The stability of radio-frequency plasma-treated polydimethylsiloxane surfaces

Polydimethylsiloxane (PDMS) is a widely used material for manufacturing lab-on-chip devices. However, the hydrophobic nature of PDMS is a disadvantage in microfluidic systems. To transform the hydrophobic PDMS surface to hydrophilic, it was treated with radio-frequency (RF) air plasma at 150, 300, and 500 mTorr pressures for up to 30 min. Following the surface treatment, the PDMS specimens were stored in air, deionized water, or 0.14 M NaCl solution at 4 degrees C, 20 degrees C, and 70 degrees C. The change in the hydrophilicity (wettability) of the PDMS surfaces was followed by contact angle measurements and Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy as a function of time. As an effect of the RF plasma treatment, the contact angles measured on PDMS surfaces dropped from 113 +/- 4 degrees to 9 +/- 3 degrees . The chamber pressure and the treatment time had no or negligible effect on the results. However, the PDMS surface gradually lost its hydrophilic properties in time. The rate of this process is influenced by the difference in the dielectric constants of the PDMS and its ambient environment. It was the smallest at low temperatures in deionized water and largest at high temperatures in air. Apparently, the OH groups generated on the PDMS surface during the plasma treatment tended toward a more hydrophilic/less hydrophobic environment during the relaxation processes. The correlation between the FTIR-ATR spectral information and the contact angle data supports this interpretation.     

Surface Properties of Polydimethylsiloxane-Based Inorganic/Organic Hybrid Films Deposited on Polyimide Sheets by the Sol-Gel Method

Polydimethylsiloxane (PDMS)-based inorganic/organic hybrids films were prepared on polyimide sheets by the sol-gel method using silanol-terminated PDMS and titanium tetraisopropoxide as starting materials. The effect of heat-treatment temperature on the surface property of the hybrid films was examined in terms of contact angle of water and Tapping-Mode Atomic Force Microscopy (AFM). AFM phase images showed the presence of domains, 200–500 nm in size, on the surface of these films after heat-treatment below 300°C. These regions were more hydrophilic than the rest of the area. The domains disappeared at 300°C and the surface became homogeneous surface of the peak to valley value, about 10 nm. It is also uniformly hydrophobic and a maximum contact angle (about 115°C) was obtained.     

Anode Engineering of Highly Efficient Polymer Solar Cells Using Treated ITO

ITO substrates were treated with organic solvent cleaning(OSC), SC1 treatment[V(NH₄OH):V(H₂O₂): V(H₂O)=1:1:5], O₂ plasma and UV ozone, respectively. Combined investigations of atom force microscopy(AFM), water contact angle measurements, ultraviolet photoemission spectroscopy(UPS) and X-ray photoemission spectroscopy(XPS) demonstrated that UV ozone treatment could give rise to the smoothest surface, the most hydrophilic property and the highest work function(WF) of ITO due to the removal of hydrophobic C-O impurity from the ITO surface and the enrichments of more oxygen on the ITO surface. When PEDOT:PSS film[(poly(3,4-ethylenedioxy- thiophene):poly(styrene sulfonate)] was deposited on the ITO substrates treated with UV ozone, it showed a lower root-mean- square roughness in AFM images, a higher transmission in UV-Vis transmission spectra and a higher WF in UPS spectra than the PEDOT:PSS films deposited on the ITO substrates treated by other three methods. As a result, the power conversion efficiency of polymer solar cells(PSCs) based on PTB7:PC₇₁BM as an active layer and ITO treated by UV ozone as an anode can reach 8.48% because of the simultaneously improved short circuit current, open circuit voltage and fill factor compared to the PSCs with ITO treated with other three methods.     

