Azopolymer Thin Films Research Articles

Phase Behaviors and Photoresponsive Thin Films of Syndiotactic Side-Chain Liquid Crystalline Polymers with High Densely Substituted Azobenzene Mesogens.

Azobenzene-containing polymers (azopolymers) are a kind of fascinating stimuli-responsive materials with broad and versatile applications. In this work, a series of syndiotactic C1 type azopolymers of Pm-Azo-Cn with side-chain azobenzene mesogens of varied length alkoxy tails (n=1, 4, 8, 10) and different length alkyl spacers (m=6, 10) have been prepared via Rh-catalyzed carbene polymerization. The thermal properties and ordered assembly structures of thus synthesized side chain liquid crystalline polymers (SCLCPs) have been systematically investigated with differential scanning calorimetry (DSC), polarized optical microscopy (POM) and variable-temperature small/wide-angle X-ray scattering (SAXS/WAXS) analyses. P10-Azo-C1 and P10-Azo-C4 with shorter alkoxy tails exhibited hierarchical structures SmB/Colob and transformed into SmA/Colob at a higher temperature, while P10-Azo-C8 and P10-Azo-C10 with longer alkoxy tails only displayed side group dominated layered SmB phase and transformed into SmA phase at higher temperatures. For P6-Azo-C4 with a shorter spacer only showed a less ordered SmA phase owing to interference by partly coupling between the side chain azobenzene mesogens and the helical backbone. More importantly, the series high densely substituted syndiotactic C1 azopolymer thin films, exhibited evidently and smoothly reversible photoresponsive properties, which demonstrated promising photoresponsive device applications.

Structured polarized laser beams for controlled spiral-shaped mass transfer in azopolymer thin films

We present an approach for the realization of controlled spiral-shaped mass transfer in azopolymer thin films and the fabrication of spiral microreliefs. For such laser processing, we propose to use light fields with structured polarization distributions generated by a transmissive spatial light modulator. The projection lithography approach is utilized, transferring the pattern directly to the surface of azopolymer thin films. The shaped polarization distributions with different dependencies of the polarization vector orientation on the azimuthal angle allow us to drive surface waves on the sample along a spiral trajectory. Additionally, the ability to control the concavity of the formed microreliefs is demonstrated. This approach can be effectively modified for the direct laser fabrication of more complex nano-/micro-elements as well as their arrays.

High photoinduced birefringence in thermally treated layers of the azopolymer PAZO with significantly changed absorbance spectrum

In this experimental work we present the effect of thermal treatment of azopolymer thin films on their absorbance spectra and how that influences the photoinduced birefringence of the azopolymer. The azopolymer we use – PAZO (poly[1-[4-(3-carboxy-4-hydroxyphenylazo)benzenesulfonamido]-1,2ethanediyl, sodium salt]) is commonly investigated material for polarization holography because it is easily accessible and has well pronounced photoanisotropic properties. In a recent study it was discovered that its absorbance spectrum gradually changes upon heating to 250°C and as a result the absorbance in the range 400-600 nm is increased. That raises the question is it possible to increase the photoinduced birefringence for wavelengths that are far away from the peak of absorbance of the azopolymer PAZO, located approximately at 360 nm. For example, there are powerful lasers at 532 nm, which could be used for optical recording instead of traditionally used lasers in the blue and UV range. To answer this question, we investigated thin film samples of PAZO deposited on quartz substrate and measured continually their spectra of absorbance while heating the samples from room temperature to 250°C. We also measured the photoinduced birefringence using pump laser at 532 nm before and after the thermal procedure. Thus, we report significant increase of the birefringence at 532 nm after the thermal treatment and mention some potential applications.

