Memristive devices and methods for setting the resistance of a memristive device include a first mixed conducting layer formed from a first material having a resistance that changes depending on an ion concentration and having multiple coexisting phases from concentration-dependent metastability. A second metastable, mixed conducting layer is formed from the first material. A barrier layer between the first conductor layer and the second conductor layer is formed from a second mixed conducting material having a chemical potential that prevents thermal ion diffusion between the first and second layer. The barrier layer provides an electrical threshold, above which ions are transferred between the first and second layer and below which the resistance of the device is read.
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