1-羟基-5-十二烷氧基-萘LB膜结构和取向的光谱研究

用红外透射,反射光谱及紫外可见吸收光谱方法研究了１－羟基－５－十二烷基－萘ＬＢ膜及溶液状态下的结构,分子取向。研究结果表明分子在溶液中主要是以单体形式存在;在ＬＢ膜中是以聚集体形式存在。     

Molecular Orientation and Aggregation in the Langmuir-Blodgett Films of 4-[4′-(4″-Decyloxy Phenylazo) Naphthloxy] Butyl Trimethylammonium Dextran Sulfate Studied by Ultra-Violet and Infrared Spectroscopy

Infrared transmission, Reflectance-Absorption (RA) and Ultra-Violet (UV) spectra were measured for mono-and multi-layers Langmuir-Blodgett (LB) films of 4-[4′-(4″-decyIoxy phenylazo)naphthloxy] butyl trimethylammonium bromide formed with SDS to study the molecular orientation and aggregation. The results indicate that the compound do not aggregate in the LB films, and the alkyl tail is nearly perpendicular to the substrate surface and the chromorphore part adopts trans-zigzag conformation. These results also suggest that the molecular orientation and aggregation are not depend upon the number of monolayers The comparison of infrared transmission and RA spectra indicates that the hydrocarbon chain is nearly perpendicular to the substrate surface, but the two rings in the chromophore part are tilted considerably from the surface normal.     

Electrical transport study of structural phase transitions in C60 films and the effect of swift heavy ion irradiation

Three phase transitions (face centered to simple cubic, surface rearrangement from (2×2) to (1×1) and glass transition) in fullerene thin films and the effect of 150 MeV Ti ion irradiation on these transitions have been studied, using temperature dependence of electrical resistivity measurements. The structural properties of the C₆₀ thin films are studied by X-ray diffraction, atomic force microscopy and UV-vis spectroscopy. It is observed that defect creation by ion irradiation in the films lead to quenching and broadening of structural phase transitions but the transition temperatures did not show significant shifting under ion irradiation.     

Langmuir and Langmuir-Blodgett (LB) films of tetrapyridyl metalloporphyrins

We report on the formation of Langmuir films of 5,10,15,20-tetra(4-pyridyl) 21H,23H-porphine, hereafter named tetrapyridyl porphyrins with distinct central ions (2H⁺, Zn²⁺, Cu²⁺, Ni²⁺). The films were characterized with surface pressure and surface potential isotherms and in situ UV-vis absorbance. The measurements indicated strong aggregation of porphyrin monomers at the air-water interface, with a red shift of the Soret band in comparison with the spectrum obtained from CHCl₃ solutions. The shift was larger for the non-substituted H₂TPyP, and depended on the metal ion. Significantly, aggregation occurred right after spreading of the Langmuir film, with no further shifts in the UV-vis spectra upon compression of the film, or even after transferring them onto solid substrates in the form of Langmuir-Blodgett (LB) films. The buildup of LB films from H₂TPyP and ZnTPyP was monitored with UV-vis spectroscopy, indicating an equal amount of material deposited in each deposition step. Using FTIR in the transmission and reflection modes, we inferred that the H₂TPyP molecules exhibit no preferential orientation in the LB films, while for ZnTPyP there is preferential orientation, with the porphyrin molecules anchored to the substrate by the lateral pyridyl groups.     

Fourier Transform Infrared Spectroscopic Investigation on Langmuir-Blodgett Films of Octadecanoyl Ester of 1-(2-Carboxyethyl) Thymine: Molecular Orientation,Molecular Recognition to Complementary Base of Nucleic Acid and Order-Disorder Transition

