[show abstract][hide abstract] ABSTRACT: We report on conductivity behavior of very thin gold layer deposited on a photosensitive polymer film. Under irradiation with light interference pattern, the azobenzene containing photosensitive polymer film undergoes deformation at which topography follows a distribution of intensity, resulting in the formation of a surface relief grating. This process is accompanied by a change in the shape of the polymer surface from flat to sinusoidal together with a corresponding increase in surface area. The gold layer placed above deforms along with the polymer and ruptures at a strain of 4%. The rupturing is spatially well defined, occurring at the topographic maxima and minima resulting in periodic cracks across the whole irradiated area. We have shown that this periodic micro-rupturing of a thin metal film has no significant impact on the electrical conductivity of the films. We suggest a model to explain this phenomenon and support this by additional experiments where the conductivity is measured in a process when a single nanoscopic scratch is formed with an AFM tip. Our results indicate that in flexible electronic materials consisting of a polymer support and an integrated metal circuit, nano- and micro cracks do not alter significantly the behavior of the conductivity unless the metal is disrupted completely.
[show abstract][hide abstract] ABSTRACT: We report on a change in the properties of monomolecular films of polyelectrolyte molecules, induced by illuminating the silicon substrate on which they adsorb. It was found that under illumination the thickness of the adsorbed layer decreases by at least 27% and at the same time the roughness is significantly reduced in comparison to a layer adsorbed without irradiation. Furthermore, the homogeneity of the film topography and the surface potential is shown to be improved by illumination. The effect is explained by a change in surface charge density under irradiation of n- and p-type silicon wafers. The altered charge density in turn induces conformational changes of the adsorbing polyelectrolyte molecules. Their photo-controlled adsorption opens new possibilities for selective manipulation of adsorbed films. This possibility is of potential importance for many applications such as the production of well defined coatings in biosensors or micro-electronics.
[show abstract][hide abstract] ABSTRACT: 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 azo-benzene 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.
[show abstract][hide abstract] ABSTRACT: In this paper we report on an opto-mechanical scission of polymer chains within photosensitive diblock-copolymer brushes grafted to flat solid substrates. We employe surface-initiated polymerization of methylmethacrylate (MMA) and t-butyl methacrylate (tBMA) to grow diblock-copolymer brushes of poly(methylmethacrylate-b-t-butyl methacrylate) following the atom transfer polymerization (ATRP) scheme. After the synthesis, de-protection of the PtBMA block yields poly(methacrylic acid) (PMAA). To render PMMA-b-PMAA copolymers photosensitive, cationic azobenzene containing surfactants are attached to the negatively-charged outer PMAA block. During irradiation with an ultraviolet (UV) interference pattern, the extent of photo-isomerization of the azobenzene groups varies spatially and results in a topography change of the brush, i.e., formation of surface relief gratings (SRG). The SRG formation is accompanied by local rupturing of the polymer chains in areas from which the polymer material recedes. This opto-mechanically induced scission of the polymer chains takes place at the interfaces of the two blocks and depends strongly on the UV irradiation intensity. Our results indicate that this process may be explained by employing classical continuum fracture mechanics, which might be important for tailoring the phenomenon for applying it to post-structuring of polymer brushes.
[show abstract][hide abstract] ABSTRACT: The interface between thin films of metal and polymer materials play a significant role in modern flexible microelectronics viz., metal contacts on polymer substrates, printed electronics and prosthetic devices. The major emphasis in metal-polymer interface is on studying how the externally applied stress in the polymer substrate leads to the deformation and cracks in metal film and vice versa. Usually, the deformation process involves strains varying over large lateral dimensions due to excessive stress at local imperfections. Here we show that the seemingly random phenomena at macroscopic scales can be rendered rather controllable at sub-micron length scales. Recently, we have created a metal-polymer interface system with strains varying over periods of several hundred nanometers. This was achieved by exploiting the formation of surface relief grating (SRG) within the azobenzene containing photosensitive polymer film upon irradiation with light interference pattern. Up to a thickness of 60 nm, the adsorbed metal film adapts neatly to the forming relief, until it ultimately ruptures into an array of stripes by formation of highly regular and uniform cracks along the maxima and minima of the polymer topography. This surprising phenomenon has far-reaching implications. This is the first time a direct probe is available to estimate the forces emerging in SRG formation in glassy polymers. Furthermore, crack formation in thin metal films can be studied literally in slow motion, which could lead to substantial improvements in the design process of flexible electronics. Finally, cracks are produced uniformly and at high density, contrary to common sense. This could offer new strategies for precise nano-fabrication procedures mechanical in character.
