Vibrational Spectroscopy and Analytical Electron Microscopy Studies of Fe–V–O and In–V–O Thin Films

Summary.  Orthovanadate (M ³⁺VO₄; M = Fe, In) and vanadate (Fe₂V₄O₁₃) thin films were prepared using sol-gel synthesis and dip coating deposition. Using analytical electron microscopy (AEM), the chemical composition and the degree of crystallization of the phases present in the thin Fe–V–O films were investigated. TEM samples were prepared in both orientations: parallel (plan view) and perpendicular (cross section) to the substrate. In the first stages of crystallization, when the particle sizes were in the nanometer range, the classical identification of phases using electron diffraction was not possible. Instead of measuring d values, experimentally selected area electron diffraction (SAED) patterns were compared to calculated (simulated) patterns in order to determine the phase composition. The problems of evaluating the ratio of amorphous and crystalline phases in thin films are reported. Results of TEM and XRD as well as IR and Raman spectroscopy showed that the films made at lower temperatures (300°C) consisted of nanograins embedded in the dominating amorphous phase. Characteristic vibrational spectra allowed to distinguish between the different crystalline phases, since the IR and Raman bands showed broadening due to the decreasing particle size of the films thermally treated at lower temperatures. Vibrational analysis also showed that the electrochemical cycling of crystalline films led to spectra that were in close agreement with the spectra of the nanocrystalline films prepared at lower temperatures. The formation of a nanocrystalline structure is therefore a prerequisite for obtaining a higher charging/discharging stability of Fe–V–O and In–V–O films. Received October 4, 2001. Accepted (revised) November 23, 2001