Fourier transform infrared (FTIR) transmission, polarized transmission, reflection absorption (RA) and Attenuated total reflection (ATR) spectroscopy were employed to investigate the molecular orientation and molecular recognition to the complementary base at the air / water interface of a novel nucleolipid amphiphile, octadecanoyl ester of 1-(2-carboxyethyl) thymine. It has been found that the molecules are biaxially oriented and the hydrocarbon chain titled considerably from the substrate normal as well as the chromophoric part in the LB film Molecular recognition through complementary bases pairing takes place at the air / water interface between the thymine moiety in the head group of the amphiphile and adenosine in the subphase, the hydrogen involved in the host-guest interactions has been detected by using FTIR-ATR technique. FTIR transmission spectra measured at elevated temperatures revealed that the order-disorder transition of the LB film which contains the complementary base occurs at lower temperature. To our best knowledge, investigation of the order-disorder transitions in nucleolipid amphiphile LB films and comparative studies of the order-disorder transitions between nucleolipid amphiphile LB film that contains and does not contain the complementary bases have been virtually nonexistent, so far.     

Assemblies, characterization, and luminescent enhancement of organized molecular films based on rare earth complexes

Langmuir-Blodgett (LB) films of different molar percentages of Eu(TTA)₃Phen (TTA=2-thenoyltrifluoroacetone; Phen=1,10-phenanthroline) with Gd(TTA)₃Phen coexisting with arachidic acid (AA) (complexes:AA=1:l, in molar ratio) were fabricated and the luminescence enhancement of Eu(III) in the films was studied in this investigation. The monolayers and LB films were characterized by π-A isotherms, fluorescence microscopy, UV-vis spectroscopy and low-angle X-ray diffraction. High-quality LB films and strongly luminescent films were obtained. It was learned from the present study that an efficient intermolecular energy transfer occurred from Gd(TTA)₃Phen to Eu(TTA)₃Phen in the films, which resulted in the luminescence enhancement effect. According to the proposed model of the “active enhancement circle” the distance of energy transfer from Gd-, Tb-, La-, and Y-complex to Eu-complex were calculated to be 1.2, 1.2, 0.7 and 1.0 nm, respectively.     

Synthesis and characterization of CdS/PVA nanocomposite films

A series CdS/PVA nanocomposite films with different amount of Cd salt have been prepared by means of the in situ synthesis method via the reaction of Cd²⁺-dispersed poly vinyl-alcohol (PVA) with H₂S. The as-prepared films were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet-visible (UV-vis) absorption, photoluminescence (PL) spectra, Fourier transform infrared spectroscope (FTIR) and thermogravimetric analysis (TGA). The XRD results indicated the formation of CdS nanoparticles with hexagonal phase in the PVA matrix. The primary FTIR spectra of CdS/PVA nanocomposite in different processing stages have been discussed. The vibrational absorption peak of CdS bond at 405 cm⁻¹ was observed, which further testified the generation of CdS nanoparticles. The TGA results showed incorporation of CdS nanoparticles significantly altered the thermal properties of PVA matrix. The photoluminescence and UV-vis spectroscopy revealed that the CdS/PVA films showed quantum confinement effect.     

Growth of pentacene on Ag(1 1 1) surface: A NEXAFS study

Thin films of pentacene (C₂₂H₁₄) have become widely used in the field of organic electronics. Here films of C₂₂H₁₄ of thickness ranging from submonolayer to multilayer were thermally deposited on Ag(1 1 1) surface. The determination of molecular geometry in pentacene films on Ag(1 1 1) studied by X-ray absorption at different stages of growth up to one monolayer is presented.XAS spectra at the C K-edge were collected as a function of the direction of the electric field at the surface. The different features of the spectra were assigned to resonances related to the various molecular unoccupied states by the comparison with the absorption coefficient of the pentacene gas phase. The transitions involving antibonding π states show a pronounced angular dependence for all the measured coverages, from submonolayer to multilayer. The spectra analysis indicates a nearly planar chemisorption of the first pentacene layer with a tilt angle of 10°.     

Absorption Spectra of C<Subscript>60</Subscript> Fullerene Monomolecular Films

The absorption spectra of C₆₀ fullerene thin (from submonolayer to 5–6 monolayers) films deposited on different substrates have been studied. It has been shown that the spectra of the submonolayer and thick (more than 100 monolayers) films virtually coincide. The behavior of fullerene on the surface of different polymers can be judged from changes in the absorption spectra.     

