The development of neuromorphic computing systems that emulate the analog charge states and plasticity of the brain’s neuron-synapse architecture has been a major driver of resistance switching materials exploration. Materials that demonstrate changes in conductance with tunable ratios and volatility of resistance states within a single layer are highly desirable. Although excellent resistance switching device performance has been demonstrated in a range of transition metal oxides, a lack of understanding of the fundamental microscale evolution of a material during resistance switching presents a key limitation to controlling switching parameters. Here, we examine the role of materials defects on local resistance switching structures in two representative transition metal oxide materials: HfOv2 thin films and hydrothermally synthesized VOv2 single crystals. In each material, we seek to clarify the structure of resistance switching domains and the kinetics of domain formation resulting from intentional defect introduction.
This thesis is therefore divided into two main parts concerning (1) the introduction of planar defects in HfOv2 filamentary resistance switching devices, and (2) the impact of introduction of point defects on the metal-insulator transition in VOv2 single crystals. Part I (Sections 2 – 3) details investigation of Cu ion migration rates in Cu/HfOv2/p+Si and Cu/HfOv2/TiN devices in which oxide microstructure varies between amorphous, polycrystalline, and oriented polycrystalline. Ion migration across the oxide layer is shown to be rate limiting and faster in polycrystalline layers than in amorphous HfO2 layers at equivalent electric field. Moreover, the 3D shape of conductive filaments is investigated by a scribing atomic force microscopy experiment in Cu/HfOv2/p+Si devices and reveals a broad range of filament shapes under identical electrical stress conditions. Thermal dissipation is interpreted as the principal determinant of filament area, while oxide microstructure is shown to direct the location of filaments within the device. In part II (Sections 4 – 5), the hysteresis of the metal-insulator transition (switching volatility) in VOv2 is shown to intrinsically derive from nucleation limited transformations in individual particles. Here, hysteresis is a strong function of particle size, but may be increased or decreased by synthesis techniques that affect the concentration and potency of intrinsic point defects. Upon chemical doping with boron at interstitial lattice sites, a unique kinetic effect on the hysteresis of the current driven metal-insulator transition in two terminal BxVOv2 devices is observed. Dependence of the critical switching current on thermal relaxation time and temperature is characterized and recommendations for further kinetic testing are made. Finally, a few experimental extensions of the work presented in this thesis are made in Section 6
