Bio-inspired water repellent surfaces produced by ultrafast laser structuring of silicon

We report here an efficient method for preparing stable superhydrophobic and highly water repellent surfaces by irradiating silicon wafers with femtosecond laser pulses and subsequently coating them with chloroalkylsilane monolayers. By varying the laser pulse fluence on the surface one can successfully control its wetting properties via a systematic and reproducible variation of roughness at micro- and nano-scale, which mimics the topology of natural superhydrophobic surfaces. The self-cleaning and water repellent properties of these artificial surfaces are investigated. It is found that the processed surfaces are among the most water repellent surfaces ever reported. These results may pave the way for the implementation of laser surface microstructuring techniques for the fabrication of superhydrophobic and self-cleaning surfaces in different kinds of materials as well.     

The wettability of polytetrafluoroethylene and polymethylmethacrylate by aqueous solutions of Triton X-100 and propanol mixtures

Measurements of advancing contact angles (θ) were carried out for aqueous solutions of Triton X-100 (TX-100) and propanol mixtures at constant TX-100 concentration equal to 1 × 10⁻⁷, 1 × 10⁻⁶, 1 × 10⁻⁵, 1 × 10⁻⁴, 6 × 10⁻⁴ and 1 × 10⁻³ M, respectively, on polytetrafluoroethylene (PTFE) and polymethyhmethacrylate (PMMA). Using obtained results the changes of cosθ and adhesional tension against surface tension of all series of aqueous solutions of TX-100 and propanol mixtures (γ_LV) for PTFE and PMMA surfaces were shown. On the basis of these changes it was deduced that adsorption of TX-100 and propanol mixtures at PTFE-solution and solution-air interfaces is the same but the adsorption of TX-100 and propanol mixtures at solution-air interface is considerably higher than at PMMA-solution one. In the case of PTFE this conclusion was confirmed by relationship between cosθ and the reciprocal of the surface tension of solution. Extrapolation of the relationships between cosθ and/or adhesional tension and the surface tension of solutions to the points corresponding to the cosθ = 1 and adhsional tension equal to the surface tension of solution, the critical surface tension of PTFE and PMMA wetting was determined. The average values of critical surface tension of wetting determined from these relationships for PTFE are lying in the range of its surface tension values determined from contact angles of different kinds of liquids, which can be find in the literature, but for PMMA are considerably lower than the surface tension. The double value of the critical surface tension of PTFE wetting is equal to adhesion work of the solution to its surface and for PMMA there is not any correlation between these magnitudes.Using the measured values of the contact angles and Young equation the PTFE(PMMA)-aqueous solution interfacial tension was determined. The interfacial tension values of PTFE-aqueous solution were also calculated from the Fainerman and Miller equation in which the correcting parameter of nonideality of the surface monolayer was introduced and compared to those obtained from Young equation. From this comparison it results that the changes of PTFE-solution interface tension as a function of propanol concentration can be described by the Fainerman and Miller equation.     

Anti-icing performance of superhydrophobic surfaces

This article studies the anti-ice performance of several micro/nano-rough hydrophobic coatings with different surface chemistry and topography. The coatings were prepared by spin-coating or dip coating and used organosilane, fluoropolymer or silicone rubber as a top layer. Artificially created glaze ice, similar to the naturally accreted one, was deposited on the nanostructured surfaces by spraying supercooled water microdroplets (average size ∼80 μm) in a wind tunnel at subzero temperature (−10 °C). The ice adhesion strength was evaluated by spinning the samples in a centrifuge at constantly increasing speed until ice delamination occurred. The results show that the anti-icing properties of the tested materials deteriorate, as their surface asperities seem to be gradually broken during icing/de-icing cycles. Therefore, the durability of anti-icing properties appears to be an important point for further research. It is also shown that the anti-icing efficiency of the tested superhydrophobic surfaces is significantly lower in a humid atmosphere, as water condensation both on top and between surface asperities takes place, leading to high values of ice adhesion strength. This implies that superhydrophobic surfaces may not always be ice-phobic in the presence of humidity, which can limit their wide use as anti-icing materials.     

