Hydrogen terminated Si surface

Scheme 20 Hydrosilylation of an alkene by hydrogen-terminated Si(l 11) surface.

In 1993, Linford firstly reported a quite useful method to prepare monolayers of alkyl chains by thermal hydros-ilylation of hydrogen-terminated silicon surfaces [25]. Alkyl chains are covalently bound to Si surface by Si-C bonds. This thermal hydrosilylation could be attributed to a free-radical process with 1-alkene. First, a diacyl peroxide initiator was used to produce free radicals. However, at higher temperature, only hydrogen-terminated silicon and a neat solution of 1-alkene or 1-alkyne can form Si-C linkages [26]. Furthermore, lately it is found that such Si-C covalent links can be observed even in dilute solutions of 1-alkenes [27]. In that case, the density of monolayer packing strongly depends on the reaction temperature. 

Immobilization of Gold Nanoparticles onto Hydrogen-Terminated Silicon Surface by Si-C Covalent Bonds... 

Wet preparation of metal nanoparticles and their covalent immobilization onto silicon surface has been surveyed in this manuscript. Thiol-metal interaction can be widely used in order to functionalize the surface of metal nanoparticles by SAM formation. Various thiol molecules have been used for this purpose. The obtained functionalized particles can be purified to avoid the effect of unbounded molecules. On the other hand, hydrogen-terminated silicon surface is a good substrate to be covered by Si-C covalently bonded monolayer and can be functionalized readily by this link formation. Nanomaterials, such as biomolecules or nanoparticles, can be immobilized onto silicon surface by applying this monolayer formation system. 

Robertson has summarized the three recent classes of models of a-Si H deposition [439]. In the first one, proposed by Ganguly and Matsuda [399, 440], the adsorbed SiHa radical reacts with the hydrogen-terminated silicon surface by abstraction or addition, which creates and removes dangling bonds. They further argue that these reactions determine the bulk dangling bond density, as the surface dangling bonds are buried by deposition of subsequent layers to become bulk defects. 

Why do we believe that a Cu monolayer is inserted between SAM and gold substrate The 2D-deposit grows and dissolves extremely slowly. Another indication is that the 2D deposit is very stable and shows no displacement by the scanning tip. Cu clusters on top of an alkanethiol-SAM would be only weakly bound and should be easily pushed away by the tip at higher tunnel currents, very much like metal clusters on a hydrogen-terminated Si(lll) surface, which for that very reason are difficult to image by STM (or AFM [122]). And finally, the cyclic voltammograms (Fig. 33) point to the formation of a buried monolayer . 

Figure 8.3 Hydrogen-terminated Si(l 11), Si(lOO) and porous silicon surfaces.

Therefore, surface modification strategies for the formation of direct silicon-carbon bonds require, first, a special pre-treatment of the silicon surface to prevent oxidation and, second, an activation of the silicon surface for subsequent reaction with organic moieties. This has been achieved by treatment of the silicon surface with hydrofluoric acid to generate a hydrogen-terminated Si(lll) surface, which can further react with unsaturated co-functionahzed alkenes in the presence of UV irradiation or by thermal activation [27,44,45]. Using this method, carboxylic acid modified silicon substrates have been successfully generated and coupled to thiol modified ONDs via a polylysine/sulfosuccinimidyl 4-(M-maleimidomethyl)-cyclohexane-l-carboxylate couphng (Fig. 12). 

Figure 5.6. STM image of a hydrogen-terminated Si(lll) surface. The image shows a 10 nm x 10 nm region of the surface, from Ref. [20]. Reproduced by permission of the Royal Society of Chemistry.

Quayum, M. E., Kondo, T., Nihonyanagi, S., Miyamoto, D. and Uosaki, K. Formation of organic monolayer on a hydrogen terminated Si(l 11) surface via silicon-carbon bond monitored by ATR FT-IR and SFG spectroscopy Effect of orientational order on the reaction rate. Chemistry Letters, 208 (2002). 

Table 1. Interactions of various adsorbates with a hydrogen terminated Si(100)-2 x 1 surface. References are primarily related to atomic scale STM investigations.

Y. Terada, B.-K. Choi, S. Heike and M. Fujimori, Injection of molecules onto hydrogen terminated Si(100) surfaces via a pulse valve, J. Appl. Phys. 93, 10014 (2003). 

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