Nanoscale Structural Insights into Thermochromic VO₂ Thin Films Using Tip-Enhanced Raman Spectroscopy

Thermochromic vanadium dioxide (VO₂) thin films, known for their reversible metal-insulator transition (MIT) near 68 °C, are promising candidates for energy-efficient applications such as smart window coatings. However, optimizing their structural and interfacial properties to enhance thermochromic performance remains a significant challenge. Traditional characterization techniques such as X-ray diffraction and transmission electron microscopy face inherent limitations in simultaneously providing detailed chemical information and nanoscale spatial resolution─capabilities that are essential for resolving localized structural heterogeneity and interfacial phenomena. This study employs hyperspectral tip-enhanced Raman spectroscopy (TERS) imaging to address these limitations and investigate the nanoscale structure of pristine VO₂ and VO₂/TiO₂ thin films. TERS imaging revealed nanoscale regions of lattice deformations and nanocrystallites with different orientations in VO₂ thin films, resulting in a high density of grain boundaries that elevate the MIT temperature. In VO₂/TiO₂ bilayers, TERS detected coexisting anatase and brookite phases in the TiO₂ layer, with tensile strain in the brookite phase and the VO₂/TiO₂ interface characterized by localized intermixing and strain. These novel insights underscore the polycrystalline nature of the thin films grown with pulsed layer deposition technique and highlight the critical role of nanoscale structural and interfacial properties in determining thermochromic performance of VO₂-based thin films. Furthermore, this study demonstrates the effectiveness of TERS as a robust nanoanalytical tool for advancing the design of VO₂-based smart coatings and functional materials.