The role of adsorption of sodium bis(2-ethylhexyl) sulfosuccinate in wetting of glass and poly(methyl methacrylate) surface

Advancing contact angles, θ, for aqueous solutions of the anionic surfactant, sodium bis(2-ethylhexyl) sulfosuccinate (AOT) were measured on glass and poly(methyl methacrylate) (PMMA) surface. Using the obtained results we determined the properties of aqueous AOT solutions in wetting of these surfaces. It occurs that the wettability of glass and PMMA by these solutions depends on the concentration of AOT in solution. There is almost linear dependence between the contact angle (θ) and concentration of AOT (log C) in the range from 5 × 10⁻⁴ to 2.5 × 10⁻³ M/dm³ (value of the critical micelle concentration of AOT—CMC) both for glass and PMMA surface. For calculations of AOT adsorption at solid (glass, PMMA)-solution drop-air system interfaces the relationship between the adhesion tension (γ_LV cos θ) and surface tension (γ_LV) and the Gibbs and Young equations were taken into account. From the measurement and calculation results the slope of the γ_LV cos θ − γ_LV curve was found to be constant and equal 0.7 for glass and −0.1 for PMMA over the whole range of AOT concentration in solution. From this fact it can be concluded that if Γ_SV is equal zero then Γ_SL > 0 for the PMMA-solution and Γ_SL < 0 for glass-solution systems. It means that surfactant concentration excess at PMMA-solution interface is considerably lower than at solution-air interface, but this excess of AOT concentration at glass-solution interface is lower than in the bulk phase. By extrapolating the linear dependence between the adhesion and surface tension the value of the critical surface tension (γ_c) of wetting for glass and PMMA was also determined, that equaled 25.9 and 25.6 mN/m for glass and PMMA, respectively. Using the value of the glass and PMMA surface tension as well as the measured surface tension of aqueous AOT solutions in Young equation, the solid-liquid interface tension (γ_SL) was found. There was a linear dependence between the γ_SL and γ_LV both for glass and PMMA, but there were different slope values of the curves for glass and PMMA, i.e. −0.7 and 0.1, respectively. The dependence between the work of adhesion (W_A) and surface tension (γ_LV) was also linear of different slopes for glass and for PMMA surface.     

Analysis of semiconductor surface phonons by Raman spectroscopy

Only recently Raman spectroscopy (RS) has advanced into the study of surface phonons from clean and adsorbate-covered semiconductor surfaces. RS allows the determination of eigenfrequencies as well as symmetry selection rules of surface phonons, by k-conservation limited to the Brillouin zone-center, and offers a significantly higher spectral resolution than standard surface science techniques such as high-resolution electron energy loss spectroscopy. Moreover, surface electronic states become accessible via electron–phonon coupling. In this article the fundamentals of Raman scattering from surface phonons are discussed and its potential illustrated by considering two examples, namely Sb-monolayer-terminated and clean InP(110) surfaces. Both are very well understood with respect to their atomic and electronic structure and thus may be regarded as model systems for heteroterminated and clean semiconductor surfaces. In both cases, localized surface phonons as well as surface resonances are detected by Raman spectroscopy. The experimental results are compared with surface modes predicted by theoretical calculations. On InP(110), due to the high spectral resolution of Raman spectroscopy, several surface modes predicted by theory can be experimentally verified. Surface electronic transitions are detected by changing the energy of the exciting laser light indicating resonances in the RS cross section. Received: 7 April 1999 / Accepted: 25 June 1999 / Published online: 16 September 1999     

Laser microstructuring for fabricating superhydrophobic polymeric surfaces

In this paper we show the fabrication of hydrophobic polymeric surfaces through laser microstructuring. By using 70-ps pulses from a Q-switched and mode-locked Nd:YAG laser at 532 nm, we were able to produce grooves with different width and separation, resulting in square-shaped pillar patterns. We investigate the dependence of the morphology on the surface static contact angle for water, showing that it is in agreement with the Cassie-Baxter model. We demonstrate the fabrication of a superhydrophobic polymeric surface, presenting a water contact angle of 157°. The surface structuring method presented here seems to be an interesting option to control the wetting properties of polymeric surfaces.     

Superhydrophobic surfaces via electroless displacement of nanometric Cu layers by Ag

This paper explores the possibility of making hydrophobic and superhydrophobic surfaces from electroless displacement of Cu by Ag⁺, in the case where Cu oxidation is limited owing to Cu layers of nanometric thicknesses. The morphology of the Ag layers is studied by scanning electron microscopy for Cu thicknesses between 10 and 80 nm. The mapping of the elemental content of the layers by electron dispersive X-ray analysis also has been used to clarify the particle growing by diffusion limited aggregation. It is shown that the average size and the shape complexity of the Ag particles increase with the Cu thickness. The addition of dimethyl sulfoxide in the Ag⁺ aqueous solution improves the surface homogeneity, increases the particle density and decreases their sizes. The wetting behaviour of the surfaces, after grafting with octadecanethiol, has been studied from measurements of the contact angles of a drop of water. According to the thickness of the initial Cu layer and the morphology of the Ag layer, contact angles range between 110° and 154°. Superhydrophobic surfaces are obtained from 80 nm thick Cu layers.     

