Direct patterning of negative nanostructures on self-assembled monolayers of 16-mercaptohexadecanoic acid on Au(111) substrate via dip-pen nanolithography

Both bare and self-assembled monolayer (SAM) protected gold substrate could be etched by allyl bromide according to atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometric (ICPMS) analysis results. With this allyl bromide ink material, negative nanopatterns could be fabricated directly by dip-pen nanolithography (DPN) on SAMs of 16-mercaptohexadecanoic acid (MHA) on Au(111) substrate. A tip-promoted etching mechanism was proposed where the gold-reactive ink could penetrate the MHA resist film through tip-induced defects resulting in local corrosive removal of the gold substrate. The fabrication mechanism was also confirmed by electrochemical characterization, energy dispersive spectroscopy (EDS) analysis and fabrication of positive nanopatterns via a used DPN tip.

Electrochemical growth and characterization of polyoxometalate-containing monolayers and multilayers on alkanethiol monolayers self-assembled on gold electrodes

A general strategy has been developed for fabrication of ultrathin monolayer and multilayer composite films composed of nearly all kinds of polyoxometalates (POMs), including isopolyanions (IPAs), and heteropolyanions (HPAs). It involves stepwise adsorption between the anionic POMs and a cationic polymer on alkanethiol (cysteamine and 3-mercaptopropionic acid) self-assembled monolayers (SAMs) based on electrostatic interaction. Here a Keggin-type HPA SiMo11VO405- was chosen as a main representative to elucidate, in detail, the fabrication and characterization of the as-prepared composite films. A novel electrochemical growth method we developed for film formation involves cyclic potential sweeps over a suitable potential range in modifier solutions. It was comparatively studied with a commonly used method of immersion growth, i.e., alternately dipping a substrate into modifier solutions. Growth processes and structural characteristics of the composite films are characterized in detail by cyclic voltammetry, UV-vis spectroscopy (UV-vis), X-ray photoelectron spectroscopy (XPS), micro-Fourier transform infrared reflection-absorption spectroscopy (FTIR-RA), and electrochemical quartz crystal microbalance (EQCM). The electrochemical growth is proven to be more advantageous than the immersion growth. The composite films exhibit well-defined surface waves characteristic of the HPAs' redox reactions. In addition, the composite films by the electrochemical growth show a uniform structure and an excellent stability. Ion motions accompanying the redox processes of SiMo11VO405- in multilayer films are examined by in situ time-resolved EQCM and some results are first reported. The strategy used here has been successfully popularized to IPAs as well as other HPAs no matter what structure and composition they have.

Viologen-thiol self-assembled monolayers for immobilized horseradish peroxidase at gold electrode surface

A stable, well-behaved self-assembled monolayer (SAM) of viologen-functionalized thiol was used to immobilize and electrically connect horseradish peroxidase (HRP) at gold electrode. Viologen groups in SAMs facilitated the electron transfer from the electrode to the protein active site so that HRP exhibited a quasi-reversible redox behavior. HRP adsorbed in the SAMs is very stable, and close to a monolayer with the surface coverage of 6.5 x 10(-11) mol/cm(2). The normal potential of HRP is -580 mV vs Ag/AgCl corresponding to ferri/ferro active center and the standard electron transfer rate constant is 3.41 s(-1) in 0.1 M phosphate buffer solution (pH 7.1). This approach shows a great promise for designing enzyme electrodes with other redox proteins and practical use in tailoring a variety of amperometric biosensor devices. Copyright (C) 1997 Elsevier Science Ltd.

Crystallization of SrCO3 on a self-assembled monolayer substrate: an in-situ synchrotron X-ray study

Self-assembled monolayers (SAMs) of alkanethiols on gold surfaces show great promise in controlling the nucleation and growth of inorganic minerals from solution. In doing so, they mimic the role of some biogenic macromolecules in natural biomineralisation processes. Crystallization on SAM surfaces is usually monitored ex-situ; by allowing the process to commence and to evolve for some time, removing the substrate from the mother solution, and then examining it using microscopy, diffraction etc. We present here for the first time, the use of high energy monochromatic synchrotron X-radiation in conjunction with a two dimensional detector to monitor in situ, in a time resolved fashion, the growth of SrCO3 (strontianite) crystals on a SAM substrate.

