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We have used polarized confocal Raman microspectroscopy and scanning near-field optical microscopy with a resolution of 60 nm to characterize photoinscribed grating structures of azobenzene doped polymer films on a glass support. Polarized Raman microscopy allowed determining the reorientation of the chromophores as a function of the grating phase and penetration depth of the inscribing laser in three dimensions. We found periodic patterns, which are not restricted to the surface alone, but appear also well below the surface in the bulk of the material. Near-field optical microscopy with nanoscale resolution revealed lateral two-dimensional optical contrast, which is not observable by atomic force and Raman microscopy.
In this paper we report on the interaction between photosensitive azobenzene-containing polymer films and on top adsorbed graphene multilayers. The photosensitive polymer film changes its topography under irradiation with light interference patterns according to their polarization distribution. The multilayer graphene follows the deformation of the polymer film and stretches accordingly. Using confocal Raman microspectroscopy we can detect the appearance of additional peaks in the Raman spectrum of the photosensitive polymer film upon irradiation indicating a molecular interaction at the interface between the graphene multilayer and the polymer matrix. Multi-component analysis of the specific Raman bands shows that the interaction involves the graphene rings and the aromatic rings of the azobenzenes causing the strong adhesion between the two materials.
Azo-modified photosensitive polymers offer the interesting possibility to reshape bulk polymers and thin films by UV-irradiation while being in the solid glassy state. The polymer undergoes considerable mass transport under irradiation with a light interference pattern resulting in the formation of surface relief grating (SRG). The forces inscribing this SRG pattern into a thin film are hard to assess experimentally directly. In the current study, we are proposing a method to probe opto-mechanical stresses within polymer films by characterizing the mechanical response of thin metal films (10 nm) deposited on the photosensitive polymer. During irradiation, the metal film not only deforms along with the SRG formation but ruptures in a regular and complex manner. The morphology of the cracks differs strongly depending on the electrical field distribution in the interference pattern, even when the magnitude and the kinetics of the strain are kept constant. This implies a complex local distribution of the opto-mechanical stress along the topography grating. In addition, the neutron reflectivity measurements of the metal/polymer interface indicate the penetration of a metal layer within the polymer, resulting in a formation of a bonding layer that confirms the transduction of light-induced stresses in the polymer layer to a metal film.
In this paper, we report on differences in the response of photosensitive azobenzene containing films upon irradiation with the intensity or polarization interference patterns. Two materials are studied differing in the molecular weight: an azobenzene-containing polymer and a molecular glass formed from a much smaller molecule consisting of three connected azobenzene units. Topography changes occurring along with the changes in irradiation conditions are recorded using a homemade set-up combining an optical part for generation and shaping of interference patterns and an atomic force microscope for acquiring the kinetics of film deformation. In this way, we could reveal the unique behavior of photosensitive materials during the first few minutes of irradiation: the change in topography is initially driven by an increase in the azobenzene free volume along with the transcis isomerization, followed by the mass transport finally resulting in the surface relief grating. This study demonstrates the great potential of our setup to experimentally highlight puzzling processes governing the formation of surface relief gratings. (C) 2014 AIP Publishing LLC.
Mapping a plasmonic hologram with photosensitive polymer films: standing versus propagating waves
(2014)
We use a photosensitive layer containing azobenzene moieties to map near-field intensity patterns in the vicinity of nanogrids fabricated within a thin silver layer. It is known that azobenzene containing films deform permanently during irradiation, following the pattern of the field intensity. The photosensitive material reacts only to stationary waves whose intensity patterns do not change in time. In this study, we have found a periodic deformation above the silver film outside the nanostructure, even if the latter consists of just one groove. This is in contradiction to the widely accepted viewpoint that propagating surface plasmon modes dominate outside nanogrids. We explain our observation based on an electromagnetic hologram formed by the constructive interference between a propagating surface plasmon wave and the incident light. This hologram contains a stationary intensity and polarization grating that even appears in the absence of the polymer layer.
In this paper, we show how graphene can be utilized as a nanoscopic probe in order to characterize local opto-mechanical forces generated within photosensitive azobenzene containing polymer films. Upon irradiation with light interference patterns, photosensitive films deform according to the spatial intensity variation, leading to the formation of periodic topographies such as surface relief gratings (SRG). The mechanical driving forces inscribing a pattern into the films are supposedly fairly large, because the deformation takes place without photofluidization; the polymer is in a glassy state throughout. However, until now there has been no attempt to characterize these forces by any means. The challenge here is that the forces vary locally on a nanometer scale. Here, we propose to use Raman analysis of the stretching of the graphene layer adsorbed on top of polymer film under deformation in order to probe the strength of the material transport spatially resolved. With the well-known mechanical properties of graphene, we can obtain lower bounds on the forces acting within the film. Upon the basis of our experimental results, we can deduce that the internal pressure in the film due to grating formation can exceed 1 GPa. The graphene-based nanoscopic gauge opens new possibilities to characterize opto-mechanical forces generated within photosensitive polymer films.
When azobenzene-modified photosensitive polymer films are irradiated with light interference patterns, topographic variations in the film develop that follow the electric field vector distribution resulting in the formation of surface relief grating (SRG). The exact correspondence of the electric field vector orientation in interference pattern in relation to the presence of local topographic minima or maxima of SRG is in general difficult to determine. In my thesis, we have established a systematic procedure to accomplish the correlation between different interference patterns and the topography of SRG. For this, we devise a new setup combining an atomic force microscope and a two-beam interferometer (IIAFM). With this set-up, it is possible to track the topography change in-situ, while at the same time changing polarization and phase of the impinging interference pattern. To validate our results, we have compared two photosensitive materials named in short as PAZO and trimer. This is the first time that an absolute correspondence between the local distribution of electric field vectors of interference pattern and the local topography of the relief grating could be established exhaustively. In addition, using our IIAFM we found that for a certain polarization combination of two orthogonally polarized interfering beams namely SP (↕, ↔) interference pattern, the topography forms SRG with only half the period of the interference patterns. Exploiting this phenomenon we are able to fabricate surface relief structures below diffraction limit with characteristic features measuring only 140 nm, by using far field optics with a wavelength of 491 nm. We have also probed for the stresses induced during the polymer mass transport by placing an ultra-thin gold film on top (5–30 nm). During irradiation, the metal film not only deforms along with the SRG formation, but ruptures in regular and complex manner. The morphology of the cracks differs strongly depending on the electric field distribution in the interference pattern even when the magnitude and the kinetic of the strain are kept constant. This implies a complex local distribution of the opto-mechanical stress along the topography grating. The neutron reflectivity measurements of the metal/polymer interface indicate the penetration of metal layer within the polymer resulting in the formation of bonding layer that confirms the transduction of light induced stresses in the polymer layer to a metal film.