Diffusion in ultrathin liquid films

Inhomogeneous molecular diffusion in layered structures of thin liquid films deposited on solid surfaces is observed via wide field single molecule microscopy. The fluorescence dyes Rhodamine 6G and Oregon Green 514 are used to probe the diffusion in tetrakis(2-ethylhexoxy)-silane and polydimethylsiloxane. A broad distribution of diffusion constants is observed which can be attributed to diffusion within distinct layers of the liquid. Comparison with computer simulations shows that diffusion is normal but depends strongly on the distance of the molecules from the solid surface. Diffusion within layers is faster than between the layers and additional temperature activation is necessary to speed up interlayer diffusion.     

Low‐voltage efficient electroosmotic pumps with ultrathin silica nanoporous membrane

In this work, an efficient electroosmotic pump (EOP) based on the ultrathin silica nanoporous membrane (u‐SNM), which can drive the motion of fluid under the operating voltage as low as 0.2 V, has been fabricated. Thanks to the ultrathin thickness of u‐SNM (～75 nm), the effective electric field strength across u‐SNM could be as high as 8.27 × 10⁵ V m^?1 in 0.4 M KCl when 1.0 V of voltage was applied. The maximum normalized electroosmotic flow (EOF) rate was as high as 172.90 mL/min/cm²/V, which was larger than most of other nanoporous membrane based EOPs. In addition to the ultrathin thickness, the high porosity of this membrane (with a pore density of 4 × 10¹² cm^?2, corresponding to a porosity of 16.7%) also contribute to such a high EOF rate. Moreover, the EOF rate was found to be proportional to both the applied voltage and the electrolyte concentration. Because of small electrokinetic radius of u‐SNM arising from its ultrasmall pore size (ca. 2.3 nm in diameter), the EOF rate increased with increasing the electrolyte concentration and reached the maximum at a concentration of 0.4 M. This dependence was rationalized by the variations of both zeta potential and electrokinetic radius with the electrolyte concentration.     

Additive route to lithographically defined nanoporous silica, polymer, and carbon films

A facile method was investigated for patterning microporous and mesoporous silica, polymer, and carbon films using a combination of lithography and solid-state chemistry. This process exploits the difference in chemical reactivity between the lithographically exposed and unexposed regions to control the reaction of a target precursor from the vapor phase. A block copolymer film loaded with a photoacid generator is utilized as a preformed template, and tetraethylorthosilicate (TEOS) and furfuryl alcohol (FA) are the silica and carbon precursors, respectively. Following UV exposure and reaction with vaporized precursors, thermal decomposition of the polymeric template yields a mesoporous film in the exposed regions. Dense line-space patterns down to 1.5 microm features were resolved with I-line lithography. Sharper features were formed using FA; this behavior is attributed to the requirement for water in the system during TEOS condensation. Moisture in the system appears to lead to enhanced diffusion of the photoacid and a small decrease in the feature resolution. This methodology provides a simple etch-free route to patterning mesoporous films using commercially available materials.     

Mass transport and electrode accessibility through periodic self-assembled nanoporous silica thin films

Ordered nanoporous silica films have attracted great interest for their potential use to template nanowires for photovoltaics and thermoelectrics. However, it is crucial to develop films such that an electrode under the nanoporous film is accessible to solution species via facile mass transport through well-defined pores. Here, we quantitatively measure the electrode accessibility and the effective species diffusivity for nearly all the known nanoporous silica film structures formed by evaporation-induced self-assembly upon dip-coating or spin-coating. Grazing-angle of incidence small-angle X-ray scattering was used to verify the nanoscale structure of the films and to ensure that all films were highly ordered and oriented. Electrochemical impedance spectroscopy (EIS) was then used to assess the transport properties. A model has been developed that separates the electrode/film kinetics and the film transport properties from the film/solution interface and bulk solution effects. Accounting for this, the accessible area of the nanoporous film coated FTO electrode (1-theta) is obtained from the high-frequency data, while the effective diffusivity of the ferrocene dimethanol (D(FDM)) redox couple is obtained from intermediate frequencies. It was found that the degree of order and orientation in the film, in addition to the symmetry/topology, is a dominant factor that determines these two key parameters. The EIS data show that the (211) oriented double gyroid, (110) oriented distorted body center cubic, and (211) distorted primitive cubic silica films have significant accessibility (larger than 26% of geometric area). However, the double-gyroid films showed the highest diffusivity by over an order of magnitude. Both the (10) oriented 2D hexagonal and (111) oriented rhombohedral films were found to be highly blocking with only small accessibility due to microporosity. The impedance data were also collected to study the stability of the nanoporous silica films in aqueous solutions as a function of pH. The distorted primitive silica film showed much faster degradation in pH 7 solution when compared to a blocking film such as the 2D hexagonal. However, silica films maintained their structure at pH 2 for at least 12 h.     