Light-Induced Thermal and Optical Behavior of Functionalized Side-Chain Push–Pull Azo Polymer Thin Films

Light-Induced Thermal and Optical Behavior of Functionalized Side-Chain Push–Pull Azo Polymer Thin Films

Two-Dimensional Polarization Holographic Gratings in Azopolymer Thin Films: Polarization Properties in the Presence or Absence of Surface Relief

During polarization holographic recording in azopolymer thin films, usually together with the volume anisotropic grating, a surface relief grating (SRG) is also formed. By using two consecutive exposures, it is possible to obtain a two-dimensional (2D) grating. To the best of our knowledge, the polarization properties of such gratings have not been studied yet. To determine the influence of the surface relief on the polarization selectivity of the 2D gratings, we propose two methods to suppress the SRG formation: by varying the recording conditions or varying the sample structure. In these experiments we have used the commercially available azopolymer PAZO, poly[1-4-(3-carboxy-4-hydrophenylazo) benzene sulfonamido]-1,2-ethanediyl, sodium salt] to perform the polarization holographic recording using a 442 nm He-Cd laser. As indicated by our results, when the surface relief is present, it strongly dominates the response of the 2D grating and it behaves almost as a scalar polarization insensitive grating. Conversely, when the SRG formation is suppressed, the polarization properties of the 2D grating in all four diffracted orders are very well pronounced. In this way, we demonstrate that we can easily control SRG formation and, if desired, obtain 2D grating with high surface relief modulation, or alternatively record polarization-selective 2D gratings with virtually no surface relief.

Direct magnetic and surface relief patterning using carbazole-based azopolymer

The results on using of carbazole-based azopolymer layers (Polyepoxypropylcarbazole:Methyl Red with magnetic particles of Fe2SO4) for the recording of 1-D and 2-D surface relief gratings are presented in this report. Morphology study using AFM and MFM of obtained structures has shown their good quality. Surface relief gratings with profile height up to 1.2 µm were obtained during the holographic recording using blue laser. Along with surface relief grating it was shown the direct formation of magnetic relief. Possibility of simultaneous direct fabrication of surface and magnetic relief by optical holographic recording using azopolymer thin films as recording media was shown.

Viscoplastic Modeling of Surface Relief Grating Growth on Isotropic and Preoriented Azopolymer Films.

We report on solving of two intriguing issues concerning the inscription of surface relief gratings within azopolymer thin films under irradiation with SS, PP and RL interference patterns. For this, we utilize the orientation approach and viscoplastic modeling in combination with experimental results, where the change in surface topography is acquired in situ during irradiation with modulated light. First, the initial orientation state of polymer backbones is proved to be responsible for the contradictory experimental reports on the efficiency of the SS interference pattern. Different orientation states can influence not only the phase of SS grating but also its height, which is experimentally confirmed by using special pretreatments. Second, the faster growth of gratings inscribed by the RL interference pattern is shown to be promoted by a weak photosoftening effect. Overall, the modeled results are in good agreement with the order of relative growth efficiency: RL-PP-SS.

In-line and off-axis polarization-selective holographic lenses recorded in azopolymer thin films via polarization holography and polarization multiplexing.

Polarization-selective diffractive in-line and off-axis lenses are recorded in azopolymer thin films using polarization holography. A simple, yet efficient, and to the best of our knowledge, new method is used to suppress the surface relief grating formation and to improve the polarization properties of the lenses. The in-line lenses are converging for right circularly polarized (RCP) light and diverging for left circularly polarized (LCP) light. Bifocal off-axis lenses are recorded by polarization multiplexing. By rotating the sample at 90° between the exposures, the two focal points of these lenses are located in orthogonal directions O x and O y, so we can refer to these novel lenses as 2D bifocal polarization holographic lenses. The light intensity in their focuses depends on the reconstructing light polarization. According to the recording scheme, they can either reach maximum intensities simultaneously (for LCP or RCP), or alternatively, one of them can be at maximum for LCP, while the other for RCP. These lenses may be used as polarization controllable optical switches, in the field of self-interference incoherent digital holography or for other photonics applications.

