Metastable phases of the photoswitchable molecular magnet K0.3Co[Fe(CN)6]0.77 ⋅ nH2O in sub-micrometer particles have been structurally investigated by synchrotron powder x-ray diffraction (PXRD) measurements. The K0.3Co[Fe(CN)6]0.77 ⋅ nH2O bulk compound (studied here with a sample having average particle size of 500 nm) undergoes a charge transfer coupled spin transition (CTCST), where spin configurations change between a paramagnetic CoII( S = 3/2) –FeIII( S = 1/2) high-temperature (HT) state and a diamagnetic CoIII( S = 0) –FeII( S = 0) low-temperature (LT) state. The bulk compound exhibits a unique intermediate (IM) phase, which corresponds to a mixture of HT and LT spin states that depend on the cooling rate. Several hidden metastable HT states emerge as a function of thermal and photo stimuli, namely: (1) a quench (Q) state generated from the HT state by flash cooling, (2) a LTPX state obtained by photoexcitation from the LT state derived by thermal relaxation from the Q state, and (3) an IMPX state accessed by photo-irradiation from the IM state. A sample with a smaller particle size, 135 nm, is investigated for which the particles are on the scale of the coherent LT domains in the IM phase within the larger 500 nm sample. PXRD studies under controlled thermal and/or optical excitations have clarified that themore »
Understanding the pathways and time scales underlying electrically driven insulator-metal transitions is crucial for uncovering the fundamental limits of device operation. Using stroboscopic electron diffraction, we perform synchronized time-resolved measurements of atomic motions and electronic transport in operating vanadium dioxide (VO2) switches. We discover an electrically triggered, isostructural state that forms transiently on microsecond time scales, which is shown by phase-field simulations to be stabilized by local heterogeneities and interfacial interactions between the equilibrium phases. This metastable phase is similar to that formed under photoexcitation within picoseconds, suggesting a universal transformation pathway. Our results establish electrical excitation as a route for uncovering nonequilibrium and metastable phases in correlated materials, opening avenues for engineering dynamical behavior in nanoelectronics.
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- p. 352-355
- American Association for the Advancement of Science (AAAS)
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- National Science Foundation
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