Silicon dioxide surface reactions

Adhesion of polyimides to inorganic substrates is of great importance to the microelectronics industry [1, 2]. The polyimide films are deposited most often by spin coating the polyamic acid (PAA) usually from a TV-methylpyrrolidone (NMP) solution onto the substrate surface followed by thermal imidization at temperatures up to 400<>C. The most studied polyimide is the pyromellitic dianhydride-oxydianiline (PMDA-ODA), which exhibits excellent mechanical and dielectric properties, but not so good adhesion characteristics. The latter has been generally overcome by application of an adhesion promoter, such as y-aminopropyltriethoxysilane [3-7]. The reactions of APS (coated from water solution) with the silicon dioxide surface as well as with polyamic acid have been well characterized by Linde and Gleason [4] however, we do not have such detailed information available on APS interaction with other ceramic surfaces. 

Reactions at the silicon nitride - solution interface - The use of potentiometric titrations in nonaqueous solvents indicates that there are possibly several different kinds of acid and base sites on the silicon nitride depending on the prior environmental history of the powd. The results are generally consistent with potentiometric titrations us d to evaluate the silicon dioxide surface. Future work will focus on further potentiometric as well as conductometric titrations on silicon nitride as well as model systems such as silicon dioxide. 

The selective removal of the silicon dioxide surface layer in this fashion has several applications, e.g. to provide an active Si site for (1) further chemical diffusion reactions (with As, P or B species) and (2) electrical contacts. 

For some materials, the most notable being silicon, heating alone sufiBces to clean the surface. Commercial Si wafers are produced with a thin layer of silicon dioxide covering the surface. This native oxide is inert to reaction with the atmosphere, and therefore keeps the underlying Si material clean. The native oxide layer is desorbed, i.e. removed into the gas phase, by heating the wafer in UHV to a temperature above approximately 1100 °C. This procedure directly fonus a clean, well ordered Si surface. 

Silica used as a filler for rubbers is silicon dioxide, with particle sizes in the range of 10-40 nm. The silica has a chemically bound water content of 25% with an additional level of 4-6% of adsorbed water. The surface of silica is strongly polar in nature, centring around the hydroxyl groups bound to the surface of the silica particles. In a similar fashion, other chemical groups can be adsorbed onto the filler surface. This adsorption strongly influences silica s behaviour within rubber compounds. The groups found on the surface of silicas are principally siloxanes, silanol and reaction products of the latter with various hydrous oxides. It is possible to modify the surface of the silica to improve its compatibility with a variety of rubbers. 

For oxide CMP, the purpose of the solution is two fold. First, water weakens the Si—O bond in a silicon dioxide film and softens the surface as it becomes hydrated with Si—OH bonds [6,7]. Figure 10 shows the reaction mechanism. Second, the solution is to provide a basic environment (pH > 10), which accelerates the hydration rate. An environment with high pH values will allow the polishing-induced reaction to be further accelerated because the surface Si(OH) species will be partially dissolved into water. In the meantime, the zeta potential of silica increases with increasing pH values. At high zeta potentials silica particles will repel each other, whereby a better-suspended slurry is formed. 

Different forms of silicon dioxide have been used as supports for solid-phase organic synthesis. Silica gel is a rigid, insoluble material, which does not swell in organic solvents. Commercially available silica gel differs in particle size, pore size (typically 2-10 nm), and surface area (typically 200-800 m2/g). Like macroporous, highly cross-linked polystyrene, silica gel enables efficient and rapid transfer of solvents and reagents to its entire surface. Because the synthetic intermediates are only located on the surface of the support, enzyme-mediated reactions can be realized on silica [189,190], Silica gel is particularly well suited for continuous-flow synthesis because its volume stays constant and diffusion rates are high. 

Other classes of silanes, namely alkoxy, halogenated, and other silanes [3, 9], are known to react with —OH containing compounds, and, therefore, should also function as adhesion promoters or surface modifiers for —OH containing substrates. Texas Instruments, for example, employed a 2% xylene solution of phenyltrichlorosilane to provide resist image adhesion to various oxide wafer substrates [10]. References 3, 9, and 10 describe many of these materials applied to silicone dioxide substrates. As for HMDS treatment, ESCA evidence of reactions to verify covalent bonding to surface silanol groups will be provided in... 

A typical embodiment for the porous layer technology is described in several patents and patent applications, e.g., a US patent application in 2006. This patent application describes a method for the preparation of silicon dioxide dispersions wherein the surface of the silicon dioxide is modified by treatment with the reaction products of a compound of trivalent aluminum with amino-organo-silane. The invention relates to recording sheets for inkjet printing having such a dispersion incorporated in the porous inkreceiving layer. Another US patent describes the preparation of nanoporous alumina oxide or hydroxide which contains at least one element of the rare earth metal series with atomic numbers 57 to 71. 

Due to its high surface area, surface chemistry and physics dominate the properties of fumed silica. The O—Si-O being 0.3 to 0.4 nm let estimate about only 20 silicon dioxide units spanning the diameter of a primary particle of amorphous silica. Fumed silica therefore has an extremely high surface to bulk ratio up to about 10 %. This is why even bulk methods of chemical analysis are suitable to follow chemical reactions on its surface elemental analysis, IR or NMR methods, etc. 

Fumed silica is a highly dispersed silicon dioxide of large industrial importance and a wide spectrum of applications. Due to its production in a flame process fumed silica exhibits a smooth and nonporous particle surface. Additionally to its high surface area fumed silica bears isolated and statistically distributed surface silanol groups that render this product hydrophilic. A most important technical reaction, therefore, is the silylation and hydrophobization of the hydrophilic surface. 

The chip laboratories also present some difficulties not found in macroscopic laboratories. The main problem concerns the large surface area of the capillaries and reaction chambers relative to the sample volume. Molecules or biological cells in the sample solution encounter so much wall that they may undergo unwanted reactions with the wall materials. Glass seems to present the least of these problems, and the walls of silicon chip laboratories can be protected by formation of relatively inert silicon dioxide. Because plastic is inexpensive, it seems a good choice for disposable chips, but plastic also is the most reactive with the samples and the least durable of the available materials. 

D. J. Monk, D. S. Soane, and R. T. Howe, A review of the chemical reaction mechanism and kinetics for hydrofluoric acid etching of silicon dioxide for surface micromachining applications. Thin Solid Films 232, 1, 1993. 

Boehm, H.-P. and Schneider, M. (1959). The hydroxyl groups on the surface of the amorphous silicon dioxide Aerosil and their reactions (in German). Z. Anorg. Allg. Chem., 301, 326-35. 

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