(Nanocarbons Division SES Young Investigator Award) Surface Chemistry of Nanocarbon Field-Effect Transistors: From Fundamental Physics to Biosensing
Authors: Bouilly Delphine 
Published: August 2024

Conductive carbon nanomaterials are particularly well-suited to form field-effect biosensors (bioFETs) because they are stable in aqueous media and can be chemically coupled to biomolecules. Their reduced dimensionality, either 2D (graphene) or 1D (carbon nanotubes), is key to their sensitivity: because they are entirely surfaces, these materials present remarkable electrical transport properties that are easily altered by microscopic surface interactions. Biochemical processes occurring in close proximity to their surface can therefore be transduced as changes in their electrical conductance. Selectivity for specific biochemical events, however, must be engineered via functionalization of the nanomaterial, i.e. by modifying its surface with bioactive or biorecognition elements (e.g., antibodies, aptamers, enzymes, polymer layer). Our group recently analyzed a corpus of studies presenting graphene field-effect transistors (GFETs) as bioanalytical sensors for the quantitative detection of biomarkers in the form of nucleic acids, proteins, ions or small molecules [1]. We found a striking variance in the reported sensing performance between these studies, that could not be explained by controlling for differences in graphene material, analyte type and for evolution over the years. Our hypothesis is that the lack of microscopic control on the biointerface is likely the most important source of variation in such bioFETs, highlighting the critical need to improve our knowledge and control of the functionalization of nanocarbon materials.

In this talk, I will discuss our work investigating the interplay between surface chemistry and electrical properties in nanocarbon field-effect transistors. In the first part, I will focus on covalent additions using aryldiazonium salts. I will review what we have learned on the fundamental physics of this chemistry from experiments and simulations on carbon nanotube devices [2-5], in particular on its disruptive character because of the formation of sp
3 defects in the carbon lattice. More recently, we investigated this same chemistry on GFET devices and observed a heterogeneous response in their electrical conductance. Aiming to solve this, we developed a novel approach to precisely trigger and stop the reaction in situ using the applied gate voltage [6], enabling unprecedented control on the functionalization rate and yield on GFETs. In the second part, I will describe our ongoing efforts to characterize and control the biofunctionalization of GFETs through non-covalent pyrene derivatives, using a combination of electrical measurements, microscopy and spectroscopy techniques, and theoretical simulations. Finally, I will discuss our ongoing translational projects in oncology, on adapting nanocarbon-based bioFETs in cancer diagnostics applications.

[1] Béraud et al, Analyst 146 (2), 403-428 (2021)

[2] Bouilly et al, Applied Physics Letters 101 (5), 053116 (2012)

[3] Bouilly et al, ACS nano 9 (3), 2626-2634 (2015)

[4] Bouilly et al, Nano Letters 16 (7), 4679-4685 (2016)

[5] Côté et al, Physical Chemistry Chemical Physics 24 (7), 4174-4186 (2021)

[6] Bazan et al, Nano Letters 22 (7), 2635-2642 (2022)