Optical properties and component composition of layers of cyanine dyes on dielectric supports: influence of asymmetry of the molecular electron density distribution

The component composition of molecular layers of dicarbocyanine dyes of cationic type on glass is determined by the absorption spectroscopy methods. For symmetric and asymmetric molecules the component composition depends on the chemical structure of a molecule and its interaction with the substrate, which are responsible for the electron density distribution in a molecule. The interaction with the substrate depends on the thickness of a layer and the orientation of a layer molecule on the substrate. The increase in the separation between the molecule and the substrate in thicker layers decreases the interaction with the substrate and the asymmetry of a molecule. In symmetric and slightly asymmetric dyes the value of the charge difference on the end groups decreases with increasing layer thickness, whereas in dyes with a large asymmetry, both the value and the sign of the charge difference change. The above results are confirmed by data on the computer simulation of the charge distribution in a dicarbocyanine cation upon its interaction with the oxygen anion on the substrate.     

Thermally induced variations in the conformational composition and spatial orientation of molecular components of a dicarbocyanine dye layer

The effect of heating on the spatial orientation and concentration of the components of dicarbocyanine dye layers on a glass substrate is studied experimentally. Layers of two types differing in the spatial orientation angles of all their components (monomeric all-trans and β-mono-cis isomers, dimers, and J aggregates) are considered. It is shown that storing of samples at temperatures of 150–200°C causes partial thermal destruction but does not change the absorption spectra of the molecular components. Heating of the layer of the first type changes neither the orientation nor the relative concentration of the components. Heating of the layer of the second type leads to irreversible changes in the orientation angles of all the molecular components and causes the β-mono-cis isomer and the dimer to transform into the all-trans isomer and the J aggregate. The dependences of the orientation angle on the heating time have the form of saturating functions. The rate of variation of the orientation angle and its limiting value in the saturation region increase with increasing temperature of heating. At high temperatures, the layer of the second type transforms completely into the layer with the first type of spatial orientation. A mechanism of the changes in the angles of the spatial orientation of the layer components, which includes the stages of thermal isomerization and reorientation of each molecular component, as well as rearrangement of its environment, is proposed. Energetic and kinetic parameters of all the stages of layer reconstruction satisfying the experimental results obtained in the region from 150 to 230°C are determined.     

Formation mechanisms of equilibrium component composition of molecular layers of polymethine dyes

We study the concentration dependences for the absorption spectra and component composition of molecular layers from three homologous series of symmetric polymethine dyes of different electron-donating ability of their terminal heterocyclic groups. We find that a change in the layer thickness leads to a change in the width and position of the spectrum due to a change in the number of absorption bands. The number of bands of monomers increases with increasing chain length and electron-donating ability. The concentration ratio of monomers and associated forms depends on the spatial orientation of molecules in the layer. The electron-donating ability of terminal groups affects the angle between the chromophores of molecules that form a dimer and the intensity ratio between the short- and long-wavelength absorption bands of dimers. We conclude that the effect of the thickness of the layer on its spectral parameters is determined by the degree of intramolecular electron asymmetry that arises as a result of the interaction of chemically symmetric molecules with charges of the substrate surface and upon intermolecular interaction. This asymmetry leads to changes in free energies of ground states of monomeric molecules and, as a consequence, to an increase in equilibrium concentrations of cis-stereoisomeric forms in the layer.     

The Influence of the Molecular Structure of Cyanine Dye on the Component Composition of Molecular Layers

The formation of the component composition of symmetric cationic cyanine dyes on glass is studied. The absorption spectra of layers of three homologous series of dyes with end heterocyclic groups of different spatial and chemical compositions are measured, and the absorption spectra of monomer components and aggregates are separated. The component compositions of layers of different thicknesses are compared. It is shown that the widening of the absorption spectra of molecular layers against the spectra of ethanol solutions of these compounds is caused mainly by the formation of various monomer stereoisomers and molecular aggregates and their interaction with the substrate surface and the neighborhood. The number of isomer forms and their relative concentrations depend on the layer thickness, the electron donor ability and spatial structure of end groups, and the cation conjugation chain length. The influence of the anion manifests itself only in the concentration ratio of the formed monomers and a small shift of the maxima of their absorption bands. The increase in the number of monomer forms produced in the layer corresponds to the increase in the conjugation chain length. Spatial obstacles created by heterocyclic groups inhibit the formation of definite stereoisomers, which reduces the number of components of the layer.     

