Electric field induced switching behaviors of monolayer-modified silicon surfaces: surface designs and molecular dynamics simulations

Electric field induced switching behaviors of a series of low-density omega-carboxyalkyl modified H-Si(111) and the mixed omega-carboxyalkyl/alkyl covered H-Si(111) have been simulated by using molecular dynamics (MD) simulation techniques. The external electric fields may drive surface-confined molecules to reversibly change conformations between the all-trans (switching "on") and the mixed trans-gauche (switching "off") states. Such surfaces switch wettabilities between the hydrophilic state and the moderately hydrophobic state. It has been found in broad ranges of intensities of applied electric fields, -2.0 x 10(9) V/m < or = E(down) < or = 0 and 1.8 x 10(9) V/m < or = E(up) < or = 7.3 x 10(9) V/m, both the low-density (11.1%-33.3%) omega-carboxyalkyl and the mixed omega-carboxyalkyl/alkyl (in mole fraction of 0.4 < or = N(carboxyalkyl) : N(alkyl) < or = 3.0) monolayers covering H-Si(111) exhibit conformational switching in the aqueous medium. The critical intensity of the electric field, E(up) = 1.8 x 10(9) V/m, which is required to trigger the switches is observed by our MD simulations and further rationalized by a thermodynamical model. Some important factors in the control of switching performances, such as the steric hindrances, the formation of the electric double layer at the monolayer/electrolyte solution interface, the hydration effects of carboxylate anions, the components of surrounding electrolyte solutions, as well as the rigidity of surface-confined chains are elucidated. The lower ionic strength and additions of acetonitrile molecules in the surrounding aqueous solution can reduce the value of critical intensity of the electric field and hence facilitate the realization of switching. Some practical considerations in construction and optimum design of switching surfaces are also suggested.     

Bilayer Molecular Assembly at a Solid/Liquid Interface as Triggered by a Mild Electric Field

The construction of a spatially defined assembly of molecular building blocks, especially in the vertical direction, presents a great challenge for surface molecular engineering. Herein, we demonstrate that an electric field applied between an STM tip and a substrate triggered the formation of a bilayer structure at the solid–liquid interface. In contrast to the typical high electric‐field strength (10⁹ V m^?1) used to induce structural transitions in supramolecular assemblies, a mild electric field (10⁵ V m^?1) triggered the formation of a bilayer structure of a polar molecule on top of a nanoporous network of trimesic acid on graphite. The bilayer structure was transformed into a monolayer kagome structure by changing the polarity of the electric field. This tailored formation and large‐scale phase transformation of a molecular assembly in the perpendicular dimension by a mild electric field opens perspectives for the manipulation of surface molecular nanoarchitectures.     

Development of a new methodology to study drop shape and surface tension in electric fields

Development of a new methodology for the study of both shape and surface tension of conducting drops in an electric field is presented. This methodology, called axisymmetric drop shape analysis-electric fields (ADSA-EF), generates numerical drop profiles in an electrostatic field, for a given surface tension. Then, it calculates the true value of the surface tension by matching theoretical profiles to the shape of experimental drops, using the surface tension as an adjustable parameter. ADSA-EF can be employed to simulate and study drop shapes in the electric field and to determine its effect on liquid surface tension. The method can also be used to measure surface tension in microgravity, where current drop-shape techniques are not applicable. The axisymmetric shape of the drop is the only assumption made in the development of ADSA-EF. The new scheme is applicable when both gravity and electrostatic forces are present. Preliminary measurements using ADSA-EF suggest that the surface tension of water increases by about 2% when an electric field with the magnitude of 10(6) V/m is applied.     

