Reversible and Irreversible Responses of Defect-Engineered Graphene-Based Electrolyte-Gated pH Sensors

We have studied the role of defects in electrolyte-gated graphene mesh (GM) field-effect transistors (FETs) by introducing engineered edge defects in graphene (Gr) channels. Compared with Gr-FETs, GM-FETs were characterized as having large increments of Dirac point shift (similar to 30-100 mV/pH) that even sometimes exceeded the Nernst limit (59 mV/pH) by means of electrostatic gating of H+ ions. This feature was attributed to the defect-mediated chemisorptions of H+ ions to the graphene edge, as supported by Raman measurements and observed cycling characteristics of the GM FETs. Although the H+ ion binding to the defects increased the device response to pH change, this binding was found to be irreversible. However, the irreversible component showed relatively fast decay, almost disappearing after 5 cycles of exposure to solutions of decreasing pH value from 8.25 to 6.55. Similar behavior could be found in the Gr-FET, but the irreversible component of the response was much smaller. Finally, after complete passivation of the defects, both Gr-FETs and GM-FETs exhibited only reversible response to pH change, with similar magnitude in the range of 68 mV/pH.