Low energy electron diffraction and auger electron spectroscopy studies of the structure of adsorbed gases on solid surfaces

Low energy electron diffraction (LEED) studies of the structure of adsorbed molecules on crystal surfaces revealed that ordered surface structures predominate under most conditions of the experiments. In the absence of chemical reactions with the substrate, the degree of ordering depends on the heats of adsorption, ΔH_ads, and the activation energies for surface diffusion, ΔE_D1. Since ΔH_ads is usually markedly larger than ΔE_D1, small changes of substrate temperature facilitate ordering without appreciable increase in desorption rates. The surface structures of adsorbed gases that have been reported so far have been tabulated. For molecules whose size is compatible with the interatomic distance of the substrate, rules of ordering can be proposed that permit prediction of the structure of the adsorbed layer that is likely to form. These rules indicate close packing due to attractive interactions in the adsorbed layer, and that the rotational multiplicity of the substrate is likely to be maintained by the adsorbate structure. When molecules whose dimensions are larger than the substrate interatomic distance are adsorbed, the conditions that control ordering are more complex and simple rules may not be readily applicable.The surface structures of adsorbed gases have also been studied on high Miller Index substrate surfaces. These surfaces are characterized by ordered steps separated by terraces of low index surface orientation. Many gases have different ordering characteristics on stepped surfaces than on low index crystal faces due to the stronger substrate-adsorbate interactions in these surfaces. The dissociation of diatomic molecules at steps induces the formation of new types of surface structures (frequently one-dimensional) and the dehydrogenation of hydrocarbons at steps induces the formation of ordered carbonaceous surface structures that would not nucleate on low index substrate planes.So far, mostly work function changes upon adsorption gave indication of the magnitude of charge transfer upon adsorption and on forming of new surface chemical bonds. Most recently, chemical shifts of the Auger transitions of the substrate atoms and of the adsorbed molecules upon chemisorption, have been found to provide additional information on charge redistribution during adsorption.     

Effect of the third component on charge transfer character in ternary organic solar cells with a cascade-type electronic structure

By incorporating a third component into the host donor/acceptor organic components, we theoretically investigate the effects of its electronic structure and spatial location on charge transfer character. It is found that both of the two factors can modulate the distribution of transferred charges, and thus change the role of the third component in charge transfer (i.e., electron donor or acceptor). The binding energy of the formed charge transfer (CT) state is also determined by the two factors. Especially, we find an optimized spatial location of the third component, at which the binding energy of the formed CT state has a minimum value. It suggests that charge separation can be promoted. These findings will provide us a clear direction on how to optimize the electronic structure and spatial location of the third component to further improve the charge transfer and separation in ternary organic solar cells.     

Effect of the layer charge on the interaction of porphyrin dyes in layered silicates dispersions

Interaction between tetracationic porphyrin, 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP), and layered silicates in aqueous dispersions was studied using absorption, steady-state and time-resolved fluorescence spectroscopies. The charge density of silicates increases in order synthetic laponite (LAP)<Kunipia F montmorillonite (KF)<synthetic fluorohectorite (FHT). Interpretations of the spectra of layered silicate-porphyrin (LSP) systems considered models of dye adsorption on clay mineral colloid particles, analyzing phenomena occurring in similar systems such as structural changes of TMPyP and the formation of dye molecular assemblies. Structural changes of TMPyP, including flattening of the porphyrin molecule, do not fully explain all the spectral observations. One should mention variations of the Q-bands and fluorescence spectra in dependence on the layer charge. The molecular association of the TMPyP molecules is expected to occur to a certain extent in dependence on the layer charge of a clay mineral template. H-aggregates were not observed in any system. Only FHT colloids induced the formation of at least two components with significantly different spectral properties.     

