Single-layered light-emitting diodes possessing methoxy-modified pyrazoloquinoline dyes in poly-N-vinylcarbazole matrix

A principal opportunity to operate by current-voltage and electroluminescent-current dependences for the single-layered light-emitting diodes (LED) on the basis of the polyvinylcarbazole (PVK) polymers doped by methoxy-substituted pyrazoloquinoline (PQ) emitting dye chromphore is demonstrated. The principal light-emitting parameters in the architecture ITO/PQ: PVK/Ca (Al) were investigated. The maximally achieved quantum efficiency of the investigated LED was equal to about 0.87% and corresponded to the brightness about the 44 Cd/m². The absence of blue shift for the electroluminescence (EL) compared to PL may indicate on an absence of near-the-surface exciton diffusion for the methoxy-PQ contrary to the phenyl-methyl-substituted PQ. The quantum chemical calculations have shown principal role of the dye chromophore state dipole moments in the observed carrier kinetics determining the EL.     

Photoinduced non-linear optical diagnostic of SiNxOy/Si111 interfaces

Anisotropic (elliptically polarized) photoinduced second harmonic generation (PISHG) in SiN_xO_y/Si1 1 1 films was proposed for contact-less monitoring of specimens with different nitrogen to oxygen (N/O) ratios. As a source for the photoinducing light, we used a nitrogen Q-switched pulse laser at wavelengths of 315, 337 and 354 nm as well as doubled frequency YAG–Nd laser wavelength (λ=530 nm). The YAG : Nd pulse laser (λ=1.06 μm; W=30 MW; τ=10–50 ps) was used to measure the PISHG. All measurements were done in a reflected light regime. We found that the output PISHG signal was sensitive to the N/O ratio and the film thickness. Measurements of the PISHG versus pumping wavelengths, powers, incident angles as well as independent measurements of the DC-electric field induced second harmonic generation indicate the major role played in this process by axially symmetric photoexcited electron–phonon states. The SiN_xO_y films were synthesized using a technique of chemical evaporation at low pressures. Films with thickness varying between 10 and 30 nm and with an N/O ratio between 0 and 1 were obtained. Electrostatic potential distribution at the Si1 1 1–SiN_xO_y interfaces was calculated. Comparison of the experimentally obtained and quantum chemically calculated PISHG data are presented. High sensitivity of anisotropic PISHG to the N/O ratio and film thickness is revealed. The role of the electron–phonon interactions in the dependencies observed is discussed. We have shown that the PISHG method has higher sensitivity than the traditional extended X-ray absorption fine structure spectroscopic and linear optical method for films with the N/O ratio higher than 0.50.     

Molecular dynamics modeling in quantum chemical calculations. Optical absorption spectra of 1,3-Dimethyl-1H-Pyrazolo[3,4-b]quinoline derivatives

Paper presents the quantum chemical modeling of the optical absorption spectra of 6-fluoro, 6-bromo, 7-trifluoromethyl, 6-cyano and 6-carboethoxy derivatives of 1,3-Dimethyl-1H-Pyrazolo[3,4-b]quinoline. The calculations are performed by means of the semiempirical quantum chemical methods (AM1 or PM3) in combination with molecular dynamics (MD) simulations at T=300 K. It is shown that a particular rotational dynamics of the methyl, trifluoromethyl or ethyl groups practically does not influence the optical absorption in the spectral range 200-500 nm whereas broadening of absorption bands may be well reproduced within MD simulations including all types of nuclei vibrations. The results of calculations are compared with the measured spectra of optical absorption. The quantum chemical method AM1 in combination with MD simulations gives for all dyes the best agreement between the calculated and measured spectral positions of the first absorption band (absorption threshold).     