Vibrational spectroscopy of dimethylchlorooctadecylsilane covalently bonded to ultrathin silica films immobilized on Ag surfaces

FTIR and Raman spectroscopies have been used to characterize the structure and conformational order of dimethylchlorooctadecylsilane (DOS) covalently bonded to ultrathin silica films supported on Ag substrates. Ultrathin silica films of ca. 30 A thickness prepared from sol-gel methods are immobilized on Ag surfaces modified with a self-assembled monolayer of (3-mercaptopropyl)trimethoxysilane (3MPT). This layered structure provides a unique opportunity for acquiring complementary spectral data from both FTIR and Raman spectroscopies, which are useful in elucidating alkylsilane conformation pertaining to stationary phases for reversed-phase liquid chromatography (RPLC). Characterization of octadecyltrichlorosilane (OTS) layers on thin silica films of ca. 800 A thickness on 3MPT-modified Ag surfaces has been reported previously. Differences between the ultrathin silica films used in this study and the thin silica films used in this previous study are considered. The results from both FTIR and Raman spectroscopy presented here suggest that bonded DOS alkyl chains are in a disordered, liquid-like state with close to monolayer surface coverage.     

Vibrational spectroscopy of dimethylchlorooctadecylsilane covalently bonded to ultrathin silica films immobilized on Ag surfaces

FTIR and Raman spectroscopies have been used to characterize the structure and conformational order of dimethylchlorooctadecylsilane (DOS) covalently bonded to ultrathin silica films supported on Ag substrates. Ultrathin silica films of ca. 30 Å thickness prepared from sol-gel methods are immobilized on Ag surfaces modified with a self-assembled monolayer of (3-mercaptopropyl)trimethoxysilane (3MPT). This layered structure provides a unique opportunity for acquiring complementary spectral data from both FTIR and Raman spectroscopies, which are useful in elucidating alkylsilane conformation pertaining to stationary phases for reversed-phase liquid chromatography (RPLC). Characterization of octadecyltrichlorosilane (OTS) layers on thin silica films of ca. 800 Å thickness on 3MPT-modified Ag surfaces has been reported previously. Differences between the ultrathin silica films used in this study and the thin silica films used in this previous study are considered. The results from both FTIR and Raman spectroscopy presented here suggest that bonded DOS alkyl chains are in a disordered, liquid-like state with close to monolayer surface coverage.     

Enzyme encapsulation in nanoporous silica spheres

Encapsulating enzymes in mesoporous silica spheres via immobilization, followed by assembling an organic/inorganic nanocomposite shell on the particle surface leads to high loadings, high enzymatic activity and stability, and protection from proteolysis.     

Photomagnetic hybrid ultrathin films

Two novel types of photomagnetic hybrid ultrathin film (film A and B) of metal cyanides have been fabricated by means of the modified Langmuir–Blodgett method using a smectite clay mineral. Film A is composed of an amphiphilic azobenzene cation, a montmorillonite, and Prussian Blue in which photocontrol in the magnetization was realized by the photoisomerization of azobenzene chromophore. The observed photomagnetic efficiency was large (ca. 11%) due to the well-organized structure of the ultrathin film. Film B is composed of a quaternary ammonium salt, a montmorillonite, and Co–Fe Prussian Blue in which the photoinduced magnetization caused by the electron transfer exhibited an anisotropic response with regards to the direction of the applied magnetic field. This phenomenon is ascribed to the unique structure of Co–Fe Prussian Blue formed onto the clay layer. Contribution to special issue “Magnetic field effects in Electrochemistry”     

