Reversible light-induced capacitance switching of azobenzene ether/PMMA blends

Fully reversible light-induced switching of the capacitance with changes larger than 50% has been achieved by using photo-active thin polymer films. The films consist of PMMA polymer blended with high concentrations of branched azobenzene ether dye molecules. Polymer thin sheet capacitors can be easily produced by spin coating and drop casting in various thicknesses ranging from 100 nm to 8 μm, respectively. Reversible capacitance switching is induced by illumination with UV and visible light, respectively. The capacitance change is correlated to the trans to cis isomerization of the azobenzene ether molecules and the alignment of the molecular dipoles in the film. Switching times depend on chromophore concentration, film thickness and light intensity used. The influence of wavelength of the light, of the temperature as well as of an electrical field applied during illumination on the capacitance change is addressed.     

Photo-induced isomerization of poly 4′-(6-acryloxy) hexyloxy-4-methoxyazobenzene ultra-thin solid film prepared by Langmuir–Blodgett technique

The photo-induced response of an ultra thin polymeric film of poly 4′-(6-acryloxy) hexyloxy-4-methoxyazobenzene (P5) is investigated. A monolayer of P5 at a gas–water interface possesses a mean molecular area of 28.0 Å²/monomer-repeat. Multilayer films of P5 were prepared by horizontal deposition at a surface pressure of 25 mN/m². The uniformity of the transfer process is shown by UV–vis absorption spectra where a linear relationship between the absorption maxima and the number of transferred layer was observed. The average layer thickness of the transferred film determined by XRD measurements is 34.0 Å. This is longer than the length of the azobenzene side group. The transferred film shows a blue shift of the π–π¹ transition from 357 nm for the P5 in solution to 340 nm for the P5 in the film. This suggests the formation of H-aggregate with a head-to-head arrangement of the dipole within the film. The optical property of the transferred film is changed by the irradiation of the film with the UV light at 385 nm. An irreversible change in its molecular packing in the film is seen in the shift of the UV–vis absorption maxima and the change in morphology as observed by AFM. The film morphology changes from being a smooth film into an island-like surface when exposed to the UV irradiation. The layer structure in the film is destroyed. A mass transport is observed during the cis–trans thermal back isomerization process. This suggests that movement of the P5 took place in both the trans–cis isomerization process and the cis–trans back isomerization process. The first movement leads to a molecular expansion while the second, to a molecular contraction.     

The first detection of photomodulation by both DC and in-phase AC susceptibility for organic/inorganic hybrid materials containing cyano-bridged Gd–Cr complex and azobenzene

New organic/inorganic hybrid material containing a ferrimagnetic cyano-bridged binuclear complex, [Gd(DMF)₄(H₂O)₃Cr(CN)₆]·H₂O (DMF=N,N′-dimethylformamide), and photochromic azobenzene in poly(methylmethacrylate) (PMMA) cast films has been prepared. We characterized magnetic properties of bulk [Gd(DMF)₄(H₂O)₃Cr(CN)₆]·H₂O and confirmed that it was not changed by light illumination at all. For the first time, we could detect reversible changes of both DC and in-phase AC susceptibility for the hybrid materials accompanying with cis–trans photoisomerization of azobenzene after UV and visible light illumination for 3 min at 3 K. We also discuss the kind of detectable magnetic changes (e.g. DC, in-phase AC, and both DC and in-phase AC) and the nature of some photo-magnetic functional hybrid materials (cis–trans photoisomerization and increase/decrease of magnetization) known to estimate their mechanism and interactions.     