High-quality oriented ZnO films grown by sol-gel process assisted with ZnO seed layer

High-quality oriented ZnO films were prepared on silicon and quartz glass by sol-gel, assisted with a ZnO seed layer. The effects of the seed layer on the orientation, morphology and optical properties of ZnO films were investigated. Results show that the seed layer can effectively induce the growth of high-quality oriented ZnO films on two substrates, and the effectiveness of the seed layer strongly depends on preparation conditions, i.e., the spin-coating layer number and the preheating temperature. ZnO films with five layers on the seed layer preheated at 500 °C exhibit the single (0 0 2) orientation, which is much stronger than that on the flat substrate. Additionally, ZnO films on the seed layer show a denser internal structure and higher optical quality than that on the flat substrate. At ten layers, however, ZnO films on the seed layer show the multiple-orientation, which is similar to that on the flat substrate. Finally, the physical mechanism underlying the growth behavior of ZnO films assisted with the seed layer was discussed.     

Off-centre charge model of the planar electric double layer for asymmetric 2:1/1:2 valencies

ABSTRACT

Grand canonical Monte Carlo simulation results are reported for the structure and capacitance of a planar electric double layer containing off-centre charged rigid sphere cations and centrally charged rigid sphere anions. The ion species are assigned asymmetric valencies, +2:?1 and +1:?2, respectively, and set in a continuum dielectric medium (solvent) characterised by a single relative permittivity. An off-centre charged ion is obtained by displacing the ionic charge from the centre of the sphere towards its surface, and the physical double layer model is completed by placing the ionic system next to a uniformly charged, non-penetrable, non-polarizable planar electrode. Structural results such as electrode-ion singlet distribution functions, ionic charge density and orientation profiles are complemented by differential capacitance results at electrolyte concentrations of 0.2?mol/dm³ and 1?mol/dm³, respectively, and for various displacements of the cationic charge centre. The effect of asymmetry due to off-centre cations and valency asymmetry on the double layer properties is maximum for divalent counterions and when the cation charge is closest to the hard sphere surface.     

Potential-dependent structure of the interfacial water on the gold electrode

Doubly tunable sum frequency generation (SFG) spectra demonstrate that the water molecules at gold/electrolyte interface change their orientation with applied potential. At negative potentials, water molecules in the double layer align with their oxygen atom pointing to the solution. As potential became positive to be close to the potential of zero charge (PZC), the SFG signal decreased, suggesting the OH groups of the water molecule are either in random orientation or parallel to the electrode. As potential became more positive than the PZC, the SFG signal increased again with the oxygen-up orientation as same as in the negative potential region, indicating that water molecules interact with the adsorbed sulfate anions. The peak position of the SFG spectra indicates a relatively disordered state of water molecules at the gold electrode surface, in contrast to the previously observed ice-like structure of water at electrolyte/oxide interfaces.     

Charged double layer at the boundary between a symmetric plasma and a wall

It is shown that the features of formation and structure of a stationary charged layer at the interface between a symmetric plasma and a wall depend to a considerable extent on the ratios τ_± (for both plasma components) of the thermal velocity to the velocity of the plasma flow at the beginning of the layer, as well as on the polarity and magnitude of electric potential φ_W of the wall. The conditions under which a double layer-type structure can be formed in the near-wall layer of the symmetric plasma are formulated. The charge double layer contains two sublayers with opposite polarities of charge for a fixed polarity of the wall. The charge polarity of sublayer adjoining the plasma is opposite to the polarity of the wall, while the sublayer adjoining the wall has a charge of the same polarity as that of the wall. The ranges of symmetric plasma parameters for which the double layer exists are determined. It is found that a structure of this type can be formed nor for all parameters of the plasma, for which a charged layer exists; the possibility of formation of this structure depends on τ_± as well as on the sign of the potential of the wall.     

Electric-field-induced polarization of the layer of condensed ions on cylindrical colloids

In concentrated suspensions of charged colloids, interactions between colloids can be induced by an external electric field through the polarization of charge distributions (within the diffusive double layer and the layer of condensed ions) and/or electro-osmotic flow. In case of rod-like colloids, these field-induced inter-colloidal interactions have recently been shown to lead to anomalous orientation perpendicular to the external field, and to phase/state transitions and dynamical states, depending on the field amplitude and frequency of the external field. As a first step towards a (semi-) quantitative understanding of these phenomena, we present a linear-response analysis of the frequency-dependent polarization of the layer of condensed ions on a single, long and thin cylindrical colloid. The in-phase and out-phase response functions for the charge distribution and the electric potential are calculated for arbitrary orientation of the cylindrical colloid. The frequency-dependent degree of alignment, which is proportional to the electric-field-induced birefringence, is calculated as well, and compared to experiments on dilute fd virus suspensions.     

