Hydrophobic monolayer preparation by Langmuir-Blodgett and chemical adsorption techniques

Alkylsiloxane and perfluoroalkylsiloxane monolayers are prepared on siliceous surfaces using the techniques of Langmuir-Blodgett deposition and solid-liquid chemical adsorption. Acid-catalyzed hydrolysis and polycondensation reactions provide two-dimensional siloxane networks at the liquid-vapor interface, which can be compressed to mean molecular areas of approximately 22 and approximately 32 A(2) for pendent hydrocarbon and fluorocarbon chains, respectively. Subsequent Langmuir-Blodgett transfer onto glass substrates at moderate surface pressures leads to compact monolayers for single-component precursors, while mixed alkyl- and perfluoroalkylsilanes produce nonhomogeneous films characterized by transfer ratios greater than unity. As an alternate monolayer preparation technique, silane polymerization was performed directly on siliceous surfaces via a chemical adsorption mechanism. XPS analysis of a chemically adsorbed 1H,1H,2H,2H-perfluorodecylsiloxane film confirms a single adsorbed monolayer thickness in which the pendent fluoroalkyl chains align nonperpendicularly with respect to the surface. The surface free energy was determined to be 11.4 dyn cm(-1) based on static contact angle measurements. AFM imaging shows the presence of surface defects due to oligomer deposition during the drying process. The use of solubilized trichloro-based silane coupling agents under anhydrous conditions is shown to produce surfaces with a minimal number of surface defects. The presence of undissolved silane material in the bulk solution significantly increases the number of surface defects.     

Study of two grafting methods for obtaining a 3-aminopropyltriethoxysilane monolayer on silica surface

In order to establish a 3-aminopropyltriethoxysilane (APTES) grafting procedure with limited number of APTESs noncovalently linked to the silica surface, two different methods of grafting (in acid-aqueous solution and in anhydrous solution) were compared. The grafted surface state was investigated by atomic force microscopy (AFM). The stability of the grafting was checked at different temperatures by AFM. Continuous and plane APTES grafted surfaces were successfully prepared using both grafting preparations. The grafting in an anhydrous solution behaves homogeneously and stably compared to the grafting in an acid-aqueous solution. Moreover, with anhydrous solution, results showed that a unique monolayer of APTES was grafted.     

Forming Lipid Bilayer Membrane Arrays on Micropatterned Polyelectrolyte Film Surfaces

A novel method of forming lipid bilayer membrane arrays on micropatterned polyelectrolyte film surfaces is introduced. Polyelectrolyte films were fabricated by the layer‐by‐layer technique on a silicon oxide surface modified with a 3‐aminopropyltriethoxysilane (APTES) monolayer. The surface pK_a value of the APTES monolayer was determined by cyclic voltammetry to be approximately 5.61, on the basis of which a pH value of 2.0 was chosen for layer‐by‐layer assembly. Micropatterned polyelectrolyte films were obtained by deep‐UV (254 nm) photolysis though a mask. Absorbed fluorescent latex beads were used to visualize the patterned surfaces. Lipid bilayer arrays were fabricated on the micropatterned surfaces by immersing the patterned substrates into a solution containing egg phosphatidylcholine vesicles. Fluorescence recovery after photobleaching studies yielded a lateral diffusion coefficient for probe molecules of 1.31±0.17 μm² s^?1 in the bilayer region, and migration of the lipid NBD PE in bilayer lipid membrane arrays was observed in an electric field.     

