Enhancement of resonant bleaching of <Emphasis Type="Italic">J</Emphasis>-aggregates upon lengthening of an exciting radiation

Thin films of J-aggregates of a new amphiphilic thiacarbocyanine dye of the benthiazole series are prepared and the nonlinear optical response of molecular J-aggregates is studied for femto-and nanosecond exciting radiation pulses. It is found that the nonlinear optical response of J-aggregates exhibits substantial enhancement upon an increase in the pulse duration, which cannot be described by the saturation effect in the model of a two-level system. This effect is considered using a three-level model taking into account the formation of self-trapped exciton states in molecular J-aggregates.     

Effect of hydrophobicity of cationic carbocyanine dyes DiOC<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> on their binding to anionic surfactant micelles

The interaction of a series of cationic dialkyloxacarbocyanine perchlorate (DiOC _n ) dyes of different degrees of hydrophobicity with micelles of an anionic surfactant, sodium dodecylsulfate (SDS), has been studied spectrophotometrically in aqueous solutions. The Benesi–Hildebrand equation was used to calculate binding constants (K _b ) of the dyes to surfactant micelles, the fraction of dye bound to the micelles (f _mic ), and the standard free-energy change (ΔG ⁰) for the transfer of dye from the aqueous to micellar phase. It has been shown that the interaction of oppositely charged dye molecules and surfactant micelles is controlled by both electrostatic and hydrophobic interactions. A small increase in dye hydrophobicity due to lengthening of the hydrocarbon radical has been shown to cause an abrupt nonlinear increase of the fmic value. This points to a key role of hydrophobic interactions in the binding of dye molecules with the micelles.     

On the Formation of Nanostructures from Stilbazolium-like Dyes

Nanostructures with well-defined shape and highly monodisperse size were fabricated from model stilbazolium-like dyes with specific molecular structural and conformational characteristics. With the help of absorption and fluorescence optical spectroscopy, the correlated spectroscopy (COSY) and two- dimensional nuclear Overhauser effect spectroscopy (2D NOESY) techniques, along with X-ray diffraction (XRD) measurement, distinctively different aggregation processes of the model molecules are demonstrated. For model dye molecule with linear donor–π system–acceptor (D–π–A) structure, strong D–A pair, and planar conformation, specific intermolecular interaction was identified and special crystal structures as well as spectral properties were observed. For model dye molecules bearing nonlinear D–π–A–π–D structure, weak D–A pair but actual amphiphilic characteristics, a special aggregation process was confirmed and a focused size distribution of the produced nanostructures was obtained.     

Impact of molecular tilt angle on the absorption spectra of pentacene:perfluoropentacene blends

We investigate the relation between the optical properties and the average molecular tilt angle for blends of pentacene and perfluoropentacene, which can be considered as a prototypical donor–acceptor complex. Combining near‐edge X‐ray absorption fine‐structure spectroscopy and optical spectroscopy we study thin films of these compounds prepared at three different substrate temperatures T_sub. For T_sub =180 K we observe a larger average tilt angle than for blends prepared at higher substrate temperatures. This orientational change has significant impact on the uniaxial anisotropic optical properties of the mixed films which we measure post growth as well as in real‐time during growth. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Anti-stokes luminescence of Zn<Subscript>0.6</Subscript>Cd<Subscript>0.4</Subscript>S solid solutions with adsorbed organic dye molecules and few-atom silver clusters

For microcrystals of Zn_0.6Cd_0.4S with adsorbed molecules of a number of organic dyes, we have observed sensitized anti-Stokes luminescence excited by radiation with wavelengths in the range 610–750 nm and flux density 10¹⁴–10¹⁵ photons/cm²·sec. The positions of the bands in the excitation spectra for such luminescence match those of the absorption spectra for the adsorbed dye molecules, which is evidence in favor of a cooperative mechanism for its appearance. We have shown that enhancement of the anti-Stokes luminescence is possible when silver atoms and few-atom clusters appear on the Zn_0.6Cd_0.4S surface in addition to the dye molecules. We hypothesize that its excitation in the latter case occurs as a result of two-photon optical transitions. These transitions occur sequentially, with transfer of an electron or the electronic excitation energy from the dye molecules to silver atoms and few-atom clusters adsorbed on the surface of Zn_0.6Cd_0.4S, creating deep localized states in the bandgap with photoionization energies 1.80–2.00 eV. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 617–621, September–October, 2007.     

