Spinodal Decomposition in the TiO2-VO2 System

Spinodal decomposition is a ubiquitous phenomenon leading to phase separation from a uniform solution. We show that a spinodal decomposition occurs in a unique combination of two rutile compounds of TiO2 and VO2, which are chemically and physically distinguished from each other: TiO2 is a wide-gap insulator with photocatalytic activities, and VO2 is assumed to be a strongly correlated electron system which exhibits a dramatic metal insulator transition at 342 K. The spinodal decomposition takes place below 830 K at a critical composition of 34 mol % Ti, generates a unidirectional composition modulation along the c axis with a wavelength of approximately 6 nm, and finally results in the formation of self-assembled lamella structures made up of Ti-rich and V-rich layers stacked alternately with 30-50 nm wavelengths. A metal insulator transition is not observed in quenched solid solutions with intermediate compositions but emerges in the thin V-rich layers as the result of phase separation. Interestingly, the metal insulator transition remains as sharp as in pure VO2 even in such thin layers and takes place at significantly reduced temperatures of 310-340 K, which is probably due to a large misfit strain induced by lattice matching at the coherent interface.