Adsorption of sodium bis(2-ethylhexyl) sulfosuccinate and wettability in polytetrafluoroethylene-solution-air system

The role of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) adsorption at water-air and polytetrafluoroethylene-water (PTFE) interfaces in wetting of low energy PTFE was established from measurements of the contact angle of aqueous AOT solutions in PTFE-solution drop-air systems and the aqueous AOT solution surface tension measurements. For calculations of the adsorption at these interfaces the relationship between adhesion tension (γ_LV cos θ) and surface tension (γ_LV), and the Gibbs and Young equations were taken into account. On the basis of the measurements and calculations the slope of the γ_LV cos θ-γ_LV curve was found to be constant and equal −1 over the whole range of surfactant concentration in solution. It means that the amount of surfactant adsorbed at the PTFE-water interface, Γ_SL, is essentially equal to its amount adsorbed at water-air interface, Γ_LV. By extrapolating the linear dependence between γ_LV cos θ and γ_LV to cos θ = 1 the determined value of critical surface tension of PTFE surface wetting, γ_C, was obtained (23.6 mN/m), and it was higher than the surface tension of PTFE (20.24 mN/m). Using the value of PTFE surface tension and the measured surface tension of aqueous AOT solution in Young equation, the PTFE-solution interface tension, γ_SL, was also determined. The shape of the γ_SL-log C curve occurred to be similar to the isotherm of AOT adsorption at water-air interface, and a linear dependence existed between the PTFE-solution interfacial tension and polar component of aqueous AOT solution. The dependence was found to be established by the fact that the work of adhesion of AOT solution to the PTFE surface was practically constant amounting 46.31 mJ/m² which was close to the work of water adhesion to PTFE surface.     

The role of adsorption of dodecylethyldimethylammonium bromide and benzyldimethyldodecylammonium bromide surfactants in wetting of polytetrafluoroethylene and poly(methyl methacrylate) surfaces

The role of adsorption of dodecylethyldimethylammonium bromide (C₁₂(EDMAB)) and benzyldimethyldodecylammonium bromide (BDDAB) at water-air and polytetrafluoroethylene (PTFE)-water and poly(methyl methacrylate) (PMMA)-water interface, in wetting of PTFE and PMMA surface, was established from the measured values of the contact angle (θ) of aqueous C₁₂(EDMAB) and BDDAB solutions in PTFE (PMMA)-solution drop-air system, and from the measured values of the surface tension of aqueous C₁₂(EDMAB) and BDDAB solutions. Adsorption of C₁₂(EDMAB) and BDDAB at water-air interface was determined earlier from the Gibbs equation. Adsorption at solid-water interface was deduced from the Lucassen-Reynders equation based on the relationship between adhesion tension (γ_LV cos θ) and surface tension (γ_LV). The slope of the γ_LV cos θ-γ_LV curve was found to be constant and equal to −1, and about −0.3 for PTFE and PMMA surface, respectively (in the case of both surfactant studied: C₁₂(EDMAB) and BDDAB, and in the whole range of surfactants concentration in solution). It means that the amount of the surfactant adsorbed at the PTFE-water interface, Γ_SL, was essentially equal to its amount adsorbed at water-air interface, Γ_LV. However, Γ_SL at the PMMA-water interface was about three times smaller as compared to that at water-air interface. By extrapolating the linear dependence between γ_LV cos θ-γ_LV and dependence between cos θ-γ_LV and cos θ = 1 we determined the value of the critical surface tension of PTFE and PMMA surface wetting, γ_c. The obtained values of γ_c for PTFE surface were equal 23.4 and 23.8 mN/m, 23.1 and 23.2 mN/m for C₁₂(EDMAB) and BDDAB, respectively and they were higher than the surface tension of PTFE (20.24 mN/m). On the other hand, the obtained values of γ_c for PMMA surface were equal 31.4 and 30.9 mN/m, 31.7 and 31.3 mN/m for C₁₂(EDMAB) and BDDAB, respectively and they were smaller than the surface tension of PMMA (39.21 mN/m). Using the values of PTFE and PMMA surface tension and the measured values of the surface tension of aqueous C₁₂(EDMAB) and BDDAB solutions in the Young equation, the PTFE (PMMA)-solution interfacial tension, γ_SL, was also determined. Next, the work of adhesion (W_A) was deduced, and it occurred that the dependence between the W_A and the surface tension (γ_LV) for both studied solids was linear. However, the values of the W_A for PMMA change as a function of log C (C—surfactant concentration) changed from 91.7 to 68.5 mJ/m² and from 91.8 to 65.1 mJ/m² for C₁₂(EDMAB) and BDDAB, respectively. On the other hand, the work of adhesion of both studied surfactants solutions to the PTFE surface was practically constant (an average value was equal 45.8 and 45.4 mJ/m², respectively). These values were close to the value of the work of water adhesion to PTFE surface (45.5 mJ/m²).     