γ-CuI超快闪烁转换屏的制备与性能表征

以石英基片为衬底,采用真空热蒸发法,通过调控衬底温度制备出了具有微柱结构、柱径在μm量级、厚度约17 μm的γ-CuI超快闪烁转换屏。在X射线激发下,所制备的γ-CuI超快转换屏具有峰位在430 nm的快成分发射峰和峰位在700 nm的慢成分发射带,其中快成分发射峰占总发光的主要部分;随着衬底温度由170 ℃升高至210 ℃,转换屏430 nm发射峰的强度会逐渐减弱,而700 nm发射带的强度则逐渐增强,这可能是由于较高的衬底温度会造成碘流失从而引起转换屏中碘空位增加、铜空位减少所致(Cu/I增大),碘流失的假设得到了卢瑟福背散射实验的验证。γ-CuI超快转换屏的晶体结构呈(111)晶面择优取向,且不随衬底温度而变化,当衬底温度升高至210 ℃时,由于CuI分子获得的动能增加,转换屏还会出现微弱的(220)和(420)晶面的取向。当衬底温度由170℃增至190 ℃时,转换屏的微柱结构会随之优化,微柱结构明显,但当衬底温度进一步增至210 ℃时,由于表面扩散和体扩散效应加剧,微柱结构会随之退化。最后,采用刃边法测量了所制备γ-CuI转换屏的空间分辨率,结果显示170,190和210 ℃衬底温度条件下所制备的转换屏,其空间分辨率分别为：4.5,7.2和5.6 lp·mm-1,微柱结构有助于提高转换屏的空间分辨率。     

顺式与反式偶氮苯衍生物分子非线性光学性质理论研究

利用密度泛函理论(DFT)B3LYP/6-31G(d,p)方法优化了一系列顺式与反式偶氮苯衍生物分子,在此基础上结合有限场(FF)方法和密度泛函理论对分子非线性光学(NLO)性质及电子光谱进行了计算分析,结果表明:顺式与反式结构的变化对其偶极矩、分子内电荷分布与转移以及前线轨道跃迁都造成影响,从而影响分子的第一超极化率.同时相对于顺式偶氮苯衍生物分子,反式分子具有较大的二阶非线性光学系数.     

Coverage dependent organic–metal interaction studied by high-resolution core level spectroscopy: SnPc (sub)monolayers on Ag(1 1 1)

We study the electronic structure of tin-phthalocyanine (SnPc) molecules adsorbed on a Ag(1 1 1) surface by high-resolution photoelectron spectroscopy. We particularly address the effect of different SnPc coverages on the interaction and charge transfer at the interface. The results give evidence for a covalent molecule–substrate interaction, which is temperature and coverage dependent. The valence and core level spectra as well as the work function measurements allow us monitoring subtle differences in the strength of the interface interaction, thus demonstrating the sensitivity of the methods. The results consistently show the effect of charge exchange between substrate and molecules which obviously leads to a net charge transfer into the SnPc molecules, and which is increased with decreasing coverage. Surprisingly, the Sn3d core levels are neither effected by variations of charge transfer and interaction strength, nor by a possible “Sn-up” or “Sn-down” orientation, which have been observed for sub-monolayers.     

In-depth characterization and computational 3D reconstruction of flagellar filament protein layer structure based on in situ spectroscopic ellipsometry measurements

In this study, we have reconstructed the statistical 3D structure of hundreds of nanometers thick surface immobilized flagellar filament protein layers in their native environment, in buffer solution. The protein deposition onto the surface activated Ta₂O₅ film was performed in a flow cell, and the immobilization process was followed by in situ spectroscopic ellipsometry. A multilayer optical model was developed, in that the protein layer was described by five effective medium sublayers. Applying this method, an in-depth analysis of the protein layer formation was performed. Based on the kinetics in the distribution of the surface mass density, the statistical properties of the filamentous film could be determined computationally as a function of the measurement time. It was also demonstrated that the 3D structure of the protein layer can be reconstructed based on the calculated in-depth mass density profile. The computational investigation revealed that the filaments can be classified into two individual groups in approximately equal ratio according to their orientation. In the first group the filaments are close to laying position, whereas in the second group they are in a standing position, resulting in a significantly denser sublayer close to the substrate than at a larger distance.     

