J-aggregates of pseudoisocyanine with long alkyl substituents in thin films: Synthesis, spectral properties, and thermal stability

The formation and properties of J-aggregates in thin solid films of pseudoisocyanines with long N-alkyl groups, obtained by centrifuging from solutions in organic solvents, were studied. It is shown for the first time that nonsymmetric cyanine dyes, containing a C₂H₅ group at one nitrogen atom and a C₁₀H₂₁, C₁₅H₃₁, or C₁₈H₃₇ group at another nitrogen atom, spontaneously form J-aggregates stable at room temperature and pressing a narrow absorption band with a half-width at half maximum of 200 cm^?1. The thermal stability of J-aggregates in thin films of pseudoisocyanines with alkyl substituents decreases in the following order: C₂H₅-C₂H₅> C₂H₅-C₆H₁₃>C₂H₅-C₁₈H₃₇>C₂H₅-C₁₀H₂₁>C₂H₅-C₁₅H₃₁. By introducing 1-octadecyl-2-methylquinolinium iodide in the film, it was found that the J-aggregates studied consist of a small number (2–4) of dye molecules.     

Design, formation and characterization of a novel multifunctional window with VO2 and TiO2 coatings

A novel multifunctional window was demonstrated using VO₂-based thermochromic films with a TiO₂ antireflection coating. A strong enhancement in luminous transmittance of VO₂ was calculated using either a single layer or a double layer of TiO₂ for antireflection, with the double layer giving the better performance. A TiO₂ (25 nm)/VO₂ (50 nm)/TiO₂ (25 nm) structure, of which the film thickness has been optimized to a maximum integrated luminous transmittance (T_lum) by calculation, was formed on SiO₂ glass by sputtering in turn a V target in Ar+O₂ for VO₂ and a TiO₂ target in Ar for TiO₂. Optical properties were measured with a spectrophotometer, and the integrated solar and luminous properties were calculated based on the measured spectra. A maximum increase in T_lum by 86% (from 30.9% to 57.6%) was obtained for VO₂ after double-layer TiO₂ antireflection coating. The deposited VO₂ film on SiO₂ exhibits good thermochromism with a sharp optical transition at 58.5 °C, which decreased slightly to 57.5 °C after TiO₂ coating. The proposed window is the most advanced among those similarly reported in being multifunctional with automatic solar/heat control, ultraviolet stopping and possibly a wide range of photocatalytic functions in addition to a high value of the luminous transmittance. PACS 42.79.Wc; 78.20.-e; 71.30.+h     

Theoretical study of structures of Ga5N5 cluster

The structures and energies of a Ga₅N₅ cluster have been calculated using a full-potential linear-muffin-tin-orbital (FP-LMTO) method, combined with molecular dynamics technique. Twenty-four structures for a Ga₅N₅ cluster have been obtained. The most stable structure is a C₁ planar structure with a N₃ subunit. The Ga₅N₅ clusters show a preference for a N₃ subunit, revealing the same behavior as in the Ga₃N₃ and Ga₄N₄ clusters. The existence of strong N–N bonds dominates the structure of a Ga₅N₅ cluster. Through the calculation of the density of states we found that the most stable structure of Ga₅N₅ clusters presented semiconductor-like properties.     

Permittivity of BaTiO3 epitaxial films grown on the YBa2Cu3O7−δ(001) surface

The epitaxial heterostructures YBa₂Cu₃O_7?δ and YBa₂Cu₃O_7?δ/(5 nm)SrTiO₃/BaTiO₃/(5 nm)SrTiO₃/YBa₂Cu₃O_7?δ are grown by the laser evaporation method on an LaAlO₃(100) substrate. The permittivity of a BaTiO₃ layer is approximately doubled (T=300 K) when a SrTiO₃ thin layer is inserted between a ferroelectric layer and superconducting cuprate electrodes. A maximum in the temperature dependence of the permittivity for a barium titanate layer in the YBa₂Cu₃O_7?δ/(5 nm)SrTiO₃/BaTiO₃/(5 nm)SrTiO₃/YBa₂Cu₃O_7?δ heterostructure is shifted by 70–80 K toward the low-temperature range with respect to its location in the corresponding dependence for the BaTiO₃ bulk single crystal. The bias voltage dependence of the permittivity for the BaTiO₃ grown layers exhibits a clearly pronounced hysteresis (T=300 K). The superconducting transition temperature for the lower YBa₂Cu₃O_7?δ electrode in a superconductor/ferroelectric/superconductor heterostructure considerably depends on the rate of its cooling after the completion of the formation process.     

