Azobenzene Functionalized “T-Type” Poly(Amide Imide)s vs. Guest-Host Systems - A Comparative Study of Structure-Property Relations

This paper describes the synthesis and characterization of new “T-type” azo poly(amide imide)s as well as guest-host systems based on the “T-type” matrices. The matrices possessed pyridine rings in a main-chain and azobenzene moieties located either between the amide or imide groups. The non-covalent polymers contained the molecularly dispersed 4-phenylazophenol or 4-[(4-methyl phenyl)diazinyl]phenol chromophores that are capable of forming intermolecular hydrogen bonds with the pyridine rings. The FTIR spectroscopy and the measurements of the thermal, optical and photoinduced optical birefringence were employed for the determination of the influence of H-bonds and the specific elements of polymer architecture on physicochemical properties. Moreover, the obtained results were compared to those described in our previous works to formulate structure-property relations that may be considered general for the class of “T-type” azo poly(amide imide)s

Photoresponsive behaviour of “T-type” azopolyimides. The unexpected high efficiency of diffraction gratings, modulations and stability of the SRG in azopoly(ether imide)

In this paper, we compare the light-induced properties of three “T-type“ polyimide containing azobenzene chromophores with the properties of their structural counterparts containing azopyridine moieties. The processes of photoinduced birefringence generation and surface relief grating (SRG) formation are efficient in azobenzene polyimides, while in the azopyridine analogues the processes are non-detectable. Density functional theory calculations performed to reveal a possible structural reason for the lack of optical response in the azopyridine materials showed a formation of intramolecular H-bonds. Azopoly(ether imide) with 2,2′-diphenylopropane structure despite relatively low chromophore content exhibited one of the highest diffraction efficiency (ca. 20%) and the largest modulation of the SRG (260 nm) as have ever been observed for azopolyimides. Two years after inscription, modulation of the SRG was still observed without a decrease in the relief depth, which is important in applications requiring long-term stability of SRGs

Surface Relief Modulated Grating in Azo Polymer—From the Tailoring of Diffraction Order to Reshaping of a Laser Beam

Among light-responsive materials for photonics, azo polymers occupy an important position due to their optical response and the related concepts of consecutive applications. However, scientific insight is still needed to understand the effects of irradiation on the modification of the azo polymer structure and the effect of this modification on incoming probing light. In this work, we report on a surface relief grating with a maximum depth of a record-high value of 1.7 µm, inscribed holographically in a custom synthesized glassy azo polymer belonging to the poly(ether imide) family. We show that the specifically deformed polymer, forming an amplitude-modulated relief grating, has a unique dual effect on an incoming light beam of different diameters. When illuminated by a narrow probe beam, the structure acts as a variable-depth grating, enabling a continuous tuning of the diffraction efficiencies in the entire theoretically predicted range and, thus, generating or eliminating diffracted waves of specified order. Alternatively, when illuminated by a wide probe beam, the whole structure acts as an optical component reshaping the Gaussian light intensity profile into the profiles resembling the squares of Bessel functions of the zeroth- or higher orders. Moreover, a physical justification of the effects observed is provided

Tunable Polarization Gratings Based on Nematic Liquid Crystal Mixtures Photoaligned with Azo Polymer-Coated Substrates

Liquid crystal polarization gratings are of great interest for optical communications as elements performing beam steering, splitting, multiplexing or beam combining. Material birefringence, cell thickness or a period of the liquid crystal director pattern influence, among other features, spectroscopic and electro-optical characteristics of fabricated devices, determining thus their functionality and applicability. Here, we report on liquid crystal polarization gratings that allow for complete maximization of the first-order diffraction efficiency (resulting in total elimination of the zeroth-order diffraction) for any wavelength of an incident beam from green to the near-infrared spectral region by applying a low electric voltage. The gratings with periods as small as 10 μm were obtained by holographic exposure of the cell substrates coated with light-sensitive azo polymer alignment layers, and then filled with three different liquid crystal mixtures. The influence of gold nanoparticle dopants in the liquid crystalline mixtures on spectroscopic and electro-optical properties of the devices is presented. Moreover, on the basis of the measured transmittance spectra of the fabricated gratings, the unknown birefringence of liquid crystal mixtures as well as their effective birefringence due to molecular reorientation in the electric field in the visible and near IR region were determined

Effect of 2-Methylthiazole Group on Photoinduced Birefringence of Thiazole-Azo Dye Host–Guest Systems at Different Wavelengths of Irradiation

The photoinduced birefringence behaviors of host–guest systems based on heterocyclic thiazole–azo dyes with different substituents, dispersed into PMMA matrix, were investigated under three excitation wavelengths, i.e., 405 nm, 445 nm or 532 nm. The wavelengths fell on the blue side, near the maximum or on the red side of the absorption bands of trans-azo dyes, respectively. We found that photoinduced birefringence was generated at a similar extent in all studied systems, except the system containing a 2-methyl-5-benzothiazolyl as thiazole–azo dye substituent. For this material, the achieved birefringence value was the highest among the whole series, regardless of the excitation wavelength. Moreover, we identified the optimal irradiation wavelength for efficient birefringence generation and showed that large absorption of excitation light by trans isomer does not account for achieving a significant degree of molecular alignment. The obtained results indicate that thiazole–azo dye with a 2-methyl-5-benzothiazolyl substituent shows promising photoinduced birefringence, and can be considered a dye potentially suitable for optical applications

Physico-Chemical and Light-Induced Properties of Quinoline Azo-dyes Polymers

We present investigation of optical and photochromic properties as well as of surface quality of thin films of novel methacrylic polymers with 8-hydroxyquinoline azo-dyes in side-chain. Additionally, thermal stability of polymer powders was examined and their glass transition temperature was determined. Optical properties (extinction coefficient and refractive index) were determined by spectroscopic ellipsometry (SE) combined with absorbance measurements. Photoresponsive behavior was investigated by determination of photoisomerization rates under irradiation with unpolarized 365 nm light, as well as by conduction of holographic grating inscription experiment. Thin film quality was determined by atomic force microscopy (AFM) measurements. Thermal analysis was performed by thermogravimetric (TG), derivative thermogravimetric (DTG) and differential scanning calorimetry (DSC) measurements. We found that optical properties as well as photoisomerization rates of investigated polymers are dependent on the substituent in the para position of the phenyl ring. Surface relief grating inscription was successfully generated only for materials with chromophores containing dimethylamino (N(CH3)2) and methyl (CH3) substituents, but all materials exhibited birefringence grating in the bulk. Surface of most thin films was very smooth, but its quality was impaired by neutral (H) as well as carboxyl (COOH) substituent. Thermal stability of copolymers with side-chain chromophores was improved compared to pure poly(methyl methacrylate) (PMMA)