Aqueous dip-coating route to dense and porous silica thin films using silica nanocolloids with an aid of polyvinylpyrrolidone

An aqueous dip-coating route without using volatile alcohols for preparing dense and porous silica thin films is presented. The films were prepared by dip-coating on Si(100) and silica glass substrates using aqueous suspension of 8–11 nm colloidal silica where no alcohols were added. The addition of polyvinylpyrrolidone (PVP) in the suspension greatly improved the wettability, allowing homogeneous films to be formed on the substrates while the substrates showed poor wettability without PVP. When the as-deposited films were fired at 500–1,000 °C, optically transparent porous films with smooth surface were obtained. The porous films had homogeneous distribution and packing of silica nanoparticles, refractive indices of 1.24–1.33, and pencil hardness lower than 6B. The porous films underwent significant densification by viscous sintering when fired at temperatures over 1,000 °C. The viscous sintering was accompanied by the progress of condensation reaction and by the structural relaxation of siloxane network, which was revealed in the infrared absorption spectra. The resulting dense films had optical transparency, smooth surface, pencil hardness over 9H and refractive indices close to that of silica glass.     

Neutron reflectivity study of lipid membranes assembled on ordered nanocomposite and nanoporous silica thin films

Single bilayer membranes of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) were formed on ordered nanocomposite and nanoporous silica thin films by fusion of small unilamellar vesicles. The structure of these membranes was investigated using neutron reflectivity. The underlying thin films were formed by evaporation induced self-assembly to obtain periodic arrangements of silica and surfactant molecules in the nanocomposite thin films, followed by photocalcination to oxidatively remove the organics and render the films nanoporous. We show that this platform affords homogeneous and continuous bilayer membranes that have promising applications as model membranes and sensors.     

Polydiacetylene nanowires in ultrathin films

In this paper the results of studies carried out on thin films of new poly[bis(carbazol-9-ylmethyl)diacetylene]s (PCDAs) are reported. The preparation of the films has required clever synthesis to make processable the conjugated polymers without degrading their optoelectronic properties. To this end, the parent poly(diacetylene), (polyDCHD), has been modified by introducing long alkyl or acyl chains in the 3 and 6 positions of the carbazole rings. Electronic absorption spectra and linear and nonlinear optical characterization of three types of PCDAs are reported and compared.     

pH-sensitive bipolar ion-permselective ultrathin films

pH-Sensitive bipolar ion-permselective films of polyelectrolyte multilayers were prepared by layer-by-layer (LbL) assembly and photo-cross-linking of benzophenone-modified poly(acrylic acid) (PAA-BP) and poly(allylamine hydrochloride) (PAH-BP). The multilayer structure and ionizable group composition was finely tuned by changing the pH of the dipping solution. This structure and composition was in turn "preserved" by photo-cross-linking, forming highly stable membrane films. Since PAA-BP and PAH-BP are weak polyelectrolytes, it is possible to control the number of unbound, un-ionized -COOH or -NH2 groups in the multilayer by changing the pH. Moreover, the pH of the deposited film also plays an important role in determining selective latter permselectivity. For example, PAA-BP/PAH-BP multilayers deposited from two pH conditions, pH = 3 (PAA-BP) and pH = 6 (PAH-BP), showed pH-switchable permselectivity for both cationic (pH = 10) and anionic (pH = 3) probe molecules in a single film. The system offers advantages in film stability and introducing reversible selective ion permeability over previous multilayer film and cross-linking methods.     

