Nanocomposite Photoanisotropic Materials for Applications in Polarization Holography and Photonics.

Photoanisotropic materials, in particular azodyes and azopolymers, have attracted significant research interest in the last decades. This is due to their applications in polarization holography and 4G optics, enabling polarization-selective diffractive optical elements with unique properties, including circular polarization beam-splitters, polarization-selective bifocal lenses, and many others. Numerous methods have been applied to increase the photoinduced birefringence of these materials, and as a result, to obtain polarization holographic elements with a high diffraction efficiency. Recently, a new approach has emerged that has been extensively studied by many research groups, namely doping azobenzene-containing materials with nanoparticles with various compositions, sizes, and morphologies. The resulting nanocomposites have shown significant enhancement in their photoanisotropic response, including increased photoinduced birefringence, leading to a higher diffraction efficiency and a larger surface relief modulation in the case of polarization holographic recordings. This review aims to cover the most important achievements in this new but fast-growing field of research and to present an extensive comparative analysis of the result, reported by many research groups during the last two decades. Different hypotheses to explain the mechanism of photoanisotropy enhancement in these nanocomposites are also discussed. Finally, we present our vision for the future development of this scientific field and outline its potential applications in advanced photonics technologies.

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.

Noise analysis in outdoor dynamic speckle measurement.

The dynamic speckle method (DSM) is an effective tool for the estimation of speed of processes. The speed distribution is encoded in a map built by statistical pointwise processing of time-correlated speckle patterns. For industrial inspection, the outdoor noisy measurement is required. The paper analyzes the efficiency of the DSM in the presence of environmental noise as phase fluctuations due to the lack of vibration isolation and shot noise due to ambient light. The usage of normalized estimates for the case of non-uniform laser illumination is studied. The feasibility of the outdoor measurement has been proven by numerical simulations of noisy image capture and real experiments with test objects. Good agreement has been demonstrated in both the simulation and experiment between the ground truth map and the maps extracted from noisy data.

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.

Reversible supramolecular chiral structures induced in azopolymers by elliptically polarized light: influence of the irradiation wavelength and intensity.

Photoinduced supramolecular chiral structures in azo materials have been extensively studied for the development of all-optical switches and because of their influence on the properties of certain types of polarization holographic gratings. Here, we investigate chiral structures induced by irradiation with elliptically polarized light in thin films of four azopolymers denoted as PAZO, P1, P1-2, which are amorphous, and P2, which is liquid crystalline. Their formation is characterized in real time by the kinetics of azimuth rotation. The influence of the irradiation wavelength and intensity is also analyzed. The largest azimuth rotation per unit thickness is achieved in PAZO (33°/µm) and P1-2 (25°/µm). Reversibility of the chiral structures is demonstrated by a tenfold change in the direction of rotation. Our results also indicate that chiral structures formation occurs significantly faster than the induction of linear birefringence.

Intensity-based dynamic speckle method using JPEG and JPEG2000 compression.

Statistical processing of speckle data enables observation of the speed of processes. In intensity-based pointwise dynamic speckle analysis, a map related to speed's spatial distribution is extracted from a sequence of speckle patterns formed on an object under coherent light. Monitoring of time evolution of a process needs storage, transfer, and processing of a large number of images. We have proposed lossy compression of these images using JPEG and JPEG2000 formats. We have compared the maps computed from noncompressed and decompressed synthetic and experimental images, and we have proven that both compression formats can be applied in the dynamic speckle analysis.

Tautomeric influence on the photoinduced birefringence of 4-substituted phthalimide 2-hydroxy Schiff bases in PMMA matrix.

The photoinduced birefringence of two 4-substituted phthalimide 2-hydroxy Schiff bases, containing salicylic (4) and 2-hydroxy-1-naphthyl (5) moieties has been investigated in PMMA matrix. Their optical behaviour as nanocomposite films was revealed by combined use of DFT quantum chemical calculations (in ground and excited state) and experimental optical spectroscopy (UV-Vis and fluorescence). The results have shown that solid-state reversible switching takes place by enol/keto tautomerization and Z/E isomerization. Birefringence study was performed in the PMMA nanocomposite films using pump lasers at λrec = 355 nm and λrec = 442 nm. Fast response time and high stability of anisotropy up to 58% for (4) and 95% for (5) after turning off the excitation laser, was observed, which makes these materials appropriate candidates for cutting-edge optical information technology materials. The possibility for multiple cycles of recording, reading and optical erasure of the photoinduced birefringence at λrec = 442 nm in 5 has been demonstrated. The obtained results have shown that the maximum value of the measured birefringence is close to the anisotropic characteristics of the most frequently used azo materials.

Quantization of dynamic speckle patterns with spatially varying statistics.

Raw data compression is mandatory for monitoring of processes by dynamic speckle analysis when two-dimensional activity maps are built by pointwise statistical processing of correlated speckle patterns formed on the surface of diffusely reflecting objects under laser illumination. Coarse quantization of speckle patterns enables storage and transfer of a huge amount of images, but it may be inefficient at spatially varying speckle statistics, such as for patterns recorded at non-uniform illumination or reflectivity. We prove efficacy of coarse quantization of the raw speckle data with varying statistics for a normalized algorithm by simulation and a polymer drop drying experiment. Both uniform and non-uniform quantization are proposed for treating such data. Decreasing the bit depth from 8 to 3 is possible without worsening the quality of the activity map.