[show abstract][hide abstract] ABSTRACT: The effect of illumination on the thickness and roughness of monolayers
of polycationic molecules of polyethyleneimine deposited from solution
onto a silicon substrate was discovered and investigated. The
super-bandgap illumination of the substrate during polyethyleneimine
adsorption causes a decrease in both the roughness and integral
thickness of the organic layer on n- and p-Si substrates.
[show abstract][hide abstract] ABSTRACT: When photosensitive azobenzene-containing polymer films are irradiated with light interference patterns, topographic variations in the film develop that follow the local distribution of the electric field vector. The exact correspondence of e.g., the vector orientation in relation to the presence of local topographic minima or maxima is in general difficult to determine. Here, we report on a systematic procedure how this can be accomplished. For this, we devise a new set-up combining an atomic force microscope and two-beam interferometry. 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. This is the first time that an absolute correspondence between the local distribution of electric field vectors and the local topography of the relief grating could be established exhaustively. Our setup does not require a complex mathematical post-processing and its simplicity renders it interesting for characterizing photosensitive polymer films in general.
Journal of Applied Physics 06/2013; 113(22). · 2.21 Impact Factor
[show abstract][hide abstract] ABSTRACT: In this paper, we report on in-situ atomic force microscopy (AFM) studies of topographical changes in azobenzene-containing photosensitive polymer films that are irradiated with light interference patterns. We have developed an experimental setup consisting of an AFM combined with two-beam interferometry that permits us to switch between different polarization states of the two interfering beams while scanning the illuminated area of the polymer film, acquiring corresponding changes in topography in-situ. This way, we are able to analyze how the change in topography is related to the variation of the electrical field vector within the interference pattern. It is for the first time that with a rather simple experimental approach a rigorous assignment can be achieved. By performing in-situ measurements we found that for a certain polarization combination of two interfering beams [namely for the SP (↕, ↔) polarization pattern] the topography forms surface relief grating with only half the period of the interference patterns. Exploiting this phenomenon we are able to fabricate surface relief structures with characteristic features measuring only 140 nm, by using far field optics with a wavelength of 491 nm. We believe that this relatively simple method could be extremely valuable to, for instance, produce structural features below the diffraction limit at high-throughput, and this could significantly contribute to the search of new fabrication strategies in electronics and photonics industry.
Applied Physics A 01/2013; 113(2):263-272. · 1.55 Impact Factor
[show abstract][hide abstract] ABSTRACT: The light-induced reversible switching of the swelling of microgel particles triggered by photo-isomerization and binding/unbinding of a photosensitive azobenzene-containing surfactant is reported. The interactions between the microgel (N-isopropylacrylamide, co-monomer: allyl acetic acid, crosslinker: N,N′-methylenebisacrylamide) and the surfactant are studied by UV-Vis spectroscopy, dynamic and electrophoretic light scattering measurements. Addition of the surfactant above a critical concentration leads to contraction/collapse of the microgel. UV light irradiation results in trans-cis isomerization of the azobenzene unit incorporated into the surfactant tail and causes an unbinding of the more hydrophilic cis isomer from the microgel and its reversible swelling. The reversible contraction can be realized by blue light irradiation that transfers the surfactant back to the more hydrophobic trans conformation, in which it binds to the microgel. The phase diagram of the surfactant-microgel interaction and transitions (aggregation, contraction, and precipitation) is constructed and allows prediction of changes in the system when the concentration of one or both components is varied. Remote and reversible switching between different states can be realized by either UV or visible light irradiation.
[show abstract][hide abstract] ABSTRACT: We report on sub-wavelength structuring of photosensitive azo-containing polymer films induced by a surface plasmon interference intensity pattern. The two surface plasmon waves generated at neighboring nano-slits in the metal layer during irradiation interfere constructively, resulting in an intensity pattern with a periodicity three times smaller than the wavelength of the incoming light. The near field pattern interacts with the photosensitive polymer film placed above it, leading to a topography change which follows the intensity pattern exactly, resulting in the formation of surface relief gratings of a size below the diffraction limit. We analyze numerically and experimentally how the depth of the nano-slit alters the interference pattern of surface plasmons and find that the sub-wavelength patterning of the polymer surface could be optimized by modifying the geometry and the size of the nano-slit.
[show abstract][hide abstract] ABSTRACT: Here we demonstrate how a surface plasmon (SP) generated near field pattern in the vicinity of a nano-scale pin hole can be used to generate reversible topography changes in a photosensitive polymer film above the opening. This can be achieved by simply changing the polarization state of the plasmon generating incoming light. In the case of linear polarization, the near field intensity pattern causes the film to laterally expand/contract according to the direction of the polarization. For circular polarization, two pronounced rims corresponding to maxima in the topography are observed. In all cases, the topographical variation is in close agreement with the SP intensity distribution computed from finite difference time domain simulation. Our results demonstrate the versatility of using SP near fields to imprint a variety of structures into photosensitive polymer films using only a single metallic mask.