Infrared synthesis of SO3 by homogeneous gas-phase CO2 laser-driven reactions

By using a CO₂ laser operated at 10.6μm, a bimolecular reaction was induced in a binary SO₂/O₂ gas mixture, with a sensitizer gas (SF₆) as photo-absorbing species.The infrared (IR) synthesis of SO₃ was performed in a flowing gas device equipped with a continuous trapping system of the reaction product. Vibrational energy transfer processes presumably should play a specific role in SO₂ excitation and reaction in the presence of SF₆.     

Frustration driven magnetic states of A-site spinels probed by <Emphasis Type="Italic">μ</Emphasis>SR

The normal A-site spinels MnAl₂O₄, FeAl₂O₄, CoAl₂O₄, as well as related mixed (Mn_0.5Fe_0.5Al₂O₄) and partially inverted (Fe_1.4Al_1.6O₄) spinels have been studied by μSR. The magnetic ions are subject to magnetic frustration by competing interactions. In all materials and at all temperatures the μSR spectra consist of two signals suggesting a bimodal distribution of the fluctuation rates of magnetic moments. A characteristic temperature T _M is found in each compound, representing either a magnetic phase transition into a long-range ordered state (MnAl₂O₄, Fe_1.4Al_1.6O₄) or the formation of a spin liquid phase (FeAl₂O₄, CoAl₂O₄, Mn_0.5Fe_0.5Al₂O₄). The magnetic ground state of MnAl₂O₄ shows coexistence of antiferromagnetic and spin liquid phases. In FeAl₂O₄ and CoAl₂O₄ long-range order is suppressed altogether, the ground state can be characterized as a fast relaxing spin liquid coexisting with a small fraction of paramagnetic spins. The partial replacement of Mn by Fe in Mn_0.5Fe_0.5Al₂O₄ prevents long-range order and leads to a spin liquid state in the low temperature limit. The partial occupancy of B-sites by magnetic ions in Fe_1.4Al_1.6O₄ strengthens the exchange coupling, allowing the formation of long-range magnetic order at a rather high temperature (~100 K). Magnetic phase diagrams are presented demonstrating that for the studied compounds the magnetic properties are determined by the degree of frustration.     

Hydrostatic pressure effect on the metal-insulator transition in LaO0.7Ca0.3Mn1−x(Fe/Ge)xO3 perovskites

Abstract

The temperature dependences of the resistivity of La_0.7Ca_0.3Mn_1?xFe_xO₃ and La_0.7Ca_0.3Mn_1?xFe_xO₃ (0 < × < 0.04) mixed crystals were studied under hydrostatic pressures up to 15kbar. The substitution of Fe for Mn results in an increase of the resistivity and a continuous decrease of the metal-insulator transition temperature T_mi while the substitution of Ge for Mn leads to a more complicated T_mi(x)-curve. In all cases T_mi shifts under pressure with a rate between 1.6 and 2.9K/kbar and a correlation between T_mi and its pressure derivative dT_mi/dP is observed which is in accordance with the general trend of dT_mi/dP versus T_mi as derived for other manganites and is discussed in terns of a competition between superexchange and double exchange.     

Structural studies of phase transitions in crystalline and liquid halides (ZnCl<Subscript>2</Subscript>, AlCl<Subscript>3</Subscript>) under pressure

The results of investigating the phase diagrams of ZnCl₂ and AlCl₃ halides, as well as the structure of the shortrange order of the corresponding melts under pressures up to 6.5 GPa, by the method of energy-dispersive x-ray diffraction are reported. When a ZnCl₂ crystal is compressed, a phase transition occurs from the γ phase (HgI₂ structure type) to the δ phase (distorted CdI₂ structure, WTe₂ type). The structural studies of the liquid state of ZnCl₂ and AlCl₃ indicate that the intermediate-range order decreases rapidly in the tetrahedral network of both melts as the pressure increases to 1.8 and 2.3 GPa for ZnCl₂ and AlCl₃, respectively. With further compression, the transitions in both melts occur with a change in the structure of the short-range order and with an increase in the coordination number. In this case, the transition in AlCl₃ occurs at ≈4 GPa and is a sharp first order transition, whereas the transition in ZnCl₂ occurs more smoothly in a pressure range of 2–4 GPa with a maximum intensity near 3 GPa. Thus, the AlCl₃ and ZnCl₂ compounds exemplify the existence of two phenomena—gradual decay of intermediate-range structural correlations and a sharper liquid-liquid coordination transition.     