Effect of the plasmon-exciton interaction on optical properties of core-shell nanoparticles

The plasmon-exciton interaction in composite nanoparticles consisting of a metal (Au) core coated with two layers of organic materials, i.e., a monomolecular dielectric interlayer and a layer of cyanine dye J-aggregate was studied. In contrast to previously studied systems, metal in nanoobjects under consideration is at a distance of 1.2 nm from the J-aggregate, which allows maintaining the interaction of metal plasmons and J-aggregate excitons and weakening luminescence quenching at the same time. The particle morphology was studied by transmission electron and atomic-force microscopy. Bands caused by the dye J-aggregate formation on the surface were detected in the absorption spectrum of such particles. Fast dynamics (several picoseconds) of optical density variation was detected by the pump-probe method. The photoluminescence spectrum contains a narrowband characteristic of J-aggregates, which is excited due to a locally strengthened field of metal core plasmons.     

Critical current of an inhomogeneous Josephson junction at an intergrain boundary with a random distribution of dislocations

The critical current J _c(θ) of an intergrain boundary is calculated as a function of the contact misorientation angle θ of the granules. It is assumed that the ordering parameter is suppressed in regions near boundaries with an enhanced mechanical stress induced by randomly distributed surface dislocations. The stress distribution function is determined using a probabilistic approach. Assuming that the weak coupling at the boundary is Josephson coupling, an analytic expression is found for the angular dependence J _c(θ) (for tilt and twist boundaries). The magnitude of the residual critical current of a boundary in a strong magnetic field is estimated. Fiz. Tverd. Tela (St. Petersburg) 40, 393–402 (March 1998)     

Multi-purpose nonlinear optical microscope. Its principle and applications to polar thin-film observation

Multi-purpose nonlinear optical microscope is an optical microscope which images 2D distribution of the optical second harmonic (SH) waves from a specimen. Image contrast can be obtained either by inhomogeneous distribution of nonlinear optical tensor components or by the interference between SH waves from a specimen and a standard plate. This microscope also functions as a fluorescence (FL) microscope, and SH and FL images can be obtained from the same part of a specimen. Absorption and FL spectra from a specific part of a specimen are measured through an optical fiber which connects an ocular with a polychromator. These functions are especially useful for investigation of the J-aggregate state of polar dye molecules. Several photographs taken by the microscope revealed the structure of merocyanine dye/arachidic acid mixed monolayer and the role of bridge ions in the subphase. Fiz. Tverd. Tela (St. Petersburg) 41, 764–769 (May 1999) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

Microwave spectrum ofcis 3-fluorophenol

The microwave spectrum ofcis 3-fluorophenol involving rotational states up toJ=28 has been observed and analysed in the frequency range 23–25 GHz in the ground vibrational state at room temperature. Analysis yields three rotational and five quartic centrifugal distortion constants. A tentativer ₀ structure has been proposed satisfying the observed rotational constants. The small value of the inertia defect Δ=0·07 confirms the planarity of the conformer.     

Thermally stimulated recombination processes and luminescence in Li<Subscript>6</Subscript>(Y,Gd,Eu)(BO<Subscript>3</Subscript>)<Subscript>3</Subscript> crystals

The thermally stimulated recombination processes and luminescence in crystals of the lithium borate family Li₆(Y,Gd,Eu)(BO₃)₃ have been investigated. The steady-state luminescence spectra under X-ray excitation (X-ray luminescence spectra), the temperature dependences of the X-ray luminescence intensity, and the glow curves for the Li₆Gd(BO₃)₃, Li₆Eu(BO₃)₃, Li₆Y_0.5Gd_0.5(BO₃)₃: Eu, and Li₆Gd(BO₃)₃: Eu compounds have been measured in the temperature range 90–500 K. In the X-ray luminescence spectra, the band at 312 nm corresponding to the ⁶ P _J → ⁸ S _7/2 transitions in the Gd³⁺ ion and the group of lines at 580–700 nm due to the ⁵ D ₀ → ⁷ F _J transitions (J = 0–4) in the Eu³⁺ ion are dominant. For undoped crystals, the X-ray luminescence intensity of these bands increases by a factor of 15 with a change in the temperature from 100 to 400 K. The possible mechanisms providing the observed temperature dependence of the intensity and their relation to the specific features of energy transfer of electronic excitations in these crystals have been discussed. It has been revealed that the glow curves for all the crystals under investigation exhibit the main complex peak with the maximum at a temperature of 110–160 K and a number of weaker peaks with the composition and structure dependent on the crystal type. The nature of shallow trapping centers responsible for the thermally stimulated luminescence in the range below room temperature and their relation to defects in the lithium cation sublattice have been analyzed.     