Hybrid Dispersion Model Characterization of PAZO Azopolymer Thin Films over the Entire Transmittance Spectrum Measured in the UV/VIS/NIR Spectral Region.

Notwithstanding the significant optical applicability of PAZO polymer films, there are no accurate data about their optical characteristics. To remedy this shortcoming, in this study three PAZO polymer thin films are characterized, with dissimilar thicknesses, on glass substrates using only one UV/VIS/NIR transmittance spectrum T(λ) per sample and an original hybrid dispersion model (HDM). HDM is based on the Tauc-Lorentz model, the new amorphous dispersion formula, the Tauc-Lorentz-Urbach model of Foldyna and the Tauc-Lorentz-Urbach model of Rodriguez. HDM with two oscillators is employed in characterizations of the PAZO polymer films in the range [300, 2500] nm, whereby the root-mean-square deviation (RMSD) of the fitted transmittance spectrum with respect to T(λ) does not exceed 1.6 × 10-3. Decreasing RMSD by 2.3% to 94.4% is demonstrated by employing HDM compared with the above mentioned four popular dispersion models, for each one of the studied films. HDM is applicable to amorphous films independent of their thickness as well as to cases of non-transparent substrate.

Writing and reading with the longitudinal component of light using carbazole-containing azopolymer thin films

It is well known that azobenzene-containing polymers (azopolymers) are sensitive to the polarization orientation of the illuminating radiation, with the resulting photoisomerization inducing material transfer at both the meso- and macroscale. As a result, azopolymers are efficient and versatile photonic materials, for example, they are used for the fabrication of linear diffraction gratings, including subwavelength gratings, microlens arrays, and spectral filters. Here we propose to use carbazole-containing azopolymer thin films to directly visualize the longitudinal component of the incident laser beam, a crucial task for the realization of 3D structured light yet remaining experimentally challenging. We demonstrate the approach on both scalar and vectorial states of structured light, including higher-order and hybrid cylindrical vector beams. In addition to detection, our results confirm that carbazole-containing azopolymers are a powerful tool material engineering with the longitudinal component of the electric field, particularly to fabricate microstructures with unusual morphologies that differentiate from the total intensity distribution of the writing laser beam.

Surface Relief Grating on Chitosan-N,N-dimethyl-4-(2-pyridylazo)aniline Thin Film.

We deposited homogeneous, thin, yellow-colored films of chitosan (Chi)-N,N-dimethyl-4-(2-pyridylazo)aniline (PADA) dye from an acid Chi–PADA solution by spin-coating on glass substrates. We characterized Chi, PADA, and Chi–PADA films by ATR–FTIR spectroscopy, which revealed a slight shift of 3170 and 3268 cm−1 bands, indicating H-bonding between the chitosan hydroxyl (OH) group and the amine (N) of the PADA pyridine ring. Based on these analyses, it was possible to determine the efficiency of the hydrogen bonds to form a Surface Relief Grating (SRG) on azo-polymer thin film. Moreover, we performed UV–VIS spectroscopy analysis of this film, which showed a broad band extending from 400 to 700 nm, with the maximum occurring at 428 nm. Therefore, we selected, within the absorption band, the 532 nm green laser wavelength to irradiate the azo-polymer films at room temperature. For the first time, natural polymer derivative and dye sample Chi–PADA thin films showed unique photoresponsive behavior under irradiation with two interfering laser beams. This permitted us to generate surface inscription patterning known as an SRG, which we confirmed by atomic force microscopy (AFM) and for which we determined a grating depth up to 50 nm. The present study opens the new possibility of using natural polymer-dye thin films.

Microscopic-characterization of photo-induced birefringence of azo-polymer thin film by focused surface plasmon

In this paper, we develop a technique to quantitatively evaluate the orientational dependence of local anisotropic properties (of azo-polymers fabricated in the form of thin films ∼ 100 nm) by means of focused surface plasmon. The magnitude of photo-induced birefringence and orientation of fast axis at microscopic sites in thin films are extracted by the developed method on evaluating the propagation constants of surface plasmon obtained from the elliptical absorption pattern in the reflected spatial frequency distribution. Low birefringence (∼0.01) has been successfully measured with ultra-low probe volume.