Photosensitized heterogeneous chemistry of ozone on organic films

The interactions of ozone with benzophenone and phenol solid films have been investigated under simulated atmospheric conditions with respect to relative humidity, pressure, temperature, and O3 concentration using a coated flow tube reactor. The steady-state reactive uptake coefficients (gammass) of ozone on benzophenone films ranged from below 10(-6) in dark conditions to approximately 4 x 10(-6) under UV-A irradiation and decreased with increasing O3 concentration in the range 28-320 ppbv. A similar trend was observed for the initial uptake coefficient (gammai) which varied from ca. 1.5 x 10(-6) in the dark to approximately 7 x 10(-6) under UV-A irradiation. The uptake coefficients under irradiation were strongly dependent on the relative humidity (from 5 to 70%), with their lowest values at high humidity (70% RH). The ozone uptakes for multilayer coverage turned out to be independent of the deposited mass of the organic compound. The benzophenone-phenol mixture also showed photoenhanced uptake with a larger steady-state uptake under visible irradiation, approximately 2.9 x 10(-6). Contact angle measurements showed an increase of the organic film hydrophobicity for the benzophenone-phenol mixture upon combined exposure to light and ozone. A linear dependence of the kinetic values on the photon flux has been demonstrated and when extrapolated to the solar spectral irradiance would lead to uptake coefficients of approximately 10(-5). UV-vis analysis and contact angle measurements of the organic film after irradiation and ozone exposure showed relevant changes only in the mixture, with an increase in the hydrophobic character of the film and the appearance of a new absorption band up to 450 nm.     

Wetting and absorption of water drops on Nafion films

Water drops on Nafion films caused the surface to switch from being hydrophobic to being hydrophilic. Contact angle hysteresis of >70 degrees between advancing and receding values were obtained by the Wilhelmy plate technique. Sessile drop measurements were consistent with the advancing contact angle; the sessile drop contact angle was 108 degrees . Water drop adhesion, as measured by the detachment angle on an inclined plane, showed much stronger water adhesion on Nafion than Teflon. Sessile water and methanol drops caused dry Nafion films to deflect. The flexure went through a maximum with time. Flexure increased with contact area of the drop, but was insensitive to the film thickness. Methanol drops spread more on Nafion and caused larger film flexure than water. The results suggest that the Nafion surface was initially hydrophobic but water and methanol drops caused hydrophilic sulfonic acid domains to be drawn to the Nafion surface. Local swelling of the film beneath the water drop caused the film to buckle. The maximum flexure is suggested to result from motion of a water swelling front through the Nafion film.     

Investigating the interface of superhydrophobic surfaces in contact with water

Neutron reflectivity (NR) is used to probe the solid, liquid, vapor interface of a porous superhydrophobic (SH) surface submerged in water. A low-temperature, low-pressure technique was used to prepare a rough, highly porous organosilica aerogel-like film. UV/ozone treatments were used to control the surface coverage of hydrophobic organic ligands on the silica framework, allowing the contact angle with water to be continuously varied over the range of 160 degrees (superhydrophobic) to <10 degrees (hydrophilic). NR shows that the superhydrophobic nature of the surface prevents infiltration of water into the porous film. Atomic force microscopy and density functional theory simulations are used in combination to interpret the NR results and help establish the location, width, and nature of the SH film-water interface.     

Fabrication of flexible gold films with periodic sub-micrometer roughness and their wettability control by modification of SAM

Flexible honeycomb gold films supported by polymer sheets are fabricated by using polystyrene particle monolayers. The surfaces of the flexible gold films are covered with self-assembled monolayers (SAMs) of hydrophobic or hydrophilic thiol compounds, and the wettability of the modified surface is evaluated by measurements of the contact angles of water droplets. The contact angle of the film covered with hydrophobic SAM is ca. 150 degrees, which is greater than the value of 112 degrees for a flat gold surface, while the values for hydrophilic SAM are below 10 degrees.     

Wetting properties of model biological membranes

Various aspects of native and model biological membrane wettability are discussed. Among others hydration of mono-, bi-, and multi-layers of lipids as well as wettability of macroscopic surfaces of solid supported lipid films was investigated via apparent contact angle measurements and calculation of the apparent surface free energy of the films. The effects of relative humidity on the layer hydration and contact angle changes are also discussed. Finally, the effect of liposomes and enzymes (due to the hydrolysis reactions) on the hydrophobic/hydrophilic character of the film surfaces is overviewed.     

Stability of monomolecular films of archaebacterial tetraether lipids on silicon wafers: a comparison of physisorbed and chemisorbed monolayers

The monomolecular organisation of symmetric, chemically modified tetraether lipids caldarchaeol-PO(4) was studied using Langmuir film balance, ellipsometry, and atomic force microscopy (AFM). Solid silicon wafer substrates were modified to hydrophobic, hydrophilic, and amino-silanised surfaces; and Langmuir-Blodgett (LB)-films were transferred onto each. LB-caldarchaeol-PO(4) films were subjected to further rinsing with organic solvent and additional physical treatments, to compare their resistance and stability on chemisorbed (amino-silanised) and physisorbed (hydrophobic and hydrophilic) surfaces. The resistance and stability of these monolayer films was characterized by ellipsometry and AFM, and film thickness was determined using ellipsometry. AFM was also employed to observe surface morphology. Monolayer films on hydrophobic surfaces were found to be more resistant to rinsing with organic solvent and additional physical treatments than monolayer films on either amino-silanised or hydrophilic surfaces. The hydrophobic effect with hydrophobic surfaces appears to support the formation of stronger caldarchaeol-PO(4) films on silicon wafer substrates, with increased resistance and stability.     