Self Assembled Monolayers of Alkanethiolson Silver Surfaces

This short review compiles the studies on self assembled alkanethiol monolayers formed on silver surfaces with respect to their structure and stability. Alkanethiol-based assemblies on silver surfaces are poor cousins of thiol monolayers on gold. The formation of well-ordered monolayers on silver surfaces is relatively more difficult than the corresponding systems on gold since the inherent oxide film on silver interferes with the formation and stability of the assembly. There are contradictory reports on the nature and physicochemical characteristics of alkanethiol monolayers on silver surfaces. This review attempts to highlight various studies in the literature including our efforts in this area.

Case studies on the formation of chalcogenide self-assembled monolayers on surfaces and dissociative processes

This report examines the assembly of chalcogenide organic molecules on various surfaces, focusing on cases when chemisorption is accompanied by carbon-chalcogen atom-bond scission. In the case of alkane and benzyl chalcogenides, this induces formation of a chalcogenized interface layer. This process can occur during the initial stages of adsorption and then, after passivation of the surface, molecular adsorption can proceed. The characteristics of the chalcogenized interface layer can be significantly different from the metal layer and can affect various properties such as electron conduction. For chalcogenophenes, the carbon-chalcogen atombond breaking can lead to opening of the ring and adsorption of an alkene chalcogenide. Such a disruption of the pi-electron system affects charge transport along the chains. Awareness about these effects is of importance from the point of view of molecular electronics. We discuss some recent studies based on X-ray photoelectron spectroscopy that shed light on these aspects for a series of such organic molecules.

Preparation and Tribological Studies of Stearic Acid Self-Assembled Monolayers on Polymer-Coated Silicon Surface

We present a good alternative method to improve the tribological properties of polymer films by chemisorbing a long-chain monolayer on the functional polymer surface. Thus, a novel self-assembled monolayer is successfully prepared on a silicon substrate coated with amino-group-containing polyethyleneimine (PEI) by the chemical adsorption of stearic acid (STA) molecules. The formation and structure of the STA-PEI film are characterized by means of contact-angle measurement and ellipsometric thickness measurement, and of Fourier transformation infrared spectrometric and atomic force microscopic analyses. The micro- and macro-tribological properties of the STA-PEI film are investigated on an atomic force microscope (AFM) and a unidirectional tribometer, respectively. It has been found that the STA monolayer about 2.1-nm thick is produced on the PEI coating by the chemical reaction between the amino groups in the PEI and the carboxyl group in the STA molecules to form a covalent amide bond in the presence of N,N'-dicyclohexylcarbodiimide (DCCD) as a dehydrating regent. By introducing the STA monolayer, the hydrophilic PEI polymer surface becomes hydrophobic with a water contact angle to be about 105degrees. Study of the time dependence of the film formation shows that the adsorption of PEI is fast, whereas at least 24 h is needed to generate the saturated STA monolayer. Whereas the PEI coating has relatively high adhesion, friction, and poor anti-wear ability, the STA-PEI film possesses good adhesive resistance and high load-carrying capacity and anti-wear ability, which could be attributed to the chemical structure of the STA-PEI thin film. It is assumed that the hydrogen bonds between the molecules of the STA-PEI film act to stabilize the film and can be restored after breaking during sliding. Thus, the self-assembled STA-PEI thin film might find promising application in the lubrication of micro-electromechanical systems (MEMS).