Directing the growth of highly aligned gold nanorods through a surface chemical amidation reaction

This paper describes the seed-mediated growth of highly aligned gold nanorods (Au NRs) over large areas directly on a Si(100) surface. The Si(100) surface is NH2-functionalized with (aminopropyl)triethoxysilane (APTES) followed by a DCC-catalyzed surface amidation reaction with acetic acid. After exposure to a gold nanoparticle (Au NP) "seed" solution, chemical seed-mediated growth of the surface-bound seeds via reduction of AuCl4- by ascorbic acid in the presence of cetyltrimethylammonium bromide leads to the growth of highly aligned Au NRs on the surface. About 80% of the NRs are aligned in the same direction within a +/-30 degrees range. Au NRs account for 19% of the nanostructures with average aspect ratio (AR) of approximately 20. The alignment direction did not correlate with the atomic arrangement of the Si(100) crystal since it varied over different regions of the sample, rotating by 90 degrees from top to bottom of an approximately 5 mm sample. Si crystallinity may still be important since alignment is not observed on amorphous glass. Surface functionalization is the key since alignment is only observed following the amidation reaction and not on NH2-functionalized, SH-functionalized, or bare Si(100) surfaces. Alignment also occurred for Au NRs grown on Si(100)/APTES reacted with succinic acid and on Ag NRs grown on Si(100)/APTES/acetic acid surfaces. This unique alignment of metal NRs promoted by a surface amidation chemical reaction may find use in nanoelectronics, chemical sensing, and plasmonics applications.     

Reaction of N-phenyl maleimide with aminosilane monolayers

Reaction of N-phenyl maleimide (NPM) with silica surfaces modified with a self-assembled monolayer of (aminopropyl)triethoxysilane (APTES) was investigated using infrared spectroscopy (FTIR), elemental analysis, and titration assays. This reaction is of interest as a test case for using amine-maleimide coupling for immobilization of biomolecules. Addition of NPM to surface APTES residues was consistently sub-stoichiometric, with typical yields of about 75% on monolayers with a coverage of 1.15 APTES residues/nm2. Titration analysis found negligible presence of imide alkene C=C bonds in modified supports, indicating that addition of NPM to APTES proceeded via amine attack at the imide olefinic bond. FTIR measurements also revealed presence of amide bands which intensified over periods of 10 h. These observations were attributed to a slower secondary process in which APTES amines attack imide carbonyls to produce amide linkages. Stability of NPM-modified surfaces was examined under room temperature storage in pH 7 buffer up to 72 h and for 2 h exposure to buffer at temperatures up to 90 degrees C. It was found that stability was determined by robustness of APTES-silica attachment, with about 30% loss under the harshest conditions investigated.     

Selective Growth of GaN on Slope Cone-shaped Patterned Sapphire Substrate

Cone-shaped patterned sapphire substrate was prepared by inductively coupled plasma etching and GaN nucleation layer was grown on it by metal-organic chemical vapor deposition.A selective growth of GaN nucleation layer was found on the slope of the cone-shaped patterned sapphire substrat,and the distribution morphology of GaN had significantly changed after it was recrystallized.GaN selective growth and redistribution were analyzed by investigating the distribution of crystallographic planes on the cone surface and the atom array of specific planes at atom level.     

Factors affecting the preparation and properties of electrodeposited silica thin films functionalized with amine or thiol groups

Well-adherent sol-gel-derived silica films functionalized with amine or thiol groups have been electrogenerated on gold electrodes and both the deposition process and the film properties have been studied by various physicochemical techniques. Electrodeposition was achieved by combining the formation of a self-assembled "nanoglue" on the electrode surface, the sol-gel process, and the electrochemical manipulation of pH to catalyze polycondensation of the precursors. Gold electrodes pretreated with mercaptopropyltrimethoxysilane (MPTMS) were immersed in sol solutions containing the selected precursors (tetraethoxysilane, TEOS, in mixture with (3-aminopropyl)triethoxysilane, APTES, or MPTMS) where they underwent a cathodic electrolysis to generate the hydroxyl ions that are necessary to catalyze the formation of the organosilica films on the electrode surface. Special attention was given to analyze the effects of deposition time and applied potential and to compare APTES and MPTMS films. Characterization was made using quartz crystal microbalance, scanning electron microscopy, cyclic voltammetry, and atomic force microscopy (including in situ monitoring). The electrodeposition process was found to occur at two growing rates: a first slow stage giving rise to rather homogeneous, yet rough, films with thickness in the sub-mum range (increasing continuously when increasing the deposition time), which was followed by a faster gelification step resulting in much thicker (>1 microm) and rougher macroporous deposits. These two successive situations were observed independently on the applied potential except that more cathodic values led to narrower sub-microm ranges (as expected from the larger amounts of the electrogenerated hydroxyl catalyst). Thiol-functionalized silica films were deposited more rapidly than the amine ones and, for both of them, permeability to redox probe was found to decrease when increasing the film thickness because of higher resistance to mass transport.     

