N-alkanethiolate Self-assembled Monolayers Research Articles

Effects of chain-chain interaction on the configuration of short-chain alkanethiol self-assembled monolayers on a metal surface.

Surface-specific sum frequency generation vibrational spectroscopy is applied to study the molecular configuration of short-chain n-alkanethiol self-assembled monolayers (SAMs with n = 2-6) on the Au surface. For monolayers with n≥ 3, the alkanethiols are upright-oriented, with the CH3 tilt angle varying between ∼33° and ∼46° in clear even-odd dependency. The ethanethiol monolayer (n = 2) is, however, found to exhibit a distinct lying-down configuration with a larger methyl tilt angle (67°-79°) and a smaller CH2 tilt angle (56°-68°). Such a unique configurational transition from n = 2 to n≥ 3 discloses the steric effect owing to chain-chain interaction among neighboring molecules. Through density functional theory calculations, the transition is further confirmed to be energetically favorable for thiols on a defective reconstructed Au(111) surface but not on the pristine one. Our study highlights the roles of the chain-chain interaction and the substrate surface atomic structure when organizing SAMs, offering a strategic pathway for exploiting their applications.

A Guide for the Electrochemical Stability of Thiolate Self-Assembled Monolayers on Gold in Various Electrolytes

Self-assembled monolayers (SAMs) are widely used in surface chemistry to modify surfaces for various applications such as biosensing1, electronics2, and electrocatalysis3. SAMs are attractive due to their high surface coverage and stability. Although studies have been conducted to test the effects of temperature, air exposure, and solvent degradation on SAMs stability 4,5, the electrochemical stability of SAMs has not been as extensively studied. Existing literature on this topic mainly focuses on the reductive desorption limits of thiolate SAMs in alkaline conditions6,7. Recent work by Ramos et al. demonstrated pH-dependent stable potential windows in which SAMs remained intact on electrode surfaces of different metals8. However, there is still a need to verify and expand on this work.To address this need, we aim to create a comprehensive guide on the electrochemical stability of thiolate SAMs on gold electrodes. We will use cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), and electrochemical surface plasmon resonance (EC-SPR) to probe and verify the stable electrochemical potential windows in both aqueous and non-aqueous electrolytes. We have conducted studies on three aqueous solutions at three distinct pH, perchloric acid, potassium hydroxide, and sodium chloride. For non-aqueous solvents we tested a wide range of different organic solvents including acetonitrile, dimethylformamide, propylene carbonate, and various alcohols. Our findings demonstrate that the main factor for SAM stability in aqueous and non-aqueous electrolytes is the pH and solubility of the SAM, respectively. Our poster will present our current work and outlook on this topic.(1) Dauphin-Ducharme, P.; Ploense, K. L.; Arroyo-Currás, N.; Kippin, T. E.; Plaxco, K. W. Electrochemical Aptamer-Based Sensors: A Platform Approach to High-Frequency Molecular Monitoring In Situ in the Living Body. In Biomedical Engineering Technologies: Volume 1; Ossandon, M. R., Baker, H., Rasooly, A., Eds.; Methods in Molecular Biology; Springer US: New York, NY, 2022; pp 479–492. https://doi.org/10.1007/978-1-0716-1803-5_25.(2) Hatton, R. A.; Willis, M. R.; Chesters, M. A.; Rutten, F. J. M.; Briggs, D. Enhanced Hole Injection in Organic Light-Emitting Diodes Using a SAM-Derivatised Ultra-Thin Gold Anode Supported on ITO Glass. J. Mater. Chem. 2003, 13 (1), 38–43. https://doi.org/10.1039/B208169P.(3) Shang, H.; Wallentine, S. K.; Hofmann, D. M.; Zhu, Q.; Murphy, C. J.; Baker, L. R. Effect of Surface Ligands on Gold Nanocatalysts for CO2 Reduction. Chem. Sci. 2020, 11 (45), 12298–12306. https://doi.org/10.1039/D0SC05089J.(4) Schlenoff, J. B.; Li, M.; Ly, H. Stability and Self-Exchange in Alkanethiol Monolayers. J. Am. Chem. Soc. 1995, 117 (50), 12528–12536. https://doi.org/10.1021/ja00155a016.(5) Laibinis, P. E.; Whitesides, G. M. Self-Assembled Monolayers of n-Alkanethiolates on Copper Are Barrier Films That Protect the Metal against Oxidation by Air. J. Am. Chem. Soc. 1992, 114 (23), 9022–9028. https://doi.org/10.1021/ja00049a038.(6) Salvarezza, R. C.; Carro, P. The Electrochemical Stability of Thiols on Gold Surfaces. J. Electroanal. Chem. 2018, 819, 234–239. https://doi.org/10.1016/j.jelechem.2017.10.046.(7) Beulen, M. W. J.; Kastenberg, M. I.; van Veggel, F. C. J. M.; Reinhoudt, D. N. Electrochemical Stability of Self-Assembled Monolayers on Gold. Langmuir 1998, 14 (26), 7463–7467. https://doi.org/10.1021/la981031z.(8) Ramos, N.; Medlin, J. W.; Holewinski, A. Electrochemical Stability of Thiolate Self-Assembled Monolayers on Au, Pt, and Cu; preprint; Chemistry, 2022. https://doi.org/10.26434/chemrxiv-2022-dt7dk. Figure 1

