Debye-Hückel theory for interfacial geometries

The Debye-Hückel theory for bulk electrolyte solutions is generalized to planar interfacial geometries, including screening effects due to mobile salt ions which are confined to the interface and solutions with in general different salt concentrations and dielectric constants on the two sides of the interface. We calculate the general Debye-Hückel interaction between fixed test charges, and analyze a number of relevant special cases as applicable to charged colloids and charged polymers. Salty interfaces, which are experimentally realized by monolayers or bilayers made of cationic and anionic surfactants or lipids, exert a strong attraction on charged particles of either sign at large separations from the interface; at short distances image-charge repulsion sets in. Likewise, the effective interactions between charged particles are strongly modified in the neighborhood of such a salty interface. On the other hand, charged particles which are immersed in a salt solution are repelled from the air (or a substrate) interface, and the interaction between two charges decays algebraically close to such an interface. These general results have experimentally measurable consequences for the adsorption of charged colloids or charged polymers at monolayers, solid substrates, and interfaces.     

Phase transition detection by surface photo charge effect in liquid crystals

The surface photo charge effect (SPCE) was applied for the first time at structure and phase transitions study of hydrogen bonded in dimer liquid crystals (HBDLCs). Due to the high sensitivity of this method, besides first-order phase transitions, characteristic for the p,n-octyloxibenzoic acids (8OBA), an order transition was definitely detected within the nematic range. We state that the SPCE, arising at the solid–HBDLCs interface due to the double electrical layer, is invariably concomitant with solid surface–liquid interfaces, and indicates that the changes of the characteristics of this layer, under incident optical irradiation, induce surface charge rearrangement and alternating potential difference. A mechanism of induction of the SPCE at the interface of solid surface–anisotropic liquids is proposed. We also indicate that this mechanism can be adapted for solid surface–isotropic liquid interface, including colloids (milk) and fog (aerosols)–condensed medium.     

Soft X-ray microscopy and spectroscopy at the molecular environmental science beamline at the Advanced Light Source

We present examples of the application of synchrotron-based spectroscopies and microscopies to environmentally relevant samples. The experiments were performed at the molecular environmental science beamline (11.0.2) at the Advanced Light Source, Lawrence Berkeley National Laboratory. Examples range from the study of water monolayers on Pt(1 1 1) single crystal surfaces using X-ray emission spectroscopy and the examination of alkali halide solution/water vapor interfaces using ambient pressure photoemission spectroscopy, to the investigation of actinides, river water biofilms, Al-containing colloids and mineral–bacteria suspensions using scanning transmission X-ray spectromicroscopy. The results of our experiments show that spectroscopy and microscopy in the soft X-ray energy range are excellent tools for the investigation of environmentally relevant samples under realistic conditions, i.e., with water or water vapor present at ambient temperature.     

Colloidal interactions in two-dimensional nematic emulsions

We review theoretical and experimental work on colloidal interactions in two-dimensional (2D) nematic emulsions. We pay particular attention to the effects of (i) the nematic elastic constants, (ii) the size of the colloids, and (iii) the boundary conditions at the particles and the container. We consider the interactions between colloids and fluid (deformable) interfaces and the shape of fluid colloids in smectic-C films.     

Charging of heated colloidal particles using the electrolyte Seebeck effect

We propose a novel actuation mechanism for colloids, which is based on the Seebeck effect of the electrolyte solution: Laser heating of a nonionic particle accumulates in its vicinity a net charge Q, which is proportional to the excess temperature at the particle surface. The corresponding long-range thermoelectric field E is proportional to 1/r(2) provides a tool for controlled interactions with nearby beads or with additional molecular solutes. An external field E(ext) drags the thermocharged particle at a velocity that depends on its size and absorption properties; the latter point could be particularly relevant for separating carbon nanotubes according to their electronic band structure.     

Static polarizability effects on counterion distributions near charged dielectric surfaces: A coarse-grained Molecular Dynamics study employing the Drude model

Coarse-grained implicit solvent Molecular Dynamics (MD) simulations have been used to investigate the structure of the vicinal layer of polarizable counterions close to a charged interface. The classical Drude oscillator model was implemented to describe the static excess polarizability of the ions. The electrostatic layer correction with image charges (ELCIC) method was used to include the effects of the dielectric discontinuity between the aqueous solution and the bounding interfaces for the calculation of the electrostatic interactions. Cases with one or two charged bounding interfaces were investigated. The counterion density profile in the vicinity of the interfaces with different surface charge values was found to depend on the ionic polarizability. Ionic polarization effects are found to be relevant for ions with high excess polarizability near surfaces with high surface charge.     

Interfacial tunneling barrier heights in triple-layer dielectrics

The understanding of charge transport through multilayer dielectrics requires the knowledge of tunneling barrier heights at all interfaces. In this work a method was employed that yields consistent values for the relevant barrier heights by analyzing the I(V) characteristics of an appropriate set of oxide-nitride-oxide (ONO) triple-layers. The charge transport turns out to be determined by the nitride-oxide interface with a barrier height over 1 eV larger than for the Si-SiO₂ interface. It is discussed whether there is dominant hole or electron transport.     