Formation, structure, and reactivity of amino-terminated organic films on silicon substrates

Amino-functionalized organic films were prepared by self-assembling 3-aminopropyltriethoxysilane (APTES) on silicon wafers in either anhydrous toluene or phosphate-buffered saline (PBS) for varied deposition times. Fourier transform infrared spectroscopy (FTIR) and ellipsometry have shown that the structure and thickness of APTES films are governed by the deposition time and reaction solution. Deposition from an anhydrous toluene solution produces APTES films ranging from 10 to 144 A in thickness, depending on the reaction time. FTIR spectra indicate that film growth initially proceeds by adsorption of APTES to the silicon surface followed by siloxane condensation, and after an extended period of time APTES molecules accumulate on the underlying APTES film by either covalent or noncovalent interactions. In contrast, spectroscopically indistinguishable APTES films in thickness ranging from 8 to 13 A were formed when deposition was conducted in aqueous solutions. Measured water contact angles indicate that APTES films deposited in aqueous solutions are more hydrophilic compared to those prepared in toluene solutions. Fluorescence measurements revealed that APTES films prepared in toluene solutions contain more reactive surface amino groups by ca. 3 to 10 times than those prepared in aqueous solutions for the identical reaction time.     

Self-assembled monolayers of alkylphosphonic acid on GaN substrates

In this paper we describe the formation and characterization of self-assembled monolayers of octadecylphosphonic acid (ODPA) on epitaxial (0001) GaN films on sapphire. By immersing the substrate in its toluene solution, ODPA strongly adsorbed onto UV/O 3-treated GaN to give a hydrophobic surface. Spectroscopic ellipsometry verified the formation of a well-packed monolayer of ODPA on the GaN substrate. In contrast, adsorption of other primarily substituted hydrocarbons (C n H 2 n+1 X; n = 16-18; X = -COOH, -NH 2, -SH, and -OH) offered less hydrophobic surfaces, reflecting their weaker interaction with the GaN substrate surfaces. A UV/O 3-treated N-polar GaN had a high affinity to the -COOH group in addition to ODPA, possibly reflecting the basic properties of the surface. These observations suggested that the molecular adsorption was primarily based on hydrogen bond interactions between the surface oxide layer on the GaN substrate and the polar functional groups of the molecules. The as-prepared ODPA monolayers were desorbed from the GaN substrates by soaking in an aqueous solution, particularly in a basic solution. However, ODPA monolayers heated at 160 degrees C exhibited suppressed desorption in acidic and neutral aqueous solution maybe due to covalent bond formation between ODPA and the surface. X-ray photoelectron spectroscopy provided insight into the effect of the UV/O 3 treatment on the surface composition of the GaN substrate and also the ODPA monolayer formation. These results demonstrate that the surface of a GaN substrate can be tailored with organic molecules having an alkylphosphonic acid moiety for future sensor and device applications.     

In situ observation of interfacial bonding of an organic monolayer confined between two solid surfaces

Silicon substrates coated with a long-chain hydrocarbon monolayer terminated by carboxylic acid ester groups were brought into molecular contact with different solid counter surfaces ranging from inert hydrocarbon surfaces to hydrophilic oxide surfaces. The interaction of the terminal ester groups with the counter surface was probed with infrared spectroscopy. Interfacial hydrogen bonds are reversibly formed upon contact formation, and the total degree of bonding can be adjusted by variation of the hydroxyl group density of the counter surface and quantified from the monolayer IR spectra.     