Tunable and reversible surface wettability transition of vertically aligned ZnO nanorod arrays

Vertically aligned zinc oxide (ZnO) nanorods (NRs) with different surface morphology were grown by metal organic chemical vapor deposition (MOCVD) on sapphire substrate. To study the effect of surface morphology on wettability, the contact angle (CA) of water was measured. It was demonstrated that the CA of the deposited ZnO NRs varied between 104° and 135° depending upon the surface morphology. The ZnO NRs became super-hydrophilic after ultraviolet (UV) illumination. However, the NR arrays were reconverted to their previous hydrophobic state after low temperature annealing (50 °C) in open atmosphere. Structural effect and preferential adsorption of water molecules on the defective sites of UV illuminated surface was used to explain the transition mechanism. Under the alternations of heat treatment and UV illumination, a reversible transition between hydrophobicity and super-hydrophilicity were observed.     

A novel photo‐responsive organogel based on azobenzene

A novel triarmed cis‐1, 3, 5‐cyclohexanetricarboxamides gelator, functionalized by three azobenzene moieties grafted with three long alkyl chains, was designed and synthesized. The gelator can gel most of the organic solvents in low concentration. The morphologies of the xerogels show one‐dimensional aggregated bundles or helical fibres. The azobenzene groups in the gel state form H‐type aggregation and perform expected trans–cis photoisomerization with a gel to sol phase transition upon irradiation of UV light. The main driving force for gelation is intermolecular hydrogen bonding between amides and π–π interaction of azobenzene moieties. Copyright © 2008 John Wiley & Sons, Ltd.     

The first observation of photoinduced tuning of AC magnetization for organic–inorganic hybrid materials composed of Mn12-acetate and azobenzene

New organic–inorganic hybrid material composed of typical single-molecule magnet [Mn₁₂(CH₃COO)₁₆(H₂O)₄O₁₂]·2CH₃COOH·4H₂O (Mn₁₂-acetate) and photochromic azobenzene in PMMA cast films was prepared to observe novel photomagnetic phenomenon. We characterized it by means of UV–visible absorption and IR spectra to confirm photoisomerization of azobenzene even at room temperature. We measured temperature and field dependence of DC susceptibility, and temperature and frequency dependence of AC susceptibility as comparing with bulk precipitates of Mn₁₂-acetate. We found some differences in hysteresis loops for them. After alternate illumination of UV or visible light for 3 min at 3 K, we could observe reversible decrease or increase of in-phase AC susceptibility (and little changes of DC susceptibility) for the hybrid materials accompanying cis–trans photoisomerization of azobenzene.     

Controlling wettability by light: illuminating the molecular mechanism

The functionalisation of a surface with an organic monolayer containing photoactive moieties such as the azobenzene chromophore opens an elegant route for controlling its wettability by light. In this paper we investigate the microscopic origin of the macroscopic change in wettability upon photo-induced cis-trans isomerization of a copolymeric diphenyl-diazene Langmuir-Blodgett monolayer. Polarised UV-Vis and FTIR spectroscopy have been used to monitor the orientational order of various functional groups, Atomic Force Microscopy and Imaging Ellipsometry is employed for the quantification of the surface roughness and morphology, contact angle and surface potential measurements are carried out for a characterisation of the polar ordering. The data analysis is further supported by semi-empirical and ab-initio calculations of the molecular dipole moments and the normal IR-modes of the fluorinated chromophore. The combination of all these techniques provides a detailed molecular picture. The data suggest that changes in the projection of the dipole moment onto the surface normal caused by isomerization of the azobenzene are responsible for the observed changes in the surface energy. This knowledge allowed us to predict guidelines for the synthesis of molecules in order to maximize the wetting contrast upon photo-irradiation. Received 5 September 2002 Published online: 16 April 2003 RID="a" ID="a"e-mail: hubert.motschmann@mpikg-golm.mpg.de     

Hydrophobic recovery of UV/ozone treated poly(dimethylsiloxane): adhesion studies by contact mechanics and mechanism of surface modification