Characterization of Polarization Holographic Gratings Obtained on Azopolymer Thin Films by Digital Holographic Microscopy

Polarization diffraction gratings are formed by one-step polarization holographic recording in azopolymer thin films. The evolution of the gratings parameters, such as the modulation of diffraction efficiency and relief depth with regard to different exposure dose is analyzed. Phase-shifting digital holographic microscopy is applied for the measurement of the light-induced polarization diffraction gratings. For the accurate hologram acquisition and reconstruction of the complex amplitude transmitted by the gratings, we performed all-optical (without moving components) phase-shifting implemented within in the imaging system of the digital holographic microscope. The experimental measurement results and theoretical predictions were compared and analyzed.

Topological reconstruction of a stretched transparent surface relief grating via an optical diffraction pattern.

The optical characterization of transparent and stretchable patterned surfaces replicated from the fabrication of quasicrystal structures on azopolymer thin films is presented. The complexity of the quasicrystal surface fabrication is obtained by superimposed multiple light exposures. Azopolymer surface patterns are used as a replica molding master. The microscopic elongation of nanocavities induced by macroscopic stretchings of the elastomeric quasicrystal replication is characterized via optical diffraction. An original numerical method is presented to reconstruct the structured surface deduced from the optical diffraction measurements. The measurements show that drastic topologic changes, e.g., going from cavities to a canal, happens on the surface. This could be ingeniously used for creating actionable structured surfaces or nanoparticles trapping surfaces.

Polarization holographic recording of vortex diffractive optical elements on azopolymer thin films and 3D analysis via phase-shifting digital holographic microscopy.

Direct fabrication of complex diffractive optical elements (DOEs) on photosensitive thin films is of critical importance for the development of advanced optical instruments. In this paper, we design and investigate DOEs capable of generating optical vortices. Analog and digital approaches for one-step polarization holographic recording of vortex DOEs on new carbazole-based azopolymer thin films are described. First configuration involves analog polarization holographic recording using a vortex phase retarder and has as a result the DOE producing a diffraction pattern with phase singularities aligned in a single line. Similar diffraction picture is achieved by the single-beam digital holographic recording setup with an integrated spatial light modulator. In the third system, the implemented double-beam digital polarization holographic recording setup yields simultaneously a spatial multiplexed vortex pattern. Diffraction efficiency evolution of these three types of DOEs are monitored and compared. The phase-shifting digital holographic microscope with an electrically controlled liquid crystal variable retarder is applied to investigate the phase and surface topography of the inscribed diffractive optical elements. The comparison between the digital and analog micro-patterning techniques contributes new evidence to limited data on the influence of the analog and digital generation of the spiral wavefront on the performance of vortex DOEs.

Probing of the mechanical properties and monitoring of the drying process of azopolymer thin films for optical recording

Azopolymers prepared in the form of thin films are promising candidates as media for optical recording due to their photo-anisotropic properties. The thermo-physical and mechanical properties of the prepared films, as well as the uniformity of their thickness and smoothness of the formed layers are important characteristics for application of these materials. In the present study, thin films of two amorphous and one liquid crystalline azopolymers were characterized and, in the experiment, a commercially available amorphous azopolymer was included as a base for comparison. Atomic force microscopy was applied for surface topography determination for thin film samples of all four azopolymers and roughness parameters as the average roughness and root mean square values are estimated. These values show that amorphous azopolymers are characterized by a high smoothness and a flatter surface while the thin film from the liquid crystalline polymer shows a structure with pronounced topographic features and thus exhibits much higher surface roughness. The conducted depth-sensing indentation of non-exposed thin films prepared by spin-coating on glass substrates allowed to determine mechanical properties such as universal and indentation hardness, elastic modulus and elastic part of indentation work. The creep behavior of the tested materials was also analyzed and the elastic-plastic behavior for all azopolymers was established. The most pronounced plastic behavior was observed for the liquid crystalline one. We obtained different temporal scales of the drying process of solutions of the tested materials in a polymer casting experiment by a quantitative dynamic speckle analysis. Analysis involved statistical processing of correlated sequences of laser speckle patterns, reflected the properties of the respective materials and was supported by the reported mechanical characteristics.

