Atomic Hourglass and Thermometer Based on Diffusion of a Mobile Dopant in VO2

J Am Chem Soc. 2020 Sep 9;142(36):15513-15526. doi: 10.1021/jacs.0c07152. Epub 2020 Aug 27.

Abstract

Transformations between different atomic configurations of a material oftentimes bring about dramatic changes in functional properties as a result of the simultaneous alteration of both atomistic and electronic structure. Transformation barriers between polytypes can be tuned through compositional modification, generally in an immutable manner. Continuous, stimulus-driven modulation of phase stabilities remains a significant challenge. Utilizing the metal-insulator transition of VO2, we exemplify that mobile dopants weakly coupled to the crystal lattice provide a means of imbuing a reversible and dynamical modulation of the phase transformation. Remarkably, we observe a time- and temperature-dependent evolution of the relative phase stabilities of the M1 and R phases of VO2 in an "hourglass" fashion through the relaxation of interstitial boron species, corresponding to a 50 °C modulation of the transition temperature achieved within the same compound. The material functions as both a chronometer and a thermometer and is "reset" by the phase transition. Materials possessing memory of thermal history hold promise for applications such as neuromorphic computing, atomic clocks, thermometry, and sensing.