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Though present in small amounts and migrating at low rates, intrinsic cation defects play a central role in governing the operational lifetime of oxide-ion conducting materials through slow degradation processes such as interdiffusion, kinetic demixing, grain growth, and creep. In this study, a new experimental approach to characterizing the behavior of such slow-moving, minority defects is presented. Diffusion is probed in samples with a constant cation-defect concentration well above the equilibrium values. This approach is applied to monoclinic hafnium dioxide, m-HfO2. To this end, nanocrystalline thin films of m-HfO2 were prepared by atomic layer deposition. Diffusion experiments with ZrO2 as a diffusion source were performed in the temperature range 1173 ≤ T/K ≤ 1323 in air. The Zr diffusion profiles obtained subsequently by secondary ion mass spectrometry exhibited the following two features: the first feature was attributed to slow bulk diffusion and the second was attributed to combined fast grain-boundary diffusion and slow bulk diffusion. The activation enthalpy of Zr diffusion in bulk HfO2 was found to be (2.1 ± 0.2) eV. This result is consistent with the density-functional-theory calculations of hafnium-vacancy migration in m-HfO2, which yield values of ∼2 eV for a specific path. The activation enthalpy of the grain-boundary diffusion of (2.1 ± 0.3) eV is equal to that for bulk diffusion. This behavior is interpreted in terms of enhanced cation diffusion along space-charge layers. [ABSTRACT FROM AUTHOR]

Bipolar redox-based resistive random-access memory cells are intensively studied for new storage class memory and beyond von Neumann computing applications. However, the considerable variability of the resistance values in ON and OFF state as well as of the SET voltage remains challenging. In this paper, we discuss the physical origin of the significant reduction in the switching variability of HfO2-based devices achieved by the insertion of a thin TiOx layer between the HfO2 layer and the oxygen exchange metal layer. Typically, HfO2 single layer cells exhibit an abrupt SET process, which is difficult to control. In contrast, self-compliance effects in the HfO2/TiOx bilayer devices lead to an increased stability of SET voltages and OFF-state resistances. The SET process is gradual and the RESET becomes abrupt for higher switching currents. Comparison of the experimental data with simulation results achieved from a physics-based compact model for the full description of the switching behavior of the single layer and bilayer devices clearly reveal three major effects. The TiOx layer affects the temperature distribution during switching (by modifying the heat dissipation), forms an additional series resistance and changes the current conduction mechanism in the OFF state of the bilayer device compared to the single layer device. [ABSTRACT FROM AUTHOR]