Nanoscale Patterning of Flat Carbon Surfaces by Scanning Probe Lithography and Electrochemistry

Abstract

We report the formation of carbon surfaces patterned at the nanoscale with organic functionalities. Thin (<10 nm) films are covalently grafted to the surface via the electrochemical reduction of aryl diazonium salts. Areas of the film are removed with an AFM tip, and a second modifier is electrochemically grafted to the exposed surface. The pattern can incorporate different chemical functionalities, or alternatively topographical patterns can be assembled, where the same functionality is present throughout the pattern.

Advances in Interfacial Design for Electrochemical Biosensors and Sensors: Aryl Diazonium Salts for Modifying Carbon and Metal Electrodes

“…Proposed reaction mechanism for the reductive adsorption of aryl diazonium salts to electrode surfaces advantages. One example of the advantages of multilayers being formed from aryl diazonium salts is the nanoscale patterning of layers as demonstrated by Downard and coworkers [95]. In this procedure, an initial layer was deposited followed by specific regions being scratched away, in a process similar to nanoshaving [96], using an AFM tip.…”

New insight into 4-nitrobenzene diazonium reduction process: Evidence for a grafting step distinct from NO2 electrochemical reactivity

“…On the one hand, it has been used to evidence the difference of reactivity between graphene single and multilayers [20], to identify diamond surface terminations and measure the density of hydrogen atoms bonded to the surface [21] or to illustrate nanoscale patterning of carbon surface [22]. On the other hand, NBD was reported to modify the electrical properties of graphene field-effect transistors [23] or to help at covalent immobilization of organometallic model of enzyme onto carbon surface [24].…”

Covalent Modification of Glassy Carbon Surfaces by Using Electrochemical and Solid‐Phase Synthetic Methodologies: Application to Bi‐ and Trifunctionalisation with Different Redox Centres

“…[56] Recently, Downard et al published the micro-and nanoscale patterning of carbon surfaces with different organic functionalities using soft lithography, AFM, and electrochemically assisted grafting. [57,58] Gooding et al, [59] and more recently BØlanger et al, [60] have reported another interesting method for the simultaneous bifunctionalisation of a GC electrode by differently substituted phenyl groups, achieved by electrochemical reduction from a solution containing a mixture of the corresponding diazonium salts. The major disadvantage of using electrochemical reduction of substituted aryl diazonium salts for surface modification is the low stability and availability of diazonium salts bearing suitable functional groups.…”