Effect of Interdiffusion and Crystallization on Threshold Switching Characteristics of Nb/Nb₂O₅/Pt Memristors

The resistive switching response of two terminal metal/oxide/metal devices depends on the stoichiometry of the oxide film, and this is commonly controlled by using a reactive metal electrode to reduce the oxide layer. Here, we investigate compositional and structural changes induced in Nb/Nb₂O₅ bilayers by thermal annealing at temperatures in the range of 573-973 K and its effect on the volatile threshold switching characteristics of Nb/Nb₂O₅/Pt devices. Changes in the stoichiometry of the Nb and Nb₂O₅ films are determined by Rutherford backscattering spectrometry and energy-dispersive X-ray (EDX) mapping of sample cross sections, while the structure of the films is determined by X-ray diffraction, Raman spectroscopy, and transmission electron microscopy (TEM). Such analysis shows that the composition of the Nb and Nb₂O₅ layers is homogenized by interdiffusion at temperatures less than the crystallization temperature (i.e., >773 K) but that this effectively ceases once the films crystallize. This is explained by comparison with the predictions of a simple diffusion model which shows that the compositional changes are dominated by oxygen diffusion in the amorphous oxide, which is much faster than that in the crystalline phases. We further show that these compositional and structural changes have a significant effect on the electroforming and threshold switching characteristics of the devices, the most significant being a marked increase in their reliability and endurance after crystallization of the oxide films. Finally, we examine the effect of annealing on the quasistatic negative differential resistance characteristics and oscillator dynamics of devices and use a lumped element model to show that this is dominated by changes in the device capacitance resulting from interdiffusion.