Stability of thiol-based self-assembled monolayer functionalized electrodes in EG-OFET-based applications

The surface passivation of thermally deposited Au using n-alkanethiol self-assembled monolayers (SAMs) as insulating monolayers in electrolyte-gated organic-field effect transistor (EG-OFET) and its impact on EG-OFET operation has been clarified. We used three different n-alkanethiols derivates, namely propanethiol (P-SAM), hexanethiol (H-SAM), and octanethiol (O-SAM), with different chain lengths (C3, C6, and C8). The non-uniform distribution of the used SAMs on the inhomogeneous Au surface significantly affects the net capacitance, i.e., the serial capacitance of the double layer (CDL) and blocking layer (CBL) capacitance of the functionalized gate. The SAM-functionalized gates were exposed to cyclic electrical stress (forward and reverse) for 128 cycles with gate voltage (VG) sweep from 0.1 to −0.4 V at constant drain voltage (VD = -0.4 V) and compared to a bulk-gold reference gate electrode. The registered transfer curves showed increased drain currents that saturated during prolonged cycling. Two figures of merit, i.e., threshold voltage (Vth) and hysteresis, were extracted from the recorded transfer curves, and their responses were studied separately. We found that both Vth and hysteresis increase with cycling. The change is small but constantly increases for the short-chain P-SAM, while for the longer-chain H- and O-SAM, the initial change is more prominent, reaching saturation after approximately 25 cycles. We have investigated the surface roughness of different gate electrodes through Atomic Force Microscopy (AFM) to confirm the packing density of thiol molecules. We also performed 80 h long-term stability data using cyclic voltammetry measurements for each thiol-functionalized electrode. No signs of desorption could be found, as evidenced by XPS. The results are consistent with previously suggested models for electrical transport across such SAMs, confirming that these monolayers restrict faradic processes at the electrodes by passivating the Au surface.

Implication of Current–Voltage Curve Shape in Molecular Electronics

The transmission function, T(E), widely used as a toy model in molecular electronics, relies exclusively on a Lorentzian-shaped energy level. The shape of the energy level may be sensitive to the inhomogeneity of the active monolayer in a tunnel junction, yet it is usually ignored or underestimated in explaining the charge tunneling behavior. This article describes the interplay between the supramolecular packing feature of a self-assembled monolayer (SAM) and the shape of an energy level in T(E). Using a T(E) based on the Gaussian–Lorentzian product (GLP), line-fitting analysis was conducted over experimentally obtained current density–voltage curves of n-alkanethiolate SAMs to determine the mixing ratio between Gaussian and Lorentzian functions. It was revealed that the contribution of the Gaussian to the shape of the energy level in T(E) was dominant for solid-like SAMs whereas that of the Lorentzian was dominant for liquid-like SAMs. The energy-level shape also responded to defects induced by the surface roughness of the bottom electrode. We further demonstrated that our approach can be applied to rectifying junctions, using ferrocenyl-terminated n-alkanethiolate SAM. These findings indicate that shape analysis over the current–voltage curve, intimately related to the shape of the energy level of T(E), may provide implications for the packing features of SAMs reminiscent of spectral line fitting in spectroscopy.