Atomistic simulation of the formation of nanoporous silica films via molecular chemical vapor deposition on nonporous substrates

To distinguish thin deposited film characteristics clearly from the influence of substrate morphological properties, the growth mechanism and the macroscale and nanoscale properties of nanoporous SiO(2) films deposited on nonporous silica (SiO(2)) substrates from chemical precursors Si(OH)(4) and TEOS (tetraethoxysilane) via low-pressure chemical vapor deposition are the primary targets of this study. This work employs a kinetic Monte Carlo (KMC) simulation method coupled to the Metropolis Monte Carlo method to relax the strained silica structure. The influence of the deposition temperature (473, 673, and 873 K) on the properties of the SiO(x) layers is addressed via analysis of the film growth rates, density profiles of the deposited thin films, pore size distributions, carbon depth profiles (with respect to TEOS), and voidage analysis for layers of different thicknesses (8-18 nm). A comparison of simulation with experimental results is also carried out.     

Diffusion of nanoparticles in dense fluids

The diffusion process of a single spherical nanoparticle immersed in a fluid solvent is studied by molecular dynamics simulations. When the nanoparticle mass stays constant, it is shown that, at short times, the decay of the nanoparticle velocity autocorrelation function is strongly modified when the particle diameter increases. It is also shown that, at large times, the characteristic algebraic decay induced by the hydrodynamic correlations between the solvated particle and the solvent presents a scaling behavior depending on the particle diameter.     

Next generation, sequentially assembled ultrathin films: beyond electrostatics

Over the last 15 years, the layer-by-layer (LbL) assembly technology has proven to be a versatile method for surface modification. This approach is likely to find widespread application because of its simplicity and versatility; however, the conventional use of highly charged materials with limited responsive behaviour presents some key limitations. In this tutorial review, the formation of multilayer thin films prepared through non-electrostatic interactions is reviewed. We discuss the assembly of films via a number of different methodologies, with particular emphasis on those that provide enhanced orientational control, stimuli-responsive behaviour, and improved film stability.     

Preparation, structure, and optical properties of nanoporous gold thin films

Thin nanoporous gold (np-Au) films, ranging in thickness from approximately 40 to 1600 nm, have been prepared by selective chemical etching of Ag from Ag/Au alloy films supported on planar substrates. A combination of scanning electron microscopy (SEM) imaging, synchrotron grazing incidence small angle X-ray scattering, and N2 adsorption surface area measurements shows the films to exhibit a porous structure with intertwined gold fibrils exhibiting a spectrum of feature sizes and spacings ranging from several to hundreds of nanometers. Spectroscopic ellipsometry measurements (300-800 nm) reveal the onset of surface plasmon types of features with increase of film thicknesses into the approximately 200 nm film thickness range. Raman scattering measurements for films functionalized with a self-assembled monolayer formed from 4-fluorobenzenethiol show significant enhancements which vary sharply with film thickness and etching times. The maximum enhancement factors reach approximately 10(4) for 632.8 nm excitation, peak sharply in the approximately 200 nm thickness range for films prepared at optimum etching times, and show high spot to spot reproducibility with approximately 1 microm laser spot sizes, an indication that these films could be useful as durable, highly reproducible surface-enhanced Raman substrates.     

Ion transport in sulfonated nanoporous colloidal films

The surface of self-assembled nanoporous silica colloidal crystalline films comprised of 184-nm-diameter silica spheres has been sulfonated using 1,3-propanesultone. The transport of ions through the sulfonated films has been studied using cyclic voltammetry in water as a function of ion charge, pH, and solution ionic strength. We found that the flux of anions through the sulfonated colloidal films is reduced, while the flux of cations is increased, compared to the unmodified colloidal films. This behavior is pH-dependent and is due to electrostatic repulsion/attraction that can be modulated by changing the ionic strength of the contacting solution.     

Pore morphologies in disordered nanoporous thin films

Materials with nanometer size heterogeneities are commonplace in the chemical and biological sciences (e.g, polymer blends, microemulsions, gels) and often exhibit complex morphologies. Although this morphology has a dramatic effect on the materials' properties, it is often difficult to accurately characterize. We describe a method, using small-angle X-ray scattering data, of generating representative three-dimensional morphologies of isotropic two-phase materials where the morphology is disordered, and we apply this to thin films containing nanometer sized pores with a range of porosities (4-44%). These representations provide a visualization of the pore morphology, give the pore size scale and extent of interconnection, and permit the determination of the transitions from closed pore to interconnected pores to bicontinuous morphology.