Improved method for the preparation of carboxylic acid and amine terminated self-assembled monolayers of alkanethiolates

We present an improved method to prepare carboxylic acid (COOH) and amine (NH2) terminated self-assembled monolayers (SAMs) of alkanethiolates. In this method, a small amount of CF3COOH (for COOH-SAM) or N(CH2CH3)3 (for NH2-SAM) is added into the ethanolic solution of alkanethiols during SAM formation. The freshly formed COOH- and NH2-SAMs are then rinsed with an ethanolic solution of NH4OH or CH3COOH, respectively. Both SAMs prepared with the improved method show better quality in terms of surface chemical composition, roughness, and wettability as measured by X-ray photoelectron spectroscopy, atomic force microscopy, and contact angle, respectively. The formation of better SAMs can be attributed to the disruption of interplane hydrogen bonds.     

Covalent attachment of a transition metal coordination complex to functionalized oligo(phenylene-ethynylene) self-assembled monolayers

We have investigated the reaction of tetrakis(dimethylamido)titanium, Ti[N(CH(3))(2)](4), with N-isopropyl-N-[4-(thien-3-ylethynyl) phenyl] amine and N-isopropyl-N-(4-{[4-(thien-3-ylethynyl) phenyl]ethynyl}phenyl) amine self-assembled monolayers (SAMs), on polycrystalline Au substrates. The structure of the SAMs themselves has also been investigated. Both molecules form SAMs on polycrystalline Au bound by the thiophene group. The longer-molecular-backbone molecule forms a denser SAM, with molecules characterized by a smaller tilt angle. X-ray photoelectron spectroscopy (XPS) and angle-resolved XPS have been employed to examine the kinetics of adsorption, the spatial extent of reaction, and the stoichiometry of reaction. For both the SAMs, adsorption is described well by first-order Langmuirian kinetics, and adsorption is self-limiting from T(s) = -50 to 30 degrees C. The use of angle-resolved XPS clearly demonstrates that the Ti[N(CH(3))(2)](4) reacts exclusively with the isopropylamine end group via ligand exchange, and there is no penetration of the SAM, followed by reaction at the SAM-Au interface. Moreover, the SAM molecules remain bound to the Au surface via their thiopene functionalites. From XPS, we have found that, in both cases, approximately one Ti[N(CH(3))(2)](4) is adsorbed per two SAM molecules.     

Corrosion resistant performances of alkanoic and phosphonic acids derived self-assembled monolayers on magnesium alloy AZ31 by vapor-phase method

Alkanoic and phosphonic acid derived self-assembled monolayers (SAMs) were formed on magnesium alloy by the vapor phase method. AFM and XPS studies showed that SAMs were formed on Mg alloy. The chemical and anticorrosive properties of the SAMs prepared on magnesium alloys were characterized using contact angle measurements, X-ray photoelectron spectroscopy (XPS), and electrochemical measurements. Water contact angle measurements revealed that, although SA and ISA have the same headgroup to anchor to the magnesium alloy surface, the packing density on the magnesium alloy surface could be considerably different. The contact angle hysteresis of SAMs with a carboxylate headgroup is much larger than that of SAMs with a phosphonic acid group. The XPS O 1s peaks indicated more likely a mix of mono-, bi-, or tridentate binding of phosphonic acid SAM to the oxide or hydroxide surface of the Mg alloy. The electrochemical measurements showed that the phosphonic acid derived SAM had better corrosion resistance compared to alkanoic acid derived SAM. The chemical stability of SAMs modified magnesium alloy was investigated using water contact angle and XPS measurements. The water contact angle and XPS measurements revealed that the molecular density of OP and PFEP on magnesium alloy would be higher than those of SA and ISA on magnesium alloy.     