微波加热法快速制备纳米银及其SERS活性研究

将一定浓度的硝酸银及柠檬酸三钠混合后,用微波加热法根据加热时间及加热方式的不同,制备出了5个纳米银溶胶样品.用电泳仪、吸收光谱、透射电镜对这5个样品进行了表征,发现加热时间短时,纳米银表面带正电,加热时间长时纳米银表面带负电,且加热时间长时吸收峰红移,纳米银尺寸增大.为测试该纳米银溶胶是否具有表面增强喇曼散射 (SERS)活性,选用了阳离子型分子碱性品红（Fuchsine basic ）、亚甲基蓝（Methylene blue）,阴离子型分子苯甲酸（Benzoic acid）,中性分子丫啶橙(Alcidine orange)、苏丹红(Sudan red)作为其SERS活性的测试分子,进行SERS研究.结果发现,所制备的纳米银除样品5对苏丹红分子无增强效应外,其余样品对所选分子都具有较好的增强效果.     

Beyond Millikan: the dynamics of charging events on individual colloidal particles

By measuring the stable charge on oil drops in air, Millikan demonstrated the discrete nature of electric charge. We extend his approach to the charge on solid-liquid interfaces, and focus on the dynamics of the discrete fluctuations. Our measurements are accurate and fast enough to observe changes of one elementary charge. Experiments over thousands of seconds yield information about the fast dynamics of electrochemical reactions, relevant for physicochemical and biological systems. As an example, we study (dis)charging processes on colloidal particles in a nonpolar liquid.     

有机半导体异质界面电荷传输解析模型研究

有机半导体多层薄膜器件的性质很大程度上由有机-有机界面的传输性质所决定，但是现有的关于有机-有机界面的分析模型很难适用于实际器件的模拟.以Miller-Abrahams跳跃传导理论为基础，充分考虑有机-有机界面和金属-有机界面性质的不同，建立了一个新的描述有机-有机异质界面电荷传输的解析模型.结果表明有机异质界面的载流子传输不仅取决于界面的肖特基势垒，而且还取决于界面附近两边的电场强度和载流子浓度.此模型可用于有机半导体多层薄膜器件的电流密度、电场分布和载流子浓度分布的自洽计算. 关键词： 有机半导体 界面 载流子传输     

电解法制备纳米银溶胶及其SERS活性研究

分别用柠檬酸三钠溶液、硝酸银和聚乙烯醇混合液作为电解液,用银棒作为电极,加上7 V直流电压,通电1 h,用电解方法得到了纳米银溶胶。为测试该纳米银溶胶是否具有表面增强拉曼散射1(SERS)活性,选用了阳离子型分子碱性品红(Fuchsine basic)、亚甲基蓝(Methylene blue),阴离子型分子苯甲酸(Benzoic acid),甲基橙(Methyl orange)、中性分子吖啶橙(Alcidine orange)、苏丹红(Sudan red)作为测试分子,进行SERS研究,结果发现用两种电解液制备的纳米银都具有很强的SERS活性,但用硝酸银和聚乙烯醇混合液作为电解液制备的纳米银溶胶具有更广泛的SERS 活性。在该方法制备的纳米银上,得到了在常规方法制备的胶态纳米银上及用柠檬酸三钠溶液作为电解液制备的纳米银上得不到的甲基橙分子的SERS谱,对可能的原因进行了讨论。     

The net charge at interfaces between insulators

The issue of the net charge at insulating oxide interfaces is briefly reviewed with the ambition of dispelling myths of such charges being affected by covalency and related charge density effects. For electrostatic analysis purposes, the net charge at such interfaces is defined by the counting of discrete electrons and core ion charges, and by the definition of the reference polarization of the separate, unperturbed bulk materials. The arguments are illustrated for the case of a thin film of LaAlO(3) over SrTiO(3) in the absence of free carriers, for which the net charge is exactly 0.5e per interface formula unit, if the polarization response in both materials is referred to zero bulk values. Further consequences of the argument are extracted for structural and chemical alterations of such interfaces, in which internal rearrangements are distinguished from extrinsic alterations (changes of stoichiometry, redox processes), only the latter affecting the interfacial net charge. The arguments are reviewed alongside the proposal of Stengel and Vanderbilt (2009 Phys. Rev. B 80 241103) of using formal polarization values instead of net interfacial charges, based on the interface theorem of Vanderbilt and King-Smith (1993 Phys. Rev. B 48 4442-55). Implications for non-centrosymmetric materials are discussed, as well as for interfaces for which the charge mismatch is an integer number of polarization quanta.     

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.     