Nonlocal excitonic–mechanical interaction in a nanosystem

The dynamics of a nanoparticle during its dipole interaction with an excitonic excitation in an extended quasi-one-dimensional polarizable medium is investigated. Bundles of J-aggregates of dye molecules are considered as an example of the latter. The nonlocal excitonic–mechanical interaction between the field of an amplifying or absorbing nanoparticle and excitons in a bundle has been simulated numerically. It has been found that the interaction between the field of the induced nanoparticle dipole and the fields of the molecular dipoles in an aggregate can lead to a change in the particle trajectory and excitonic pulse shape. The possibility of controlling the nanoparticle by excitonic pulses and the reverse effect of the nanoparticle field on the dynamics of excitons due to the nonlocal excitonic–mechanical interaction has been demonstrated.     

Effects of preannealing temperature of ZnO thin films on the performance of dye-sensitized solar cells

The preferred (002) orientation zinc oxide (ZnO) nanocrystalline thin films have been deposited on FTO-coated glass substrates by sol–gel spin-coating technology and rapid thermal annealing for use in dye-sensitized solar cells (DSSC). The effects of preannealing temperature (100 and 300°C) on the microstructure, morphology and optical properties of ZnO thin films were studied. The ZnO thin films were characterized by X-ray diffraction (XRD), scanning electron microscopic (SEM) and Brunauer–Emmett–Teller (BET) analysis. The photoelectric performance of DSSC was studied by I–V curve and the incident photon-to-current conversion efficiency (IPCE), respectively. From the results, the intensities of (002) peaks of ZnO thin films increases with increasing preannealing temperature from 100°C to 300°C. The increase in pore size and surface area of ZnO films crystallized at the increased preannealing temperature contributed to the improvement on the absorption of N3 dye onto the films, the short-circuit photocurrent (J _sc) and open-circuit voltage (V _oc) of DSSC. The higher efficiency (η) of 2.5% with J _sc and V _oc of 8.2 mA/cm² and 0.64 V, respectively, was obtained by the ZnO film preannealed at 300°C.     

Optical characteristics of nickel and boron carbonitride films in Si(100)/Ni/BC<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>N<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> structures

The optical characteristics of nickel films deposited on Si(100) substrates by vacuum thermal evaporation have been studied. The thickness and optical constants of the films are determined using monochromatic zero ellipsometry, while the inverse problems are solved within the three-layer optical model of the samples. It is shown that thermal annealing leads to a change in the optical constants of nickel films in the heating-temperature range of 500–900°C. Boron carbonitride layers deposited on silicon substrates with a nickel sublayer are analyzed within multilayer optical models, which make it possible to determine the refractive index and absorption coefficient distributions along the thickness of the synthesized Si(100)/Ni/BC _x N _y structure.     

Interaction of dyes with Ag<Subscript>2</Subscript>S nanoclusters adsorbed on AgBr microcrystals

The photoexcitation relaxation is considered in a system consisting of a molecular and J-aggregated dye adsorbed on the surface of silver sulfide nanosized clusters (nanoclusters) placed on AgBr microc-rystals. It is found that the photoexcitation in the region of the dye absorption relaxes not only via the fluorescence, but also via the phosphorescence of nanoclusters. It is shown that, depending on the dye, the phosphorescence of nanoclusters is most efficiently excited in the absorption region of either molecular or J-aggregated states of dyes. It is assumed that this difference is caused by different nature of the adsorption of dyes on the nanocluster surface and by different interactions between the photoexcited states of dye molecules and J aggregates. These results can find wide applications in various fields of nanophotonics and allow one to both control the photoexcitation relaxation processes in nanocluster-dye systems and to observe new manifestations of these processes.     

Nonenzymatic Direct Assay of Hydrogen Peroxide at Neutral pH Using the Eu<Subscript>3</Subscript>Tc Fluorescent Probe

A detailed study is presented on the use of an easily accessible probe (the europium–tetracycline 3:1 complex; referred to as Eu₃Tc) for determination of hydrogen peroxide (HP). Eu₃Tc undergoes a 15-fold increase in luminescence intensity on exposure to an excess of HP. Data are given on the time dependence of the reaction, on the pH dependence of the absorption and emission spectra of both the probe and its complex with HP, and on the effect of stoichiometry between Eu³⁺ and Tc on selectivity and signal change. HP can be quantified in aqueous solution of pH 6.9 over a 2–400 μM concentration range with a limit of detection of 960 nM. The assay is validated using standard additions, and mean recoveries are found to be between 97.0 and 101.8%. Species that interfere in concentrations below 1 mM include phosphate, copper(II), fluoride and citrate. The addition of detergents causes the response curves towards HP to shift to higher HP concentrations. The method is critically assessed with respect to other common optical methods for determination of HP.     