Enhanced Thermopower of Saturated Molecules by Noncovalent Anchor-Induced Electron Doping of Single-Layer Graphene Electrode.

Enhancing thermopower is a key goal in organic and molecular thermoelectrics. Herein, it is shown that introducing noncovalent contact with a single-layer graphene (SLG) electrode improves the thermopower of saturated molecules as compared to the traditional gold-thiolate covalent contact. Thermoelectric junction measurements with a liquid-metal technique reveal that the value of Seebeck coefficient in large-area junctions based on n-alkylamine self-assembled monolayers (SAMs) on SLG is increased up to fivefold compared to the analogous junction based on n-alkanethiolate SAMs on gold. Experiments with Raman spectroscopy and field-effect transistor analysis indicate that such enhancements benefit from the creation of new in-gap states and electron doping through noncovalent interaction between the amine anchor and the SLG electrode, which leads to a reduced energy offset between the Fermi level and the transport channel. This work demonstrates that control of interfacial bonding nature in molecular junctions improves the Seebeck effect in saturated molecules.

Olefin-Bridged Bidentate Adsorbates for Generating Self-Assembled Monolayers on Gold

A series of custom-designed olefin-bridged bidentate adsorbates composed of an olefin group linking symmetrical hydrocarbon moieties of varying chain lengths was synthesized and used for the preparation of self-assembled monolayers (SAMs) on gold. The structures of the adsorbates are in the form Z-[CH3(CH2)m]2(C═C)[CH2SH]2 (OBCnSH) where m = 12-15 and n = m + 3 (OBC15SH, OBC16SH, OBC17SH, and OBC18SH). The influence of the olefin linker on the structural and interfacial properties of the SAMs was investigated and compared to SAMs formed from analogous n-alkanethiols. Characterization techniques included ellipsometry, X-ray photoelectron spectroscopy (XPS), polarization modulation-infrared reflection-adsorption spectroscopy (PM-IRRAS), and contact angle measurements. The OBCnSH SAMs exhibited ellipsometric thicknesses that were similar to their monodentate counterparts, suggesting that the new olefin-bridged adsorbates pack similarly to the monodentate analogs. Characterization by PM-IRRAS revealed that the OBCnSH SAMs were as conformationally ordered as those derived from the reference n-alkanethiols with the exception of the adsorbate with the shortest chain length OBC15SH, which exhibited low coverage and a liquid-like structure. Unlike the SAMs derived from the n-alkanethiols, the OBCnSH SAMs failed to exhibit "odd-even" effects. However, the OBCnSH SAMs displayed similar hexadecane contact angles as their n-alkanethiol counterparts with the exception of OBC15SH, which exhibited markedly diminished hexadecane contact angles. The similar structural and interfacial properties of the OBCnSH SAMs, when compared to analogous n-alkanethiol SAMs, render the molecular architecture of the olefin-bridged dithiol as a robust platform for the synthesis of adsorbates with two chemically distinct tailgroups for use in the preparation and study of phase-incompatible "conflicted" interfaces.

Molecular Origin of the Odd-Even Effect of Macroscopic Properties of n-Alkanethiolate Self-Assembled Monolayers: Bulk or Interface?

