Monolayer‐derivative functionalization of non‐oxidized silicon surfaces

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Abstract
This article describes a variety of monolayers anchored directly onto silicon surfaces without an oxide interlayer, their formation mechanisms, their technological applications, and our personal views on the future prospects for this field. The chemical modification of non‐oxidized silicon surfaces utilizing monolayers was first reported in 1993. The basic finding that a non‐oxidized silicon surface could be neutralized with alkyl chains through direct covalent linkage, i.e., silicon–carbon, has offered chemical scientists ease of handling even in an ambient environment and, thus, research has been predictably focused on forming anti‐stiction coating films for nano‐ and micro‐electromechanical systems (NEMS/MEMS). Such surface reforming has also been achieved by using other monolayers, which form interfacial bonds, e.g., silicon–nitrogen and silicon–oxygen. The resultant monolayer surfaces are useful for silicon‐based applications including molecular electron transfer films, monolayer templates, molecular insulators, capsulators, and bioderivatives. Such monolayers are applicable not only for surface modification, but also for manipulating individual nanomaterials. By modifying the terminal groups of monolayers with nanomaterials including nanocrystals and biomolecules, the nanomaterials can remarkably be immobilized directly onto non‐oxidized silicon surfaces based on the formation mechanisms of the monolayer. Such immobilizations will revolutionize the analysis of the specific features and capabilities of individual nanomaterials. Furthermore, the path will be opened for the development of more advanced monolayer‐derived chip technology. To achieve this goal, it is extremely important to thoroughly understand the functionalization processes on silicon, since the resultant internal structures and properties of monolayer‐derivative silicon may strongly depend on their course of formation. © 2005 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 5: 145–159; 2005: Published online in Wiley InterScience ( www.interscience.wiley.com) DOI 10.1002/tcr.20041