Optical anisotropy induced at five different wavelengths in azopolymer thin films: Kinetics and spectral dependence

Azopolymers are highly efficient materials, able to register the polarization state of light. They have broad range of applications from diffractive optical elements with unique polarization properties to biophysics.We present a study of birefringence kinetics, induced with five different pump lasers with wavelengths 355, 442, 491, 514 and 532 nm in thin films of widely used amorphous azopolymer PAZO – poly[1-[4-(3-carboxy-4-hydroxyphenylazo)benzene sulfon amido]-1,2-ethanediyl, sodium salt]. During the real-time measurement, the value of the photoinduced birefringence (Δn) is determined at 635 nm, using a DPSS laser. When saturation is reached, the spectrum of the birefringence is measured. Our results indicate that the investigated azopolymer can be used for applications in a wide wavelength range.

Improvement of the photoinduced birefringence in azopolymer PAZO doped with TiO2 nanoparticles via thermal treatment

Abstract We present a study of the photoinduced birefringence in nanocomposite films of the azopolymer PAZO (poly[1-[4-(3-carboxy-4-hydroxyphenylazo)benzenesulfon amido]-1,2-ethanediyl, sodium salt]) doped with TiO2 nanoparticles (NP) with different concentrations before and after thermal annealing. The NP represent nanopowder with primary particle size 21 nm. The concentration of the NP was varied from 0% (non-doped azopolymer film) to 5 wt%. The thermal process, applied to the nanocomposite films, includes 1 h heating at 200°C. Previous studies of PAZO show that the polymer is stable up to 270°C. We study the dependence of the maximal birefringence induced with He-Cd laser (λ= 442 nm) on the concentration of the TiO2 NP in the azopolymer thin films as well as thermal effect on the absorbance spectra of the thin films. As indicated by our results, the birefringence is higher for the thermally annealed samples. An increase of the photoinduced birefringence is also observed for the nanocomposite layers with 1% NP for the non-annealed films, and with 2% NP for the annealed films.

Direct quantitative imaging of the writing stage in a photosensitive azopolymer by digital holography.

In this paper, we demonstrated that the gradual formation of a surface relief grating (SRG) in azopolymer thin films under continuous light exposure could be directly observed in situ and in real-time, allowing full-field characterization with high spatial resolution. We reported here for the first time, to the best of our knowledge, that digital holography (DH) can be adopted for investigating and monitoring an inscribed holographic surface relief grating (SRG) of azopolymers by two-beam laser interference lithography over a wide area. The writing process could be assessed through quantitative phase imaging (QPI). The reported results show that the proposed method is a truly valuable diagnostic tool that can be useful for investigating the spatial distribution of the writing process, which can eventually contribute to shedding light on the still unclear origin and related mechanism of SRG formation in azopolymers.

Characterization of Cells Interactions with Patterned Azopolymer-Based Materials using SEM, AFM and Video Microscopy

Introduction:Artificial Extracellular Matrices (ECMs) are promising tools for the study of cell behaviors.Methods:Here, we report a protocol for the use of a reconfigurable biocompatible azopolymer thin film through a photoinduced reconfigurable structuration of its surface to study nerve growth, differentiation and cell guidance.Results & Discussion:We show that this protocol combined with a spontaneous self-photoinduced polymer is suitable for time-lapse fluorescence video microscopy and can be easily adapted to electron microscopy techniques (SEM) and near-field imaging techniques (AFM).