Photophysical characterizations of 2-(4-biphenylyl)-5 phenyl-1,3,4-oxadiazole in restricted geometry

Langmuir and Langmuir-Blodgett (LB) films of non-amphiphilic 2-(4-Biphenylyl)-5-phenyl-1,3,4-oxadiazole (abbreviated as PBD) mixed with stearic acid (SA) as well as with the inert polymer matrix poly(methyl methacrylate) (PMMA) have been studied. Surface pressure versus area per molecule (π-A) isotherm studies suggest that PBD molecules very likely stand vertically on the air-water interface and this arrangement allows the PBD molecules to form stacks and remain sandwiched between SA/PMMA molecules. At lower surface pressure, phase separation between PBD and matrix molecules occurs due to repulsive interaction. However, at higher surface pressure, PBD molecules form aggregates. The UV-vis absorption and steady-state fluorescence spectroscopic studies of the mixed LB films of PBD reveal the nature of the aggregates. H-type aggregate predominates in the mixed LB films, whereas I-type aggregate predominates in the PBD-PMMA spin-coated films. The degree of deformation produced in the electronic levels are largely affected by the film thickness and the surface pressure of lifting.     

Preparation and electronic structure of phase pure K3C60

Phase pure K₃C₆₀ films have been grown using vacuum distillation. The structure of such films could be shown to be face centered cubic consistent with X-ray diffraction studies. The electronic structure of the films has been studied using electron energy-loss spectroscopy in transmission. From C1s core excitation measurements the unoccupied density of states has been determined. Performing the dielectric function has been derived in a wide energy range (0–45 eV). It is shown that the low energy part of the optical conductivity cannot be understood within a simple free electron model but that interband transitions between the three conduction bands have to be taken into account. The spectral weight of interband transitions between valence and conduction bands shows strong momentum dependence due to optical selection rules demonstrating the molecular-like nature of the electronic states.     

利用偶氮苯有序单分子膜探讨银岛膜表面增强光谱机制

利用偶氮苯有序单分子膜探讨银岛膜表面增强光谱机制张锦ａ赵江于化忠何会新张浩力ａ朱涛力虎林ａ刘忠范（北京大学化学与分子工程学院智能材料研究中心（ＣＩＭＲ）北京１００８７１）（ａ兰州大学化学系兰州７３００００）ＴｏｗａｒｄｓｔｈｅＭｅｃｈａｎｉｓｍｏｆ...     

Theoretical studies on the structural and spectra properties of two C74 fullerenes and the chlorinated species C74Cl10

The geometrical/electronic structures, X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy of two especially C₇₄ fullerenes (D_3h–C₇₄ and C₁–C₇₄) and the chlorinated species C₁–C₇₄Cl₁₀, which are newly isolated in the experiment, have been calculated by means of the density functional theory (DFT) method. Effective changes in the electronic structure and simulated X-ray spectra have been observed after chlorination. Strong isomer dependence has been found in both spectra, thus the ‘fingerprints’ in the spectra can be employed as a tool to identify the isomers. The ultraviolet-visible (UV-vis) absorption spectrum of C₁–C₇₄Cl₁₀ has been performed by using the time-dependent DFT method. The generated UV-vis spectrum coincides with the previous experimental counterpart. The results of this work can provide useful information especially for isomer identification and further study on fullerenes by means of the aforementioned spectroscopy techniques.     

Room temperature deposition of amorphous SiC thin films using low energy ion bombardment

Silicon carbide (SiC) films are prepared by single- and dual-ion beam sputtering deposition at room temperature, respectively. An assisting argon ion beam (ion energy Ei=150 eV) bombards directly the substrate surface to modify the SiC film surface. The thin films are characterized by the Fourier transform infrared spectroscopy (FTIR) and the Raman spectra. With assisting ion beam bombardment, the density of the Si–C bond in the film increases. Meanwhile, the excess carbon or the size of the sp² bonded clusters and the amorphous Si (a-Si) phase decrease. These results indicate that the composition of the films is mainly Si–C bond. UV-vis transmission shows that the E_opt increases steadily from 1.85 eV for the amorphous SiC (a-SiC) films without bombardment to about 2.29 eV for those with assisting ion beam bombardment.     

