Synthesis and surface characterization of alkylthioacetyl-capped self-assembled monolayers on gold surface

A novel alkylthioacetyl-capped hydroxyethyl methacrylate monomer and its corresponding homopolymer have been synthesized and characterized. Direct chemisorption of these moieties have been carried out on gold-coated substrate and found to form a strong surface bonding. The surface coverage and the properties of the resultant self-assembled layers have been investigated by multiple surface characterization techniques (i.e. ellipsometry, GA-FTIR, XPS, AFM, and contact angle measurements). These analyses have all confirmed the occurrence of complete chemisorption reactions with typical n-alkanethiol self-assembled characteristics.     

Characterization of iron surface modified by 2-mercaptobenzothiazole self-assembled monolayers

A self-assembled monolayer of 2-mercaptobenzothiazole (MBT) adsorbed on the iron surface was prepared. The films were characterized by electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared reflection spectroscopy (FT-IR) and scanning electron microscopy (SEM). Besides, the microcalorimetry method was utilized to study the self-assembled process on iron surface and the adsorption mechanism was discussed from the power-time curve. The results indicated that MBT was able to form a film spontaneously on iron surface and the presence of it could protect iron from corrosion effectively. However, the assembling time and the concentration influence the protection efficiency. Quantum chemical calculations, according to which adsorption mechanism was discussed, could explain the experimental results to some extent.     

Computing surface dipoles and potentials of self-assembled monolayers from first principles

We discuss methodological aspects of first principles calculations of surface dipoles and potentials in general, and surface-adsorbed self-assembled monolayers in particular, using density functional theory with a slab/super-cell approach. We show that calculations involving asymmetric slabs may yield highly erroneous results for the surface dipole and demonstrated the efficacy of a simple dipole correction scheme. We explain the importance of the electrostatic dipole distribution, show how to compute it, and establish conditions for the equivalence of calculations for the dipole distribution and the electrostatic potential distribution.     

Azobenzene-functionalized alkanethiols in self-assembled monolayers on gold

Self-assembled monolayers (SAMs) of 4-trifluoromethyl-azobenzene-4′-methyleneoxy-alkanethiols (CF₃– C₆H₄–N=N–C₆H₄–O–(CH₂) _n –SH on (111)-oriented poly-crystalline gold films on mica were examined by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS). The spectra are analyzed with the help of density-functional-theory calculations of the isolated molecule. Only one doublet is detected in the sulphur 2p spectra of the investigated SAMs, consistent with a thiolate bond of the molecule to the gold surface. The C 1s XP spectra and the corresponding XAS π ^* resonance exhibit a rich structure which is assigned to the carbon atoms in the different chemical surroundings. Comparing XPS binding energies of the azobenzene moiety and calculated initial-state shifts reveals comparable screening of all C 1s core holes. While the carbon 1s XPS binding energy lies below the π ^*-resonance excitation-energy, the reversed order is found comparing core ionization and neutral core excitation of the nitrogen 1s core-hole of the azo group. This surprising difference in core-hole binding energies is interpreted as site-dependent polarization screening and charge transfer among the densely packed aromatic moieties. We propose that a quenching of the optical excitation within the molecular layer is thus one major reason for the low trans to cis photo-isomerization rate of azobenzene in aromatic-aliphatic SAMs.     

Control of surface properties of self-assembled monolayers by tuning the degree of molecular asymmetry

We have studied self-assembled monolayers (SAMs) of asymmetric dialkyldisulfide derivatives of the form CH₃-(CH₂)_11+m-S-S-(CH₂)₁₁-OH with m = −4, −3, 0, +2 and +4 on gold. Sub-nanoscale changes in the length of the CH₃-terminated alkylchain have been used to selectively protrude one particular end group in the resulting film. The alteration of the chain length in only two methylene units already results in changes of surface properties, which have been detected with local (chemical force microscopy) and macroscopic (contact angle) techniques. In particular, advancing contact angles can be adjusted between 40° and 80°. The adhesion between a hydrophobic tip and these SAMs in water is determined by the chemical nature of the protruding end group. Chemical force microscopy, X-ray photoelectron spectroscopy and infrared reflection absorption spectroscopy have shown that these SAMs are composed of mixed, well-packed CH₃- and OH-alkylthiolate branches. The surface composition ratio is close to 1:1 for all investigated SAMs.     