Silicone elastomers (Sylgard 184 and 170), based on poly(dimethylsiloxane) (PDMS), were surface treated by a combined exposure to UV and ozone. The effects of the treatments were analyzed as a function of time elapsed after stopping the treatments using different standard surface characterization techniques, such as water contact angle measurements, XPS and atomic force microscopy (AFM). However, the primary focus of this study was to apply the Johnson–Kendall–Roberts (JKR) contact mechanics approach to investigate PDMS samples prior to and following UV/ozone surface treatment. A gradual formation of a hydrophilic, silica-like surface layer with increasing modulus was observed with increasing UV/ozone exposure. A subsequent hydrophobic recovery after UV/ozone exposure was observed, as indicated by increasing contact angles. This supports the hypothesis that the hydrophobic recovery is mainly caused by the gradual coverage of a permanent silica-like structure with free siloxanes and/or reorientation of polar groups. PDMS containing a homogenously dispersed filler (Sylgard 184), exhibited a decreasing surface roughness (by AFM) when the oxidized surface region “collapsed” into a smooth SiO_x layer (final surface roughness <2 nm). PDMS containing heterogeneously distributed, aggregated filler particles (Sylgard 170), exhibited an increasing surface roughness with treatment dose, which was attributed to the “collapse” of the oxidized surface region thus exposing the contours of the underlying filler aggregates (final surface roughness ∼140 nm). A dedicated device was designed and built to study the contact mechanics behavior of PDMS prior to, and following surface treatment. The value of the combined elastic modulus obtained for PDMS lens and semi-infinite flat surface system showed an increase in full agreement with the formation of a silica-like layer exhibiting a high elastic modulus (compared with untreated PDMS). The work of adhesion observed in JKR experiments exhibited an increasing trend as a function of treatment done in agreement with contact angle data. JKR experiments showed hydrophobic recovery behavior as anticipated from contact angle measurements. Single pull-off force measurements by JKR and numerical analysis of full-approach JKR curves were in quantitative agreement regarding practical work of adhesion values.     

Adhesion studies of latex film surfaces on the meso- and nanoscale

In this paper the effects of surface roughness and annealing temperature (T) of latex coating films on adhesion are discussed for the different stages of the film formation process. The surface free energy of latex films was assessed in terms of practical work of adhesion (W) (or adherence) using a custom-built adhesion-testing device (ATD), atomic force microscopy (AFM), and contact angle measurements. For preannealed latex films surface roughness averages (R_a) were determined from AFM height images and were related to the values of W obtained from ATD measurements at room temperature. The results obtained using these tests exhibiting surface behavior on different length scales indicate a dependence of the measured adhesion on surface roughness and temperature, as well as on the length scale of the measurements.First preannealed samples were studied, which were obtained by heat treatment above the respective glass transition temperatures (T_g). Increasing the temperature of preannealing resulted in a decrease of the adherence observed in ATD experiments at room temperature. However, on the nanoscale, using AFM, no significant variation of the adherence was observed. This observation can be explained by roughness arguments. Preannealing decreases roughness which results in lower adherence values measured by ATD while for essentially single asperity AFM experiments roughness has an insignificant effect. Specimens were also annealed over a constant period of time (90 min) at different temperatures. At the end of the heat treatment, adhesion was measured at the treatment temperature by ATD. The amplified effect of temperature observed in this case on adherence is attributed to the combination of roughness decrease and increasing test temperature. In a third set of experiments completely annealed samples were studied by ATD as well as by AFM as a function of temperature. With increasing T values ATD showed a decrease in adherence, which is attributed to a decreasing surface free energy of the annealed films at elevated T values. AFM, on the other hand, showed an opposite trend which is assigned to increasing penetration of the tip into the tip/wetting polymer samples versus increasing temperature. Finally, annealing isotherms as a function of time were investigated by ATD in situ at different temperatures. This last set of experiments allowed us to optimize annealing time and temperature to achieve complete curing.     