Quantitative analysis of mixed self-assembled monolayers using ToF-SIMS

The spacing of chemical functional groups on self-assembled monolayers (SAMs) plays an important role in controlling the density of biomolecules in biochips and biosensors. In this sense, a mixed SAM made of two different terminal groups is a useful organic surface since spacing can be easily controlled by changing a relative mole fraction in a mixture solution. In this study, an acetylene-OCH₂O(EG)₃(CH₂)₁₁S-S(CH₂)₁₁(EG)₃OCH₂O-propene (Eneyne) SAM and mixed SAMs made by a mixture of (S(CH₂)₁₁(EG)₃OCH₂O-acetylene)₂ (Diyne) and (S(CH₂)₁₁(EG)₃OCH₂O-propene)₂ (Diene) were produced on gold substrates and measured by using ToF-SIMS. The secondary ion yield ratio of [Au·S(CH₂)₁₁(EG)₃OCH₂O-acetylene]⁻ to [Au·S(CH₂)₁₁(EG)₃OCH₂O-propene]⁻ was measured for each mixed SAM and plotted as a function of the mole fraction of Diyne to Diene in a SAM solution. The ion yield ratio of a mixed SAM produced from a solution with a mole fraction of 0.5 (i.e., 1:1 mixture) was 0.3, which corresponded well to the ion yield ratio measured from an Eneyne SAM. A time-dependent experiment of Eneyne SAM formation and immersion experiment of Eneyne SAM into Diyne solution or into Diene solution were performed. The relative ion yield ratio of 0.3 was due to a different secondary ion formation and not due to the difference in the amount of adsorbates on the surface, nor to the different binding strengths onto the gold surface. Our study shows that a mixed SAM with well-controlled spacing can be produced and quantified by using the ToF-SIMS technique.     

Bestimmung der 15N-Häufigkeit von N2O und N2 mittels emissionsspektrometrischer continuous-flow-Messung

Abstract

Tests were made for a quantitative decomposition of N₂O to N₂ and for the setting of a statistical equilibrium in mixtures with gaseous nitrogen of nonrandom distribution by emission spectrometric continuous-flow-measurements. Under high-frequency-discharge conditions a residence time of 0.5 seconds is enough for a quantitative decomposition. In this time the statistical balance in the mixture of N₂O and N₂ is reached. The determination of the relative ¹⁵N abundance in pure N₂O or N₂ gases or in mixtures of N₂O and N₂ in a continuous-flow-emissionspectrometer can directly be achieved.     

Theoretical study of the reaction of H2 with a Cu2Pt2 cluster

The study of the interaction of a pyramidal tetramer of Cu₂Pt₂ with the H₂ is reported here through ab initio multiconfigurational self-consistent field (MC-SCF) calculations, plus extensive multireference configuration interaction (MR-CI), variational and perturbative calculations. The lowest three electronic states X ¹A′, a ³A′ and a ¹A′ of the bare cluster were considered in order to study this interaction. For the H₂ C_s approaching a Pt vertex, results show that the Cu₂Pt₂ pyramid cluster in its X ¹A′ and a ¹A′ states can spontaneously capture and dissociate the H₂. For the H₂ C_s approaching a Cu vertex, where H₂ is located in the C_s reflecting plane, the Cu₂Pt₂ cluster in its X ¹A′ electronic state shows capture of the hydrogen molecule after surmounting an energy barrier; moreover, in this approach the Cu₂Pt₂ cluster in its a ¹A′ electronic state shows spontaneous capture of the hydrogen molecule. For the H₂ approaching a Cu vertex, where the C_s reflecting plane bisects the H₂ molecule, the Cu₂Pt₂ cluster in its three lowest-lying states is able to capture the hydrogen molecule after surmounting a small barrier. The Cu₂Pt₂+H₂ C_s face-on interactions show a lower H₂ activation than that which was obtained in the equivalent Pt₄+H₂ interactions.     