Effect of electric fields on contact angle and surface tension of drops

Contact angles of sessile drops were experimentally investigated in the electric field. The experimental setup was designed such that the electric field was applied to all three interfaces. The advanced Automated Polynomial Fitting (APF) methodology was employed to measure contact angles with high accuracy. The significance of the observations and trends was examined by conducting statistical tests of hypothesis. It was found that contact angles of polar liquids such as alcohols increase in the electric field. However, no significant trend was observed for nonpolar liquids such as alkanes. The change in the contact angle was found to be stronger for liquids with longer molecules. It was shown that the polarity of the electric field is not an underlying factor in the observed trends. Using the equation of state for interfacial tensions, the observed shift in contact angles was translated into a corresponding change in surface tension of the liquids. The results suggest that the surface tension of alcohols increases by one to two percent (depending on the size of molecules) when an electric field of the order of magnitude of 10(6) V/m is applied.     

Conductivity of molten sodium chloride in an arbitrarily weak dc electric field

We use nonequilibrium molecular-dynamics (NEMD) simulations to characterize the response of a fluid subjected to an electric field. We focus on the response for very weak fields. Fields accessible by conventional NEMD methods are typically of the order of 10(9) V m(-1), i.e., several orders of magnitude larger than those typically used in experiments. Using the transient time-correlation function, we show how NEMD simulations can be extended to study systems subjected to a realistic dc electric field. We then apply this approach to study the response of molten sodium chloride for a wide range of dc electric fields.     

Electro-optic behaviour of a non-polar nematic liquid crystal and its mixtures

In this work we report preliminary results on the properties of a non-polar bicyclohexane nematic liquid crystal. Moreover, its binary mixtures both with a low viscosity phenylcyclohexane and with a normal polar nematic liquid have been investigated. The elastic, viscous and electro-optical properties of these compounds are presented. The non-polar compound, and its mixture with a low percentage of the well known liquid crystal MBBA, exhibit an electrohydrodynamic behaviour in which the conducting regime is absent, while the dielectric regime spreads to low frequencies. Additionally, at higher frequencies of the applied electric field, a regime whose thresholds are linear in frequency is observed. On the other hand, the mixture formed by 50 wt % of the non-polar compound with MBBA exhibits at low frequencies the usual behaviour, followed at higher frequencies by the linear regime.     

Electro-optic behaviour of a non-polar nematic liquid crystal and its mixtures

In this work we report preliminary results on the properties of a non-polar bicyclohexane nematic liquid crystal. Moreover, its binary mixtures both with a low viscosity phenylcyclohexane and with a normal polar nematic liquid have been investigated. The elastic, viscous and electro-optical properties of these compounds are presented. The non-polar compound, and its mixture with a low percentage of the well known liquid crystal MBBA, exhibit an electrohydrodynamic behaviour in which the conducting regime is absent, while the dielectric regime spreads to low frequencies. Additionally, at higher frequencies of the applied electric field, a regime whose thresholds are linear in frequency is observed. On the other hand, the mixture formed by 50 wt % of the non-polar compound with MBBA exhibits at low frequencies the usual behaviour, followed at higher frequencies by the linear regime.     

Rearrangements in an alkylthiolate self-assembled monolayer using electrostatic interactions between nanoscale asperity and organomercaptan molecules

Chemically induced rearrangements of amphifunctional molecules have been demonstrated using strong nonuniform electric fields (10(8)-10(10) V m(-1)) induced in the vicinity of nanoscale asperities. Electrostatic interactions utilizing these rearrangements of alkylthiolates assembled on Au(111) result in the nanopatterning of raised nanostructure (1.5-9 nm high, 15-100 nm wide) arrays on a second time scale by manipulating an atomic force microscope (AFM) tip above the monolayer. It is suspected that, as a result of the oxidative cleavage initiated by a weak bias of the tip, the S end of the alkylthiolate chain carrying a sulfenium cation is attracted to the (lifting) tip, forming bi- and higher-layer structures in the vicinity of the tip apex. Stabilization of the multiple-layered structures is accomplished via mutual attraction and entanglement of hydrocarbon chains. The rearrangements suggest a novel and general approach for nanoscale architecture in self-assembled systems.     