Reversible wettability of nanostructured ZnO thin films by sol-gel method

Nanostructured ZnO thin films were deposited on Si(1 1 1) and quartz substrate by sol-gel method. The thin films were annealed at 673 K, 873 K, and 1073 K for 60 min. Microstructure, surface topography, and water contact angle of the thin films have been measured by X-ray diffractometer, atomic force microscopy, and water contact angle apparatus. XRD results showed that the ZnO thin films are polycrystalline with hexagonal wurtzite structure. AFM studies revealed that rms roughness changes from 2.3 nm to 7.4 nm and the grain size grow up continuously with increasing annealing temperature. Wettability results indicated that hydrophobicity of the un-irradiated ZnO thin films enhances with annealing temperature increase. The hydrophobic ZnO surfaces could be reversibly switched to hydrophilic by alternation of UV illumination and dark storage (thermal treatment). By studying the magnitude and the contact angle reduction rate of the light-induced process, the contribution of surface roughness is discussed.     

Fractal analysis and atomic force microscopy measurements of surface roughness for Hastelloy C276 substrates and amorphous alumina buffer layers in coated conductors

In coated conductors, surface roughness of metallic substrates and buffer layers could significantly affect the texture of subsequently deposited buffer layers and the critical current density of superconductor layer. Atomic force microscopy (AFM) is usually utilized to measure surface roughness. However, the roughness values are actually relevant to scan scale. Fractal geometry could be exerted to analyze the scaling performance of surface roughness. In this study, four samples were prepared, which were electro polished Hastelloy C276 substrate, mechanically polished Hastelloy C276 substrate and the amorphous alumina buffer layers deposited on both the substrates by ion beam deposition. The surface roughness, described by root mean squared (RMS) and arithmetic average (R_a) values, was analyzed considering the scan scale of AFM measurements. The surfaces of amorphous alumina layers were found to be fractal in nature because of the scaling performance of roughness, while the surfaces of Hastelloy substrates were not. The flatten modification of AFM images was discussed. And the calculation of surface roughness in smaller parts divided from the whole AFM images was studied, compared with the results of actual AFM measurements of the same scan scales.     

Optical properties of cadmium sulfide nanocrystal film prepared by electrochemical synthesis at liquid-liquid interface

Dendritic nanocrystalline CdS film was deposited at liquid-liquid interface of surfactants and an electrolyte containing 4 mmol L⁻¹ cadmium chloride (CdCl₂) and 16 mmol L⁻¹ thioacetamide (CH₃CSNH₂) with an initial pH value of 5 at 15 °C by electrochemical synthesis. The nanofilm was characterized by transmission electron microscopy (TEM), field emission scanning electron microscope (FE-SEM), atomic force microscopy (AFM), ultraviolet visible (UV-vis) absorption spectroscopy and fluorescence spectroscopy. The surface morphology and particle size of the nanofilm were investigated by AFM, SEM and TEM, and the crystalline size was 30-50 nm. The thickness of the nanofilm calculated by optical absorption spectrum was 80 nm. The microstructure and composition of the nanofilm was investigated by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), showing its polycrystalline structure consisting of CdS and Cd. Optical properties of the nanofilm were investigated systematically by UV-vis absorption and fluorescence spectroscopy. A λ_onset blue shift compared with bulk CdS was observed in the absorption spectra. Fluorescence spectra of the nanofilm indicated that the CdS nanofilm emitted blue and green light. The nanocomposites film electrode will bring about anodic photocurrent during illumination, showing that the transfer of cavities produces photocurrent.     

Surface characterization and microstructure of ITO thin films at different annealing temperatures

In this study, the electron beam evaporation method is used to generate an indium tin oxide (ITO) thin film on a glass substrate at room temperature. The surface characteristics of this ITO thin film are then investigated by means of an AFM (atomic force microscopy) method. The influence of postgrowth thermal annealing on the microstructure and surface morphology of ITO thin films are also examined. The results demonstrate that the film annealed at higher annealing temperature (300 °C) has higher surface roughness, which is due to the aggregation of the native grains into larger clusters upon annealing. The fractal analysis reveals that the value of fractal dimension D_f falls within the range 2.16-2.20 depending upon the annealing temperatures and is calculated by the height-height correlation function.     

