We
have engineered pH sensitivity of graphene-based ion-sensitive
field-effect transistors (ISFETs) by applying plasma treatment on
graphene with two different plasma sources, CF4 and O2 plasma. The CF4 plasma treatment, leaving F-terminated
sites on graphene, results in a lower sensitivity of 23 mV/pH, while
the O2 plasma treatment, leaving O-terminated sites, results
in a higher sensitivity of 40 mV/pH. The validity of the aforementioned
plasma treatments on graphene was confirmed by Raman spectra and X-ray
photoelectron spectroscopy (XPS). Both plasma-treated graphene samples
exhibit good stability with low drift and a small hysteresis width
in measuring the pH of the solution, resulting from the two-dimensional
(2D) feature of graphene. Finally, a reference-less ISFET that comprises
two graphene films with different engineered sensitivities was demonstrated.
Both engineered graphene films are directly exposed to the electrolyte
solution, with the CF4-treated graphene replacing the reference
electrode and the O2-treated graphene as the sensing layer.
As surface potentials of the two films are opposite in sign, this
device exhibits an overall sensitivity as the difference in sensitivities
(i.e., 14.5 mV/pH) of the two individual films. More importantly,
the long-term drift behaviors of the two films also cancel each other
and the drift rate reaches as low as 0.38 mV/h for this reference-less
device. This approach brings opportunities for future high-performance
2D-based ISFETs with extremely low drift and high stability.