Electric field induced resistive switching in M³⁺_xV_(1-x)O₂ (M³⁺= Ga³⁺, Al³⁺) single crystals at temperatures below the T to M2 phase transition

The phase diagram of VO$_2$ strained or doped with several trivalent ions consists of four phases; in order of increasing temperatures, three (M1, T and M2) are insulating while the fourth (R), above ~340 K, is metallic. These phases and the three phase transitions have been thoroughly investigated for about half a century by a wide variety of techniques, including electronic transport. While an upwards jump of the resistance of up to a factor of 2 was observed at the T-M2 transition and a drop of several orders of magnitude was observed at the M2$\to$R one, resistive switching at the M1$\to$T transition remained elusive over all these years. Here we report on the investigation of Ga- and Al-doped VO$_2$ single crystals, following the rather surprising appearance of a small and steep drop of a factor of ~ 0.12 in the resistance of Ga-doped VO$_2$ single crystals detected by pulsed and DC I-V measurements carried out at room temperature, below the T$\to$M2 phase transition. Similar results were obtained also from measurements on Al-doped VO2 single crystals. Raman spectra of Ga-, and Al-doped crystals resolved their structures as function of temperature. The accumulated results of the measurements on Ga-, and Al-doped single crystals provide evidence for identifying the resistive switching at T$_{\rm RS}$<T$_{\rm T\to M2}$ with the M1$\to$T transition.