Elucidating the influence of the monolayer interface versus bulk on the macroscopic properties (e.g., surface hydrophobicity, charge transport, and electron transfer) of organic self-assembled monolayers (SAMs) chemically anchored to metal surfaces is a challenge. This article reports the characterization of prototypical SAMs of n-alkanethiolates on gold (CH3(CH2)nSAu, n = 6-19) at the macroscopic scale by electrochemical impedance spectroscopy and contact angle goniometry, and at the molecular level, by infrared reflection absorption spectroscopy. The SAM capacitance, dielectric constant, and surface hydrophobicity exhibit dependencies on both the length (n) and parity (nodd or neven) of the polymethylene chain. The peak positions of the CH2 stretching modes indicate a progressive increase in the chain conformational order with increasing n between n = 6 and 16. SAMs of nodd have a greater degree of structural gauche defects than SAMs of neven. The peak intensities and positions of the CH3 stretching modes are chain length independent but show an odd-even alternation of the spatial orientation of the terminal CH3. The correlations between the different data trends establish that the chain length dependencies of the dielectric constant and surface hydrophobicity originate from changes in the polymethylene chain conformation (bulk), while the odd-even variation arises primarily from a difference in the chemical composition of the interface related to the terminal group orientation. These findings provide new physical insights into the structure-property relation of SAMs for the design of ultrathin film dielectrics as well as the understanding of stereostructural effects on the electrical characteristics of tunnel junctions.

Interaction of the (2√3 × 3)rect. Adsorption-Site Basis and Alkyl-Chain Close Packing in Alkanethiol Self-Assembled Monolayers on Au(111): A Molecular Dynamics Study of Alkyl-Chain Conformation.

We show that the adsorption site basis of the (2√3 × 3)rect. phase of n-alkanethiol self-assembled monolayers plays a key role in determining the molecular conformation of the close-packed alkyl chains. Ten proposed reconstructed Au–S interfaces are used to explore the minimized energy alkyl-chain packing of n-decanethiol molecules using molecular dynamics with the all-atom description. In this comparative study, all models have the same alkyl-chain surface density of four molecules per unit cell; thus, differences are due to the headgroup spacing within the 4-molecule basis as opposed to the average surface density. We demonstrate for the first time the 4-molecule-basis twist structure driven by the packing of alkanethiol molecules in a large simulation box (100 molecules, 25 unit cells) using molecular dynamics. Our results validate the prediction put forward by Mar and Klein that to achieve the 4-molecule-basis twist symmetry observed by the experiment, the headgroups must deviate from the high-symmetry (√3 × √3)R30° sites. The key structural parameters: tilt, twist, and end-group height, as well as their spatial order, are compared with experimental results, which we show is a highly sensitive approach that can be used to vet proposed Au–S interfacial models.

Fast and sensitive detection of carbaryl pesticide trace by using 2D-arrays of Au and Au/Ag core/shell nanoparticles

We report on (i) the synthesis of monodisperse Au and Au-core/Ag-shell nanoparticles (NPs) with controllability of the Au-core in the range of 20–50 nm and fixing the thickness of the Ag shell of ∼20 nm, and (ii) the arrangement of two-dimensional (2D) arrays of Au core and Au-core/Ag-shell NPs on the 1 cm2 ITO substrates. Various Au NPs with uniform size-distribution were synthesised by seed-mediated growth method at ambient conditions. All synthesised 2D-arrays with homogeneous and dense monolayers of NPs (coverage ∼85%) were prepared by hybrid deposition method based on the mixed n-alkanethiolate self-assembled monolayer. We have used the fabricated 2D-arrays from the 20-nm Au-core/Ag-shell NPs as a surface-enhanced Raman scattering (SERS) substrate to take the Raman scattering spectra of carbaryl pesticide at very low concentration of 0.01 ppm.

