanadium oxide films and subsequent annealing in a controlled environment. X‐ray diffraction studies confirmed the formation of VO2 (B), V6O13, V4O9, and V3O7. We meticulously measured the room‐temperature Raman spectra of these phases, offering robust reference data for the easy identification of vanadium oxides in unknown samples. Finally, we studied low‐temperature phase transitions in VO2 (B) and V6O13. [ABSTRACT FROM AUTHOR]

The relation between the structure of VO 2 and the process of the semiconductor-to-metal phase transition (SMT) is an important applied issue that is not completely understood yet. Raman spectroscopy is one of the most frequently used techniques in such studies. It allows not only monitoring SMT in situ but also detection of minor inclusions of other vanadium oxides that may form initially or as a result of the SMT. Raman analysis relies on the fingerprint vibration patterns of different oxide phases, but for some of the vibrational modes reported so far, the attribution to certain oxide compounds is still ambiguous. In the present work, we establish the origin of the modes between 800 and 1100 cm−1 based on the detailed study of a series of thin films fabricated by magnetron sputtering, with different ratios of oxide phases. By studying Raman spectra at different excitation wavelengths, we conclude that the difference in phase composition derived from Raman and XRD is not solely due to different sensitivities of these techniques to different oxides, including resonant effects in Raman, but is also the matter of interpretation of the vibrational patterns of mixed oxide phases. Importantly, the presence of other V x O y phases (V 2 O 5 , V 3 O 7 , V 4 O 9) does not affect qualitatively the SMT of the main VO 2 phase. More difference in SMT is observed between Si and quartz substrates, indicating that the SMT mechanism in such films is governed primarily by the characteristics of the initial VO 2 phase, rather than by "impurity" phases V x O y. • The origin of several vibrational peaks of vanadium oxides are clarified. • Resonance effects in the intensity of Raman peaks are observed. • Different sensitivity of Raman spectroscopy and X-ray diffraction to different oxides. • Phase transition in VO 2 is not affected significantly by surrounding other phases. [ABSTRACT FROM AUTHOR]