Comprehensive investigation of self-assembled monolayer formation on ferromagnetic thin film surfaces

We report a simple, universal method for forming high surface coverage SAMs on ferromagnetic thin (< or =100 nm) films of Ni, Co, and Fe. Unlike previous reports, our technique is broadly applicable to different types of SAMs and surface types. Our data constitutes the first comprehensive examination of SAM formation on three different ferromagnetic surface types using two different surface-binding chemistries (thiol and isocyanide) under three different preparation conditions: (1) SAM formation on electroreduced films using a newly developed electroreduction approach, (2) SAM formation on freshly evaporated surfaces in the glovebox, and (3) SAM formation on films exposed to atmospheric conditions beforehand. The extent of SAM formation for all three conditions was probed by cyclic voltammetry for surfaces functionalized with either (11-thiolundecyl)ferrocene (Fc-(CH2) 11-SH) or (11-isocyanoundecyl)ferrocene (Fc-(CH2) 11-NC). SAM formation was also probed for straight-chain molecules, hexadecanethiol and hexadecaneisocyanide, with contact angle measurements, X-ray photoelectron spectroscopy, and reflection-absorption infrared spectroscopy (RAIRS). The results show that high surface coverage SAMs with low surface-oxide content can be achieved for thin, evaporated Ni and Co films using our electroreduction process with thiols. The extent of SAM formation on electroreduced films is comparable to what has been observed for SAMs/Au and to what we observe for SAMs/Ni, Co, and Fe samples prepared in the glovebox.     

Supported bilayer lipid membrane arrays on photopatterned self-assembled monolayers

This work demonstrates the use of photocleavable cholesterol derivatives to create supported bilayer lipid membrane arrays on silica. The photocleavable cholesteryl tether is attached to the surface by using the reaction of an amine-functionalized self-assembled monolayer (SAM) and the N-hydroxysuccinimide-based reagent 9. The resultant SAM contains an ortho-nitrobenzyl residue that can be cleaved by photolysis by using soft (365 nm) UV light regenerating the original amine surface, and which can be patterned using a mask. The photoreaction yield was approximately 75 % which was significantly higher than previously found for related ortho-nitrobenzyl photochemistry on gold substrates. The SAMs were characterized by means of contact angle measurements, ellipsometry and X-ray photoelectron spectroscopy. Patterned surfaces were characterized with SEM and AFM. After immersing the patterned surface into a solution containing small unilamellar vesicles of egg phosphatidylcholine (PC), supported lipid membranes were formed comprised of lipid bilayer over the amine functionalized "hydrophilic" regions and lipid monolayer over the cholesteryl "hydrophobic" regions. This was confirmed by fluorescence microscopy and AFM. FRAP studies yielded a lateral diffusion coefficient for the probe molecule of 0.14+/-0.05 microm(2) s(-1) in the bilayer regions and approximately 0.01 microm(2) s(-1) in the monolayer regions. This order of magnitude difference in diffusion coefficients effectively serves to isolate the bilayer regions from one another, thus creating a bilayer array.     

Acid-base properties and zeta potentials of self-assembled monolayers obtained via in situ transformations

Siloxane-anchored, self-assembled monolayers (SAMs) on single crystal Si were prepared with a variety of surface functional groups using a single commercially available surfactant (1-bromo-11-(trichlorosilyl)undecane) followed by in situ transformations. Polar (thioacetate and thiol), nonpolar (methyl), acidic (sulfonic and carboxylic), basic (various amines), and ionic (alkylammonium) surface functionalities were prepared. For primary amine and sulfonate surfaces, the degree of surface charge as a function of pH was determined ex situ using X-ray photoelectron spectroscopy (XPS). Sulfonate SAMs exhibited much higher effective pKa (approximately 2) than dilute sulfonic acid (-5 to -6), and amine SAMs exhibited much lower pKa (approximately 3) than dilute organic amines (approximately 10). This is attributed to the stabilization of nonionized groups by adjacent ionized groups in the SAM. Zeta potentials of these SAMs as a function of pH were consistent with the XPS results and indicated that ionizable SAM surfaces can generate surface potentials much higher than those of nonionic SAMs (thioacetate, methyl) and typical oxide surfaces.     

A mild photoactivated hydrophilic/hydrophobic switch

Surface modification using light is one of the most powerful methods for controlling the physical and chemical properties offunctionalized surfaces. In this paper, we report on systems where soft UV irradiation (lambda = 365 nm) converts a "low" activity fluorocarbon to a "high" activity amine-functionalized surface. An amine-functionalized SAM (self-assembled monolayer) is first masked using a tertiary amine catalyzed reaction with an N-hydroxysuccinimidyl carbonyl reagent. This mild, room-temperature reaction introduces a hydrophobic photocleavable nitrobenzyl "protecting group" terminated with a fluorocarbon end-chain. UV irradiation (lambda = 365 nm) of this hydrophobic/fluorocarbon surface cleaves the nitrobenzyl residue, returning the surface to the original hydrophilic/amine-functionalized state. This provides a mild, generic method of producing surfaces with hydrophilic/hydrophobic patterns or patterned with amine functional residues. Two different protecting groups, one terminated with a single and the other with three fluorocarbon end chains, are compared. In the case of the more bulky protecting group, only a small proportion of the amine residues react, but the surface is equally hydrophobic and the amine residues equally well shielded from further reaction. Surfaces are characterized by X-ray photoelectron spectroscopy, ellipsometry, surface potential, and contact angle measurements. Images of the photopatterned SAMs were obtained using scanning electron microscopy.     