Selective Cu Electrodeposition for Sub-Micrometer Redistribution Layers

The density of integrated circuit (IC) was doubled by shrinking the feature size in semiconductor industry. An improvement in density of standard interconnection and the packaging technology is much slower than the IC trends. To overcome the increasing I/O interconnect gap, the semiconductor packaging technology has been driven by many researchers and companies over the many years. The redistribution layers (RDL), one of the important parts for the package process, play a role to rearrange I/O connections from the die to substrate. For fine line pitch below 10μm, the damascene RDL process was proposed. The flow of damascene RDL process was composed of photoresist patterning, a metal layer deposition, Cu electrodeposition and chemical-mechanical planarization (CMP). During the Cu electrodeposition for the damascene RDL process, Cu overburdens were formed on top surfaces of sub-micrometer trenches. Typically the CMP process has been used to remove these overburdens in semiconductor industry, however, this surface planarization process caused an increase in process cost. For prevent the Cu overburden at low cost, the selective Cu electrodeposition which is process filling only trench is required. The selective Cu electrodeposition can be achieved by μCP with various additives. The microcontact printing (μCP) process which transfers the self-assembled monolayers (SAMs) on the top surface of trenches can be one of the solutions preventing the Cu deposition on these top surfaces.[1-2] SAMs are organic molecules that formed spontaneously on the solid surface by chemisorption and organization of alkanethiol, silane, and so forth.[3] In this research, flat polydimethylsiloxane (PDMS) stamp is used for providing on the top surface of patterned substrate. Selective Cu electrodeposition was proceeded on trench in CuSO4 1 M/H2SO4 0.58M electrolyte with various additives. In this study, electrochemical behavior of additives was studied by cyclic voltammetry and selective electrodeposition process was investigated with various additives, applied potential, charge density. The µCP process show the effective suppression of Cu growth on the top surface of trenches so that Cu overburden thickness was significantly reduced. This result reveals the feasibility of Cu trench-selective deposition below 10 μm. The μCP method with various additives shows the possibility of replacing surface planarization process which removes overburden of Cu for the RDL process.. [1]Y.Xia and G. Whitesides, "Soft lithography", Annu. Rev. Mater. Sci., vol. 28, no. 1, pp. 153-184, 1998. [2]S.Alom Ruiz and C. Chen, "Microcontact printing: A tool to pattern", Soft Matter, vol. 3, no. 2, pp. 168-177, 2007. [3]P.Laibinis, G. Whitesides, D. Allara, Y. Tao, A. Parikh and R. Nuzzo, "Comparison of the structures and wetting properties of self-assembled monolayers of n-alkanethiols on the coinage metal surfaces, copper, silver, and gold", J. Am. Chem. Soc., vol. 113, no. 19, pp. 7152-7167, 1991.

Electrostatic Repulsion-Induced Desorption of Dendritic Viologen-Arranged Molecules Anchored on a Gold Surface through a Gold-Thiolate Bond Leading to a Tunable Molecular Template.

We investigated the adsorption and desorption behavior of self-assembled monolayers (SAMs) on gold derived from dendritic viologen-arranged molecules with an ω-mercaptodecyl group (A n, n (dendritic generation) = 0-3) at the apex of the dendritic structure in polar solvents. The adsorption of the dendritic molecules occurred quickly and saturated within a few minutes in an acetonitrile/ethanol (1/1, v/v) mixture at a concentration of 2 mM. Atomic force microscopy images of the SAMs showed flat surfaces regardless of the dendritic generation because the peripheral viologen units were closely packed at the surface of the molecular layer. Individual A3 molecules immobilized on the substrate were observed by scanning tunneling microscopy measurements of a mixed SAM with decanethiol. The desorption behaviors of dendritic molecules from the A n-SAMs in several solvents such as water were also investigated. The spontaneous desorption of the A n-SAM occurred more rapidly than that of a conventional n-alkanethiol SAM. However, the desorption was inhibited by adding electrolytes such as NaNO3 due to the shielding effect on the electrostatic repulsion between the dendritic molecules. These results indicate that the surface density of the dendritic molecules can be controlled through the desorption.

Properties of Self-Assembled Monolayers Revealed via Inverse Tensiometry.

Self-assembled monolayers (SAMs) have emerged as a simple platform technology and hence have been broadly studied. With advances in state-of-the-art fabrication and characterization methods, new insights into SAM structure and related properties have been delineated, albeit with some discrepancies and/or incoherencies. Some discrepancies, especially between experimental and theoretical work, are in part due to the misunderstanding of subtle structural features such as phase evolution and SAM quality. Recent work has, however, shown that simple techniques, such as the measurement of static contact angles, can be used to delineate otherwise complex properties of the SAM, especially when complemented by other more advanced techniques. In this article, we highlight the effect of nanoscale substrate asperities and molecular chain length on the SAM structure and associated properties. First, surfaces with tunable roughness are prepared on both Au and Ag, and their corresponding n-alkanethiolate SAMs are characterized through wetting and spectroscopy. From these data, chain-length- and substrate-morphology-dependent limits to the odd-even effect (structure and properties vary with the number of carbons in the molecules and the nature of the substrate), parametrization of gauche defect densities, and structural phase evolution (liquidlike, waxy, crystalline interfaces) are deduced. An evaluation of the correlation between the effect of roughness and the components of surface tension (polar-γp and dispersive-γd) reveals that wetting, at nanoscale rough surfaces, evolves proportionally with the ratio of the two components of surface tension. The evolution of conformational order is captured over a range of molecular lengths and parametrized through a dimensionless number, χc. By deploying a well-known tensiometry technique (herein the liquid is used to characterize the solid, hence the term inverse tensiometry) to characterize SAMs, we demonstrate that complex molecular-level phenomena in SAMs can be understood through simplicity.