Study of the self-assembling of n-octylphosphonic acid layers on aluminum oxide

The deposition of n-octylphosphonic acid on aluminum oxide was studied. The substrate was pretreated in order to achieve a root-mean-square roughness of <1 nm, a hydroxyl fraction of 30%, and a thickness of approximately 170 nm. It was proven using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) that, rather than a monolayer, an organic multilayer was formed. The growth mechanism was identified as a Stranski-Krastanov one. It was also shown that the use of AFM, probing the surface topography, is essential for a reliable quantification and interpretation of data obtained with XPS.     

Wet chemical functionalization of III-V semiconductor surfaces: alkylation of gallium arsenide and gallium nitride by a Grignard reaction sequence

Crystalline gallium arsenide (GaAs) (111)A and gallium nitride (GaN) (0001) surfaces have been functionalized with alkyl groups via a sequential wet chemical chlorine activation, Grignard reaction process. For GaAs(111)A, etching in HCl in diethyl ether effected both oxide removal and surface-bound Cl. X-ray photoelectron (XP) spectra demonstrated selective surface chlorination after exposure to 2 M HCl in diethyl ether for freshly etched GaAs(111)A but not GaAs(111)B surfaces. GaN(0001) surfaces exposed to PCl(5) in chlorobenzene showed reproducible XP spectroscopic evidence for Cl-termination. The Cl-activated GaAs(111)A and GaN(0001) surfaces were both reactive toward alkyl Grignard reagents, with pronounced decreases in detectable Cl signal as measured by XP spectroscopy. Sessile contact angle measurements between water and GaAs(111)A interfaces after various levels of treatment showed that GaAs(111)A surfaces became significantly more hydrophobic following reaction with C(n)H(2n-1)MgCl (n = 1, 2, 4, 8, 14, 18). High-resolution As 3d XP spectra taken at various times during prolonged direct exposure to ambient lab air indicated that the resistance of GaAs(111)A to surface oxidation was greatly enhanced after reaction with Grignard reagents. GaAs(111)A surfaces terminated with C(18)H(37) groups were also used in Schottky heterojunctions with Hg. These heterojunctions exhibited better stability over repeated cycling than heterojunctions based on GaAs(111)A modified with C(18)H(37)S groups. Raman spectra were separately collected that suggested electronic passivation by surficial Ga-C bonds at GaAs(111)A. Specifically, GaAs(111)A surfaces reacted with alkyl Grignard reagents exhibited Raman signatures comparable to those of samples treated with 10% Na(2)S in tert-butanol. For GaN(0001), high-resolution C 1s spectra exhibited the characteristic low binding energy shoulder demonstrative of surface Ga-C bonds following reaction with CH(3)MgCl. In addition, 4-fluorophenyl groups were attached and detected after reaction with C(6)H(4)FMgBr, further confirming the susceptibility of Cl-terminated GaN(0001) to surface alkylation. However, the measured hydrophobicities of alkyl-terminated GaAs(111)A and GaN(0001) were markedly distinct, indicating differences in the resultant surface layers. The results presented here, in conjunction with previous studies on GaP, show that atop Ga atoms at these crystallographically related surfaces can be deliberately functionalized and protected through Ga-C surface bonds that do not involve thiol/sulfide chemistry or gas-phase pretreatments.     

Studies of carbon behaviour on GaN surface in ultra high vacuum (UHV)

In this study, AES was used to thermally clean GaN surfaces, and analysis was done as the temperature was gradually increased. Heating samples to 1010 °C resulted in nearly stoichiometric and contamination‐free surfaces. The behaviour of carbon on the GaN surface was studied with sputtering in AES. It was found that C was a surface issue than a crystal problem. XPS was used to identify the chemical state of the contaminants on the surface of as‐grown GaN. These were found to be in the form of gallium oxides, hydroxides, graphite and carbides. Copyright © 2005 John Wiley & Sons, Ltd.     

