In this paper, we present experimental evidence on the change of the phonon spectrum and vibrational properties of a bulk material through phonon hybridization mechanisms. The phonon spectrum in a finite material is strongly affected by the presence of free surfaces, which is the addition of a contribution from an essentially two-dimensional crystal. The phonon spectrum of a bulk material can hence be altered by a hybridization mechanism between confined phonon modes in nanostructures introduced on the surface of a bulk material and the underlying bulk phonon modes. We measured the heat capacities of bare and surface-structured silicon substrates originating from the same silicon wafer. Then, we deduced important features of the phonon spectra of the samples investigated through a rigorous analysis of the measured heat capacity curves. The results show that the shape and size of the nanostructures made on the surface of the bulk substrate have a strong effect on the phonon spectrum of the bulk material.

In situ high-temperature AFM was used to locally follow dynamic processes, leading to directed self-assembly of copolymers in the context of graphoepitaxy. We focused on the effect of heating for temperatures much higher than the Tg of the used PS-b-PMMA polymer. We showed that such conditions favors the block rearrangement, leading to very regular and perfectly aligned structures in limited times. The use of in situ AFM allowed us to locally investigate the self-organization process at high temperature, thus bringing new insights into self-assembly of block copolymers by graphoepitaxy. In particular, we demonstrate that a slight increase of temperature between 180 and 200 °C allowed overpassing an energy barrier and considerably improves the long distance arrangement, even for relatively short times.

Deep-UV (DUV) laser patterning has been widely used in recent years for micro- and nanopatterning, taking advantage of the specific properties of irradiation with high-energy photons. In this paper, we show the usefulness of DUV laser patterning for preparing surfaces with controlled chemical properties at the micro- and nanoscale. Our motivation was to develop a simple and versatile method for chemical patterning at multiscales (from mm to nm) over relatively wide areas (mm2 to cm2). The chemical properties were provided by self-assembled monolayers (SAMs), prepared on glass or silicon wafers. We first investigated their modification under our irradiation conditions (ArF laser) using AFM, XPS and contact angle measurements. Photopatterning was then demonstrated with minimum feature sizes as small as 75 nm, and we showed the possibility to regraft a second SAM on the irradiated regions. Finally, we used these chemically patterned surfaces for directed self-assembly of several types of objects, such as block copolymers, sol-gel materials and liquids by vapor condensation.