Light responsive thin films of micelles of PS-b-PVP complexed with diazophenol chromophore.

We have incorporated push-pull azobenzene units into diblock-copolymer micelles by supramolecular assembly. Specifically, we encapsulated a phenol-functionalized chromophore, DO13, within PS-b-P4VP micelles in toluene by means of H-bond interactions developed between DO13 molecules and pyridine groups of P4VP block. The solutions were spin-coated onto glass substrates resulting in multi- or mono-layered thin films of micelles with P4VP(DO13) core and PS corona. We show that the use of DO13 as a building block of micellar aggregates allowed us to manipulate the developed nanostructures. Spherical to cylindrical micellar transition was found when we increased the degree of chromophore complexation. Also, it was found that the polymer concentration in the solution plays an important role in determining the micellar nanostructures. The chain extension and change in composition of the P4VP core in the presence of the chromophore may be responsible for the structural changes observed in the micelles. The optical properties of the thin films have been investigated focusing on the effect of the micellar morphology over the photoinduced birefringence. The optical anisotropy (Δn) increased with respect to the analogous homogeneous system P4VP(DO13), indicating that the protective micelle environment can enhance the optical properties of the embedded chromophores significantly. Furthermore, we show very interesting new results in which we have related changes in optical properties to the film morphology (spheres to cylinders). This can be exploited for producing optical devices having improved optoelectronic properties and stability.

Optical storage in azobenzene-containing epoxy polymers processed as Langmuir Blodgett films.

In this study, azocopolymers containing different main-chain segments have been synthesized with diglycidyl ether of bisphenol A (DGEBA, DER 332, n=0.03) and the azochromophore Disperse Orange 3 (DO3) cured with two monoamines, viz. benzylamine (BA) and m-toluidine (MT). The photoinduced birefringence was investigated in films produced with these azopolymers using the spin coating (SC) and Langmuir Blodgett (LB) techniques. In the LB films, birefringence increased with the content of azochromophore and the film thickness, as expected. The nanostructured nature of the LB films led to an enhanced birefringence and faster dynamics in the writing process, compared to the SC films. In summary, the combination of azocopolymers and the LB method may allow materials with tuned properties for various optical applications, including in biological systems were photoisomerization may be used to trigger actions such as drug delivery.

Determining concentration depth profiles in fluorinated networks by means of electric force microscopy.

By means of electric force microscopy, composition depth profiles were measured with nanometric resolution for a series of fluorinated networks. By mapping the dielectric permittivity along a line going from the surface to the bulk, we were able to experimentally access to the fluorine concentration profile. Obtained data show composition gradient lengths ranging from 30 nm to 80 nm in the near surface area for samples containing from 0.5 to 5 wt. % F, respectively. In contrast, no gradients of concentration were detected in bulk. This method has several advantages over other techniques because it allows profiling directly on a sectional cut of the sample. By combining the obtained results with x-ray photoelectron spectroscopy measurements, we were also able to quantify F/C ratio as a function of depth with nanoscale resolution.