The application of hardware‐based neural networks can be enhanced by integrating sensory neurons and synapses that enable direct input from external stimuli. This work reports direct optical control of an oscillatory neuron based on volatile threshold switching in V₃O₅. The devices exhibit electroforming‐free operation with switching parameters that can be tuned by optical illumination. Using temperature‐dependent electrical measurements, conductive atomic force microscopy (C‐AFM), in situ thermal imaging, and lumped element modelling, it is shown that the changes in switching parameters, including threshold and hold voltages, arise from overall conductivity increase of the oxide film due to the contribution of both photoconductive and bolometric characteristics of V₃O₅, which eventually affects the oscillation dynamics. Furthermore, V₃O₅ is identified as a new bolometric material with a temperature coefficient of resistance (TCR) as high as −4.6% K⁻¹ at 423 K. The utility of these devices is illustrated by demonstrating in‐sensor reservoir computing with reduced computational effort and an optical encoding layer for spiking neural network (SNN), respectively, using a simulated array of devices.

Devices with volatile memristive switching and self‐sustained relaxation oscillations have received significant attention for their use in neuromorphic computing and solving optimization problems. However, obtaining devices with stable response and reliable oscillation remains challenging. This work describes the utility of metal/oxide interlayers in achieving reliable device performance with tuneable characteristics using Nb‐Nb₂O₅‐Pt structures. Detailed physical characterization of the Nb/Nb₂O₅ interlayer region shows that it consists of a thin, near‐stoichiometric Nb₂O₅ and an NbO_x layer with a graded oxygen content. The impact of these interlayers on device performance is assessed by investigating their switching characteristics and oscillation dynamics. It is shown that the presence of the interlayer has a direct impact on the memristive switching mode and parameters threshold switching characteristics parameters. These dependencies are explained with reference to a lumped‐element circuit model of the device and shown to be dominated by changes in device resistance caused by interlayer formation. Significantly, stable oscillation with tuneable frequency is obtained by increasing the thickness of the reactive Nb electrode. Then, by simulating an array of coupled oscillators, a unique Hamiltonian solver is demonstrated. These results provide pathways for optimizing volatile memristive switching characteristics and guidance on how such devices can be employed to solve combinatorial optimization problems.

Metal–oxide–metal devices based on amorphous VO_x are shown to exhibit one of two distinct negative differential resistance (NDR) characteristics depending on the maximum current employed for electroforming. For low compliance currents they exhibit a smooth S-type characteristic and have a temperature-dependent device resistance characterized by an activation energy of 0.25 eV, consistent with conduction in polycrystalline VO₂, while for high compliance currents they exhibit an abrupt snap-back characteristic and a resistance characterized by an activation energy of 0.025 eV, consistent with conduction in oxygen deficient VO_x. In both cases, the temperature dependence of the switching voltage implies that the conductivity change is due to the insulator–metal transition in VO₂. From this analysis, it is concluded that electroforming at low currents creates a conductive filament comprised largely of polycrystalline VO₂, while electroforming at high currents creates a composite structure comprised of VO₂ and a conductive halo of oxygen deficient VO_x. The effect of electroforming on the NDR mode is then explained with reference to a lumped element model of filamentary conduction that includes the effect of a parallel resistance created by the halo. These results provide new insight into the NDR response of vanadium-oxide-based devices and a basis for designing devices with specific characteristics.