1. Field of the Invention
The present invention relates to the preparation of substrates used in the manufacture of integrated circuits. In particular, the invention provides new and improved methods for preparing siloxane resins, including hydridosiloxanes and organohydridosiloxanes, that are free of the many disadvantages that previously attended the preparation of such materials. More particularly, the invention pertains to synthetic methods that employ phase transfer catalysts that avoid the disadvantages of previously employed catalytic systems that required hazardous catalytic reagents. The invention also pertains to synthetic methods that avoid the need for additional washing and purification steps that have heretofore been believed to be required to produce such resins.
2. Description of the Prior Art
It is known in the art that siloxane based resins are useful in the electronic and semiconductor fields to coat silicon chips and other similar components. Such coatings protect the surface of substrates and form dielectric layers between electric conductors on integrated circuits. Such coatings can be used as protective coatings, interlevel dielectric layers, doped dielectric layers to produce transistor like devices, pigment loaded binder systems containing silicon to produce capacitor and capacitor like devices, multilayer devices, 3-D devices, silicon on insulator devices, coatings for superconductors, superlattice devices and the like. These resins include hydridosiloxanes and organohydridosiloxanes containing a significant portion of organic moieties.
The production of siloxane resins, such as silsesquioxane resins, is well known in the art. For example, U.S. Pat. No. 5,486,564 describes the production of polyhydrogensilsesquioxane resins for electronic coatings. However, the process employs dangerous fuming sulfuric acid/sulfuric acid as a catalyst to produce polyhydrogensilsesquioxane. The product was contaminated with significant levels of trace metals despite washing in multiple steps with water containing decreasing percentages of sulfuric acid, followed by removal of all traces of water by azeotropic distillation. In an attempt to remedy these shortcomings, U.S. Pat. No. 5,416,190 describes fractionation of the silsesquioxane product using polar and nonpolar solvents. Other attempts to remedy these deficiencies in the production of silsesquioxane compounds employed supercritical fluid extraction in the purification process, as described by U.S. Pat. No. 5,063,267 and employed funming/concentrated sulfuric acid but with CaCO.sub.3 neutralization, as described by U.S. Pat. No. 5,010,159.
It is also known that the dielectric constant of such insulating films is an important factor where integrated circuits or IC's with low power consumption, cross-talk, and signal delay are required. As IC dimensions continue to shrink, this factor increases in importance. As a result, siloxane based resin materials, and methods for making such materials, that can provide insulating films with dielectric constants below 3.0 are very desirable. In addition, it would be desirable to have siloxane-based resins, and methods for making the resins, that provide such low dielectric constant films and which additionally have a high resistance to cracking. It would also be desirable for such films to have low stress when formed in thickness of approximately 1.0 micron (.mu.m) or greater. Additionally, it would be desirable for such siloxane-based resins, and methods for making, to provide low dielectric constant films via standard processing techniques. In this manner curing processes that require an ammonia or ammonia derivative type of atmosphere (See, U.S. Pat. No. 5,145,723, Sep. 8, 1992, Ballance et al.), an ozone atmosphere (See, U.S. Pat. No. 5,336,532, Haluska et al.), or other non-standard type of semiconductor process, are avoided.
Thus, it would be desirable to produce useful siloxane coating compositions, such as hydridosiloxane and organohydridosiloxane resins, by methods which are both efficient and which do not employ toxic catalytic reagents. It has now surprisingly been found that a reaction employing a phase transfer catalyst will produce the desired siloxane resins while avoiding all of the above described shortcomings of previous methods.
USPTO Backgrounds
USPTO Backgrounds