Effect of oxidation on the wettability of poly(dimethylsiloxane) surfaces

The wetting of amorphous poly(dimethylsiloxane) (PDMS) surfaces by water has been studied using molecular dynamics simulations. PDMS surfaces were generated by compressing a long PDMS chain between two elastic boundaries at atmospheric pressure. Oxidation of the PDMS surface, achieved in real systems by exposure to air plasma or corona discharge, was modeled by replacing methyl groups on the PDMS chain with hydroxyl groups. Three surfaces of varying degrees of oxidation were characterized by measuring the water contact angle and the roughness. The dependence of the microscopic contact angle on drop size was measured from time averaged density profiles. The macroscopic contact angle was measured directly using a cylindrical drop of infinite length with zero contact line curvature. The measured macroscopic contact angle ranged from approximately 125 degrees on the untreated surface to 75 degrees on the most oxidized surface studied. The line tension was found to increase with increasing degree of oxidation, from a negligible value on the untreated surface to approximately 5x10(-11) J m(-1) on the most heavily oxidized surface.     

XPS study on the use of 3-aminopropyltriethoxysilane to bond chitosan to a titanium surface

Chitosan, a biopolymer found in the exoskeletons of shellfish, has been shown to be antibacterial, biodegradable, osteoconductive, and has the ability to promote organized bone formation. These properties make chitosan an ideal material for use as a bioactive coating on medical implant materials. In this study, coatings made from 86.4% de-acetylated chitosan were bound to implant-quality titanium. The chitosan films were bound through a three-step process that involved the deposition of 3-aminopropyltriethoxysilane (APTES) in toluene, followed by a reaction between the amine end of APTES with gluteraldehyde, and finally, a reaction between the aldehyde end of gluteraldehyde and chitosan. Two different metal treatments were examined to determine if major differences in the ability to bind chitosan could be seen. X-ray photoelectron spectroscopy (XPS) was used to examine the surface of the titanium metal and to study the individual reaction steps. The changes to the titanium surface were consistent with the anticipated reaction steps, with significant changes in the amounts of nitrogen, silicon, and titanium that were present. It was demonstrated that more APTES was bound to the piranha-treated titanium surface as compared to the passivated titanium surface, based on the amounts of titanium, carbon, nitrogen, and silicon that were present. The metal treatments did not affect the chemistry of the chitosan films. Using toluene to bond APTES on titanium surfaces, rather than aqueous solutions, prevented the formation of unwanted polysiloxanes and increased the amount of silane on the surface for forming bonds to the chitosan films. Qualitatively, the films were more strongly attached to the titanium surfaces after using toluene, which could withstand the ultrahigh vacuum environment of XPS, as compared to the aqueous solutions, which were removed from the titanium surface when exposed to the ultrahigh vacuum environment of XPS.     

Phosphonic acid monolayers for binding of bioactive molecules to titanium surfaces

Two different phosphonic acid monolayer films for immobilization of bioactive molecules such as the protein BMP-2 on titanium surfaces have been prepared. Monolayers of (11-hydroxyundecyl)phosphonic acid and (12-carboxydodecyl)phosphonic acid molecules were produced by a simple dipping process (the T-BAG method). The terminal functional groups on these monolayers were activated (carbonyldiimidazole for hydroxyl groups and N-hydroxysuccinimide for carboxyl groups) to bind amine-containing molecules. The reactivity of the surfaces was investigated using trifluoroethylamine hydrochloride and BMP-2. Each step of the surface modification procedure was characterized by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry.     

Surfactant-resisted assembly of Fe-containing nanoparticles for site-specific growth of SWNTs on Si surface