Plasma modified polymers as a support for enzyme immobilization II. Amines plasma

Polysulfone films were modified by ammonia, n-butylamine and allylamine remote plasma using various sample-to-plasma distances. Contact angle measurements, FTIR-ATR and XPS spectroscopy proved the presence of polar, including amine, groups on the modified surface. Presence of argon in the plasma environment made the plasma more stable and in most cases left the surface more hydrophilic but with a lower amount of nitrogen moieties on it. Glucose isomerase was successfully immobilized on the plasma-treated samples. Its activity correlates well with the concentration of C-N bonds on the surface. The highest enzyme activity was achieved for samples treated with allylamine/Ar plasma close to the plasma edge.     

Enhanced super-hydrophobic and switching behavior of ZnO nanostructured surfaces prepared by simple solution--immersion successive ionic layer adsorption and reaction process

A simple and cost-effective successive ionic layer adsorption and reaction (SILAR) method was adopted to fabricate hydrophobic ZnO nanostructured surfaces on transparent indium-tin oxide (ITO), glass and polyethylene terephthalate (PET) substrates. ZnO films deposited on different substrates show hierarchical structures like spindle, flower and spherical shape with diameters ranging from 30 to 300 nm. The photo-induced switching behaviors of ZnO film surfaces between hydrophobic and hydrophilic states were examined by water contact angle and X-ray photoelectron spectroscopy (XPS) analysis. ZnO nanostructured films had contact angles of ~140° and 160°±2 on glass and PET substrates, respectively, exhibiting hydrophobic behavior without any surface modification or treatment. Upon exposure to ultraviolet (UV) illumination, the films showed hydrophilic behavior (contact angle: 15°±2), which upon low thermal stimuli revert back to its original hydrophobic nature. Such reversible and repeatable switching behaviors were observed upon cyclical exposure to ultraviolet radiation. These biomimetic ZnO surfaces exhibit good anti-reflective properties with lower reflectance of 9% for PET substrates. Thus, the present work is significant in terms of its potential application in switching devices, solar coatings and self-cleaning smart windows.     

Surface characterization of atomic oxygen beam-exposed polyimide films using contact angle measurements

Polyimide surfaces exposed to simulated low Earth orbit space environment, i.e., under hyperthermal atomic oxygen bombardment, were characterized by using atomic force microscopy, X-ray photoelectron spectroscopy, and contact angle measurements. The surface analytical results showed that the roughness and the O/C ratio at the atomic oxygen-exposed polyimide surface increased with increasing atomic oxygen fluence. The advancing and receding contact angles decreased with increasing O/C ratios at the polyimide surfaces. The Lifshitz-van der Waals component, the acid and base parameters of the surface free energy of polyimide films were calculated from the contact angles. The base parameter increased with increasing O/C ratio, whereas the acid parameter and the Lifshitz-van der Waals component did not show a remarkable change. These analytical results agree with the in situ XPS data showing the formation of surface functional groups due to atomic oxygen exposure. It was demonstrated in this study that the polyimide surface in a low Earth orbit space environment may become hydrophilic due to the bombardment by atomic oxygen. Received: 4 December 1999 Accepted: 31 August 2000     

有机半导体图案化成膜中的马兰戈尼与咖啡环效应协同作用

有机场效应晶体管在柔性传感和显示驱动应用中展示出极大的潜力,但在大面积制备高性能有机薄膜及有机场效应晶体管方面仍面临大的挑战。本文介绍了一种利用等离子处理和马兰戈尼-咖啡环效应协同作用来图案化生长有机半导体薄膜的方法。经过对等离子体处理时间、混合溶剂的比例及溶液浓度等生长条件优化,在5 cm×5 cm的基片上得到了覆盖性较为完整的2,7-二辛基[1]苯并噻吩并[3,2-b]苯并噻吩(C8-BTBT)薄膜阵列。基于此薄膜构筑了底栅顶接触晶体管阵列,器件的平均迁移率达到7.9 cm~2·V~(-1)·s~(-1),阈值电压均小于-2 V,开关电流比大于10~4。本工作对未来大面积制备高性能有机半导体薄膜及晶体管具有一定的借鉴意义。     