Field distribution in an electrospray ionization source determined by finite element method

Three‐dimensional computer models of electrospray ionization sources were constructed in COMSOL Multiphysics? to solve the static electric fields using finite element methods. The magnitude of the electric field strength for onset of electrospray and optimum signal was calculated under various conditions. The modification of the electric field distribution in the ion source by an atmospheric pressure ion lens was also investigated by plotting the equipotential surfaces, electric field lines and trajectories of charged droplets. Both the calculated and the experimental results demonstrate that the changes in the ion signal detected by the mass spectrometer are attributable to the focusing effect of the ion lens when appropriate voltages are applied on the sprayer and ion lens. The optimum signal was found by setting the sprayer voltage from 3000 to 5000 V while scanning the ion lens voltage. The calculated strengths of the electric field at the sprayer tip for optimum signals are similar although the applied voltages at the sprayer and ion lens are significantly different. Copyright © 2009 John Wiley & Sons, Ltd.     

Electrochemically nanopatterned conducting coronas of a conjugated polymer precursor: SPM parameters and polymer composition

Here we describe the formation of precisely controlled corona-type nanopatterns on electroactive polymer precursor films using scanning probe microscopy (SPM) methods. The binary composition of electroactive groups in the polymer triggers the formation of corona-type nanopatterns at particular voltages and tip writing speeds through the electrooxidation of the polymer precursor film. Various parameters such as tip speed and applied bias were explored in the nanopatterning process, and the formation of a conductive nanopattern was investigated using conducting atomic force microscopy (C-AFM). The formation of the nanopattern was attributed to the flow of electrons from the AFM tip to the polymer film in a controlled electric field distribution. We also report a new method to distinguish the polymer composition and distribution of a polymer blend film by characterizing biasing differences in the patterning of a polymer film.     

Electrorheological properties of polyaniline suspensions: field-induced liquid to solid transition and residual gel structure

Polyaniline (PANI) was synthesized via oxidative coupling polymerization in acid conditions and de-doped in solution of ammonia. The electrorheological (ER) properties of the PANI/silicone oil suspensions were investigated in oscillatory shear as functions of electric field strength, particle concentration, and host fluid viscosity. Consistent with literature, the PANI ER fluid exhibits viscoelastic behavior under the applied electric field and the ER response is strongly enhanced with increasing electric field strength and particle concentration. The dynamic moduli, G' and G' increase dramatically, by 5 orders of magnitude, as the electric field strength is increased to 2 kV/mm. A viscoelastic liquid to solid transition occurs at a critical electric field strength, in the range Ec = 50-200 V/mm, whose value depends on particle concentration and host fluid viscosity. The fibrillar structure formed in the presence of the applied field has a static yield strength tau(y), whose value scales with electric field strength as tau(y) approximately E(1.88). When the field is switched off a residual structure remains, whose yield stress increases with the strength of the applied field and particle concentration. When the applied stress exceeds the yield stress of the residual structure, fast, fully reversible switching of the ER response is obtained.     

Polarization induced electrospray ionization mass spectrometry for the analysis of liquid,viscous and solid samples

In this study, a polarization‐induced electrospray ionization mass spectrometry (ESI‐MS) was developed. A micro‐sized sample droplet was deposited on a naturally available dielectric substrate such as a fruit or a stone, and then placed close to (~2 mm) the orifice of a mass spectrometer applied with a high voltage. Taylor cone was observed from the sample droplet, and a spray emitted from the cone apex was generated. The analyte ion signals derived from the droplet were obtained by the mass spectrometer. The ionization process is similar to that in ESI although no direct electric contact was applied on the sample site. The sample droplet polarized by the high electric field provided by the mass spectrometer initiated the ionization process. The dielectric sample loading substrate facilitated further the polarization process, resulting in the formation of Taylor cone. The mass spectral profiles obtained via this approach resembled those obtained using ESI‐MS. Multiply charged ions dominated the mass spectra of peptides and proteins, whereas singly charged ions dominated the mass spectra of small molecules such as amino acids and small organic molecules. In addition to liquid samples, this approach can be used for the analysis of solid and viscous samples. A small droplet containing suitable solvent (5–10 µl) was directly deposited on the surface of the solid (or viscous) sample, placed close the orifice of mass spectrometer applied with a high voltage. Taylor cone derived from the droplet was immediately formed followed by electrospray processes to generate gas‐phase ions for MS analysis. Analyte ions derived from the main ingredients of pharmaceutical tablets and viscous ointment can be extracted into the solvent droplet in situ and observed using a mass spectrometer. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis and characterization of photorefractive polymers with triphenylamine unit and NLO chromophore unit on a side chain