Orbital-dependent charge transfer dynamics in conjugated self-assembled monolayers

Femtosecond charge transfer (CT) dynamics in a series of self-assembled monolayers with an oligo(phenylenethynylene) and oligo(phenyl) backbone is addressed by resonant Auger spectroscopy using the core hole clock method. The characteristic CT times are found to depend strongly on the character of the molecular orbital (MO) which mediates the CT process. This demonstrates that the efficiency and rate of CT through molecular frameworks can be controlled by resonant injection of the charge carriers into specific MOs.     

自组装双硫醇分子膜在交流电场下的介电特性

研究了交流电场下双巯基烷烃硫醇自组装分子膜的阻抗谱.利用汞金属作为衬底,制备出双巯基烷烃硫醇自组装分子膜,并通过交流频谱仪对其进行频谱的扫描.通过实验明确了膜的作用范围为阻抗谱中频部分,并给出相应的等效电路对阻抗谱进行了拟合.同时,根据损耗谱中损耗峰随硫醇碳链原子数的增加而向低频方向移动的现象得出双巯基硫醇Cn(n=3～10)在交流电场下的动能为14～48 meV.     

Step-wise decomposition process of azobenzene self-assembled monolayers

The step-wise decomposition of 4-(12-(dodecyldithio)dodecyloxy)azobenzene (AzoC24) in self-assembled monolayer (SAMs) on Au(1 1 1) was observed by thermal desorption spectroscopy (TDS) and X-ray photoelectron spectroscopy (XPS) under the ultra-high vacuum (UHV) condition. This decomposition process only occurred after the formation of the SAM.The TD spectra clearly showed two steps of thermal decomposition of the azobenzene moiety. At approximately 450 K, fragments of m/e = 77 and 105 were clearly observed. These fragments were decomposed species obtained by the breakage of the C-N bonds of the azobenzene moiety. At about 490 K, other fragment of m/e = 93 assigned to the phenoxy ion was detected. In order to examine the decomposition process, we measured the S 2p and N 1s XPS of the SAM at various temperatures. The results suggest that diazonium moiety is the first to be decomposed and the remaining structure is desorbed together with breakage of C-O bond between the phenoxy moiety and alkyl chain with increasing temperature.     

Excitonic luminescence in oligothiophene aggregated films and self-assembled monolayers

We studied the photoluminescence (PL) spectra of thiophene oligomers in a solution, and in a solid state: aggregated film and self-assembled monolayer (SAM). We showed a strong influence of packing conditions on the PL spectra. In the solid state a new electronic state was observed, which does not reveal itself in the solution.     

Alkylsilane self-assembled monolayers: modeling their wetting characteristics

The analysis of wetting behavior of self-assembled monolayers of alkylsilanes is presented. A simple model accounting for various surface fractions of CH₃ and CH₂ groups (self-assembly order/disorder) is used. The effect of inclusion of air in the structure of rough silanized surfaces is also considered. The importance of reduced solid–water contact area and assembly order of organic monomers is demonstrated for achieving both high contact angle and low sliding angle. As coatings with low surface energy, these materials may be of potential use for ice-repellent purposes.     

Molecular gated transistors: Role of self-assembled monolayers

In order to understand the biosensing mechanism of field-effect based biosensors and optimize their performance, the effect of each of its molecular building block must be understood. In this work the gating effect of self-assembled linker molecules on field-effect transistor was studied in detail. We have combined Kelvin probe force microscopy, current-voltage measurements, capacitance-voltage measurements, equivalent circuit modeling and device simulations in order to trace the mechanism of silicon-on-insulator biological field-effect transistors. The measurements were conducted on the widely used linker molecules (3-aminopropyl)-trimethoxysilane (APTMS) and 11-aminoundecyl-triethoxysilane (AUTES), which were self-assembled on ozone activated silicon oxide surface covering the transistor channel. In a dry environment, the work function of the modified silicon oxide decreased by more than 1.5 eV, and the transistor threshold voltage increased by about 30 V following the self-assembly. A detailed analysis indicates that these changes are due to negative induced charges on the top dielectric layer, and an effective dipole due to the polar monolayer. However, the self-assembly did not change the silicon flat-band voltage when in contact with an electrolyte. This is attributed to electrostatic screening by the electrolyte.     

