title: Spectroscopic ellipsometry meets AFM nanolithography: about hydration of bio-inert oligo(ethylene glycol)-terminated self assembled monolayers on gold.
abstract: For the first time, to our knowledge, spectroscopic ellipsometry (SE) has been combined with state-of-the-art AFM differential height measurements conducted after shaving nano-lithography of ultrathin, soft-matter films for thickness determination. We investigated self-assembled monolayers of SH-(CH2)11-EGn-OH molecules on gold, where EG is ethylene glycol units and n = 3 and 6, a prototypical non-fouling system. We performed SE measurements (245-1200 nm) focusing on the changes induced by the formation of the film (difference spectra). SE measurements, analysed by simple models, confirm the formation of the S-Au interface, transparency of the SAMs and provide a sharp picture of the ability of the EG functionality to protect the surface from unspecific adsorption of proteins. A quantitative assessment of the film thickness by SE was carried out ex situ, thanks to the optical contrast between the film and the ambient, and by AFM in liquid. The cross-check between SE and AFM height measurements combined with the comparison between in-liquid and ex situ SE measurements allowed obtaining non-perturbative information about the vertical density profile of the SAM. The in-liquid SE measurements indicate a refractive index matching between the aqueous medium and the outer part of the SAM, consistent with a disordered configuration of OEG and/or the penetration of water amid the OEG strands. A critical discussion provides a detailed insight into the subtle issues and pitfalls related to the thickness determination of soft-matter films to the monolayer limit.
authors.affiliation: Dipartimento di Fisica, Università di Genova and CNISM, via Dodecaneso 33, Genova, Italy. canepa@fisica.unige.it.
authors.forename: Ilaria
authors.initials: I
authors.lastname: Solano
authors.affiliation: Elettra Sincrotrone Trieste S.C.p.A., s.s. 14 km 163, 5 in Area Science Park, Basovizza, Trieste, Italy.
authors.forename: Pietro
authors.initials: P
authors.lastname: Parisse
authors.affiliation: Dipartimento di Fisica, Università di Genova and CNISM, via Dodecaneso 33, Genova, Italy. canepa@fisica.unige.it.
authors.forename: Federico
authors.initials: F
authors.lastname: Gramazio
authors.affiliation: Dipartimento di Fisica, Università di Genova and CNISM, via Dodecaneso 33, Genova, Italy. canepa@fisica.unige.it.
authors.forename: Ornella
authors.initials: O
authors.lastname: Cavalleri
authors.affiliation: Dipartimento di Fisica, Università di Genova and CNISM, via Dodecaneso 33, Genova, Italy. canepa@fisica.unige.it.
authors.forename: Gianangelo
authors.initials: G
authors.lastname: Bracco
authors.affiliation: Department of Medical and Biological Sciences - University of Udine, Udine, Italy.
authors.forename: Matteo
authors.initials: M
authors.lastname: Castronovo
authors.affiliation: Elettra Sincrotrone Trieste S.C.p.A., s.s. 14 km 163, 5 in Area Science Park, Basovizza, Trieste, Italy.
authors.forename: Loredana
authors.initials: L
authors.lastname: Casalis
authors.affiliation: Dipartimento di Fisica, Università di Genova and CNISM, via Dodecaneso 33, Genova, Italy. canepa@fisica.unige.it.
authors.forename: Maurizio
authors.initials: M
authors.lastname: Canepa
mesh_terms: D019855:Ethylene Glycol / Q000737:chemistry*; D006046:Gold / Q000737:chemistry*; D018625:Microscopy, Atomic Force; D013053:Spectrophotometry; D014867:Water / Q000737:chemistry
chemical_list: D014867:Water; D006046:Gold; D019855:Ethylene Glycol