Postsynthetic Route for Modifying the Metal—Insulator Transition of VO₂ by Interstitial Dopant Incorporation

The thermally driven orders-of-magnitude modulation of resistance and optical transmittance observed in VO 2 makes it an archetypal first-order phase transition material and underpins functional applications in logic and memory circuitry, electromagnetic cloaking, ballistic modulation, and thermochromic glazing to provide just a few representative examples. VO 2 can be reversibly switched from an insulating to a metallic state at an equilibrium transition temperature of 67 °C. Tuning the phase diagram of VO 2 to bring the transition temperature closer to room temperature has been a longstanding objective and one that has tremendous practical relevance. Substitutional incorporation of dopants has been the most common strategy for modulating the metal—insulator transition temperature but requires that the dopants be incorporated during synthesis. Here we demonstrate a novel postsynthetic diffusive annealing approach for incorporating interstitial B dopants within VO 2 . The postsynthetic method allows for the transition temperature to be programmed after synthesis and furthermore represents an entirely distinctive mode of modulating the phase diagram of VO 2 . Local structure studies in conjunction with density functional theory calculations point to the strong preference of B atoms for tetrahedral coordination within interstitial sites of VO 2; these tetrahedrally coordinated dopant atoms hinder the rutile → monoclinic transition by impeding the dimerization of V–V chains and decreasing the covalency of the lattice. The results suggest that interstitial dopant incorporation is a powerful method for modulating the transition temperature and electronic instabilities of VO 2 and provides a facile approach for postsynthetic dopant incorporation to reach a switching temperature required for a specific application.