辛基三乙氧基硅烷/十八烷基三氯硅烷均相混合自组装单分子膜的表征及其形成机制

使用接触角、原子力显微镜(AFM)、静电力显微镜(EFM)和傅里叶变换红外(FTIR)光谱对辛基三乙氧基硅烷(C8TES)/十八烷基三氯硅烷(OTS)均相混合自组装单分子膜(SAM)及其形成过程中样品表面的润湿性、表面形貌、表面电势和膜内分子的有序度进行了表征,对采用分步法利用C8TES分子空间位阻制备C8TES/OTS均相混合SAM的反应机制进行了研究.结果表明,C8TES/OTS均相混合SAM表面接触角为105°,样品表面平整、光滑;对样品表面电势进行分析后发现,混合SAM表面电势分布均匀,电势频率分布为典型的正态分布;在均相混合SAM的形成过程中,样品表面电势的分布始终十分均匀,电势频率分布均为典型的正态分布;C8TES/OTS均相混合SAM是一种具有上下两层分子排列密度不同的膜结构的单分子膜,其内部结构至少在500 nm×500 nm到20μm×20μm尺度上是高度均匀一致的,膜内没有明显的特征结构,具有典型的均相混合SAM特征.     

Polymerization of diacetylenes by hydrogen bond templated adlayer formation

Adlayers were formed on self-assembled monolayers (SAMs) formed by alkanethiols on gold. Base SAMs exposing amide functional groups at the SAM surface were formed with 12-mercaptododecanamide. Adlayers of diacetylene-containing monomers were then formed via amide hydrogen bonding in decalin and decalin/toluene mixtures. Grazing angle FTIR, contact angle measurements, and ellipsometry suggest that these adlayer films exhibit ordering and packing similar to that of SAMs on gold. Resonance Raman spectroscopy showed that these diacetylene adlayers could be readily polymerized by exposure to UV light.     

The reaction of tetrakis(dimethylamido)titanium with self-assembled alkyltrichlorosilane monolayers possessing -OH, -NH2, and -CH3 terminal groups

The reactions of tetrakis(dimethylamido)titanium, Ti[N(CH(3))(2)](4), with alkyltrichlorosilane self-assembled monolayers (SAMs) terminated by -OH, -NH(2), and -CH(3) groups have been investigated with X-ray photoelectron spectroscopy (XPS). For comparison, a chemically oxidized Si surface, which serves as the starting point for formation of the SAMs, has also been investigated. In this work, we examined the kinetics of adsorption, the spatial extent, and stoichiometry of the reaction. Chemically oxidized Si has been found to be the most reactive surface examined here, followed by the -OH, -NH(2), and -CH(3) terminated SAMs, in that order. On all surfaces, the reaction of Ti[N(CH(3))(2)](4) was relatively facile, as evidenced by a rather weak dependence of the initial reaction probability on substrate temperature (T(s) = -50 to 110 degrees C), and adsorption could be described by first-order Langmuirian kinetics. The use of angle-resolved XPS demonstrated clearly that the anomalous reactivity of the -CH(3) terminated SAM could be attributed to reaction of Ti[N(CH(3))(2)](4) at the SAM/SiO(2) interface. Reaction on the -NH(2) terminated SAM proved to be the "cleanest", where essentially all of the reactivity could be associated with the terminal amine group. In this case, we found that approximately one Ti[N(CH(3))(2)](4) adsorbed per two SAM molecules. On all surfaces, there was significant loss of the N(CH(3))(2) ligand, particularly at high substrate temperatures, T(s) = 110 degrees C. These results show for the first time that it is possible to attach a transition metal coordination complex from the vapor phase to a surface with an appropriately functionalized self-assembled monolayer.     