Isomerization and fluorescence characteristics of sterically hindered azobenzene derivatives

We report synthesis and isomerization behaviors of sterically hindered azobenzene derivatives (1 and 2) with decyloxy and hydroxy groups, respectively, and their fluorescence enhancement under UV light irradiation characterized by means of absorption and fluorescence spectroscopy measurements. Upon irradiation of as-prepared solution (1) with UV light (∼200 mJ/cm²) a cis-rich photostationary state was reached. Obviously different from 2 showing very fast thermal cis-to-trans isomerization within 2 min, slow cis-to-trans thermal back isomerization of 1 with a long alkyl chain at ambient temperature was observed on the time scale of weeks. In contrast to no striking changes in absorption and fluorescence spectra of compound 2, the azobenzene 1 showed green fluorescence upon prolonged irradiation with UV light (about 3-8 J/cm² exposure doses), although both the initial trans-rich and cis-rich states of azobenzene molecules were not fluorescent in solution. The stability of fluorescence efficiency caused by drying and redissolving processes was examined.     

Chemical surface composition of the polyethylene implanted by Ag ions studied by phase imaging atomic force microscopy

High density polyethylene (HDPE) has been modified by Ag⁺ ion implantation with the energy of 60 keV. The total amount of implanted silver ions was 1, 5 and 12 × 10¹⁵ ions/cm². The surface topography was observed by atomic force microscopy (AFM), while the surface composition changes were detected using phase imaging AFM. Surface topography changes were studied in detail using 3D surface parameters analyses. The average roughness decreased for the implanted HDPE indicating the flattening of the surface. Phase AFM images indicated the homogenization of the polyethylene during ion implantation, while histogram analyses confirmed the change in surface composition.     

Surface characterization of collagen/elastin based biomaterials for tissue regeneration

Collagen and elastin are the main proteins of extracellular matrix. Collagen plays a crucial role in tensile strength of tissues, whereas elastin provides resilience to many organs. Both biopolymers are readily available and biocompatible. These properties point out that collagen and elastin are good components of materials for many potential medical applications. The surface properties of biomaterials play an important role in biomedicine as the majority of biological reactions occur on the surface of implanted materials. One of the methods of surface modification is UV-irradiation. The exposition of the biomaterial on ultraviolet light can alterate surface properties of the materials, their chemical stability, swelling properties and mechanical properties as well.The aim of our work was to study the surface properties and biocompatibility of new collagen/elastin based biomaterials and consideration of the influence of ultraviolet light on these properties.The surface properties of collagen/elastin based biomaterials modified by UV-irradiation were studied using the technique of atomic force microscopy (AFM) and contact angle measurements. On the basis of the results the surface free energy and its polar component was calculated using Owens-Wendt method. To assess the biological performance of films based on collagen, elastin and their blends, the response of 3T3 cell was investigated.It was found that the surface of collagen/elastin film is enriched in less polar component - collagen. Exposition on UV light increases polarity of collagen/elastin based films, due to photooxidation process. The AFM images have shown that topography and roughness of the materials had been also affected by UV-irradiation. The changes in surface properties influence on interaction between the material's surface and cells. The investigation of 3T3 cells grown on films based on collagen, elastin and their blends, leads to the conclusion that higher content of elastin in biomaterial promotes the cell adhesion and their viability on the surface. Also the suitable dose of UV light (1, 2 h) improves the biocompatibility of the materials.     

Characterization on titanium surfaces and its effect on photocatalytic bactericidal activity