This paper describes a facile approach to the site-specific growth of single-walled carbon nanotubes (SWNTs) on silicon surfaces by chemical vapor deposition (CVD). The approach is based on the use of a surfactant as a resist to define patterns of silicon oxide nanodomains onto which nanoparticles of iron hydroxide (Fe(OH)3), 1-5 nm diameter, could be deposited. In base growth mode, the SWNTs can grow from the oxide nanodomains. By controlling the location of oxide nanodomains, site-specific growth could be obtained. The iron hydroxide nanoparticles were prepared by hydrolysis of ferric chloride (FeCl3). Patterned hydroxylated silicon oxide nanodomains were created by scanning probe oxidation (SPO) of silicon substrates modified with aminopropyltrimethoxysilane (APTMS, H2N(CH2)3Si(OCH3)3). Due to electrostatic interaction, Fe(OH)3 nanoparticles can be selectively deposited on hydroxyl groups present on silicon oxide nanodomains. To inhibit the assembly of the nanoparticles on a APTMS-coated silicon surface, sodium dodecyl sulfate (SDS) was introduced, which restricted deposition to the hydroxylated nanodomains. A model mechanism for the selective deposition mechanism has been proposed. It was possible to convert the patterned Fe(OH)3 nanoparticles to iron oxide, which served as a catalyst for the site-specific growth of SWNTs. Raman spectroscopy and AFM were used to characterize the nanotubes on the Si substrate. This will offer the possibility for future integration with conventional microelectronics as well as the development of novel devices.     

Ag on Pt(111): Changes in Electronic and CO Adsorption Properties upon PtAg/Pt(111) Monolayer Surface Alloy Formation

The electronic and chemical (adsorption) properties of bimetallic Ag/Pt(111) surfaces and their modification upon surface alloy formation, that is, during intermixing of Ag and Pt atoms in the top atomic layer upon annealing, were studied by X‐ray photoelectron spectroscopy (XPS) and, using CO as probe molecule, by temperature‐programmed desorption (TPD) and infrared reflection absorption spectroscopy (IRRAS), respectively. The surface alloys are prepared by deposition of sub‐monolayer Ag amounts on a Pt(111) surface at room temperature, leading to extended Ag monolayer islands on the substrate, and subsequent annealing of these surfaces. Surface alloy formation starts at ≈600–650 K, which is evidenced by core‐level shifts (CLSs) of the Ag(3d_5/2) signal. A distinct change of the CO adsorption properties is observed when going to the intermixed PtAg surface alloys. Most prominently, we find the growth of a new desorption feature at higher temperature (≈550 K) in the TPD spectra upon surface alloy formation. This goes along with a shift of the CO_ad‐related IR bands to lower wave number. Surface alloy formation is almost completed after heating to 700 K.     

Optical and electrochemical studies of the underpotential deposition of metals Part I. Thallium deposition on single crystal silver electrodes

The underpotential deposition of thallium on single crystal silver cathodes, orientations 100, 110 and 111, was investigated optically and voltammetrically. Careful chemical polishing of the silver surfaces was necessary to reveal the fine structure on the voltammograms reproducibly. The deposition process for the first monolayer was shown to be the formation of a layer of adsorbed atoms initially, followed by a phase transformation to form a crystal plane by two-dimensional nucleation and growth. The extent of the initial adsorption was related to the number of favourable sites on each crystal face such that the adsorbed layer formed a superlattice. The influence of the substrate structure was seen on the formation of the second thallium monolayer. The formation of this layer also involved adsorption followed by transformation into a crystal plane.     

Comparison of the Stability of Functionalized GaN and GaP

Surface functionalization via 1 H,1 H,2 H,2H‐perfluoro octanephosphonic acid was done in the presence of phosphoric acid to provide a simplified surface passivation technique for gallium nitride (GaN) and gallium phosphide (GaP). In an effort to identify the leading causes of surface instabilities, hydrogen peroxide was utilized as an additional chemical modification to cap unsatisfied bonds. The stability of the surfaces was studied in an aqueous environment and subsequently characterized. A physical characterization was carried out to evaluate the surface roughness and water hydrophobicity pre and post stability testing via atomic force microscopy and water goniometry. Surface‐chemistry changes and solution leaching were quantified by X‐ray photoelectron spectroscopy and inductively coupled plasma mass spectrometry. The results indicate a sensitivity to hydroxyl terminated species for both GaN and GaP under aqueous environments, as the increase of the degree of leaching was more significant for hydrogen peroxide treated samples. The results support the notion that hydroxyl species act as precursors to gallium oxide formation and lead to subsequent instability in aqueous solutions.