Photocatalytic reduction of an azide-terminated self-assembled monolayer using CdS quantum dots

Ordered, tightly packed aryl-azide-terminated, self-assembled monolayers (SAMs) were created on gold substrates from a new disulfide precursor. These monolayers were reduced at least partially in an aqueous environment using approximately 2 nm CdS quantum dots (Qdots) as photocatalysts to give mixed monolayers of arylamine- and aryl azide-terminated species. The CdS photocatalysts were made available for the reaction by exposure of the azide-terminated SAM to Qdots initially in solution or by preadsorption of the CdS nanoparticles on the SAM. In either case, X-ray photoelectron spectroscopy (XPS), grazing angle Fourier transform infrared spectroscopy (FTIR), and contact angle measurements were used to show the occurrence of the photocatalytic reduction. As further evidence for the presence of arylamine-terminated thiolate in the reduced SAM, these arylamine groups were successfully tagged with fluorescein isothiocyanate (FITC). The use of Qdot photocatalysts to functionalize surfaces may lead to a means to pattern surfaces at the nanoscale.     

Characterization of self-assembled monolayers of thiols on Au(111)

Self-assembled monolayers (SAMs) of n-butanethiol, n-dodecanethiol and their equimolar mixture on Au(111) were prepared and characterized by ellipsometry, contact angle measurement, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Results revealed that these SAMs are oriented ultrathin films with the thickness of nanometer scale, and the SAMs were influenced by the molecular chain length, the lattice orientation and cleanliness of the substrates. The surface of the longer chain SAM is hydrophobic. The thicknesses of three SAMs of n-butanethiol, n-dodecanethiol and their mixture revealed by ellipsometry and XPS are about 0.59 - 0.67nm, 1.60- 1.69 nm and 1.23 - 1.32nm, respectively. AFM images further demonstrated that the SAM formed by the mixture has some microdomains with two different thicknesses.     

Exchange of Methyl‐ and Azobenzene‐Terminated Alkanethiols on Polycrystalline Gold Studied by Tip‐Enhanced Raman Mapping

Mixed thiol self‐assembled monolayers (SAMs) presenting methyl and azobenzene head groups were prepared by chemical substitution from the original single‐component n‐decanethiol or [4‐(phenylazo)phenoxy]hexane‐1‐thiol SAMs on polycrystalline gold substrates. Static contact‐angle measurements were carried out to confirm a change in the hydrophobicity of the functionalized surfaces following the exchange reaction. The mixed SAMs presented contact‐angle values between those of the more hydrophobic n‐decanethiol and the more hydrophilic [4‐(phenylazo)phenoxy]hexane‐1‐thiol single‐component SAMs. By means of tip‐enhanced Raman spectroscopy (TERS) mapping experiments, it was possible to highlight that molecular replacement takes place easily and first at grain boundaries: for two different mixed SAM compositions, TERS point‐by‐point maps with <50 nm step sizes showed different spectral signatures in correspondence to the grain boundaries. An example of the substitution extending beyond grain boundaries and affecting flat areas of the gold surface is also shown.     

Stability of self-assembled monolayers on titanium and gold

Methyl- and hydroxyl-terminated phosphonic acid self-assembled monolayers (SAMs) were coated on Ti from aqueous solution. Dodecyl phosphate and dodecyltrichlorosilane SAMs were also coated on Ti using solution-phase deposition. The stability of SAMs on Ti was investigated in Tris-buffered saline (TBS) at 37 degrees C using X-ray photoelectron spectroscopy, contact angle goniometry, and atomic force microscopy. For comparison purposes, a hydroxyl-terminated thiol SAM was coated on Au, and its stability was also investigated under similar conditions. In TBS, a significant proportion of phosphonic acid or phosphate molecules were desorbed from the Ti surface within 1 day, while the trichlorosilane SAM on Ti or thiol SAM on Au was stable for up to 7 days under similar conditions. The stability of hydroxyl-terminated phosphonic acid SAM coated Ti and thiol SAM coated Au was investigated in ambient air and ultraviolet (UV) light. In ambient air, the phosphonic acid SAM on Ti was stable for up to 14 days, while the thiol SAM on Au was not stable for 1 day. Under UV-radiation exposure, the alkyl chains of the phosphonic acid SAM were decomposed, leaving only the phosphonate groups on the Ti surface after 12 h. Under similar conditions, decomposition of alkyl chains of the thiol SAM was observed on the Au surface accompanied by oxidation of thiolates.     