Adjustable wettability of paperboard by liquid flame spray nanoparticle deposition

Liquid flame spray process (LFS) was used for depositing TiO_x and SiO_x nanoparticles on paperboard to control wetting properties of the surface. By the LFS process it is possible to create either superhydrophobic or superhydrophilic surfaces. Changes in the wettability are related to structural properties of the surface, which were characterized using scanning electron microscope (SEM) and atomic force microscope (AFM). The surface properties can be ascribed as a correlation between wetting properties of the paperboard and the surface texture created by nanoparticles. Surfaces can be produced inline in a one step roll-to-roll process without need for additional modifications. Furthermore, functional surfaces with adjustable hydrophilicity or hydrophobicity can be fabricated simply by choosing appropriate liquid precursors.     

Microscopic structure and structuring of perovskite surfaces and interfaces: SrTiO3, RBa2Cu3O7-δ

3 surfaces and bicrystal interfaces and the growth of YBa₂Cu₃O_7-δ thin films on such substrates using scanning tunneling microscopy and X-ray diffraction. Proper annealing of SrTiO₃ in oxygen and/or ultrahigh vacuum produces uniformly terminated, atomically flat and well-ordered surfaces. For vicinal SrTiO₃(001) surfaces the particular annealing sequence and miscut angle sensitively determines the resulting step structure and thus the microscopic surface morphology. Steps of SrTiO₃(001) surfaces can be adjusted to a height of one, two, or multiple times the unit-cell height (a_STO=0.3905 nm). The growth of YBa₂Cu₃O_7-δ films on these substrates by pulsed laser deposition was traced from the initial nucleation to a thickness of about 300 nm. The morphology, texture, and defect structure of the films is determined by the specific structure and morphology of the pristine substrate. Anisotropic, planar defects, originating from substrate step edges, strongly modify the electronic transport properties of the film leading to critical currents up to ≈9×10⁷ A/cm² at 4 K as well as pronounced transport anisotropies. Surfaces and interface energy terms are discussed, which also determine the observed structure of bicrystal boundaries. Received: 16 April 1998/Accepted: 21 August 1998     

III-V compound semiconductor (001) surfaces

There has been renewed interest in the structure of III-V compound semiconductor (001) surfaces caused by recent experimental and theoretical findings, which indicate that geometries different from the seemingly well-established dimer models describe the surface ground state for specific preparation conditions. I review briefly the structure information available on the (001) surfaces of GaP, InP, GaAs and InAs. These data are complemented with first-principles total-energy calculations. The calculated surface phase diagrams are used to explain the experimental data and reveal that the stability of specific surface structures depends largely on the relative size of the surface constituents. Several structural models for the Ga-rich GaAs (001)(4×6) surface are discussed, but dismissed on energetic grounds. I discuss in some detail the electronic properties of the recently proposed cation-rich GaAs (001)ζ(4×2) geometry. Received: 18 May 2001 / Revised version: 23 July 2001 / Published online: 3 April 2002     

Effects of roughness on interfacial performances of silica glass and non-polar polyarylacetylene resin composites

The influence of roughness on interfacial performances of silica glass/polyarylacetylene resin composites was investigated. In order to obtain different roughness, silica glass surface was abraded by different grits of abrasives and its topography was observed by scanning electron microscopy and atomic force microscopy. At the same time, the failure mechanisms of composites were analyzed by fracture morphologies and the interfacial adhesion was evaluated by shear strength test. The results indicated that shear strength of silica glass/polyarylacetylene resin composites firstly increased and then decreased with the surface roughness of silica glass increased. The best surface roughness range of silica glass was 40-60 nm. The main mechanism for the improvement of the interfacial adhesion was physical interlocking at the interface.     