Anomalously Rapid Tunneling: Charge Transport across Self-Assembled Monolayers of Oligo(ethylene glycol).

This paper describes charge transport by tunneling across self-assembled monolayers (SAMs) of thiol-terminated derivatives of oligo(ethylene glycol) (HS(CH2CH2O)nCH3; HS(EG)nCH3); these SAMs are positioned between gold bottom electrodes and Ga2O3/EGaIn top electrodes. Comparison of the attenuation factor (β of the simplified Simmons equation) across these SAMs with the corresponding value obtained with length-matched SAMs of oligophenyls (HS(Ph)nH) and n-alkanethiols (HS(CH2)nH) demonstrates that SAMs of oligo(ethylene glycol) have values of β (β(EG)n = 0.29 ± 0.02 natom-1 and β = 0.24 ± 0.01 Å-1) indistinguishable from values for SAMs of oligophenyls (β(Ph)n = 0.28 ± 0.03 Å-1), and significantly lower than those of SAMs of n-alkanethiolates (β(CH2)n = 0.94 ± 0.02 natom-1 and 0.77 ± 0.03 Å-1). There are two possible origins for this low value of β. The more probable involves hole tunneling by superexchange, which rationalizes the weak dependence of the rate of charge transport on the length of the molecules of HS(EG)nCH3 using interactions among the high-energy, occupied orbitals associated with the lone-pair electrons on oxygen. Based on this mechanism, SAMs of oligo(ethylene glycol)s are good conductors (by hole tunneling) but good insulators (by electron and/or hole drift conduction). This observation suggests SAMs derived from these or electronically similar molecules are a new class of electronic materials. A second but less probable mechanism for this unexpectedly low value of β for SAMs of S(EG)nCH3 rests on the possibility of disorder in the SAM and a systematic discrepancy between different estimates of the thickness of these SAMs.

Quantifying Gauche Defects and Phase Evolution in Self-Assembled Monolayers through Sessile Drops.

Self-assembled monolayers (SAMs) are widely used in surface modifications, specifically in tuning the surface chemistry of materials. The structure and properties of SAMs have been extensively studied often with sophisticated tools, even for the simplest n-alkanethiolate SAMs. In SAMs, especially in linear n-alkanethiolates, the properties are dependent on the chain length, which is best manifested in the so-called odd–even effect, a simple yet not fully understood phenomenon. One main challenge is fully delineating the origin of length-dependent properties, which can be due to the structure (ideal SAMs), defect evolution, or substrate-molecule effects. This study demonstrates that utilizing the wetting behavior of polar (water) and nonpolar (hexadecane (HD)) solvents on n-alkanethiolate SAMs formed on ultraflat gold and silver surfaces, the evolution of chain-length-dependent gauche defects can be revealed and parameterized through a newly defined dimensionless number (χ). The observation of the odd–even effect in hydrophobicity, however, depends on the thiol chain length, and it was only observed on longer-chain (>C8) molecules. The trend in this odd–even effect demonstrates that there are three main transitions in the nature of wetting, hence structure, across n-alkanethiols. From wetting with HD, the role of dispersive components in wetting reveal that the SAMs are dynamic, which we attribute to rotations associated with previously reported evolution in gauche defects and changes in packing density. Therefore, from re-expression of the Young–Dupre equation, we define a new dimensionless number associated with molecular conformations, whose periodicity mirrors the energetics of Goodman’s conformations of n-alkanes in unbound states and associated four- or two-twist turns. Therefore, we infer that the evolution in surface energy is largely due to molecular conformations and associated relaxations of the bound thiolates.

