Electrolyte-Dependent Modification of Resistive Switching in Anodic Hafnia

Anodic HfO₂ memristors grown in phosphate, borate, or citrate electrolytes and formed on sputtered Hf with Pt top electrodes are characterized at fundamental and device levels. The incorporation of electrolyte species deep into anodic memristors concomitant with HfO₂ crystalline structure conservation is demonstrated by elemental analysis and atomic scale imaging. Upon electroforming, retention and endurance tests are performed on memristors. The use of borate results in the weakest memristive performance while the citrate demonstrates clear superior memristive properties with multilevel switching capabilities and high read/write cycling in the range of 10⁶. Low temperature heating applied to memristors shows a direct influence on their behavior mainly due to surface release of water. Citrate-based memristors show remarkable properties independent on device operation temperatures up to 100 °C. The switching dynamic of anodic HfO₂ memristors is discussed by analyzing high resolution transmission electron microscope images. Full and partial conductive filaments are visualized, and apart from their modeling, a concurrency of filaments is additionally observed. This is responsible for the multilevel switching mechanism in HfO₂ and is related to device failure mechanisms.