Electrochemical, spectroscopic and SPM evidence for the controlled formation of self-assembled monolayers and organised multilayers of ferrocenyl alkyl thiols on Au(111)

Organised multilayers were formed from the controlled self-assembly of ferrocene alkyl thiols on Au(111) surfaces. The control was accomplished by increasing the concentration of the thiol solutions used for the assembly. Cyclic voltammetry, ellipsometry, scanning probe microscopy (STM and AFM) and in situ FTIR spectroscopy were used to probe the differences between mono- and multilayers of the same compounds. Electrochemical desorption studies confirmed that the multilayer structure is attached to the surface via one monolayer. The electrochemical behaviour of the multilayers indicated the presence of more than one controlling factor during the oxidation step, whereas the reduction was kinetically controlled which contrasts with the behaviour of monolayers, which exhibit kinetic control for the oxidation and reduction steps. Conventional and imaging ellipsometry confirmed that multilayers with well-defined increments in thickness could be produced. However, STM indicated that at the monolayer stage, the thiols used promote the mobility of Au atoms on the surface. It is very likely that the multilayer structure is held together through hydrogen bonding. To the best of out knowledge, this is the first example of a controlled one-step growth of multilayers of ferrocenyl alkyl thiols using self-assembly techniques.

A simple bioconjugate attachment protocol for use in single molecule force spectroscopy experiments based on mixed self-assembled monolayers.

Single molecule force spectroscopy is a technique that can be used to probe the interaction force between individual biomolecular species. We focus our attention on the tip and sample coupling chemistry, which is crucial to these experiments. We utilised a novel approach of mixed self-assembled monolayers of alkanethiols in conjunction with a heterobifunctional crosslinker. The effectiveness of the protocol is demonstrated by probing the biotin-avidin interaction. We measured unbinding forces comparable to previously reported values measured at similar loading rates. Specificity tests also demonstrated a significant decrease in recognition after blocking with free avidin.

Polymer gate dielectrics with self-assembled monolayers for high-mobility organic thin-film transistors based on copper phthalocyanine

Organic thin-film transistors based on polycrystalline copper phthalocyanine (CuPc) were fabricated by using poly(vinyl alcohol) as gate dielectric. After treatment of the gate dielectric using an octadecyltrichlorosilane self-assembled monolayer, a mobility of up to 0.11 cm2/V∈s was achieved, which is comparable to that of single-crystal CuPc devices (0.1-1 cm2/V∈s). The surface morphology was analyzed and the possible reasons for the enhanced mobility are discussed. © 2009 Springer-Verlag.

The modification of self-assembled monolayer on indium tin oxide as cathode in inverted bottom-emitting organic light-emitting diodes

Self-assembled monolayers (SAMs) of a series of p-substituted benzoyl chlorides were formed on indium tin oxide as the cathode for the fabrication of inverted bottom-emitting organic light-emitting diodes (IBOLEDs). The studies on the efficiency of electron injection and device performances showed that the direct tunneling of electron and the formation of dipole associated with the monolayer-forming molecule lead to significant enhancement in electron injection. Consequently, the device efficiency is greatly improved.

Loosely packed self-assembled monolayer of N-hexadecyl-3,6-di(p-mercaptophenylacetylene)carbazole on gold and its application in biomimetic membrane research

Dithiols of N-hexadecyl-3,6-di(p-mercaptophenylacetylene)carbazole (HDMC) have been synthesized and employed to form self-assembled monolayers (SAMs) on gold. One characteristic of the HDMC molecule is its peculiar molecular structure consisting of a large and rigid headgroup and a small and flexible alkyl-chain tail. HDMC adsorbates can attach to gold substrates by a strong Au-S bond with weak van der Waals interactions between the alkyl-chain tails, leading to a loosely packed hydrophobic SAM. In this way we can couple hybrid bilayer membranes (HBMs) to gold surfaces with more likeness to a cell bilayer than the conventional HBMs based on densely packed long-chain alkanethiol SAMs. The insulating properties and stability of the HDMC monolayer as well as the HDMC/lipid bilayer on gold have been investigated by electrochemical techniques including cyclic voltammetry and impedance spectroscopy. To test whether the quality of the bilayer is sufficiently high for biomimetic research, we incorporated the pore-forming protein a-hemolysin) and the horseradish peroxidase into the bilayers, respectively.