Spectroscopic evidence for the origin of odd-even effects in self-assembled monolayers and effects of substrate roughness.

This paper reports the effects of substrate roughness on the odd-even effect in n-alkanethiolate self-assembled monolayers (SAMs) probed by vibrational sum frequency generation (SFG) spectroscopy. By fabricating SAMs on surfaces across the so-called odd-even limit, we demonstrate that differentiation of the vibrational frequencies of CH3 from SAMs derived from alkyl thiols with either odd (SAMO) or even (SAME) numbers of carbons depends on the roughness of the substrate on which they are formed. Odd-even oscillation in SFG susceptibility amplitudes was observed for spectra derived from SAME and SAMO fabricated on flat surfaces (RMS roughness = 0.4 nm) but not on rougher surfaces (RMS roughness = 2.38 nm). In addition, we discovered that local chemical environments for the terminal CH3 group have a chain-length dependence. There seems to be a transition at around C13, beyond which SAMs become "solid-like".

Empirical Evidence for Roughness-Dependent Limit in Observation of Odd-Even Effect in Wetting Properties of Polar Liquids on n-Alkanethiolate Self-Assembled Monolayers.

Substrate roughness influences the wetting properties of self-assembled monolayers (SAMs), but details on this dependency at the sub-nanometer level are still lacking. This study investigates the effect of surface roughness on interfacial properties of n-alkanethiolate SAMs, specifically wetting, and confirms the predicted limit to the observation of the odd-even effect in hydrophobicity. This article studies static contact angles of polar and nonpolar probe liquids on a series of n-alkanethiolate SAMs on surfaces with tunable roughness. We prepared Ag surfaces with root-mean-square roughness (Rrms) of ∼0.6-2.2 nm and compared the wetting properties of n-alkanethiolate SAMs fabricated on these surfaces. We measured the static contact angles, θs, formed between SAM and probe liquids [water, glycerol, and hexadecane]. Hexadecane showed an odd-even effect on all surfaces irrespective of the degree of roughness. Polar liquids (water and glycerol), however, showed a dependency on the roughness of the substrate with an odd-even effect observable only on smooth, but not rougher (Rrms ≥ 1.15 nm), surfaces. These results confirm that the previously predicted limit to observation of the odd-even effect in hydrophobicity (here extended to polar liquids) is real. From the results with glycerol, we infer that this limit is not limited just to hydrophobicity but may extend to other polar liquids. Results from hexadecane, however, suggest that this limit may not be a universal property of the SAM.

The Porter-Whitesides Discrepancy: Revisiting Odd-Even Effects in Wetting Properties of n-Alkanethiolate SAMs

This review discusses the Porter-Whitesides discrepancy in wetting properties of n-alkanethiolate self-assembled monolayers (SAMs). About 25 years ago, Whitesides and coworker failed to observe any odd-even effect in wetting, however, Porter and his coworker did, albeit in select cases. Most previous studies agreed with Whitesides’ results, suggesting the absence of the odd-even effect in hydrophobicity of n-alkanethiolate SAMs. Recent reports have, however, found the odd-even effect in hydrophobicity of n-alkanethiolate SAMs on smooth substrates, indicating that hydrophobicity, and analogous interfacial properties, of n-alkanethiolate SAMs significantly depends on the properties of substrate. Unfortunately, the Whitesides and Porter papers do not report on the quality of the surfaces used. Based on recent work, we inferred that the original discrepancy between Whitesides and Porter can be attributed to the quality of the surface. Odd-even effect of SAMs in charge transport, capacitance, friction, and SAM structure are also discussed in this review to inform the general discussion. The discrepancy between Porter's group and Whitesides’ group could be due to surface roughness, morphology, oxidation, and adventitious contaminants.

Assembly of Mid-Nanometer-Sized Gold Particles Capped with Mixed Alkanethiolate SAMs into High-Coverage Colloidal Films.