[show abstract][hide abstract] ABSTRACT: It is well-known that surface plasmon generated near fields of suitably irradiated metal nano-structures can induce a patterning in an azobenzene-modified photosensitive polymer film placed on top. The change in the topography usually follows closely and permanently the underlying near field intensity pattern. With this approach, one can achieve a multitude of morphologies by additionally changing light intensity, polarization and the kind of metal used for nano-structuring. In this paper, we demonstrate that below a critical value of the polymer film thickness, the receding polymer material induces a change in refractive index of the glass–metal–polymer system, modifying the near field intensity distribution and causing a back-reaction on the flow of polymer material. This has a profound influence on the smallest size of topographical features that can be imprinted into the polymer.
Journal of Materials Chemistry 03/2012; 22(13):5945-5950. · 5.97 Impact Factor
[show abstract][hide abstract] ABSTRACT: We report on the preparation and characterization of photosensitive polymer brushes. The brushes are synthesized through polymer analogous attachment of azo-benzene groups to surface-attached poly(methacrylic acid) (PMAA) chains. The topography of the photosensitive brushes shows a strong reaction upon irradiation with UV light. While homogeneous illumination leaves the polymer topography unchanged, irradiation of the samples with interference patterns with periodically varying light intensity leads to the formation of surface relief gratings (SRG). The height of the stripes of the grating can be controlled by adjusting the irradiation time. The SRG pattern can be erased through solvent treatment when the periodicity of the stripe pattern is less than the length of the fully stretched polymer chains. In the opposite case, photomechanical scission of receding polymer chains is observed during SRG formation, and the inscribed patterns are permanent.
The Journal of Physical Chemistry B 08/2011; 115(35):10431-8. · 3.61 Impact Factor
[show abstract][hide abstract] ABSTRACT: We report on the interaction of cationic azobenzene-containing surfactant with DNA investigated by absorption and fluorescence spectroscopy, dynamic light scattering, and atomic force microscopy. The properties of the surfactant can be controlled with light by reversible switching of the azobenzene unit, incorporated into the surfactant tail, between a hydrophobic trans (visible irradiation) and a hydrophilic cis (UV irradiation) configuration. The influence of the trans-cis isomerization of the azobenzene on the compaction process of DNA molecules and the role of both isomers in the formation and colloidal stability of DNA-surfactant complexes is discussed. It is shown that the trans isomer plays a major role in the DNA compaction process. The influence of the cis isomer on the DNA coil configuration is rather small. The construction of a phase diagram of the DNA concentration versus surfactant/DNA charge ratio allows distancing between three major phases: colloidally stable and unstable compacted globules, and extended coil conformation. There is a critical concentration of DNA above which the compacted globules can be hindered from aggregation and precipitation by adding an appropriate amount of the surfactant in the trans configuration. This is because of the compensation of hydrophobicity of the globules with an increasing amount of the surfactant. Below the critical DNA concentration, the compacted globules are colloidally stable and can be reversibly transferred with light to an extended coil state.
[show abstract][hide abstract] ABSTRACT: Using scattering scanning nearfield infrared microscopy (s-SNIM), we have imaged the nanoscale phase separation of mixed polystyrene-poly(methyl methacrylate) (PS-PMMA) brushes and investigated changes in the top layer as a function of solvent exposure. We deduce that the top-layer of the mixed brushes is composed primarily of PMMA after exposure to acetone, while after exposure to toluene this changes to PS. Access to simultaneously measured topographic and chemical information allows direct correlation of the chemical morphology of the sample with topographic information. Our results demonstrate the potential of s-SNIM for chemical mapping based on distinct infrared absorption properties of polymers with a high spatial resolution of 80 nm × 80 nm.
Physical Chemistry Chemical Physics 06/2011; 13(24):11620-6. · 3.83 Impact Factor
[show abstract][hide abstract] ABSTRACT: We report on the fabrication and characterisation of a novel type of hybrid azo-modified photosensitive polymer film with a nanoscale metallic structuring integrated into the substrate. The metal structures permit to generate surface plasmon near fields when irradiated by UV-light from the rear without directly illuminating the polymer. This allows establishment of a localized, complex-shape intensity distribution at sub-wavelength resolution with a corresponding impact on the photosensitive polymer. The possibilities of exploiting this setup are manifold. We find that just by using the change of polarization of the incident light as means of control, the topography can be driven to change between various patterns reversibly. These results are confirmed by numerical simulations and compared with in situ recorded topography changes.