Magnetic properties of UT2Si2 and UT2Ge2 (T = Co,Ni, Cu) intermetallic systems

Neutron diffraction and magnetization measurements indicate that, at low temperatures, long-range magnetic order is present in UCO₂Si₂, UNi₂Si₂, UCu₂Si₂, UNi₂Ge₂, and UCo₂Ge₂. UCo₂Si₂ and UNi₂Ge₂ are simple collinear antiferromagnets of +-+- type, UCu₂Si₂ a simple collinear ferromagnet. In UNi₂Si₂, a magnetic phase transition from a LSW type structure to collinear antiferromagnetism of +-+- type was found, while in UCu₂Ge₂, the antiferromagnetic structure of ++-- transforms into collinear ferromagnetism. Crystal structure and magnetic parameters are given. No magnetic moment on transition metal ions was found within the accuracy of a powder neutron diffraction experiment. The stability of particular magnetic ordering schemes is discussed in terms of an isotropic RKKY mechanism.     

Influence of preparation method on SrMoO4 impurity content and magnetotransport properties of double perovskite Sr2FeMoO6 polycrystals

The magnetic and electric properties of the Sr₂FeMoO₆ compound produced under different preparation conditions were studied. Depending on the preparation condition, a strong variation in the nonmagnetic SrMoO₄ impurity content was found, which in turn determined the metallic or semiconducting behavior of the resistivity of the Sr₂FeMoO₆ compound. There was also evidence that SrMoO₄ played a crucial role in modifying the low magnetic field intergrain tunneling magnetoresistance in Sr₂FeMoO₆. In addition, we have established a simple method to prepare the single phase Sr₂FeMoO₆ polycrystals.     

Structure and ionic conduction in solids: VI. Evidence for the non-existence of Na4ZrSi3O10 as a definite crystalline phase

For investigation of phase relations in the NASICON system some compositions of the general formula Na₄Zr_2−xSi₃O_{12 −2x} were prepared by sol-gel technique and the usual method of sintering the oxide mixtures. DTA measurements indicate that unannealed samples in this series must contain a glassy phase. By means of X-ray analysis of a sample of the composition Na₄ZrSi₃O₁₀ it was clearly shown that this sample does not exist as a definite compound, but must be regarded as a composite material consisting of the well known compound Na₄Zr₂(SiO₄)₃ and a glassy phase of the composition Na₄Si₃O₈. This result was proved by high resolution ²⁹Si-magic angle spinning (MAS)-NMR measurements which allow the simultaneous registration of both crystalline and glassy phases and the determination of the relative Si-content of the phases with high accuracy. In this manner the glass composition in the sample was estimated for 1.98 Na₂O·3SiO₂.     

Discussion again of the magnetic and transport property of Ag-doped LaMnO3

Samples La_1−aAg_aMnO₃ (0.05?a?0.50) were sol–gel fabricated. A part of Ag was found to dissociate and run off the samples in sintering process when sintering temperature exceeds 700 °C, resulting in a composite of La_1−xAg_xMnO₃ and MnO₂/Mn₂O₃. The magnetic and transport properties of the composite have been studied. The sample with the nominal composition La_0.7Ag_0.3MnO₃ was found to show the greatest magnetoresistance in the sample group. Detailed analysis on average Mn valence reveals a composite of (La_0.985Ag_0.015MnO₃)_0.776[(MnO₂)_0.590(Mn₂O₃)_0.410]_0.224. Its MR ratio at room temperature exceeds 24% under a field of 1.8 T. A conductivity leap has been observed around a=0.30. It suggests a kind of field-induced fluctuation in percolation in the samples investigated.     

