TY - JOUR A1 - Di Florio, G. A1 - Bruendermann, E. A1 - Yadavalli, Nataraja Sekhar A1 - Santer, Svetlana A1 - Havenith, Martina T1 - Graphene multilayer as nanosized optical strain gauge for polymer surface relief gratings JF - Nano letters : a journal dedicated to nanoscience and nanotechnology N2 - 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. KW - Surface relief grating KW - optomechanical forces KW - photosensitive polymer films KW - multilayer graphene deformation KW - confocal Raman microscopy Y1 - 2014 U6 - https://doi.org/10.1021/nl502631s SN - 1530-6984 SN - 1530-6992 VL - 14 IS - 10 SP - 5754 EP - 5760 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Di Florio, G. A1 - Bruendermann, E. A1 - Yadavalli, Nataraja Sekhar A1 - Santer, Svetlana A1 - Havenith, Martina T1 - Confocal raman microscopy and AFM study of the interface between the photosensitive polymer layer and multilayer graphene JF - Soft materials N2 - 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. KW - Graphene KW - Multilayer graphene KW - Photosensitive polymer film KW - Confocal Raman microscopy KW - AFM KW - Surface Relief Grating KW - Interfacial molecular interaction Y1 - 2014 U6 - https://doi.org/10.1080/1539445X.2014.945040 SN - 1539-445X SN - 1539-4468 VL - 12 SP - S98 EP - S105 PB - Taylor & Francis Group CY - Philadelphia ER - TY - JOUR A1 - Di Florio, Giuseppe A1 - Bruendermann, Erik A1 - Yadavalli, Nataraja Sekhar A1 - Santer, Svetlana A1 - Havenith, Martina T1 - Polarized 3D Raman and nanoscale near-field optical microscopy of optically inscribed surface relief gratings: chromophore orientation in azo-doped polymer films JF - Soft matter N2 - 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. Y1 - 2014 U6 - https://doi.org/10.1039/c3sm51787j SN - 1744-683X SN - 1744-6848 VL - 10 IS - 10 SP - 1544 EP - 1554 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Di Florio, Giuseppe A1 - Bründermann, Erik A1 - Yadavalli, Nataraja Sekhar A1 - Santer, Svetlana A1 - Havenith, Martina T1 - Polarized 3D Raman and nanoscale near-field optical microscopy of optically inscribed surface relief gratings BT - chromophore orientation in azo-doped polymer films N2 - 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. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 247 KW - glass-transition temperature KW - holographic diffraction gratings KW - chain azobenzene polymers KW - molecular-reorientation KW - amorphous polymers KW - data-storage KW - thin-films KW - dye KW - photoisomerization KW - alignment Y1 - 2013 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-95233 SP - 1544 EP - 1554 ER - TY - JOUR A1 - König, Tobias A1 - Yadavalli, Nataraja Sekhar A1 - Santer, Svetlana T1 - Near-Field induced reversible structuring of photosensitive polymer films Gold versus silver nano-antennas JF - Plasmonics N2 - We report on reversible structuring of photosensitive azo-containing polymer films induced by near-field intensity patterns emanating from illuminated nano-scale metal structures fabricated by colloidal lithography. Two different sets of these nano-antennas, consisting of either gold or silver, were investigated with respect to their ability to induce topography changes in a photosensitive polymer film placed above. Using in situ recorded atomic force microscopy micrographs of polymer topography changes during UV irradiation, we find that the response of the polymer film differs for the two metals at similar geometries of the metal nanostructures. The maximum topography change is stronger for Ag antennas as compared to the Au pattern, whereas the latter material revealed a pronounced splitting of topography maxima into two, a phenomenon less visible in the case of Ag. Finite difference time domain simulations of the electromagnetic field distribution in the vicinity of the metal structures confirm this remarkable observation. The local intensity is twice as large for the Ag as compared to the Au structures, and in each case, a splitting of the intensity pattern results, with a stronger modulation for Au. For both metals, the topography change was found to be reversible between a patterned and a flat by repeated change of irradiation conditions. KW - Photosensitive polymer films KW - Surface plasmons Y1 - 2012 U6 - https://doi.org/10.1007/s11468-012-9339-3 SN - 1557-1955 VL - 7 IS - 3 SP - 535 EP - 542 PB - Springer CY - New York ER - TY - JOUR A1 - Linde, Felix A1 - Yadavalli, Nataraja Sekhar A1 - Santer, Svetlana T1 - Conductivity behavior of very thin gold films ruptured by mass transport in photosensitive polymer film JF - APPLIED PHYSICS LETTERS N2 - 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. (C) 2013 AIP Publishing LLC. Y1 - 2013 U6 - https://doi.org/10.1063/1.4850595 SN - 0003-6951 SN - 1077-3118 VL - 103 IS - 25 PB - AMER INST PHYSICS CY - MELVILLE ER - TY - GEN A1 - Loebner, Sarah A1 - Jelken, Joachim A1 - Yadavalli, Nataraja Sekhar A1 - Sava, Elena A1 - Hurduc, Nicolae A1 - Santer, Svetlana T1 - Motion of adsorbed nano-particles on azobenzene containing polymer films N2 - We demonstrate in situ recorded motion of nano-objects adsorbed on a photosensitive polymer film. The motion is induced by a mass transport of the underlying photoresponsive polymer material occurring during irradiation with interference pattern. The polymer film contains azobenzene molecules that undergo reversible photoisomerization reaction from trans- to cis-conformation. Through a multi-scale chain of physico-chemical processes, this finally results in the macro-deformations of the film due to the changing