Device applications of self-assembled monolayers and monolayer-protected nanoclusters

The present status of self-assembled monolayers (SAMs) on different surfaces (2D systems) as well as monolayer formation on metallic and semiconducting cluster surfaces (3D SAM) to form monolayer-protected nanoclusters (MPCs) and their assemblies is reviewed briefly. Attention is focused mainly on the potential electronic and photonic applications of SAMs, MPCs and their 2D and 3D structures fabricated using covalent and hydrophobic interactions in contrast to the usual electrostatic assemblies. These examples illustrate the rational use of organic molecules and nanoclusters using the concept of self-assembly, where subtle systems of double tunnel junctions, hetero junctions and single-electron transition devices could be developed based on the structure and chemistry of multifunctional molecules. The tailoring of cluster size and cluster–cluster spacing to reveal interesting transitions in electronic properties is also demonstrated using the low temperature behavior of the 3D network of nanoclusters as an example. These devices are believed to play an important role in the coming years as the chip functions and clock frequencies reach orders of magnitude beyond those extrapolated from Moore’s law.     

Electron transfer behavior at polyoxometalate-adsorbed alkanethiol self-assembled monolayers

The interaction between polyoxometalate (POM) anions, SiMo₁₂O₄₀⁴⁻, and a self-assembled monolayer (SAM) of dodecanethiol (DT) on Au surfaces was investigated using electrochemical methods, X-ray photoelectron spectroscopy, and scanning probe microscopy. The SiMo₁₂O₄₀⁴⁻ ions adsorb on the SAM of DT on Au to form a composite organic-inorganic hybrid layer. The adsorbed SiMo₁₂O₄₀⁴⁻ ion on the SAM layer shows its characteristic redox waves with an electron transfer rate slower than that on a bare Au electrode. The electron transfer behavior at DT−SAM could be regulated by the adsorption of SiMo₁₂O₄₀⁴⁻ depending on the charge of the investigated electroactive species: a significant increase toward a positively charged Ru(NH₃)₆³⁺ ion, a moderate increase toward a neutral 1,1′-ferrocenedimethanol molecule and a slight decrease toward a negatively charged Fe(CN)₆³⁻ ion. The effect of the chain length of alkanethiols on the adsorption of SiMo₁₂O₄₀⁴⁻ ion was also investigated: as the chain length decreases, the amount of the adsorbed POM increases and the electron transfer rate through the composite layers increases. The nature of SiMo₁₂O₄₀⁴⁻ ions adsorbed on the SAMs of alkanethiols on Au is discussed in detail.     

Selective imaging of self-assembled monolayers by tunneling microscopy

The properties of thin organic films offer many challenging opportunities for science and technology. A crucial requirement for the advancement of molecular film technology is the selective characterization and modification on an atomic level. Local proximal probes like Scanning Tunneling Microscopy (STM) or Atomic Force Microscopy (AFM) bear certainly the potential for this purpose. So far, however, mainly adsorbed organic molecules lying flat on a smooth substrate have been imaged with near atomic resolution. Here, we demonstrate the ability of STM to selectively image self-assembled monolayers of long-chain molecules (hexanethiol) oriented upright on the substrate Au(111) with molecular resolution. Upon proper choice of the tunneling parameters we can image the molecular head-group anchored at the substrate and/or the molecular tail group.     

Quantitative analysis of mixed self-assembled monolayers using ToF-SIMS

The spacing of chemical functional groups on self-assembled monolayers (SAMs) plays an important role in controlling the density of biomolecules in biochips and biosensors. In this sense, a mixed SAM made of two different terminal groups is a useful organic surface since spacing can be easily controlled by changing a relative mole fraction in a mixture solution. In this study, an acetylene-OCH₂O(EG)₃(CH₂)₁₁S-S(CH₂)₁₁(EG)₃OCH₂O-propene (Eneyne) SAM and mixed SAMs made by a mixture of (S(CH₂)₁₁(EG)₃OCH₂O-acetylene)₂ (Diyne) and (S(CH₂)₁₁(EG)₃OCH₂O-propene)₂ (Diene) were produced on gold substrates and measured by using ToF-SIMS. The secondary ion yield ratio of [Au·S(CH₂)₁₁(EG)₃OCH₂O-acetylene]⁻ to [Au·S(CH₂)₁₁(EG)₃OCH₂O-propene]⁻ was measured for each mixed SAM and plotted as a function of the mole fraction of Diyne to Diene in a SAM solution. The ion yield ratio of a mixed SAM produced from a solution with a mole fraction of 0.5 (i.e., 1:1 mixture) was 0.3, which corresponded well to the ion yield ratio measured from an Eneyne SAM. A time-dependent experiment of Eneyne SAM formation and immersion experiment of Eneyne SAM into Diyne solution or into Diene solution were performed. The relative ion yield ratio of 0.3 was due to a different secondary ion formation and not due to the difference in the amount of adsorbates on the surface, nor to the different binding strengths onto the gold surface. Our study shows that a mixed SAM with well-controlled spacing can be produced and quantified by using the ToF-SIMS technique.     

