Capacitance Electrochemical pH Sensor Based on Different Hafnium Dioxide (HfO₂) Thicknesses

Abstract

Over the past years, to achieve better sensing performance, hafnium dioxide (HfO2) has been studied as an ion-sensitive layer. In this work, thin layers of hafnium dioxide (HfO2) were used as pH-sensitive membranes and were deposited by atomic layer deposition (ALD) process onto an electrolytic-insulating-semiconductor structure Al/Si/SiO2/HfO2 for the realization of a pH sensor. The thicknesses of the layer of the HfO2 studied in this work was 15, 19.5 and 39.9 nm. HfO2 thickness was controlled by ALD during the fabrication process. The sensitivity toward H+ was clearly higher when compared to other interfering ions such as potassium K+, lithium Li+, and sodium Na+ ions. Mott−Schottky and electrochemical impedance spectroscopy (EIS) analyses were used to characterise and to investigate the pH sensitivity. This was recorded by Mott–Schottky at 54.5, 51.1 and 49.2 mV/pH and by EIS at 5.86 p[H−1], 10.63 p[H−1], 12.72 p[H−1] for 15, 19.5 and 30 nm thickness of HfO2 ions sensitive layer, respectively. The developed pH sensor was highly sensitive and selective for H+ ions for the three thicknesses, 15, 19.5 and 39.9 nm, of HfO2-sensitive layer when compared to the other previously mentioned interferences. However, the pH sensor performances were better with 15 nm HfO2 thickness for the Mott–Schottky technique, whilst for EIS analyses, the pH sensors were more sensitive at 39.9 nm HfO2 thickness.

Keywords

• hafnium dioxide
• ion-sensitive layer
• pH sensors
• HfO₂ thickness
• Mott–Schottky
• electrochemical impedance spectroscopy