Acrylate‐type copolymers (TPA‐DCV) consisting of triphenylamine (TPA) unit as a hole transport agent and dicyanovinyl aniline (DCV) as a second‐order nonlinear optical (NLO) chromophore on a side chain were synthesized. The polymers showed good solubility and sufficient morphological stability after film formation. The diffraction efficiency and gain coefficient increased as glass transition temperature decreased TPA‐DCV composite doped with fullerene (C₆₀) and dibutyl phthalate had a high photoconductivity of 5.1 × 10⁻¹² S/cm at the applied electric field of 50 V/µm. Diffraction efficiency and response rate were measured as functions of the parameters determining the photoconductivity (e.g. applied electric field, the density of the photocharges generated and writing beam intensity). The maximum diffraction efficiency and gain coefficient were 12.9% and 64 cm⁻¹, respectively, at an applied electric field of 80 V/µm. The maximum response time of 700 msec was obtained at the applied electric field of 80 V/µm. Photoconductivity, response rate and diffraction efficiency increased with the increase of the applied electric field. Field dependence of the response rate is attributed to the charge generation efficiency and/or the drift mobility. A similar power dependence of the photoconductivity and the response rate on the writing beam intensity was observed. The response rate and diffraction efficiency showed a good linear relationship with the logarithm of the photoconductivity. Copyright © 2000 John Wiley & Sons, Ltd.     

Electroosmotic flow in a water column surrounded by an immiscible liquid

In this paper, we conducted numerical simulation of the electroosmotic flow in a column of an aqueous solution surrounded by an immiscible liquid. While governing equations in this case are the same as that in the electroosmotic flow through a microchannel with solid walls, the main difference is the types of interfacial boundary conditions. The effects of electric double layer (EDL) and surface charge (SC) are considered to apply the most realistic model for the velocity boundary condition at the interface of the two fluids. Effects on the flow field of ?-potential and viscosity ratio of the two fluids were investigated. Similar to the electroosmotic flow in microchannels, an approximately flat velocity profile exists in the aqueous solution. In the immiscible fluid phase, the velocity decreases to zero from the interface toward the immiscible fluid phase. The velocity in both phases increases with ?-potential at the interface of the two fluids. The higher values of ?-potential also increase the slip velocity at the interface of the two fluids. For the same applied electric field and the same ?-potential at the interface of the two fluids, the more viscous immiscible fluid, the slower the system moves. The viscosity of the immiscible fluid phase also affects the flatness of the velocity profile in the aqueous solution.     

Oxygen adsorption on gold nanofacets and model clusters

We have studied oxygen interaction with Au crystals (field emitter tips) using time-resolved (atom-probe) field desorption mass spectrometry. The results demonstrate no adsorption to take place on clean Au facets under chosen conditions of pressures (p < 10(-4) m/bar) and temperatures (T = 300-350 K). Steady electric fields of 6 V/nm do not allow dissociating the oxygen molecule. The measured O2+ intensities rather reflect ionization of O2 molecules at critical distances above the Au tip surface. Certain amounts of Au-O2 complex ions can be found at the onset of Au field evaporation. Calculations by density functional theory (DFT) show weak oxygen end-on interaction with Au10 clusters (Delta E = 0.023 eV) and comparatively stronger interaction with Au1/Au(100) model surfaces (Delta E = 0.25 eV). No binding is found on {210} facets. Including (positive) electric fields in the DFT calculations leads to an increase of the activation energy for oxygen dissociation thus providing an explanation for the absence of atomic oxygen ions from the field desorption mass spectra.     

