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.

Immunosensor Interface Based on Physical and Chemical Immunogylobulin G Adsorption onto Mixed Self-Assembled Monolayers

An immunosensor interface based on mixed hydrophobic self-assembled monolayers (SAMs) of methyl and carboxylic acid terminated thiols with covalently attached human Immunoglobulin G (hIgG), is investigated. The densely packed and organised SAMs were characterised by contact angle measurements and cyclic voltammetry. The effect of the non-ionic surfactant, Tween 20, in preventing nonspecific adsorption is addressed by ellipsometry during physical and covalent hIgG immobilization on pure and mixed SAMs, respectively. It is clearly demonstrated that nonspecific adsorption due to hydrophobic interactions of hIgG on methyl ended groups is totally inhibited, whereas electrostatic/hydrogen bonding interactions with the exposed carboxylic groups prevail in the presence of surfactant. Results of ellipsometry and Atomic Force Microscopy, reveal that the surface concentration of covalently immobilized hIgG is determined by the ratio of COOH/CH3-terminated thiols in SAM forming solution. Moreover, the ellipsometric data demonstrates that the ratio of bound anti-hIgG/hIgG depends on the density of hIgG on the surface and that the highest ratio is close to three. We also report the selectivity and high sensitivity achieved by chronoamperometry in the detection of adsorbed hIgG and the reaction with its antibody.

Detection of molecular interactions with modified ferrocene self-assembled monolayers.

Ferrocene-terminated self-assembled monolayers (Fc-SAMs) are one of the most studied molecular aggregates on metal electrodes. They are easy to fabricate and provide a stable and reproducible system to investigate the effect of the microenvironment on the electron transfer parameters. We propose a novel application for Fc-SAMs, the detection of molecular interactions, based on the modification of the SAM with target-specific receptors. Mixed SAMs were fabricated by coimmobilization on Au electrodes of thiolated alkane chains with three different head groups: hydroxy terminating head group, ferrocene head group, and a functional head group such as biotin. Upon binding, the intrinsic electric charge of the target (e.g., streptavidin) modifies the electrostatic potential at the plane of electron transfer, causing a shift in the formal potential E degrees '. The SAMs were characterized by AC voltammetry. The detection mechanism is confirmed by measurements of formal potential as a function of electrolyte pH.

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.

Controlled amine functionality in self-assembled monolayers via the hidden amine route: chemical and electronic tunability.

A synthetic strategy for fabricating a dense amine functionalized self-assembled monolayer (SAM) on hydroxylated surfaces is presented. The assembly steps are monitored by X-ray photoelectron spectroscopy, Fourier transform infrared- attenuated total reflection, atomic force microscopy, variable angle spectroscopic ellipsometry, UV-vis surface spectroscopy, contact angle wettability, and contact potential difference measurements. The method applies alkylbromide-trichlorosilane for the fabrication of the SAM followed by surface transformation of the bromine moiety to amine by a two-step procedure: S(N)2 reaction that introduces the hidden amine, phthalimide, followed by the removal of the protecting group and exposing the free amine. The use of phthalimide moiety in the process enabled monitoring the substitution reaction rate on the surface (by absorption spectroscopy) and showed first-order kinetics. The simplicity of the process, nonharsh reagents, and short reaction time allow the use of such SAMs in molecular nanoelectronics applications, where complete control of the used SAM is needed. The different molecular dipole of each step of the process, which is verified by DFT calculations, supports the use of these SAMs as means to tune the electronic properties of semiconductors and for better synergism between SAMs and standard microelectronics processes and devices.

Reversible Nanopatterning on Self-Assembled Monolayers on Gold

The reversible fabrication of positive and negative nanopatterns on 1-hexadecanethiol (HDT) self-assembled monolayers (SAMs) on Au(111) was realized by bias-assisted atomic force microscopy (AFM) nanolithography using an ethanol-ink tip. The formation of positive and negative nanopatterns via the bias-assisted nanolithography depends solely on the polarity of the applied bias, and their writing speeds can reach 800,um/s and go beyond 1000 mu m/s, respectively. The composition of the positive nanopatterns is gold oxide and the nanometer-scale gold oxide can be reduced by ethanol to gold, as proved by X-ray photoelectron spectroscopy (XPS) analysis, forming the negative nanopatterns which can be refilled with HDT to recover the SAMs.

Surface-enhanced Raman scattering of 4-aminothiophenol self-assembled monolayers in sandwich structure with nanoparticle shape dependence: Off-surface plasmon resonance condition

A universal metal-molecule-metal sandwich architecture by the self-assembly of Ag nanoparticles (NPs) and Au NPs of various shapes interconnected with 4-aminothiophenol (4-ATP) molecules was presented. These Ag NPs/4-ATP/Au NPs sandwich structures were characterized by surface enhanced Raman scattering (SERS) using an off-surface plasmon resonance condition. Enhancement factors (EF) on the order of 10(8) for 9b(b(2)) vibration mode were observed for the 4-ATP self-assembled monolayers (SAMs) in such sandwich structures. The factors are 2 orders of magnitude larger than that on the monolayer of Au NPs of various shapes under similar condition. More importantly, remarkable increase in the intensity of b(2) vibrational modes, which is characteristic of the charge transfer (CT) behavior between metal NPs and 4-ATP molecules, was observed in these sandwich structures under 1064 nm excitation. The obtained EF on these sandwich structure for 9b(b(2)) is larger than that for 7a vibration mode by a factor of similar to 10(2), demonstrating the importance of the contribution of the CT mechanism and the CT behavior of metal contacts, which play a significant role in metal-molecule-metal nanosystems.

Interfacial supramolecular self-assembled monolayers of C-60 by thiolated beta-cyclodextrin on gold surfaces via monoanionic C-60

The supramolecular self-assembled monolayers (SAMs) of C-60 by thiolated beta-cyclodextrin (CD) on gold surfaces were constructed for the first time using C-60 monoanion. The results indicate that monoanionic C-60 plays a crucial role in the formation of the C-60-containing self-assembled monolayers. The generation of C-60 monoanion and the formation process of C-60 SAMs were monitored in-situ by UV-visible and near-IR spectroscopy. The resulting C-60 SAMs were fully characterized by spectroscopic ellipsometry (SE), cyclic voltammetry, X-ray photoelectron spectroscopy (XPS), and water contact angle measurements. After the immobilization of C-60 by the SAMs of thiolated beta-CD, the film thickness increased by approximately 1 nm from 0.8 to 1.8 nm as determined by SE, demonstrating the formation of the supramolecular self-assembled monolayers of thiolated beta-CD/C-60. The new C-60 SAMs exhibited one quasi-reversible redox couple at half wave potential of -0.57 V vs SCE in aqueous solution containing 0.1 M KCl. The surface coverage of C-60 on the gold surfaces was estimated to be 1.1 x 10(-10) mol cm(-2). The XPS showed the assembly of C-60 over the thiolated beta-CD SAMs.