辛基三乙氧基硅烷/十八烷基三氯硅烷均相混合自组装单分子膜的表征及其形成机制

使用接触角、原子力显微镜（AFM）、静电力显微镜（EFM）和傅里叶变换红外（FTIR）光谱对辛基三乙氧基硅烷（C8TES）/十八烷基三氯硅烷（OTS）均相混合自组装单分子膜（SAM）及其形成过程中样品表面的润湿性、表面形貌、表面电势和膜内分子的有序度进行了表征,对采用分步法利用C8TES分子空间位阻制备C8TES/OTS均相混合SAM的反应机制进行了研究. 结果表明,C8TES/OTS均相混合SAM表面接触角为105°,样品表面平整、光滑;对样品表面电势进行分析后发现,混合SAM表面电势分布均匀,电势频率分布为典型的正态分布;在均相混合SAM的形成过程中,样品表面电势的分布始终十分均匀,电势频率分布均为典型的正态分布;C8TES/OTS均相混合SAM是一种具有上下两层分子排列密度不同的膜结构的单分子膜,其内部结构至少在500 nm×500 nm到20 μm×20 μm尺度上是高度均匀一致的,膜内没有明显的特征结构,具有典型的均相混合SAM特征.     

Profile control in surface amine gradients prepared by controlled-rate infusion

Surface amine gradients that exhibit a wide variety of profiles, including those that incorporate spatially distinct regions having steep and gradual variations in chemical functionality, have been prepared by the sol-gel process using a controlled-rate infusion method. In this work, a substrate that incorporates dimethyl and Si-OH groups is temporally modified with an aminoalkoxysilane (NH(2)(CH(2))(3)Si(OC(2)H(5))(3)) to build a gradient film for which the amine content changes over a 10-20 mm distance. Both X-ray photoelectron spectroscopy (XPS) and contact angle measurements confirm the presence of a chemical gradient across the surface of the film. As expected, a greater density of amine functionalities and lower contact angle were found at the bottom of the gradient relative to the top. The local steepness of the gradient was systematically controlled by changing the rate of infusion. Fast rates of infusion created gradient surfaces where the amine content changed slowly along the surface and never reached saturation, whereas slow rates of infusion formed a surface exhibiting a steep rise in amine content followed by saturation. The steepness of the gradient was also changed at predefined positions along its length by programming the rate of infusion. Gradients prepared using six-step, three-step, and two-step programmed infusion rates are shown. The data fit nicely to a kinetic model that assumes first-order kinetics. The ability to manipulate the gradient profile is particularly vital for applications that rely on mass transport and/or those that require spatial control of gradient properties.     

Comparison of surface confined ATRP and SET‐LRP syntheses for a series of amino (meth)acrylate polymer brushes on silicon substrates

A series of poly(amino (meth)acrylate) brushes, poly(2‐(dimethylamino)ethyl methacrylate) (PDMAEMA), poly(2‐(diethylamino)ethyl methacrylate) (PDEAEMA), poly(2‐(dimethylamino)ethyl acrylate) (PDMAEA), poly(2‐(tert‐butylamino)ethyl methacrylate) (PTBAEMA), has been synthesized via surface‐confined controlled/living radical polymerizations using surface‐confined initiator from silane self‐assembled monolayers (SAMs) on silicon (Si) wafer substrates. Chemical methods and efficacies for two types of living radical polymerization, atom transfer radical (ATRP) and single electron transfer (SET‐LRP), are described and contrasted for the surface confined polymerization of poly(amino (meth)acrylate)s. Effects of solvent, catalyst/ligand system, and temperature on polymerization success were examined. Chemical compositions after each reaction step were characterized with FTIR spectroscopy, contact angle goniometry, and X‐ray photoelectron spectroscopy while the SAM and polymer brush thicknesses were measured with spectroscopic ellipsometry. For the first time, this study demonstrates successful surface‐confined polymerization of a series of poly(amine (meth)acrylate) brushes from Si‐SAM substrates using a copper metal electron donor catalyst. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6552–6560, 2009     

Epimeric monosaccharide-quinone hybrids on gold electrodes toward the electrochemical probing of specific carbohydrate-protein recognitions