Immobilization of amphiphilic polycations by catechol functionality for antimicrobial coatings

A new strategy for preparing antimicrobial surfaces by a simple dip-coating procedure is reported. Amphiphilic polycations with different mole ratios of monomers containing dodecyl quaternary ammonium, methoxyethyl, and catechol groups were synthesized by free-radical polymerization. The polymer coatings were prepared by immersing glass slides into a polymer solution and subsequent drying and heating. The quaternary ammonium side chains endow the coatings with potent antibacterial activity, the methoxyethyl side chains enable tuning the hydrophobic/hydrophilic balance, and the catachol groups promote immobilization of the polymers into films. The polymer-coated surfaces displayed bactericidal activity against Escherichia coli and Staphylococcus aureus in a dynamic contact assay and prevented the accumulation of viable E. coli, S. aureus, and Acinetobacter baumannii for up to 96 h. Atomic force microscopy (AFM) images of coating surfaces indicated that the surfaces exhibit virtually the same smoothness for all polymers except the most hydrophobic. The hydrophobic polymer without methoxyethyl side chains showed clear structuring into polymer domains, causing high surface roughness. Sum-frequency generation (SFG) vibrational spectroscopy characterization of the surface structures demonstrated that the dodecyl chains are predominantly localized at the surface-air interface of the coatings. SFG also showed that the phenyl groups of the catechols are oriented on the substrate surface. These results support our hypothesis that the adhesive or cross-linking functionality of catechol groups discourages polymer leaching, allowing the tuning of the amphiphilic balance by incorporating hydrophilic components into the polymer chains to gain potent biocidal activity.     

Two liquid adsorptive entrapment of a pluronic polymer into the surface of polyaniline films

Pluronic triblock copolymers were entrapped on the surface of polyaniline (PANI) films by first immersing the latter in N-methylpyrrolidinone (NMP) solutions of one of the Pluronics for a short time. This softened the surface of the films and allowed the Pluronic molecules to entangle with PANI segments of the swollen film on the surface. Further, the films were taken out from the NMP solution and dipped into water, which is a nonsolvent for PANI. The rapid surface deswelling of PANI by the water resulted in the entrapment of the Pluronic on its surface, with the hydrophilic blocks toward water and the hydrophobic block imbedded in the PANI films. The modified PANI obtained was examined by X-ray photoelectron spectroscopy, water droplets contact angles, scanning electron microscopy, and wide angle X-ray diffraction. The surface of the Pluronic entrapped PANI films became more hydrophilic than the hydrophobic PANI films and decreased the amount of bovine serum albumin protein adsorbed on them. This means that, by reducing the biofouling, the life of the modified polyaniline film can be extended when the latter is employed as a biosensor.     

Wetting of β-casein layers adsorbed at the solid–aqueous interface

The wetting by water of the adsorbed layer of β-casein on hydrophobised silica and pure (hydrophilic) silica surface was investigated by dynamic contact angle measurements based on the Wilhelmy plate principle. The results are discussed in relation to adsorption data obtained for the protein on similar surfaces by in situ ellipsometry. β-casein adsorption on a hydrophobic surface leads to a significant decrease of the contact angle, in particular in terms of the receding contact angle, which decreased by about 70°. This indicates a strong shielding of the hydrophobic surface by the hydrophilic domain of β-casein. Adding a specific enzyme, endoproteinase Asp-N, which previously has been proposed to remove a large fraction of the hydrophilic segments, results in a significantly decreased wettability of the solid surface. The layer is now more hydrophobic and the hysterises is much smaller. The receding contact angle after the proteolysis is roughly 70°. The results are consistent with the hypothesis that β-casein adsorbs at the hydrophobic surface to form a monolayer with the hydrophobic part of the protein anchored at the surface, leaving the hydrophilic segments dangling into the solution. Less dramatic effects are observed in terms of changes of the wettability on the hydrophilic surface. The surface is still quite hydrophilic both after adsorbing β-casein and exposing the layer to endoproteinase Asp-N. These results confirm the differences in the structure of β-casein layers on the hydrophobic and hydrophilic surface.     

