ABSTRACT
Measurement of thermal properties of thin films is challenging. In particular, thermal characterization is very difficult in semi-transparent samples. Here, we use two photothermal methods to obtain information about the thermal diffusivity as well as thermal conductivity of azoheteroarene functionalized polymer thin layers. The photothermal beam deflection (PBD) method is employed to gather data directly on thermal conductivity and thermal diffusivity, while the thermal lens (TL) method is employed to measure the effective thermal diffusivity. Consequently, the thermal diffusivity of the layers is indirectly estimated from the effective thermal diffusivity using a well-established theoretical relationship. Despite the utilization of distinct methods, our study reveals a remarkable consistency in the highly accurate results obtained from both approaches. This remarkable agreement reaffirms the reliability and mutual compatibility of the employed methods, highlighting their shared ability to provide accurate and congruent outcomes.
ABSTRACT
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.
Subject(s)
Azo Compounds , Thiazoles , Birefringence , Polymethyl MethacrylateABSTRACT
New materials based on methacrylic polymers modified with 1-(4-nitrophenyl)piperazine side chains, differing in the distance of the chromophore from the polymer main chain and/or the separation between the chromophoric units in the chain, are obtained and characterized in terms of their potential applications in optoelectronic devices. The surface, structural, and optical properties of the investigated materials are determined using atomic force microscopy, spectroscopic ellipsometry combined with transmission measurements, Raman and Fourier transform infrared spectroscopy, as well as cyclic voltammetry. The relevant model systems are additionally analyzed with quantum chemical density functional theory calculations in order to enable the generalization of the structure-photophysical property relationships for the optimization of the material features. It is found that the structural modification of the material, relying on the transit of the piperazine moiety away from the main polymer chain, leads to the hypsochromic shift of the absorption spectrum. Moreover, the lowest refractive index values are obtained for the polymer with a distant ethylene group in the side-chains and increased separation between the piperazine units. It was shown that the optical energy band gaps of the investigated piperazine-containing polymers are in the range from 2.73 to 2.81 eV, which reveals their promising potential for the advances in photovoltaics, field effect transistors, or electrochromic devices as an alternative for other widely applied polymer materials.
ABSTRACT
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).