Carbohydrates represent one of the most significant natural building blocks, which govern numerous critical biological and pathological processes through specific carbohydrate-receptor interactions on the cell surface. We present here a new class of electrochemical probes based on gold surface-coated epimeric monosaccharide-quinone hybrids toward the ingenious detection of specific epimeric carbohydrate-protein interactions. Glucose and galactose, which represent a pair of natural monosaccharide C4 epimers, were used to closely and solidly conjugate with the 1,4-dimethoxybenzene moiety via a single C-C glycosidic bond, followed by the introduction of a sulfhydryl anchor. The functionalized aryl C-glycosides were sequentially coated on the gold electrode via the self-assembled monolayer (SAM) technique. X-ray photoelectron spectroscopy (XPS) was used to confirm the SAM formation, by which different binding energies (BE) between the glucosyl and the galactosyl SAMs on the surface, probably rendered by their epimeric identity, were observed. The subsequent electrochemical deprotection process readily furnished the surface-confined quinone/hydroquinone redox couple, leading to the formation of electrochemically active epimeric monosaccharide-quinone SAMs on the gold electrode. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) used for the detection of specific sugar-lectin interactions indicated that the addition of specific lectin to the corresponding monosaccharide-quinone surface, i.e., concanavalin A (Con A) to the glucosyl SAM and peanut agglutinin (PNA) to the galactosyl SAM, resulted in an obvious decrease in peak current, whereas the addition of nonspecific lectins to the same SAMs gave very minor current variations. Such data suggested our uniquely constructed gold surface coated by sugar-quinone hybrids to be applicable as electrochemical probes for the detection of specific sugar-protein interactions, presumably leading to a new electrochemistry platform toward the study of carbohydrate-mediated intercellular recognitions.     

Octadecyltrichlorosilane (OTS): a resist for OMCVD gold nanoparticle growth

One application of octadecyltrichlorosilane (OTS) self‐assembled monolayers (SAMs) is its use as thin film resists. In this work, we demonstrated that OTS SAMs can be reliable resists for organo‐metallic chemical vapor deposition (OMCVD) grown gold nanoparticles (Au NPs). In optical sensing applications based on Au NPs, one candidate system consists of patterned OTS SAMs and precisely grown OMCVD Au NPs for achieving a high sensitivity. As an initial step, the OTS SAMs need to perfectly resist the OMCVD Au NP growth. Hence the optimized formation of the OTS SAMs affected by different assembly times and baking temperatures was studied by contact angle, ellipsometry, XPS, SEM, and atomic force microscopy (AFM). To demonstrate the ability of the OTS SAMs to resist OMCVD Au NP growth, the OMCVD process was carried out on two sets of samples: OTS SAMs fabricated under optimized conditions on one set and the other set without OTS SAMs. High‐resolution XPS, RBS, SEM, and ultraviolet‐visible (UV‐Vis) spectroscopy were applied to study the growth of Au NPs on the samples with and without OTS SAM resists. Copyright © 2009 John Wiley & Sons, Ltd.     

Self-assembled monolayers prepared from ω-thiophene-functionalized n-alkyltrichlorosilane on silicon substrates

Self-assembled monolayers (SAMs) of thienyl-functionalized n-alkyltrichlorosilane (11-(3-thienyl)undecyltrichlorosilane [TUTS]) have been prepared by adsorption from solution and characterized by using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), contact angle measurements, ellipsometry, and scanning electron microscopy (SEM). Using contact angle and SEM measurements, the film preparation protocol was optimized, resulting in reproducible SAM formation with no adverse deposition of polysiloxane particles. XPS and ellipsometry studies confirmed the existence of SAM formation. AFM results show a smooth and homogeneous SAM, with surface roughness of Ra≤0.2 nm, which is slightly higher than the corresponding values for octadecyltrichlorosilane (OTS) SAMs. Such thiophene-based SAM surfaces can be used for surface-initiated polymerization of thiophene. The resulting formed polythiophene layers at non-compatible surfaces offer some practical applications in manufacturing [W. Plieth, A. Fikus, D. Appelhans, H.-J. Adler, German Patent Application No. 2661977 (1998); D. Appelhans, D. Ferse, H.-J. Adler, A. Fikus, W. Plieth, B. Aldolphi et al., J. Electrochem. Soc. (accepted)].