Many studies have been published on the use of TiO₂ as a photocatalyst, which decomposes various organic compounds under UV illumination by generating various radicals. The purpose of the present study was to evaluate the photocatalytic bactericidal effects of variously treated titanium surfaces on Escherichia coli K-12. The specimens were fabricated from grade 4 commercially pure titanium, 12 mm in diameter and 1 mm in thickness. Five different surfaces were prepared (MA: machined surface; AO: anodized at 300 V; NO: NaOH-treated; NW: NaOH- and water-treated; and HT: heat-treated). Surface analysis was performed using scanning electron microscopy, optical interferometer, and thin-film X-ray diffractometry. Photocatalytic activity of each group was confirmed by degradation of methylene blue (MB). The antibacterial activity was assessed by calculating the survival ratio in a drop of a culture of E. coli placed on the surface under UV illumination. Significant photocatalytic activity and bactericidal effects were observed on the titanium surfaces of AO and NW, regardless of the surface roughness (P < 0.01). The group with anatase was the most susceptible to the photocatalytic effect, while the surface without anatase showed the least susceptibility. Based on this in vitro study, the crystallography of the oxide layer on its titanium surfaces is an important factor affecting the photocatalytic bactericidal activity.     

紫外光下纳米TiO2薄膜亲水性机理的电化学研究

利用溶胶 凝胶方法在透明导电玻璃ITO (SnO2 ∶In)表面制备纳米TiO2 薄膜 ,XRD谱图表明TiO2 是锐钛矿晶型 ,AFM (Atomic Force Microscope)测得薄膜表面粒子约为 10 0nm .研究了ITO表面纳米TiO2 薄膜的光致亲水性变化 .通过循环伏安技术测定TiO2 薄膜电极在 2 5 3.7nm的紫外光照射后的电化学行为推测光致亲水性机理 .发现在紫外光照射一定时间后 ,TiO2 薄膜电极的循环伏安图在 +0 .0 35V处出现新的氧化峰 ;且随光照时间的增加 ,氧化峰的峰电流增大 ,溶液中的溶解氧对峰电流的大小有明显影响 .实验表明 ,在紫外光照下电极表面有Ti3 + 产生 ,证实了TiO2 薄膜的光致亲水性转变过程与Ti3 + 的生成导致的表面结构变化有关     

Hydrophobic switching nature of methylcellulose ultra-thin films: thickness and annealing effects

We have studied the thermosensitive property of methylcellulose (MC) thin films supported on Si substrate by static sessile drop contact angle measurements, and their surface properties and thin film structure by x-ray reflectivity (XRR) and atomic force microscopy (AFM) techniques. From the static sessile drop contact angle measurements, the MC thin films showed the characteristic hydrophilic-to-hydrophobic transition at ～70?°C, which is the lower critical solution temperature of the bulk solution volume phase separation transition. For films with thickness d ≤ R(g), the onset of such a transition is affected by the film thickness while very thick films, d ? R(g), yielded higher contact angles. Annealing the MC thin films with thicknesses ～200 ? (near the radius of gyration, R(g), of the polymer) below the bulk glass transition temperature (T(g) ～ 195?° C) would not change the hydrophobic switch nature of the film but annealing 'at' and above the bulk T(g) would change its surface property. From surface topography images by AFM, there were no significant changes in either the roughness or the film texture before and after annealing. With XRR data, we were able to determine that such changes in the surface properties are highly correlated to the film thickness changes after the annealing process. This study, we believe, is the first to examine the thermal annealing affects on the thermal response function of a thermoresponsive polymer and is important for researching how to tailor the hydrophobic switching property of MC thin films for future sensing applications.     

Roughness evolution of highly ordered nanoporous anodic aluminum oxide films

In this paper, we report on the surface roughness evolution of highly ordered anodic aluminum oxide (AAO) films based on an atomic force microscopy (AFM) study. Root mean square of the surface roughness was measured on AFM images taken from highly ordered AAO films produced by two-step anodization under different conditions including electrolyte type, anodization voltage, and anodization time. Surface roughness of highly ordered AAO films increases step by step through the two-step anodizing process including electropolishing, first-step anodization, dissolution, and second-step anodization. However, increase of the surface roughness is proportional to the anodization voltage and time. The surface roughness of AAO films changes as a function of length scale until it finally approaches a maximum termed the saturation roughness. The variation of roughness of the growth of AAO could be scaled with an anomalous dynamic behavior as it saturates over a critical length scale while the saturation roughness is dependent on the anodizing time and voltage.