Semiconductor device manufacturing: process – Coating of substrate containing semiconductor region or of... – Insulative material deposited upon semiconductive substrate
Reexamination Certificate
1999-06-02
2002-04-30
Smith, Matthew (Department: 2825)
Semiconductor device manufacturing: process
Coating of substrate containing semiconductor region or of...
Insulative material deposited upon semiconductive substrate
C438S780000, C438S781000
Reexamination Certificate
active
06380105
ABSTRACT:
FIELD OF THE INVENTION
This invention pertains generally to precursors and deposition methods for thin film nanoporous aerogels on semiconductor substrates, including deposition methods suited to aerogel thin film fabrication of nanoporous dielectrics.
BACKGROUND OF THE INVENTION
Aerogels are porous silica materials which can be used for a variety of purposes including as films (e.g. as electrical insulators on semiconductor devices or as optical coatings) or in bulk (e.g. as thermal insulators). For ease of discussion, the examples herein will be mainly of usage as electrical insulators on semiconductor devices.
Semiconductors are widely used in integrated circuits for electronic devices such as computers and televisions. Semiconductor and electronics manufacturers, as well as end users, desire integrated circuits which can accomplish more in less time in a smaller package while consuming less power. However, many of these desires are in opposition to each other. For instance, simply shrinking the feature size on a given circuit from 0.5 microns to 0.25 microns can increase energy use and heat generation by 30%. Miniaturization also generally results in increased capacitive coupling, or crosstalk, between conductors which carry signals across the chip. This effect both limits achievable speed and degrades the noise margin used to insure proper device operation. One way to reduce energy use/heat generation and crosstalk effects is to decrease the dielectric constant of the insulator, or dielectric, which separates conductors. U.S. Pat. No. 5,470,802, issued to Gnade et al., provides background on several of these schemes.
A class of materials, nanoporous dielectrics, includes some of the most promising new materials for semiconductor fabrication. These dielectric materials contain a solid structure, for example of silica, which is permeated with an interconnected network of pores having diameters typically on the order of a few nanometers. These materials may be formed with extremely high porosities, with corresponding dielectric constants typically less than half the dielectric constant of dense silica. And yet despite their high porosity, it has been found that nanoporous dielectrics may be fabricated which have high strength and excellent compatibility with most existing semiconductor fabrication processes. Thus nanoporous dielectrics offer a viable low-dielectric constant replacement for common semiconductor dielectrics such as dense silica.
The preferred method for forming nanoporous dielectrics is through the use of sol-gel techniques. The word sol-gel does not describe a product but a reaction mechanism whereby a sol, which is a colloidal suspension of solid particles in a liquid, transforms into a gel due to growth and interconnection of the solid particles. One theory is that through continued reactions within the sol, one or more molecules in the sol may eventually reach macroscopic dimensions so that it/they form a solid network which extends substantially throughout the sol. At this point (called the gel point), the substance is said to be a gel. By this definition, a gel is a substance that contains a continuous solid skeleton enclosing a continuous liquid phase. As the skeleton is porous, the term “gel” as used herein means an open-pored solid structure enclosing a pore fluid.
One method of forming a sol is through hydrolysis and condensation reactions, which can cause a multifunctional monomer in a solution to polymerize into relatively large, highly branched particles. Many monomers suitable for such polymerization are metal alkoxides. For example, a tetraethoxysilane (TEOS) monomer may be partially hydrolyzed in water by the reaction
Si(OEt)
4
+H
2
O→HO—Si(OEt)
3
+EtOH
Reaction conditions may be controlled such that, on the average, each monomer undergoes a desired number of hydrolysis reactions to partially or fully hydrolyze the monomer. TEOS which has been fully hydrolyzed becomes Si(OH)
4
. Once a molecule has been at least partially hydrolyzed, two molecules can then link together in a condensation reaction, such as
(OEt)
3
Si—OH+HO—Si(OH)
3
→(OEt)
3
Si—O—Si(OH)
3
+H
2
O
or
(OEt)
3
Si—OEt+HO—Si(OEt)
3
→(OEt)
3
Si—O—Si(OEt)
3
+EtOH
to form an oligomer and liberate a molecule of water or ethanol. The Si—O—Si configuration in the oligomer formed by these reactions has three sites available at each end for further hydrolysis and condensation. Thus, additional monomers or oligomers can be added to this molecule in a somewhat random fashion to create a highly branched polymeric molecule from literally thousands of monomers. An oligomerized metal alkoxide, as defined herein, comprises molecules formed from at least two alkoxide monomers, but does not comprise a gel.
Sol-gel reactions form the basis for xerogel and aerogel film deposition. In a typical thin film xerogel process, an ungelled precursor sol may be applied (e.g., spray coated, dip-coated, or spin-coated) to a substrate to form a thin film on the order of several microns or less in thickness, gelled, and dried to form a dense film. The precursor sol often comprises a stock solution and a solvent, and possibly also a gelation catalyst that modifies the pH of the precursor sol in order to speed gelation. During and after coating, the volatile components in the sol thin film are usually allowed to rapidly evaporate. Thus, the deposition, gelation, and drying phases may take place simultaneously (at least to some degree) as the film collapses rapidly to a dense film. In contrast, an aerogel process differs from a xerogel process largely by avoiding pore collapse during drying of the wet gel. Some methods for avoiding pore collapse include wet gel treatment with condensation-inhibiting modifying agents (as described in Gnade '802) and supercritical pore fluid extraction.
SUMMARY OF THE INVENTION
Between aerogels and xerogels, aerogels are the preferable of the two dried gel materials for semiconductor thin film nanoporous dielectric applications. Typical thin film xerogel methods produce films having limited porosity (up to 60% with large pore sizes, but generally substantially less than 50% with pore sizes useful in submicron semiconductor fabrication). While some prior art xerogels have porosities greater than 50%; these prior art xerogels had substantially larger pore sizes (typically above 100 nm). These large pore size gels have significantly less mechanical strength. Additionally, their large size makes them unsuitable for filling small (typically less than 1 mm, and potentially less than 100 nm) patterned gaps on a microcircuit and limits their optical film uses to only the longer wavelengths. A nanoporous aerogel thin film, on the other hand, may be formed with almost any desired porosity coupled with a very fine pore size. Generally, as used herein, nanoporous materials have average pore sizes less than about 25 nm across, but preferably less than 20 nm (and more preferably less than 10 nanometers and still more preferably less than 5 nanometers). In many formulations using this method, the typical nanoporous materials for semiconductor applications may have average pore sizes at least 1 nm across, but more often at least 3 nm. The nanoporous inorganic dielectrics include the nanoporous metal oxides, particularly nanoporous silica.
In many nanoporous thin film applications, such as aerogels and xerogels used as optical films or in microelectronics, the precise control of film thickness and aerogel density are desirable. Several important properties of the film are related to the aerogel density, including mechanical strength, pore size and dielectric constant. It has now been found that both aerogel density and film thickness are related to the viscosity of the sol at the time it is applied to a substrate. This presents a problem which was heretofore unrecognized. This problem is that with conventional precursor sols and deposition methods, it is extremely difficult to control both aerogel density and film thickness independently and accurately.
N
Ackerman William C.
Gnade Bruce E.
Jeng Shin-Puu
Johnston Gregory P.
Maskara Alok
Brady III Wade James
Denker David
Malsawma Lex H.
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