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.
We report on the optical photomodulation properties of all-polymer planar microcavities in which the photochromic poly((4-pentyloxy-3'-methyl-4'-(6-methacryloxyhexyloxy))azobenzene) (PMA4) acts as photoresponsive cavity layer. We induce the trans-cis isomerization process of the azobenzene group by polarized 405 nm CW-laser irradiation, while the backward process is driven by unpolarized CW-laser irradiation at 442 nm. The all-optical photoisomerization process induces a remarkable in-plane anisotropic spectral shift of the cavity modes for the first and second order photonic band gaps. The spectral and intensity modulation effects for these flexible all-polymer microcavities are discussed with respect to those so far reported in literature for analogous systems
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