Synergistic role of ion transport and barrier modulation in a two-terminal ITO/PVDF-HFP/Ag vertical memristor

Polymer-based memristive devices are gaining attention as scalable, flexible, and energy efficient alternatives for next generation non-volatile memories and neuromorphic computing applications. In this paper, we report a vertical ITO/PVDF-HFP/Ag device that leverages the ferroelectric and ionic properties of PVDF-HFP to achieve reliable resistive switching. Structural analyses confirm the dominance of the electroactive β-phase (∼65.4%) alongside α, γ, and amorphous fractions, enabling a favorable balance between ferroelectric polarization and ionic transport. Morphological studies further indicate the formation of dense and uniform films with nanoscale surface roughness, ensuring stable electrode–polymer interfaces. Electrical characterization reveals sharp impedance transitions, non-monotonic capacitance behavior, and clear bipolar switching with SET/RESET voltages of ∼+2.61/−1.8 V. The conduction mechanism follows a hybrid pathway involving ohmic transport, space charge limited conduction, and filamentary dynamics modulated by ferroelectric polarization. The device exhibits excellent endurance (1000 cycles), stable data retention, and a high ON/OFF ratio of ∼102–103, confirming robust non-volatile memory performance. Furthermore, spike amplitude dependent plasticity and spike duration dependent plasticity measurements demonstrate depression-type synaptic plasticity in the device. These findings establish PVDF-HFP as a promising ferroelectric polymer for vertical memristors, offering the dual benefits of scalability and polarization assisted switching, and emphasize its potential as a low power, high density candidate for future ReRAM and neuromorphic computing platforms.