Percolating networks formed by coated metallic nanowires have recently shown to exhibit memristive properties, opening a path for the development of neuromorphic systems. In this work, the resistive switching phenomena occurring in percolative networks of silver nanowires (AgNWs) coated with a thin layer of polyvinylpyrrolidone is studied. By performing voltage‐driven excursions, the highly‐conductive pristine state irreversibly changes to a higher resistance state. Such an electroforming procedure enables the switching among multiple resistance states. The stability and controllability of the resistance levels are found to be highly dependent on the initial state and the environmental conditions. In low relative humidity environments, the system displays the most controlled switching operation, while in high humidity environments the system shows a high conductance level. Samples with hysteretic response display sharp and spontaneous transitions to different resistance states, exhibiting multilevel memory device features. Both behaviors can be associated with regions of high local concentration of AgNWs that can couple or decouple from the conduction paths according to external stimuli. Conductivity is determined at a fundamental level by electrochemical processes at critical junctions in which water molecules play a key role. These results are relevant for the development of AgNWs‐based electronics and in‐hardware neuromorphic computing.

Nanocomposites formed by silver nanowires (AgNWs) embedded in a polymer matrix are a convenient way to deposit thin films with electrical conductance and high transparency on different substrates. Nanocomposite resists containing AgNWs in a polymethyl methacrylate solution can be effectively used to produce conductive coatings in a straightforward manner. Here, we show that by adding a sacrificial layer of polyvinyl pyrrolidone (PVP) on a glass substrate, prior to the nanocomposite resist, it is possible to obtain large-area free-standing films of about 450 nm with electrical conductance and high transparency. The films can be transferred to different surfaces and materials including non flat substrates. The formation of conductive stacks by piling two layers was also demonstrated. The optical, electrical, and structural properties of these free-standing films were studied obtaining films with transmittance T(%)=78% at 550 nm, sheet resistance Rs= (670±40) Ω·sq-1 and surface roughness Ra= (50±10) nm. We studied the strain resistance behaviour of films transferred to polyethylene terephthalate sheets under bending tests finding a sensitivity of (0.51±0.01) Ω·deg-1 and a gradual increase in the resistance during cycling. In addition, thin flexible supports can be added by covering the nanocomposite film with PDMS prior to its release, enhancing the mechanical robustness and improving the manipulation of the films.