Phase transition in thin epitaxial ferroelectric films as derived from thermal measurements

The temperature dependence of the heat capacity of thin epitaxial films BaTiO₃/MgO is studied by the dynamic 3ω method in the thickness range 50–500 nm. It is revealed that the heat capacity exhibits diffuse anomalies due to phase transitions. The temperature of the ferroelectric phase transition T _C increases with decreasing film thickness. The reasons for the strong diffuseness of the transition and the nonlinear dependence of the transition temperature on the film thickness are discussed.     

Linear birefringence studies of structural phase transitions of KCdF3

Two weakly discontinuous structural phase transitions have been observed on single domains of KCdF₃ at T_c1 = 487.5 K and at T_c2 = 472.7 K in the temperature dependence of the linear birefringence (LB). Beginning with the cubic high temperature phase the crystal becomes successively uniaxial and biaxial birefringent. Within the classical Landau approximation the LB has proved to be proportional to the square of the respective order parameter of the transformations. A relation which describes the coupling between both order parameters is discussed. In disagreement with Hidaka et al. [7] we do not observe a third phase transition near 240 K by the LB technique.     

Phase transitions in molecular crystals of <Emphasis Type="Italic">n</Emphasis>-alkane alcohols

A comparative analysis of the phase transitions in molecular crystals of n-alkane alcohols with different lengths of the (C _n H_{2n + 2}OH) chain was performed using differential scanning calorimetry (DSC). Investigation of the temperature hysteresis made it possible to reveal a number of new effects associated with the specific features of the first-order phase transitions. A quantitative analysis of the temperature dependence of the heat capacity was carried out in the framework of the theory of diffuse (Λ-shaped) first-order phase transitions.     

Influence of annealing on the structure formation and optical absorption parameters of 2-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-ylimino)-2-(4-nitrophenyl) acetonitrile thin films

The effect of annealing temperatures (343 and 425) K on structure formation and optical absorption of 2-(2,3-dihydro-1,5-dimethyl-3-oxo-2-phenyl-1H-pyrazol-4-ylimino)-2-(4-nitrophenyl)acetonitrile (DOPNA) thin films has been reported. The structural properties are investigated by X-ray diffraction and transmission electron microscope techniques. The electronic transitions of DOPNA thin films are investigated in terms of ultravioletvisible (UV-vis) spectroscopy. The absorption coefficient of films has been calculated and analyzed in order to determine the type of inter-band electronic transition as well as the value of optical band gap for films. The films have been found to have indirect allowed optical band gap: which was found to decrease by increasing annealing temperatures.     

Dielectric spectra of Bi<Subscript>0.98</Subscript>Nd<Subscript>0.02</Subscript>FeO<Subscript>3.00</Subscript> multiferroic thin films in the terahertz frequency range

Transmission and reflection spectra of Bi_0.98Nd_0.02FeO_3.00 multiferroic thin films on MgO single-crystal substrates have been measured using submillimeter spectroscopy (on a backward-wave tube spectrometer) and Fourier-transform infrared spectroscopy in the frequency range from 8 to 1000 cm⁻¹ at room temperature. The complex permittivity spectra of the films have been calculated in terms of the layered medium model. It has been revealed that a decrease in the film thickness leads to a considerable increase in the losses in a range of 30 cm⁻¹ and the corresponding fivefold increase in the static permittivity (to 500 for a film 32 nm thick). This phenomenon has been discussed in the framework of the phenomenological theory of phase transitions.     

Specific features of phase transitions in molecular crystals of diols

A comparative analysis of the phase transitions in molecular crystals of diols with different chain lengths [1,15-pentadecanediol (CH₂)₁₄(OH)₂ and 1,16-hexadecanediol (CH₂)₁₅(OH)₂] has been performed using differential scanning calorimetry. A quantitative analysis of the temperature dependence of the heat capacity within the theory of diffuse (Λ-shaped) first-order phase transitions and the use of the temperature hysteresis have revealed a number of new effects associated with the specific features of the phase transitions in molecular crystals of diols.