Self‐Assembled Monolayers: the Development of Functional Nanoscale Films

Jamison, Andrew C.; Chinwangso, Pawilai; Lee, T. Randall

doi:10.1002/9783527638482.ch5

Cited by 9 publications

(10 citation statements)

References 334 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Since HSAMs have been studied extensively, numerous reviews on this topic can be found in the literature. [12][13][14][15] The ability to functionalize alkanethiol chains with endgroups bearing the most electronegative atom also opens avenues to exploring the use of SAMs in a variety of technologies. 16 This research has been enabled by the facile preparation of terminally uorinated compounds and the incorporation of these adsorbates into FSAMs, allowing for systematic studies on the impact of such uorine incorporation on the properties of organic thin lms.…”

Section: Introductionmentioning

confidence: 99%

“…To describe the properties, Cassie's law is oen invoked, where the net character of the interface proportionately reects the character of the component parts according to the relative presence of the adsorbates in the lm. 12,56 Li et al generated SAMs from a mixture of 16,16,16-triuorohexadecanethiol (F1H15SH) and normal pentadecanethiol or hexadecanethiol via co-adsorption from isooctane. 57 The resulting surface composition approximately equaled the solution composition.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

The impact of fluorination on the structure and properties of self-assembled monolayer films

2013

Self Cite

View full text Add to dashboard Cite

The adsorption of partially fluorinated amphiphiles on metal/metal oxide surfaces allows for the generation of specifically fluorinated thin-film interfaces. Such surfaces are often compared to polytetrafluoroethylene (PTFE), which exhibits a low surface energy, accompanied by biological and chemical inertness, making perfluorinated interfaces applicable to a wide range of technologies. In thinfilm research, self-assembled monolayers derived from fluorinated alkanethiols (FSAMs) serve as welldefined systems that can be used to evaluate the physical and chemical properties of interfaces produced with varying degrees of fluorination. The characteristics of these surfaces have been attributed to both the chemical composition of the individual molecular adsorbates and the consequent structural features associated with monolayers formed from these unique partially fluorinated adsorbates. Specifically, this review seeks to correlate the structural and interfacial properties of FSAMs on gold with the structure/composition of the fluorinated moiety present in the adsorbed molecules and to highlight how the degree of fluorination influences the interfacial ordering of the individual alkanethiolate chains and the vacuum energy levels of the modified metal substrate. Additionally, the thermal stability of these organic thin films is analyzed as a function of adsorbate structure. Included are highlights of some of the studies in which FSAMs, formed from a variety of new types of surfactants, were used to modify colloidal systems, to generate anti-adhesive materials, and to enhance the stability of fluorinated thin films toward low-energy electron degradation.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The impact of fluorination on the structure and properties of self-assembled monolayer films

2013

Self Cite

View full text Add to dashboard Cite

show abstract

“…The mixture was placed under 1 atm of hydrogen and stirred at rt for 12 h. The mixture was filtered through a pad of Celite and then washed with Et 2 O (100 mL). After removal of the solvent, the product was purified by chromatography on silica gel using hexanes/ethyl acetate (70:30) as the eluent system to give 12,12,13,13,14,14,15,15,16,16,17,17-dodecafluoroeicosan-1-ol (7) in 66% yield. 1 S- (12,12,13,13,14,14,15,15,16,16,17,17-Dodecafluoroeicosyl)ethanethioate (8).…”

Section: Chemistry Of Materialsmentioning

confidence: 99%

“…31,32,34,35 Synthesis of Terminally Alkylated Partially Fluorinated A l k a n e t h i o l s . A s d e t a i l e d b e l o w , t h e a d s o r b a t e 12,12,13,13,14,14,15,15,16,16,17,17-dodecafluorononadecane-1-thiol (H2F6H11SH) was synthesized according to Scheme 1; the adsorbate 12,12,13,13,14,14,15,15,16,16,17,17-dodecafluoroeicosane-1-thiol (H3F6H11SH) was synthesized according to Scheme 2; and the adsorbates 12,12,13,13,14,14,15,15,16,16,17,17-dodecafluorohenicosane-1-thiol (H4F6H11SH), 12,12,13,13,14,14,15,15,16,16,17 Methyl 12,12,13,13,14,14,15,15,16,16,17,17-Dodecafluoro-10,17-diiodoheptadecanoate (1). In a 100 mL Schlenk flask, the starting materials 1,6-diiodoperfluorohexane (6.00 g; 10.8 mmol), AIBN (10 mol %), and methyl 10-undecenoate (1.83 g; 9.21 mmol) were dissolved in 20 mL of DCE.…”

Section: ■ Introductionmentioning

confidence: 99%

Burying the Inverted Surface Dipole: Self-Assembled Monolayers Derived from Alkyl-Terminated Partially Fluorinated Alkanethiols

et al. 2019

Self Cite

View full text Add to dashboard Cite

The direction and magnitude of surface dipoles directly affect the interfacial properties and can be tuned through molecular design. This article examines the effect of a hydrocarbon−fluorocarbon, "HC−FC", dipole on the structural and interfacial properties of self-assembled monolayers (SAMs) as the dipole is buried into the film. A series of selectively fluorinated alkanethiols with a progressively extended alkyl chain atop six fluorocarbons and an alkyl spacer of 11 hydrocarbons, H(CH 2 ) n (CF 2 ) 6 (CH 2 ) 11 SH, where n = 1−7 (HnF6H11SH) were prepared and used to generate SAMs on evaporated gold, allowing for the systematic burying of the HC−FC dipole into the film. Structural analyses of the films revealed well-ordered films with slight disorder/loose packing in the top alkyl chains. In addition, odd−even effects were observed in the orientation and wettability of the SAMs corresponding to the number of carbon atoms in the top alkyl chain, leading to the conclusion that the fluorinated segment behaves as a surrogate surface. As for the effect of the dipole on the wetting behavior of the films, the effect appears to be minimized after three methylene units; however, the structural features of the monolayers were also found to influence the wettability of the films.

show abstract

“…Organic thin films are well-known materials that can be used to modify interfacial properties. The use of self-assembled monolayers (SAMs) is a ubiquitous approach taken by several researchers to manipulate the properties of surfaces for use in a variety of applications, such as anti-adhesive/anti-fouling surfaces for biosensors, − catalyst modifiers for hydrogenation reactions, , corrosion protection for metal surfaces, , lubricants for microelectromechanical systems (MEMs), polymer brushes for biotechnology applications and patterning surfaces, , and organic thin-film transistors for semiconductors . Much of the research performed on thiolate-based SAMs involve the use of monodentate adsorbates (i.e., adsorbates with one thiol headgroup).…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2020

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Self‐Assembled Monolayers: the Development of Functional Nanoscale Films

Cited by 9 publications

References 334 publications

The impact of fluorination on the structure and properties of self-assembled monolayer films

The impact of fluorination on the structure and properties of self-assembled monolayer films

Burying the Inverted Surface Dipole: Self-Assembled Monolayers Derived from Alkyl-Terminated Partially Fluorinated Alkanethiols

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

Contact Info

Product

Resources

About