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Self-assembled monolayer
Self-assembled monolayers (SAM) of organic molecules are molecular assemblies formed spontaneously on surfaces by adsorption and are organized into more or less large ordered domains. In some cases molecules that form the monolayer do not interact strongly with the substrate. This is the case for instance of the two-dimensional supramolecular networks of e.g. (Perylene-tetracarboxylicacid-dianhydride ) (PTCDA) on gold or of e.g. porphyrins on highly oriented pyrolitic graphite (HOPG). In other cases the molecules possess a head group that has a strong affinity to the substrate and anchors the molecule to it.〔 Such a SAM consisting of a head group, tail and functional end group is depicted in Figure 1. Common head groups include thiols, silanes, phosphonates, etc.
SAMs are created by the chemisorption of "head groups" onto a substrate from either the vapor or liquid phase followed by a slow organization of "tail groups". Initially, at small molecular density on the surface, adsorbate molecules form either a disordered mass of molecules or form an ordered two-dimensional "lying down phase",〔 and at higher molecular coverage, over a period of minutes to hours, begin to form three-dimensional crystalline or semicrystalline structures on the substrate surface. The "head groups" assemble together 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.
Adsorbate molecules adsorb readily because they lower the surface free-energy of the substrate〔 and are stable due to the strong chemisorption of the "head groups." These bonds create monolayers that are more stable than the physisorbed bonds of Langmuir–Blodgett films. A Trichlorosilane based "head group", for example in a FDTS molecule reacts with an hydroxyl group on a substrate, and forms very stable, covalent bond () with an energy of 452 kJ/mol. Thiol-metal bonds, that are on the order of 100 kJ/mol, making the bond a fairly stable in a variety of temperature, solvents, and potentials.〔 The monolayer packs tightly due to van der Waals interactions,〔〔 thereby reducing its own free energy.〔 The adsorption can be described by the Langmuir adsorption isotherm if lateral interactions are neglected. If they cannot be neglected, the adsorption is better described by the Frumkin isotherm.〔
==Types==
Selecting the type of head group depends on the application of the SAM.〔 Typically, head groups are connected to a molecular chain in which the terminal end can be functionalized (i.e. adding –OH, –NH2, –COOH, or –SH groups) to vary the wetting and interfacial properties.〔 An appropriate substrate is chosen to react with the head group. Substrates can be planar surfaces, such as silicon and metals, or curved surfaces, such as nanoparticles. Alkanethiols are the most commonly used molecules for SAMs. Alkanethiols are molecules with an alkyl chain, (C-C)ⁿ chain, as the back bone, a tail group, and a S-H head group. Other types of interesting molecules include aromatic thiols, of interest in molecular electronics, in which the alkane chain is (partly) replaced by aromatic rings. An example is the dithiol 1,4-Benzenedimethanethiol (SHCH2C6H4CH2SH)). Interest in such dithiols stems from the possibility of linking the two sulfur ends to metallic contacts and this was first used in molecular conduction measurements. Thiols are frequently used on noble metal substrates because of the strong affinity of sulfur for these metals. The sulfur gold interaction is semi-covalent and has a strength of approximately 45kcal/mol. In addition, gold is an inert and biocompatible material that is easy to acquire. It is also easy to pattern via lithography, a useful feature for applications in nanoelectromechanical systems (NEMS).〔 Additionally, it can withstand harsh chemical cleaning treatments.〔 Recently other chalcogenide SAMs: selenides and tellurides have attracted attention in a search for different bonding characteristics to substrates affecting the SAM characteristics and which could be of interest in some applications such as molecular electronics. Silanes are generally used on nonmetallic oxide surfaces;〔 however monolayers formed from covalent bonds between silicon and carbon or oxygen cannot be considered self assembled because they do not form reversibly. Self-assembled monolayers of thiolates on noble metals are a special case because the metal-metal bonds become reversible after the formation of the thiolate-metal complex. This reversibility is what gives rise to vacancy islands and it is why SAMs of alkanethiolates can be thermally desorbed and undergo exchange with free thiols.
抄文引用元・出典: フリー百科事典『 ウィキペディア（Wikipedia）』
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