Dynamic speckle analysis with coarse quantization of the raw data.

Analysis of dynamic speckle formed on the surface of diffusely reflecting objects under laser illumination is a non-contact method for inspection of speed of processes. The paper deals with intensity-based implementation of the method that relies on statistical processing of correlated in time sequences of speckle images. A two-dimensional activity map is built for each sequence to visualize regions of different speed on the object surface at a given instant. A great number of images is required to track a process in time. We propose data compression by coarse quantization of the raw speckle data. Efficacy of quantization is analyzed by simulation and experiment for low- and high-contrast speckle patterns with bell-shaped and long-tailed distributions of intensity, respectively. Non-uniform quantization is proposed for long-tailed speckle intensity distributions. Decreasing the bit depth from 8 to 4 causes no change in the probability density function of the activity estimate.

Synthesis, spectroscopic and TD-DFT quantum mechanical study of azo-azomethine dyes. A laser induced trans-cis-trans photoisomerization cycle.

This paper describes the synthesis, spectroscopic characterization and quantum mechanical calculations of three azo-azomethine dyes. The dyes were synthesized via condensation reaction between 4-(dimethylamino)benzaldehyde and three different 4-aminobenzene azo dyes. Quantum chemical calculations on the optimized molecular geometry and electron densities of the trans (E) and cis (Z) isomers and their vibrational frequencies have been computed by using DFT/B3LYP density-functional theory with 6-311++G(d,p) basis set in vacuo. The thermodynamic parameters such as total electronic energy E (RB3LYP), enthalpy H298 (sum of electronic and thermal enthalpies), free Gibbs energy G298 (sum of electronic and thermal free Gibbs energies) and dipole moment µ were computed for trans (E) and cis (Z) isomers in order to estimate the ΔEtrans→cis, Δµtrans→cis,ΔHtrans→cis, ΔGtrans→cis and ΔStrans→cis values. After molecular geometry optimization the electronic spectra have been obtained by TD-DFT calculations at same basis set and correlated with the spectra of vapour deposited nanosized films of the dyes. The NBO analysis was performed in order to understand the intramolecular charge transfer and energy of resonance stabilization. Solvatochromism was investigated by UV-VIS spectroscopy in five different organic solvents with increasing polarity. The dynamic photoisomerization experiments have been performed in DMF by pump lasers λ=355nm (mostly E→Z) and λ=491nm (mostly Z→E) in spectral region 300nm - 800nm at equal concentrations and times of illumination in order to investigate the photodynamical trans-cis-trans properties of the CHN and NN chromophore groups of the dyes.

Anisotropic hybrid organic/inorganic (azopolymer/SiO2 NP) materials with enhanced photoinduced birefringence.

Hybrid materials based on combination of polymers and inorganic nanoparticles (NP) attracted considerable attention in the last decade due to their advantageous electrical, optical, or mechanical properties. Recently, we reported a significant improvement of the photoresponse by doping azopolymers with ZnO NP. To study the influence of the composition of the dopant, in our present work we have synthesized anisotropic organic/inorganic nanocomposite materials by incorporating 5-15 nm sized SiO2 NP in a side-chain azopolymer. As a result we observe an enhancement of the photoinduced birefringence in these composite materials with about 20% compared to the nondoped sample. Additionally, we discuss possible mechanisms leading to this enhancement related with the scattering caused by the NP and the increased mobility of the azochromophores in the vicinity of NP.

Increase of photoinduced birefringence in a new type of anisotropic nanocomposite: azopolymer doped with ZnO nanoparticles.

We report a significant increase of about 50% of the photoinduced birefringence in nanocomposite films of azopolymers doped with ZnO nanoparticles compared with samples made from nondoped azopolymers. This increase is most pronounced at small concentrations of the nanoparticles of 0.5% and for the amorphous polymers used in our study. We observe also an improvement of the response time of more than 25% in some of the polymers, which allows for faster and more effective polarization optical recording.

Control of the spectral position of dichromated gelatin reflection holograms.

Dichromated gelatin (DCG) is one of the best light-sensitive materials for holographic recording. However, strict technological control should be observed during deposition, gelation, and drying of DCG plates and the chemical processing of the recorded structures. Usually, for reflection holograms the gelatin layer should be sealed in order to protect it from ambient humidity, which affects the value and position of the reflection maximum. Herein we give three different recipes for tuning the reflection maximum from 430 to 700 nm by swelling the hologram thickness with a filler material that is commercially available. The mechanism of the hologram swelling, which changes the period of the recorded holographic structure, is also briefly discussed.

Resonant optical transmission from a one-dimensional relief metalized subwavelength grating.

We have studied one-dimensional (1D) relief metalized subwavelength gratings, which support resonant optical transmission. We have used pregrooved DVD stampers, metalized with a thin Al layer. The sensitivity of resonant transmission of the gratings to the cladding environment was investigated by the help of matching fluids. We have shown that the shift of the spectral position of the resonance peak can be used for sensor applications, e.g., for determination of very low concentrations of nanosized dielectric particles in distilled water.