Non-linear pH responses of passivated graphene-based field-effect transistors

Graphene-based field-effect transistors (FETs) are suitable for pH sensors due to their outstanding surface chemical properties and its biocompatibility. To improve the devices' stability and pH sensitivity, different sets of dielectric passivation layers composed of monolayer hexagonal boron nitride with and without aluminum oxide layers were evaluated. Non-linearities of the pH response were observed. Heterostructure FETs were derived from subtractive manufacturing of commercially transferred two-dimensional materials on four-inch SiO₂/Si wafers via stainless steel and polypropylene masking. Phosphate solutions (10 mM) of varying pH were incubated on bare devices, whereby liquid-gating elucidated linear changes in the Dirac voltage of hBN/graphene (−40 mV/pH) that was smaller than a device consisting only of monolayer graphene (−47 mV/pH). Graphene-based FETs were passivated with aluminum oxide nanofilms via electron beam or atomic layer deposition and were observed to have distinct Raman spectral properties and atomic force microscopy topologies corroborating the hypothesis that morphological differences of the deposited aluminum oxide influence the pH-dependent electrical properties. Atomic layer deposition of aluminum oxide on the 2D sensing areas resulted in non-linear shifting of the Dirac voltage with respect to pH that evolved as a function of deposition thickness and was distinct between graphene with and without hexagonal boron nitride as a capping monolayer. The non-linear response of varying thickness of Al_xO_y on graphene-based FETs was progressively reduced upon basic wet etching of the Al_xO_y. Overall, passivated graphene-based transistors exhibit deposition-dependent pH responses.