Chemisorption in the context of "Interface (matter)"

Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a surface. This process creates a film of the adsorbate on the surface of the adsorbent. This process differs from absorption, in which a fluid (the absorbate) is dissolved by or permeates a liquid or solid (the absorbent). While adsorption does often precede absorption, which involves the transfer of the absorbate into the volume of the absorbent material, alternatively, adsorption is distinctly a surface phenomenon, wherein the adsorbate does not penetrate through the material surface and into the bulk of the adsorbent. The term sorption encompasses both adsorption and absorption, and desorption is the reverse of sorption.

Like surface tension, adsorption is a consequence of surface energy. In a bulk material, all the bonding requirements (be they ionic, covalent or metallic) of the constituent atoms of the material are fulfilled by other atoms in the material. However, atoms on the surface of the adsorbent are not wholly surrounded by other adsorbent atoms and therefore can attract adsorbates. The exact nature of the bonding depends on the details of the species involved, but the adsorption process is generally classified as physisorption (characteristic of weak van der Waals forces) or chemisorption (characteristic of covalent bonding). It may also occur due to electrostatic attraction. The nature of the adsorption can affect the structure of the adsorbed species. For example, polymer physisorption from solution can result in squashed structures on a surface.

Self-assembled monolayers (SAM) are assemblies of organic molecules that form spontaneously on surfaces by adsorption and organize themselves into more or less distinct domains (head group, chain/backbone, and tail/end group). In some cases, molecules that form the monolayer do not interact strongly with the substrate. This is the case for porphyrins on HOPG and two-dimensional supramolecular networks of PTCDA on gold. In other cases, the head group has a strong affinity for the substrate and anchors the molecule. Such an SAM consisting of a head group, chain (labeled "tail"), and functional end group is depicted in Figure 1. Common head groups include thiols, silanes, and phosphonates.

SAMs are created by the chemisorption of head groups onto a substrate from either the vapor or liquid phase followed by a slower organization of "tail groups". Initially, at small molecular density on the surface, adsorbate molecules form either a disordered mass of molecules or an ordered two-dimensional "lying down phase". At higher molecular coverage, adsorbates can begin to form three-dimensional crystalline or semicrystalline structures on the substrate surface over a period of minutes to hours. The head groups assemble on the substrate, while the tail groups assemble far from the substrate. Areas of close-packed molecules nucleate and grow until the surface of the substrate is covered in a single monolayer.