Stress-Induced Alteration of Chlorophyll Fluorescence Polarization and Spectrum in Leaves of <Emphasis Type="Italic">Alocasia macrorrhiza</Emphasis> L. Schott

The value of intrinsic chlorophyll fluorescence polarization, and the intensity in emission spectrum were investigated in leaf segments of Alocasia macrorrhiza under several stress conditions including different temperatures (25–50°C), various concentrations of NaCl (0–250 mM), methyl viologen (MV, 0–25 μM), SDS (0–1.0%) and NaHSO₃ (0–80 μM). Fluorescence emission spectrum of leaves at wavelength regions of 500–800 nm was monitored by excitation at 436 nm. The value of fluorescence polarization (P value), as result of energy transfer and mutual orientation between chlorophyll molecules, was determined by excitation at 436 nm and emission at 685 nm. The results showed that elevated temperature and concentrations of salt (NaCl), photooxidant (MV), surfactant (SDS) and simulated SO₂ (NaHSO₃) treatments all induced a reduction of fluorescence polarization to various degrees. However, alteration of the fluorescence spectrum and emission intensity of F₆₈₅ and F₇₃₁ depended on the individual treatment. Increase in temperature and concentration of NaHSO₃ enhanced fluorescence intensity mainly at F₆₈₅, while an increase in MV concentration led to a decrease at both F₆₈₅ and F₇₃₁. On the contrary, NaCl and SDS did not cause remarkable change in fluorescence spectrum. Among different treatments, the negative correlation between polarization and fluorescence intensity was found with NaHSO₃ treatments only. We concluded that P value being measured with intrinsic chlorophyll fluorescence as probe in leaves is a susceptible indicator responding to changes in environmental conditions. The alteration of P value and fluorescence intensity might not always be shown a functional relation pattern. The possible reasons of differed response to various treatments were discussed.     

Magnetoresistivity and acoustoelectronic effects in a tilted magnetic field in <Emphasis Type="Italic">p</Emphasis>-Si/SiGe/Si structures with an anisotropic <Emphasis Type="Italic">g</Emphasis> factor

Magnetoresistivity ρ _xx and ρ _xy and the acoustoelectronic effects are measured in p-Si/SiGe/Si with an impurity concentration p = 1.99 × 10¹¹ cm⁻² in the temperature range 0.3–2.0 K and an tilted magnetic field up to 18 T. The dependence of the effective g factor on the angle of magnetic field tilt θ to the normal to the plane of a two-dimensional p-Si/SiGe/Si channel is determined. A first-order ferromagnet-paramagnet phase transition is observed in the magnetic fields corresponding to a filling factor ν = 2 at θ ≈ 59°–60°.     

Sensitized anti-Stokes luminescence centers in microcrystals of Zn<Subscript>0.6</Subscript>Cd<Subscript>0.4</Subscript>S solid solutions with adsorbed dye molecules and few-atomic silver clusters

The sensitized anti-Stokes luminescence excited by radiation with wavelengths from 610 to 750 nm and flux densities of 10¹⁴–10¹⁵ quanta/(cm²·s) is detected for microcrystals of Zn _0.6 Cd _0.4 S solid solutions with adsorbed organic malachite green and methylene blue dye molecules. The position of its excitation spectra coincides with that of the absorption spectra of adsorbed dye molecules, which suggests the cooperative mechanism of its occurrence. The possibility of amplification of the anti-Stokes luminescence by means of adsorption of silver atoms and few-atomic silver clusters, in addition to the dye molecules, on the Zn _0.6 Cd _0.4 S surface is investigated. It is assumed that in the latter case, the anti-Stokes luminescence is excited as a result of two-quantum optical transitions with electron or electron excitation energy transfer from the dye molecules adsorbed on the Zn _0.6 Cd _0.4 S surface to silver atoms and few-atomic silver clusters creating deep local states with photoionization energies of 1.8–2.0 eV in the gap. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 21–26, March, 2008.     

Effects of Plasmon–Exciton Interaction in the Spectra of Light Absorption by Hybrid Systems Consisting of Two- and Three-Layer Organometallic Nanoparticles

The effects of plasmon-exciton interaction on the spectra of light absorption by hybrid systems of two- and three-layer nanoparticles that consist of a metallic nucleus, the outer shells of ordered molecular dye J-aggregates, and an intermediate passive organic spacer between them is analyzed theoretically. It is established that the type of the absorption spectra and the efficiency of a near-field electromagnetic coupling between the particles in the system depends largely on the distance between the centers of concentric spheres and the direction of light polarization.