Nano-sized blue spectral shift in sol–gel derived mesoporous titania films

Following the spectral energy shift of the energy gap (blue shift) of the TiO₂ sol–gel derived films we have evaluated diameters of the nanocrystallites. The TiO₂ films were deposited by dip-coating technique. Two types of mesoporous films were studied: films with porosity ~16% and refractive index (2.15 at wavelength 633 nm) and films with porosity ~46% and refractive index (1.61 at wavelength 633 nm). High porosity and consequently low refractive index was achieved by adding the non-ionic surfactant Triton X-100 to the starting solution as template. The principal goal of the work is to establish the influence of the Triton X-100 on the morphology as well as to establish a possible correlation between the morphology and optical features of the titania films. The surface morphology was explored using AFM method. And the energy gap was determined from the transmission spectra. Analysis of the blue energy spectral shift is performed following the excitonic model.     

Third-order nonlinear optical figure of merits for conjugated TTF-quinone molecules

We have revealed a substantial enhancement of third-order optical figure of merits by the synthesis of a compact molecule possessing the tetrathiafulvalene (TTF) group with two backside C=O groups. Addition of the saturated methylene chain substantially suppresses the third-order optical figure of merits and even local optical hyperpolarizabilities at lambda = 532 nm. Another TTF-derivative molecule possessing ethylenic and acetylenic chains demonstrates large hyperpolarizabilities; however, generally, the figure of merit factor decreases due to the increasing optical losses as a consequence of enhanced linear absorption. At the same time, both of the chromophores have a large nonlinear optical response. General approaches for search and design of the third-order optical materials with improved properties are given.     

Manifestation of grain boundaries in the transport properties of p-sexiphenyl films

Direct current conductivity of p-sexiphenyl films with 0.2-2.5 microm thickness deposited on glass substrates was investigated at temperatures between 10 and 300 K. The molecular dynamics simulations and quantum chemical calculations of the experimentally observed conductivity have shown that there exist at least three different states of the films effectively contributing to the observed features of the dc conductivity: conductivity caused by proper crystalline states, conductivity originated from amorphous-like inter-grain region and caused by grain's boundary. Comparison of the experimental data and theoretically calculated dependences shows that the main contribution to the observed dc conductivity gives grain boundaries between polycrystalline grains and amorphous-like background, though the latter possesses a relatively low part of the total volume.     

Circularly polarized light-induced electrogyration in the Au nanoparticles on the ITO

We have found that the gold nanoparticles on the ITO substrates might be considered promising materials for circularly polarized light-induced linear electrogyration (EG). The maximal achieved value of the EG susceptibility described by third-order axial tensor caused by probe circularly polarized light at a wavelength of 1060 nm was equal to about 13 deg/mm at pulsed electric field strength 30.0 V/cm with a duration of about 1 ms. We have revealed that the maximal EG coefficient is achieved for the samples possessing maximal resistivity. The investigated composites possess long-lived EG grating which decreases by not more than 12% after 120 min of laser treatment. Applying a non-circular pump light leads to the diminishing of the observed EG.     

Aging and memory effects in a clathrate

The out-of-equilibrium low-frequency complex susceptibility of the orientational glass methanol(73%)-beta-hydroquinone-clathrate is studied using temperature-stop protocols in aging experiments. Although the material does not have a sharp glass transition aging effects including rejuvenation and memory similar to the effects in spin glasses are found at low temperatures.     

Enhancement of second-order optical susceptibilities of Er doped germanate glasses

During bicolor optical treatment by two coherent laser beams from 25 ps Erbium-glass laser (λ = 1.54 μm), we have established substantial increase of effective optical second-order susceptibility near the critical temperature points corresponding to the glass structural transformation near 435 °C. The increasing Er³⁺ content favors substantial increase of the photoinduced optical second harmonic generation (SHG). This temperature dependence of the second-order optical susceptibilities detected by the SHG correlates well with the differential scanning calorimetric (DSC) measurements. At the same time, the effect exists only in a narrow temperature range (up to 12 °C) . There was not temperature hysteresis. Possible physical mechanisms of the phenomenon observed are discussed.