elastic properties of polymer. The topographical deformation of the polymer surface is sensitive to a local distribution of the electrical field vector that allows for the generation of dynamic changes in the surface topography during irradiation with different light interference patterns. Polymer film deformation together with the motion of the adsorbed nano-particles are recorded using a homemade set-up combining an optical part for the generation of interference patterns and an atomic force microscope for acquiring the surface deformation. The particles undergo either translational or rotational motion. The direction of particle motion is towards the topography minima and opposite to the mass transport within the polymer film. The ability to relocate particles by photo-induced dynamic topography fluctuation offers a way for a non-contact simultaneous manipulation of a large number of adsorbed particles just in air at ambient conditions. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 352 KW - motion of adsorbed nano-particles KW - azobenzene containing polymer films KW - fluctuating surfaces Y1 - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-400423 ER - TY - JOUR A1 - Loebner, Sarah A1 - Jelken, Joachim A1 - Yadavalli, Nataraja Sekhar A1 - Sava, Elena A1 - Hurduc, Nicolae A1 - Santer, Svetlana T1 - Motion of Adsorbed Nano-Particles on Azobenzene Containing Polymer Films JF - Molecules N2 - We demonstrate in situ recorded motion of nano-objects adsorbed on a photosensitive polymer film. The motion is induced by a mass transport of the underlying photoresponsive polymer material occurring during irradiation with interference pattern. The polymer film contains azobenzene molecules that undergo reversible photoisomerization reaction from trans-to cis-conformation. Through a multi-scale chain of physico-chemical processes, this finally results in the macro-deformations of the film due to the changing elastic properties of polymer. The topographical deformation of the polymer surface is sensitive to a local distribution of the electrical field vector that allows for the generation of dynamic changes in the surface topography during irradiation with different light interference patterns. Polymer film deformation together with the motion of the adsorbed nano-particles are recorded using a homemade set-up combining an optical part for the generation of interference patterns and an atomic force microscope for acquiring the surface deformation. The particles undergo either translational or rotational motion. The direction of particle motion is towards the topography minima and opposite to the mass transport within the polymer film. The ability to relocate particles by photo-induced dynamic topography fluctuation offers a way for a non-contact simultaneous manipulation of a large number of adsorbed particles just in air at ambient conditions. KW - motion of adsorbed nano-particles KW - azobenzene containing polymer films KW - fluctuating surfaces Y1 - 2016 U6 - https://doi.org/10.3390/molecules21121663 SN - 1420-3049 VL - 21 SP - 397 EP - 411 PB - MDPI CY - Basel ER - TY - JOUR A1 - Papke, Thomas A1 - Yadavalli, Nataraja Sekhar A1 - Henkel, Carsten A1 - Santer, Svetlana T1 - Mapping a plasmonic hologram with photosensitive polymer films: standing versus propagating waves JF - ACS applied materials & interfaces N2 - 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. KW - propagating surface plasmons KW - nanostructured metal surface KW - azobenzene containing photosensitive material KW - surface relief grating Y1 - 2014 U6 - https://doi.org/10.1021/am503501y SN - 1944-8244 VL - 6 IS - 16 SP - 14174 EP - 14180 PB - American Chemical Society CY - Washington ER - TY - THES A1 - Yadavalli, Nataraja Sekhar T1 - Advances in experimental methods to probe surface relief grating formation mechanism in photosensitive materials T1 - Entstehung von Oberflächengittern in lichtempfindlichen Materialien N2 - 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. N2 - Azobenzolhaltige Polymere gehören zu einer Klasse funktionaler Materialien, bei denen durch ein äußeres Strahlungsfeld eine starke mechanische Reaktion ausgelöst werden kann. Durch die Bindung an das Polymerrückgrat können die Azobenzole, die unter UV-Belichtung eine Photoisomerisierung ausführen, was zum Teil drastische Effekte zur Folge hat. Unter Belichtung mit Intensitätsmustern, d.h. mit räumlich variierender Verteilung der Polarisation oder der Intensität des einfallenden Lichts verändert sich die Topographie der azobenzolhaltigen Filme, was zur Bildung von Oberflächengittern (engl. Surface Relief Gratings, SRG) führt. In dieser Arbeit wurde eine neue Methode vorgeschlagen, bei der das Verhalten elastischer/morphologischer Eigenschaften unter verschiedenen Belichtungsbedingungen, d.h. mit unterschiedlicher Verteilung der Polarisation und der Intensität in situ lokal als Funktion der Position entlang der SRG aufgenommen werden kann. Außerdem wurde hier vorgeschlagen, opto-mechanische Spannungen, die innerhalb der photosensitiven Polymerfilme während der Belichtung entstehen, mit Hilfe dünner aufgebrachter metallischen Schichten abzubilden und zu analysieren. KW - Azobenzolhaltige Polymerfilme KW - Oberflächengitter KW - In-situ Rasterkraftmikroskopie KW - Opto-mechanische Spannungen KW - Metall/Graphen/Polymer Grenzfläch KW - azobenzene polymer films KW - surface relief grating KW - in-situ atomic force microscopy KW - opto-mechanical stresses KW - metal/polymer interfaces Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-71213 ER -