Self-organized structuring of W/C multilayers on Si substrate

After aging at room temperature for several months W/C multilayers (20 periods, single layer thicknesses in the nanometer range) grown on Si-(111) substrates by pulsed laser deposition (PLD) developed homogeneously wrinkled surfaces. Their structures were studied by optical microscopy, atomic force microscopy and X-ray diffractometry. Typical dimensions of debonded areas are some 100 μm in length, about 40 μm in width and 2–3 μm in height. The formation of wrinkles is accompanied by an increase in the free surface by 1–2%. Stress relaxation is considered the driving force of this phenomenon. Received: 26 July 1999 / Accepted: 29 July 1999 / Published online: 16 September 1999     

Atomic force microscopy studies of chemical–mechanical processes on silicon(100) surfaces

Atomic force microscopy (AFM) is used to examine chemical–mechanical processes on Si(100) surfaces. The AFM tip serves as a single asperity contact to exert tribological forces as well as an imaging tool. By scanning in chemically aggressive solutions, material removal can be observed directly. In the silicon system, high-force scans are used to remove oxide and initiate etching in selected locations, followed by low-force scans to image the resulting surfaces. Material removal rates were measured as a function of applied load, number of scans, solution composition, and time. In basic solution, places where the underlying silicon is exposed etch rapidly, producing structures 100 nm or less in size. Although the surface roughness initially increases during etching, the final surfaces are smooth. The oxide is extremely sensitive to applied stress: even very light scanning accelerates oxide dissolution. Once the oxide is removed, chemical etching proceeds through the underlying silicon with or without AFM scanning; but the silicon etches more rapidly if AFM scanning is continued, due to true chemical–mechanical (tribochemical) effects.     

Superhydrophobic surfaces fabricated by microstructuring of stainless steel using a femtosecond laser

Fabrication of superhydrophobic surfaces induced by femtosecond laser is a research hotspot of superhydrophobic surface studies nowadays. We present a simple and easily-controlled method for fabricating stainless steel-based superhydrophobic surfaces. The method consists of microstructuring stainless steel surfaces by irradiating samples with femtosecond laser pulses and silanizing the surfaces. By low laser fluence, we fabricated typical laser-induced periodic surface structures (LIPSS) on the submicron level. The apparent contact angle (CA) on the surface is 150.3°. With laser fluence increasing, we fabricated periodic ripples and periodic cone-shaped spikes on the micron scale, both covered with LIPSS. The stainless steel-based surfaces with micro- and submicron double-scale structure have higher apparent CAs. On the surface of double-scale structure, the maximal apparent CA is 166.3° and at the same time, the sliding angle (SA) is 4.2°.     

Stable superhydrophobic surfaces over a wide pH range

A stable superhydrophobic surface was fabricated by solidifying poly(epoxy-terminated polydimethylsiloxane-co-bisphenol A) [P(ETPDMS-co-BPA)] copolymer on a rough substrate. The low surface energy of the copolymer and the geometric structure at micrometer scale of the surface contribute to the superhydrophobic property. The as-prepared surface shows stable superhydrophobicity over a wide pH range (1-14) and the wettability is excellent stable to heating, water, corrosive solution and organic solvent treatments. The procedure is simple and time-saving as well as utilizing non-fluorine-containing compounds.     

Structure of high-index GaAs surfaces – the discovery of the stable GaAs (2 5 11) surface

We present a brief overview of surface structures of high-index GaAs surfaces, putting emphasis on recent progress in our own laboratory. By adapting a commercial scanning tunneling microscope (STM) to our molecular beam epitaxy and ultra high vacuum analysis chamber system, we have been able to atomically resolve the GaAs( )B (8 ×1), (114)Aα2(2×1), (137), (3 7 15), and (2 5 11) surface structures. In cooperation with P. Kratzer and M. Scheffler from the Theory Department of the Fritz-Haber Institute we determined the structure of some of these surfaces by comparing total-energy calculations and STM image simulations with the atomically resolved STM images. We present the results for the {112}, {113}, and {114} surfaces. Then we describe what led us to proceed into the inner parts of the stereographic triangle and to discover the hitherto unknown stable GaAs (2 5 11) surface. Received: 16 May 2001 / Accepted: 23 July 2001 / Published online: 3 April 2002     

Growth of polymer–metal nanocomposites by pulsed laser deposition

Complex polymer–metal nanocomposites have a wide range of applications, e.g. as flexible displays and packaging materials. Pulsed laser deposition was applied to form nanostructured materials consisting of metal clusters (Ag, Au, Pd and Cu) embedded in a polymer (polycarbonate, PC) matrix. The size and amount of the metal clusters are controlled by the number of laser pulses hitting the respective targets. For Cu and Pd, smaller clusters and higher cluster densities are obtained as in the cases of Ag and Au due to a stronger reactivity with the polymers and thus a lower diffusivity. Implantation effects, differences in metal diffusivity and reactivity on the polymer surfaces, and the coalescence properties are discussed with respect to the observed microstructures on PC and compared to the metal growth on poly (methyl methacrylate), PMMA.