Composition-dependent melting behaviour of NaxK55–x core–shell nanoalloys

Molecular dynamics simulations at constant temperature are performed to investigate melting-like transition in Na₁₃K₄₂, Na₁₉K₃₆ and Na₂₆K₂₉ nanoalloys using a second-moment-approximation tight-binding analytic potential to calculate the forces on the constituent atoms. A weighted histogram analysis method is employed to remove non-ergodicity issues due to the complex potential energy surface of these nanoalloys. The heat capacity shows three distinctive steps in melting for Na₁₃K₄₂, while Na₂₆K₂₉ and Na₁₉K₃₆ have two-step and one-step melting transition, respectively. The steepest descent method is used to quench the configurations in a given interval during the simulation and also study the isomerisation processes occurring at different temperatures. Analysing the configuration energies of quenched structures for the entire nanoalloy and the core atoms separately gives more details about the melting mechanism. The Lindemann parameter is also calculated at several temperatures during the simulation which shows a gradual increase for Na₁₃K₄₂ and Na₂₆K₂₉ while a sharp change is observed for Na₁₉K₃₆. These findings are in agreement with the multi-step nature of the phase transition in Na₁₃K₄₂ and Na₂₆K₂₉ and one-step melting of the Na₁₉K₃₆ magic composition.     

Magnetization and specific heat studies of RNi4Ga (RSm,Gd and Tb)

In order to elucidate the anomalous magnetic properties in the ferromagnetically ordered state of SmNi₄Ga GdNi₄Ga and TbNi₄Ga, we have carried out a detailed study with magnetization and specific heat (SH) measurements. GdNi₄Ga shows the possibility of a filled 3d band and a helical spin arrangement below the ordering temperature. TbNi₄Ga shows a dominant crystal field effect resulting in a deviation of T_C from the de-Gennes scaling and possible Schottky anomalies in the SH. SmNi₄Ga shows a large coercivity at low temperatures. A rough estimate of the domain wall thickness in SmNi₄Ga gives a value of 8 Å.     

Superconductivity in Mo5SiB2

In the Mo-Si binary system, Mo₅Si₃ crystallizes in the W₅Si₃ (T₁ phase) structure type. However, when boron replaces silicon in this compound, a structural transition occurs from the W₅Si₃ prototype structure to the Cr₅B₃ prototype structure (T₂ phase) at the composition Mo₅SiB₂. Mo₅SiB₂ has received much attention in the literature as a candidate for structural application in high-temperature turbines, but its electronic and magnetic behavior has not been explored. In this work, we show that Mo₅SiB₂ is a bulk superconducting material with critical temperature close to 5.8 K. The specific-heat, resistivity and magnetization measurements reveal that this material is a conventional type II BCS superconductor.     

Photoinduced phenomena in amorphous As<Subscript>4</Subscript>S<Subscript>3</Subscript>Se<Subscript>3</Subscript>–Sn films

We investigate the kinetics of photodarkening and recording of holographic diffraction gratings in amorphous As₄S₃Se₃ thin-film structures doped with tin (Sn) in concentrations of 0–10 at %. It is established that an increase in the Sn concentration leads to a decrease in the photodarkening rate and degree. The photodarkening kinetics is approximated by a stretched exponential function. It is found that an increase in the Sn concentration leads to a decrease in the transmission (photodarkening) variation in the investigated As₄S₃Se₃–Sn films. It is determined that, in the recording of holographic diffraction gratings at a Sn concentration of 3–8 at %, the As₄S₃Se₃–Sn films exhibit the maximum sensitivity and diffraction efficiency of the recorded gratings. It is shown that the dependence of diffraction efficiency on the As₄S₃Se₃ film thickness has the maximum at a film thickness of 4 µm.     

Morphologies of C60 deposited on a substrate

The morphologies of deposited C₆₀ on a copper substrate from a C₆₀-benzene solution were evaluated by using Scanning Electron Microscopy. It was found that the forms of deposited C₆₀ were dependent on the aggregation of C₆₀ in its original solution. During natural vaporization of benzene solution on a copper substrate, independent C₆₀ molecules in the solution assembled into crystal C₆₀ on the substrate, whereas the aggregates of C₆₀ in the solution were remained as amorphous C₆₀ particles on the substrate. However, if spinning was employed during vaporizing solvent, the C₆₀ aggregates were destroyed, leading to the formation of crystal C₆₀. Furthermore, the speed of spinning a substrate can tune the size and shape of deposited C₆₀.