Electroosmotic transport of immiscible binary system with a layer of non‐conducting fluid under interfacial slip: The role applied pressure gradient

We investigate the transport of immiscible binary fluid layers, constituted by one conducting (top layer fluid) and another non‐conducting (bottom layer fluid) fluids in a microfluidic channel under the combined influences of an applied pressure gradient and imposed electric field. We solve the transport equation governing the flow dynamics analytically and obtain the closed‐form expressions of the velocity fields. We bring out the alteration in the flow dynamics, mainly attributable to the non‐linear interaction between interfacial slip and the electrical double layer effect over small scales as modulated by the applied pressure gradient. In particular, we show the augmentation in the net volume transport rate through the channel, emerging from an intricate competition among electrical forcing, applied pressure gradient and the viscous resistance as modulated by the interfacial slip. We believe that the results of this study may be of immense consequence for the design of various microfluidic devises, which are often used for the manipulation of two immiscible fluids in different biomedical/biochemical processes.     

纳米管掺杂聚合物稳定蓝相液晶的电场响应性能

通过将不同尺寸的多壁碳纳米管(MWNTs)掺杂到聚合物稳定蓝相(PSBP)液晶中研究了体系的蓝相温度稳定性和电场响应性能。 小尺寸MWNTs的加入使PSBP电诱导反射波谱宽化的阈值电压显著降低。 MWNTs掺杂PSBP液晶光子晶体的电响应阈值场强降低至0.1 V/μm,在1.3 V/μm电场下反射光谱谱带宽度可从20 nm拓宽至310 nm。 该材料在反射型显示、可调滤光片等领域具有潜在应用价值。     

Electric field sensitivity of conducting hydrogels with interpenetrating polymer network structure

In this article, we reported the synthesis, structure and electric field sensitivity of polyacrylate/polyaniline (PAA/PANI) and poly(2-acrylamido-2-methyl propylsulfonic acid-acrylic acid)/polyaniline [P(AMPS-AA)/PANI] conducting hydrogels with an interpenetrating polymer network (IPN) structure. Scanning electron microscope showed that the conducting hydrogels presented porous structures consisting of PANI nanofibers. The results of Fourier-transform infrared and X-ray diffraction revealed that the PANI was in its conductive emeraldine state and partial crystallization. The unique morphology and molecular structure of the conducting hydrogels were expected to show unusual electric field responses. The conducting hydrogels were subjected to an electric field in NaCl solution for bending behaviors. It was demonstrated that the electric field response was improved by increasing aniline dosage, applied voltage and concentration of aqueous NaCl solution. The bending mechanism was attributed to polyelectrolyte hydrogel matrix and emeraldine PANI nanofibers.     

Effect of high-viscosity interphases on drainage between hydrophilic surfaces

Drainage of water from the region between an advancing probe tip and a flat sample is reconsidered under the assumption that the tip and sample surfaces are both coated by a thin water "interphase" (of width approximately a few nanometers) whose viscosity is much higher than that of the bulk liquid. A formula derived by solving the Navier-Stokes equations allows one to extract an interphase viscosity of approximately 59 kPa x s (or approximately 6.6 x 10(7) times the viscosity of bulk water at 25 degrees C) from interfacial force microscope measurements with both tip and sample functionalized hydrophilic by OH-terminated tri(ethylene glycol) undecylthiol, self-assambled monolayers.     

Electric field effect on the vibration of single CO molecules in a scanning tunneling microscope junction

A low-temperature scanning tunneling microscope (STM) and ab initio calculations were used to study the electric field effect on the vibration of single CO molecules in an STM junction at 13 K. The vibrational energy of CO molecules adsorbed on silver atoms, measured by STM-based inelastic electron tunneling spectroscopy, depends on the direction of the electric field applied between the STM tip and the silver species. This characteristic can be explained by the charge separation model. The electric field modifies the binding characteristics of CO on silver as a result of a change in the charged states of the species, which leads to an increase (or a decrease) of the energies of the hindered rotation and the CO stretch on silver.