Stabilization of Au quantum point contacts by self-assembled monolayers

We examine conductance phenomenon for Au quantum point contacts (QPC) formed using a crossed-wire geometry experimental set-up. When one of the wires is coated with a self-assembled monolayer of an alkanethiol, we find that a conductance plateau indicative of a QPC can be stable for tens of seconds, exceeding typical periods of stability by several orders of magnitude. This extended stability is attributed to the inhibition of the diffusion of Au atoms away from the contact area by the presence of the self-assembled monolayer.     

Differential friction force spectroscopy of micropatterned organosilane self-assembled monolayers

Frictional properties of organosilane self-assembled monolayers (SAMs) and hydrated silicon oxide (SiOH) surfaces on a single sample substrate were studied; the frictional force difference between the surfaces was measured by employing one as a standard. Using a lateral force microscope (LFM), differential frictional force microscopic data were obtained by measuring the difference in the friction forces of the two surfaces with respect to the vertical load force applied to the LFM probe. The SAMs were prepared from n-octadecyltrimethoxysilane [ODS, H₃C(CH₂)₁₇Si(OCH₃)₃], n-(6-aminohexyl) aminopropyltrimethoxysilane [AHAPS, H₂N(CH₂)₆NH(CH₂)₃Si(OCH₃)₃], 3,3,3-trifluoropropyltrimethoxysilane [FAS3, F₃C(CH₂)₂Si(OCH₃)₃] and heptadecafluoro-1,1,2,2-tetrahydro-decyl-1-trimethoxysilane [FAS17, F₃C(CF₂)₇(CH₂)₂Si(OCH₃)₃] by chemical vapor deposition. In the vertical force range of 0 to 600 nN, the SAMs showed no damage at all, and frictional force on the SAM surfaces increased linearly with the vertical force. The order of the frictional force magnitudes determined with the SiOH-terminated probe was SiOH > AHAPS > FAS3 > FAS17 > ODS. In addition, the frictional force difference did not become zero even at a vertical force of 0 nN, that is, the frictional differences could even be imaged by LFM through probe-sample adhesion.     

Electron-beam exposure of self-assembled monolayers of 10-undecenoic acid

Tapping mode atomic force microscopy and capacitance versus voltage measurements were employed to study the effects of electron-beam exposure on self-assembled monolayers of 10-undecenoic acid. It was established that exposure increases chemical/mechanical stability, resulting in a thicker layer following a solvent treatment designed to remove residual monomers. Electron exposure also reduces the effects of pinholes in the monolayer, thereby improving dielectric quality.     

Atomic-scale X-ray structural analysis of self-assembled monolayers on Silicon

Two related self-assembled monolayers (SAMs), 4-bromostyrene (BrSty) and 4-bromophenylacetylene (BPA), are photochemically grown from solution on to the monohydride-terminated Si(111) surface. The atomic-scale structures of the resulting SAMs are examined by X-ray standing waves (XSW), X-ray reflectivity (XRR), X-ray fluorescence, atomic-force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). The coverage is 0.5 ML. The results show that in each case the molecule covalently bonds to a single Si T₁ site and stands up-right with a slight molecular tilt of 17^○ that leaves the Br terminal end over a neighboring T₄ site. The Br height is 8.5?Å (BrSty) and 8.6?Å (BPA) above the top surface Si atom. The combined XSW and XRR results rule-out two alternative bonding models predicted by DFT that have the root of the molecule bonded to two neighboring top Si surface atoms. Based on the XSW 111 and 333 coherent fractions, the BPA/Si(111) has a reduced vertical Br distribution width in comparison to BrSty. This greater rigidity in the molecular structure is correlated to a C=C bond at the root.