Self-assembled monolayer

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Self assembled monolayers (SAMs) are surfaces consisting of a single layer of molecules on a substrate. Rather than having to use a technique such as chemical vapor deposition or molecular beam epitaxy to add molecules to a surface (often with poor control over the thickness of the molecular layer), self assembled monolayers can be prepared simply by adding a solution of the desired molecule onto the substrate surface and washing off the excess.

A common example is an alkane thiol on gold. Sulfur has particular affinity for gold, with a binding energy in the range of 20–35 kcal/mol (85–145 kJ/mol). An alkane with a thiol head group will stick to the gold surface and form an ordered assembly with the alkyl chains packing together due to van der Waals forces. For alkyl thiols on gold, the extended alkyl chains typically orient with an angle of ~30 degrees from the perpendicular of the substrate, and are assumed to be in a fully extended linear arrangement. There has been a great deal of work done determining the process by which alkyl thiol on gold assemblies are produced. It is generally thought that alkyl thiol molecules first bind to the gold surface in a 'lying down' position, where the alkyl chain tails of the molecules lie flat on the gold surface. The thiol interaction provides about 20–30 kcal/mol (85–130 kJ/mol) of driving force for the initial binding, which is modeled as a Langmuir binding isotherm. These binding events continue until the lying down molecules are dense enough on the surface to interact with each other. At some point the alkyl chains lift off the substrate and point outwards, tethered by the thiol anchor to the surface. There is a shift to a mixture of lying down molecules and island domains of upright alkyl chains, tilted at 30 degrees to the normal. At this stage binding kinetics become more complex and can no longer be modeled with a simple Langmuir binding isotherm. Over time the island domains merge and cover the bulk of the substrate, and the process can be compared to a 2-D crystallization process on a surface. Alkyl thiol SAMs exhibit grain boundaries and defects even after long periods of assembly. The initial stage of SAM formation usually takes minutes or less under the normal conditions of 0.1-10 mmol/L thiol concentration in a solvent. More ordering of the assembly can take place over days or months, depending on the molecules involved.

A variety of other self-assembled monolayers can be formed, although there is always debate about the degree to which systems self-assemble. Alkyl thiols are known to assemble on many metals, inluding silver, copper, palladium, and platinum. Alkyl silane molecules (e.g. octadecyltrichlorosilane) are another well-known example of self-assembly on silicon oxide surfaces and potentially be of greater technical relevance than alkyl thiol assembly on metals. Alkyl carboxylates are known to assemble on a variety of surfaces, such as aluminium and mica.