Understanding of resistive switching mechanism through H2O2 sensing and improvement of switching characteristics by using TaOx-based material in W/Al2O3/TaOx/TiN structure have been reported for the first time. Existence of amorphous Al2O3/TaOx layer in the RRAM devices has been confirmed by transmission electron microscopy. By analyzing the oxidation states of Ta2+/Ta5+ for TaO(x )switching material and W-0/W(6+ )for WOx layer at the W/TaOx interface through X-ray photoelectron spectroscopy and H2O2 sensing,sensing, the reduction-oxidation mechanism under Set/Reset occurs only in the TaOx layer for the W/Al2O3/TaOx/TiN structures. This leads to higher Schottky barrier height at the W/Al(2)O(3 )interface (0.54 eV vs. 0.46 eV), higher resistance ratio, and long program/erase endurance of >10(8) cycles with 100 ns pulse width at a low operation current of 30 mu A. Stable retention of more than 10(4 )s at 85 degrees C is also obtained. Using conduction mechanism and reduction-oxidation reaction, current-voltage characteristic has been simulated. Both TaOx and WOx membranes have high pH sensitivity values of 47.65 mV/pH and 49.25 mV/pH, respectively. Those membranes can also sense H2O2 with a low concentration of 1 nM in an electrolyte-insulator-semiconductor structure because of catalytic activity, while the Al2O3 membrane does not show sensing. The TaO(x )material in W/Al2O3/TaOx/TiN structure does not show only a path towards high dense, small size memory application with understanding of switching mechanism but also can be used for H(2)O(2 )sensors. (C) 2017 Elsevier B.V. All rights reserved.