Nanoparticle flotation collectors II: the role of nanoparticle hydrophobicity

The ability of polystyrene nanoparticles to facilitate the froth flotation of glass beads was correlated to the hydrophobicity of the nanoparticles. Contact angle measurements were used to probe the hydrophobicity of hydrophilic glass surfaces decorated with hydrophobic nanoparticles. Both sessile water drop advancing angles, θ(a), and attached air bubble receding angle measurements, θ(r), were performed. For glass surfaces saturated with adsorbed nanoparticles, flotation recovery, a measure of flotation efficiency, increased with increasing values of each type of contact angle. As expected, the advancing water contact angle on nanoparticle-decorated, dry glass surfaces increased with surface coverage, the area fraction of glass covered with nanoparticles. However, the nanoparticles were far more effective at raising the contact angle than the Cassie-Baxter prediction, suggesting that with higher nanoparticle coverages the water did not completely wet the glass surfaces between the nanoparticles. A series of polystyrene nanoparticles was prepared to cover a range of surface energies. Water contact angle measurements, θ(np), on smooth polymer films formed from organic solutions of dissolved nanoparticles were used to rank the nanoparticles in terms of hydrophobicity. Glass spheres were saturated with adsorbed nanoparticles and were isolated by flotation. The minimum nanoparticle water contact angle to give high flotation recovery was in the range of 51° < θ(np(min)) ≤ 85°.     

Grafting of poly(ethylene oxide) to the surface of polyaniline films through a chlorosulfonation method and the biocompatibility of the modified films

Poly(ethylene oxide) (PEO) could be grafted on the surface of polyaniline (PANI) films by chlorosulfonating the films with chlorosulfonic acid followed by reacting the modified films with PEO in a pyridine solution. The modified PANI films were examined by X-ray photoelectron spectroscopy and water droplet contact angles. The surface of the PEO grafted to hydrophobic PANI films became hydrophilic and the amounts of bovine serum albumin and human blood plasma platelet adsorbed onto it were decreased by more than 80%. For comparison purposes, and because the water wetting angle can be used as a measure of biocompatibility, wetting angle experiments have been also carried out for Pluronic triblock copolymer grafted to PANI and PEO or Pluronic molecules entrapped on the surfaces of PANI films. PANI was selected as substrate because one can easily change its surface properties by PEO grafting and because being conductive can be used as a sensor.     

Surface functionalization of ultrananocrystalline diamond films by electrochemical reduction of aryldiazonium salts

The surface functionalization of ultrananocrystalline diamond (UNCD) thin films via the electrochemical reduction of aryl diazonium cations is described. The one-electron-transfer reaction leads to the formation of solution-based aryl radicals, which in turn react with the UNCD surface forming stable covalent C-C bonds. Cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), ac impedance spectroscopy, and contact angle measurements have been employed to characterize the organic overlayer and estimate the surface coverage. The grafting of 3,5-dichlorophenyl groups renders the UNCD surface hydrophobic, whereas the attachment of 4-aminophenyl groups makes the surface relatively hydrophilic. The surface coverage, estimated from the electrochemical and XPS measurements, is as high as 70% of a compact monolayer. The aminophenyl terminated surface was obtained by electrochemical reduction of the tethered nitrophenyl groups. This two-step approach yields a UNCD surface with functional moieties available for the potential covalent coupling of a wide variety of biomolecules (e.g., DNA and proteins).     

Photochemical fixation of structures in binary polymer brushes-influence of layer thickness and grafting method

Polymer brushes consisting of hydrophilic and hydrophobic polymer components (poly-4-vinylpyridine, polymethacrylic acid and polystyrene, respectively) change their surface properties (as revealed by contact angles) when they are exposed to various solvents. In brushes prepared via grafting-from methods (using a specific surface initiator) layer thicknesses up to 300 nm were obtained. Copolymerization of the brush component monomers with 2-(4'-styryl)-indene yielded photo-cross-linkable brushes, which were used to fix the brushes in either the hydrophilic or hydrophobic state. Structural patterns differing in surface properties were produced and fixed by photo-cross-linking the hydrophobic component in that samples were irradiated through a mask. The patterns turned out most stable in moderately thick layers. AFM pictures confirm the contact angle results but reveal micro-domains of the two immiscible polymers in the grafted layers.