title: Catalytic Scanning Probe Nanolithography (cSPL): Control of the AFM Parameters in Order to Achieve Sub-100-nm Spatially Resolved Epoxidation of Alkenes Grafted onto a Surface.
abstract: Scanning probe lithography (SPL) appears to be a reliable alternative to the use of masks in traditional lithography techniques as it offers the possibility of directly producing specific chemical functionalities with nanoscale spatial control. We have recently extend the range of applications of catalytic SPL (cSPL) by introducing a homogeneous catalyst immobilized on the apex of a scanning probe. Here we investigate the importance of atomic force microscopy (AFM) physical parameters (applied force, writing speed, and interline distance) on the resultant chemical activity in this cSPL methodology through the direct topographic observation of nanostructured surfaces. Indeed, an alkene-terminated self-assembled monolayer (alkene-SAM) on a silicon wafer was locally epoxidized using a scanning probe tip with a covalently grafted manganese complex bearing the 1,4,7-triazacyclononane macrocycle as the ligand. In a post-transformation process, N-octylpiperazine was covalently grafted to the surface via a selective nucleophilic ring-opening reaction. With this procedure, we could write various patterns on the surface with high spatial control. The catalytic AFM probe thus appears to be very robust because a total area close to 500 μm(2) was patterned without any noticeable loss of catalytic activity. Finally, this methodology allowed us to reach a lower lateral line resolution down to 40 nm, thus being competitive and complementary to the other nanolithographical techniques for the nanostructuration of surfaces.
authors.affiliation: Aix Marseille Université , CNRS, Université de Toulon, IM2NP UMR 7334, 13397 Marseille, France.
authors.forename: Vincent
authors.initials: V
authors.lastname: Mesquita
authors.affiliation: Aix Marseille Université , Centrale Marseille, CNRS, iSm2 UMR 7313, 13397 Marseille, France.
authors.forename: Julien
authors.initials: J
authors.lastname: Botton
authors.affiliation: Aix Marseille Université , Centrale Marseille, CNRS, iSm2 UMR 7313, 13397 Marseille, France.
authors.forename: Dmitry A
authors.initials: DA
authors.lastname: Valyaev
authors.affiliation: Aix Marseille Université , Centrale Marseille, CNRS, iSm2 UMR 7313, 13397 Marseille, France.
authors.forename: Cyril
authors.initials: C
authors.lastname: François
authors.affiliation: Aix Marseille Université , CNRS, Université de Toulon, IM2NP UMR 7334, 13397 Marseille, France.|Institut Supérieur de l'Electronique et du Numérique , CNRS, IM2NP UMR 7334, 83000 Toulon, France.
authors.forename: Lionel
authors.initials: L
authors.lastname: Patrone
authors.affiliation: Aix Marseille Université , Centrale Marseille, CNRS, iSm2 UMR 7313, 13397 Marseille, France.
authors.forename: Teodor Silviu
authors.initials: TS
authors.lastname: Balaban
authors.affiliation: Aix Marseille Université , CNRS, Université de Toulon, IM2NP UMR 7334, 13397 Marseille, France.
authors.forename: Mathieu
authors.initials: M
authors.lastname: Abel
authors.affiliation: Aix Marseille Université , Centrale Marseille, CNRS, iSm2 UMR 7313, 13397 Marseille, France.
authors.forename: Jean-Luc
authors.initials: JL
authors.lastname: Parrain
authors.affiliation: Aix Marseille Université , Centrale Marseille, CNRS, iSm2 UMR 7313, 13397 Marseille, France.
authors.forename: Olivier
authors.initials: O
authors.lastname: Chuzel
authors.affiliation: Aix Marseille Université , CNRS, Université de Toulon, IM2NP UMR 7334, 13397 Marseille, France.
authors.forename: Sylvain
authors.initials: S
authors.lastname: Clair