Disappearance of the gas-liquid phase transition for highly charged colloids

We calculate the full phase diagram of spherical charged colloidal particles using Monte Carlo free energy calculations. The system is described using the primitive model, consisting of explicit hard-sphere colloids and point counterions in a uniform dielectric continuum. We show that the gas-liquid critical point becomes metastable with respect to a gas-solid phase separation at colloid charges Q > or =20 times the counterion charge. Approximate free energy calculations with only one and four particles in the fluid and solid phases, respectively, are used to determine the critical line for highly charged colloids up to Q=2000. We propose the scaling law T*(c) approximately Q(1/2) for this critical temperature.     

基于AFM的固液界面表面电荷密度测量方法

固液界面的表面电荷会影响微纳流体系统的流体阻力,因此如何测量固液界面的表面电荷密度以及分析表面电荷的产生机理对于研究表面电荷对流体阻力的影响具有较大的意义。提出了一种基于接触式AFM的固液界面表面电荷密度测量方法。基于该方法测量了浸在去离子水和0.01 mol/L的NaCl溶液中的高硼硅玻璃和二氧化硅样本的表面电荷密度,并研究了溶液pH值对表面电荷的影响。研究结果表明高硼硅玻璃和二氧化硅由于表面硅烷基的电离带负电。溶液pH值和离子浓度的增加都会增加浸在去离子水和0.01 mol/L的NaCl溶液中高硼硅玻璃和二氧化硅的表面电荷密度的绝对值。     

Surface‐enhanced Raman measurements and DFT calculations for l‐tryptophan of varying pH in silver sol

The interaction of l ‐tryptophan (Trp) with silver colloids was investigated at between pH values of 6.11 and 10.6 of the sol. The measurements of surface‐enhanced Raman bands of Trp in the colloidal solution indicate the evolution of interaction between the metal particles and the molecules with increasing pH values for the sol. The experimental observations were explained using the estimated atomic charge distribution in the zwitterionic and anionic forms of the residue, obtained by density functional theory calculations. The variation in the ratio of the spectral intensities of the Fermi resonance bands with the pH reflects the effect of the colloidal environment on Trp. The results obtained can be used as a marker for describing the nature of the interaction of silver colloids with the specific terminus of the residue, at varying pH environments. Copyright © 2012 John Wiley & Sons, Ltd.     

Cellular solid behaviour of liquid crystal colloids 2. Mechanical properties

This paper presents the results of a rheological study of thermotropic nematic colloids aggregated into cellular structures. Small sterically stabilised PMMA particles dispersed in a liquid crystal matrix densely pack on cell interfaces, but reversibly mix with the matrix when the system is heated above . We obtain a remarkably high elastic modulus, , which is a nearly linear function of particle concentration. A characteristic yield stress is required to disrupt the continuity of cellular structure and liquify the response. The colloid aggregation in a “poor nematic” MBBA has the same cellular morphology as in the “good nematic” 5CB, but the elastic strength is at least an order of magnitude lower. These findings are supported by theoretical arguments based on the high surface tension interfaces of a foam-like cellular system, taking into account the local melting of nematic liquid and the depletion locking of packed particles on interfaces. Received 13 March 2000 and Received in final form 6 June 2000     

Tunneling through a Metal/Polymer Interface Containing a Thin Oxide Layer: Discussion of the Consequences of Oxide Presence on Charge Injection

The charge injection from oxidized metal electrodes into conjugated polymer thin films is calculated and compared with ideal metal/polymer interfaces. The presence of the oxide layer has a major influence on the magnitude of the tunneling current as well as on its behavior with applied voltage. It was also found that the fitting of the simple Fowler-Nordheim model for triangular barriers to the obtained current-voltage data from the oxidized interfaces leads to incorrect values of the potential barrier height at the metal/polymer interface. Prediction and its consequences on charge injection control in organic devices are discussed.     

Investigation of the sign of the Soret coefficient in different ionic and surfacted magnetic colloids using forced Rayleigh scattering and single-beam Z -scan techniques

The sign of the Soret coefficient S T of a large set of ionic magnetic colloids (ionic ferrofluids (IFFs)) and surfacted magnetic colloids (surfacted ferrofluids (SFFs)) is determined using forced Rayleigh scattering and the single-beam Z -scan techniques. Different samples were investigated: acid and alkaline colloids with different values of pH; colloids with different concentrations of magnetic grains; colloids with grains of different typical diameters; colloids with magnetic grains with different coating natures; colloids with different non-polar and polar liquid carriers. Our results indicate that the sign of S T depends on the sign of the surface charge of grains in IFFs. In the case of water-based SFFs, the thermodiffusive behaviour is opposite to that of IFFs; that is, grains coated with a cationic surfactant behave like negatively charged IFF (alkaline) grains and grains coated with an anionic surfactant behave like positively charged IFF (acid) grains. SFFs with grains coated with non-ionic surfactants dispersed in non-polar fluid carriers behave like SFFs with grains coated with a cationic surfactant. The nature of the liquid carrier itself is not the only determinant factor, except apparently in the case of non-polar fluids, where only S T > 0 is found. These results cannot be explained with the available theories and it is highly probable that different mechanisms are present in the thermodiffusive behaviour of these complex fluids.