We investigated the influence of the mixed n-alkanethiolate self-assembled monolayer (SAM) formed on gold nanoparticles (AuNPs: 50.0 ± 3.2 nm in diameter) on their assembly into colloidal films. Dodecanethiol and octadecanethiol were selected as the short- and long-chain alkanethiols, respectively. The mixed SAMs were formed by immersing AuNPs in a mixed alkanethiol solution at different molar ratios. Au colloidal films were fabricated on indium tin oxide substrates by our previously reported hybrid method. The composition of the two alkanethiolates in the SAM was deduced from the intensity ratio of two Raman bands at 1080 and 1105 cm(-1). The surface coverage of the colloidal films increased by forming equimolar or dodecanethiolate-dominant mixed SAMs on AuNPs instead of a pure dodecanethiolate or octadecanethiolate SAM. The highest coverage exceeded 80%. This improvement is attributed to the high dispersion stability of AuNPs covered with equimolar or dodecanethiolate-dominant mixed SAMs.

Charge Tunneling along Short Oligoglycine Chains

This work examines charge transport (CT) through self-assembled monolayers (SAMs) of oligoglycines having an N-terminal cysteine group that anchors the molecule to a gold substrate, and demonstrate that CT is rapid (relative to SAMs of n-alkanethiolates). Comparisons of rates of charge transport-using junctions with the structure Au(TS)/SAM//Ga2O3/EGaIn (across these SAMs of oligoglycines, and across SAMs of a number of structurally and electronically related molecules) established that rates of charge tunneling along SAMs of oligoglycines are comparable to that along SAMs of oligophenyl groups (of comparable length). The mechanism of tunneling in oligoglycines is compatible with superexchange, and involves interactions among high-energy occupied orbitals in multiple, consecutive amide bonds, which may by separated by one to three methylene groups. This mechanistic conclusion is supported by density functional theory (DFT).

Limits to the Effect of Substrate Roughness or Smoothness on the Odd-Even Effect in Wetting Properties of n-Alkanethiolate Monolayers.

This study investigates the effect of roughness on interfacial properties of an n-alkanethiolate self-assembled monolayer (SAM) and uses hydrophobicity to demonstrate the existence of upper and lower limits. This article also sheds light on the origin of the previously unexplained gradual increase in contact angles with increases in the size of the molecule making the SAM. We prepared Au surfaces with a root-mean-square (RMS) roughness of ∼0.2-0.5 nm and compared the wetting properties of n-alkanethiolate (C10-C16) SAMs fabricated on these surfaces. Static contact angles, θ(s), formed between the SAM and water, diethylene glycol, and hexadecane showed an odd-even effect irrespective of the solvent properties. The average differences in subsequent SAM(E) and SAM(O) are Δθ(s|n – (n+1)|) ≈ 1.7° (n = even) and Δθ(s|n – (n+1)|) ≈ 3.1° (n = odd). A gradual increase in θ(s) with increasing length of the molecule was observed, with values ranging from water 104.7-110.7° (overall Δθ(s) = 6.0° while for the evens Δθ(s)(E) = 4.4° and odds Δθ(s)(O) = 3.5°) to diethylene glycol 72.9-80.4° (overall Δθ(s) = 7.5° while for the evens Δθ(s)(E) = 2.9° and odds Δθ(s)(O) = 2.4°) and hexadecane 40.4–49.4° (overall Δθ(s) = 9.0° while for the evens Δθ(s)(E) = 3.7° and odds Δθ(s)(O) = 2.1°). This article establishes that the gradual increase in θ(s) with increasing molecular size in SAMs is due to asymmetry in the zigzag oscillation in the odd-even effect. Comparison of the magnitude and proportion differences in this asymmetry allows us to establish the reduction in interfacial dispersive forces, due to increasing SAM crystallinity with increasing molecular size, as the origin of this asymmetry. By comparing the dependence of θ(s) on surface roughness we infer that (i) RMS roughness ≈ 1 nm is a theoretical limit beyond which the odd-even effect cannot be observed and (ii) on a hypothetically flat surface the maximum difference in hydrophobicity, as expressed in θ(s), is ∼3°.