GaN基发光二极管外延中p型AlGaN电子阻挡层的优化生长

本文利用金属有机物化学气相沉积(MOCVD)方法系统地研究了p-AlGaN层掺杂机理及优化设计生长. 明确了生长温度、压力及TMAl的流量对AlGaN层Al组分的影响关系,并给出了各自不同的机理与作用. 研究发现,Al组分介于10%—30%之间能够很好地将电子限定在量子阱区域并保持高的材料晶体质量. 发展了一种新的生长技术来克服p-AlGaN层掺入效率低下和空穴注入不足的问题. 优化条件下生长的p型AlGaN电子阻挡层很大地提升了InGaN/GaN基LED的输出光功率. 关键词： 氮化镓基 LED Al组分 电子阻挡层     

海底沉积物压缩波声速比与物理特性的关系

海底沉积物因组成结构复杂导致声学特性复杂多样,多种理论解释模型存在参数较多且各具适用性现象·通过运用体积平均和等效参数的方法对海底沉积物声波传播机理进行研究,提出一种少参数的海底沉积物与底层海水的压缩波声速比通用模型(General Model of Sound Speed Ratio,GMSSR).GMSSR模型包含弹性结构分布因子、孔隙度、等效密度比、等效弹性模量比4个物理特性参数。分析海底沉积物两相介质结构的串联和并联两种极限情况分析,基于弹性结构分布因子和串并联结构的体积平均分布建立一般情况下海底沉积物的等效弹性模量表达式·应用GMSSR合理地分析各海域测量的海底沉积物声速比经验模型的共性和解释南海实测数据分散的范围,表明:(1)表层海底沉积物主要是以串联结构为主,接近于悬浮液状态或者体积分量很少的并联堆积状态;(2)等效弹性模量比的影响因素大于等效密度比,结构变化往往通过影响弹性结构分布因子而影响等效弹性模量比,从而引起声速比的变化;(3)不同研究海域的声速比-孔隙度经验关系具有相似性,可以通过GMSSR模型分析得出;(4)基于弹性结构分布因子的差异,可以合理解释南海海域测量表层海底沉积物声速比较大的分散性。      

On the nonuniform electron-density distribution in a layer adsorbed on a metal

The probability of a transition from a uniform charge distribution (UCD) in the adsorbed layer to a nonuniform one (NCD) caused by the dipole-dipole adatom repulsion is analyzed within the Anderson-Newns Hamiltonian and a simple density-of-states model for the substrate. Two limiting cases are considered, namely, an infinitely wide and a narrow band of allowed substrate states. Criteria for the UCD→NCD transition are obtained. Experimental data on reconstruction of clean metal faces are analyzed. Fiz. Tverd. Tela (St. Petersburg) 41, 1543–1547 (September 1999)     

Characteristics of biogenic calcite in the prismatic layer of a pearl oyster,Pinctada fucata

The fine structure of the calcite prism in the outer layer of a pearl oyster, Pinctada fucata, has been investigated using various electron beam techniques, in order to understand its characteristics and growth mechanism including the role of intracrystalline organic substances. As the calcite prismatic layer grows thicker, sinuous boundaries develop to divide the prism into a number of domains. The crystal misorientation between the adjacent domains is several to more than ten degrees. The component of the misorientation is mainly the rotation about the c-axis. There is no continuous organic membrane at the boundaries. Furthermore, the crystal orientation inside the domains changes gradually, as indicated by the electron back-scattered diffraction (EBSD) in a scanning electron microscope (SEM). Transmission electron microscopy (TEM) examination revealed that the domain consists of sub-grains of a few hundred nanometers divided by small-angle grain boundaries, which are probably the origin of the gradual change of the crystal orientation inside the domains. Spherular Fresnel contrasts were often observed at the small-angle grain boundaries, in defocused TEM images. Electron energy-loss spectroscopy (EELS) indicated the spherules are organic macromolecules, suggesting that incorporation of organic macromolecules during the crystal growth forms the sub-grain structure of the calcite prism.