Direct nanocrystallite size investigation in microstrained mixed phase TiO2 nanoparticles by PCA of Raman spectra

Mixed phase anatase and rutile TiO₂ nanoparticles (30-67% R/A) have been synthesized by single step laser pyrolysis. Parallel studies by XRD and Raman spectroscopy suggested possible deforming microstress inside certain samples, due to boundary interactions between neighbouring nanocrystallites in nanoparticles, phase instabilities and/or O/C contents. Microstress in nanoparticles supports anatase phase stability in competition with rutile phase. Williamson-Hall plot was used to evaluate crystallite size and strain. A tensile global microstrain in anatase crystallites, was observed for elevated C content titania nanoparticles, together with compressive microstrain in crystallites within O deficient TiO₂ nanoparticles. XPS and TEM characterization opens insights regarding the processes behind this type of behaviour. Principal Component Analysis of Raman spectra was applied for batch auto-characterization of mixed phase nanoparticles, with emphasis upon the method ability to simultaneously appreciate crystallite size for both anatase and rutile phase. The method focuses on covariational matrix of multiple samples Raman spectra. It provides results in good agreement with XRD calculated crystallite dimensions for unstrained titania, while for samples with microstrains it returns the size closer to the one predicted by Williamson-Hall plot.