Stock material or miscellaneous articles – Web or sheet containing structurally defined element or... – Physical dimension specified
Reexamination Certificate
2000-07-27
2001-10-23
Nakarani, D. S. (Department: 1773)
Stock material or miscellaneous articles
Web or sheet containing structurally defined element or...
Physical dimension specified
C428S447000, C428S448000, C428S450000
Reexamination Certificate
active
06306495
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates generally to the field of electronic and microelectronic devices, and more particularly relates to polymeric films for use in electronic and microelectronic devices, and to methods for their production.
Many varieties of polymeric films have been employed in the electronics and microelectronics industries. As industry-wide pressure increases to produce smaller and smaller electronics components, the fabrication of ultra-thin films for electronics applications becomes increasingly important. In the past, polymeric films have been employed in microelectronics applications as insulating materials, resist films, gas separation membranes, diffusion barriers, corrosion barriers, surface modification or surface sealing of porous substrates, lubricating layers for small scale machining operations (e.g., nanomachining applications) and others. Metal and metal alloy films have also been employed for these applications.
As demand increases for new wiring and electronic component materials, and as a result of the attractive qualities of copper for wiring and electronic components, the need for efficient diffusion barriers to copper rises. Copper's low electrical resistivity and high resistance to electron migration yield improved device reliability in devices which employ copper. However, copper diffusion into silicon and silica substrates at elevated temperatures can lead to device degradation. Attempts to develop efficient copper diffusion barriers for these applications have led to a number of metal film materials. J. Imahori, et al.,
Thin Solid Films
301:142 (1997) lists several metal and metal alloy films including TaC, W, Ta, Ta—Si, W—N, Ta—N, Ti—N, Ti—Si—N, and Ta—Si—N films which have been investigated for use as copper diffusion barriers. In addition, U.S. Pat. No. 5,164,332 to Kumar proposes a copper metal alloy as a copper diffusion barrier between a copper feature and an oxygen-containing polymer. The diffusion barrier is formed by coating a metal (e.g., Al) on the copper feature and heating the metal and copper to form an alloy. To be effective, materials employed as copper diffusion barriers should exhibit low thermal coefficient of expansion, ease of processing, good adhesion to copper, and minimal reactivity with copper and other microelectronics materials. Often, particularly preferred copper diffusion barriers also exhibit a low dielectric constant as well.
In addition to the need for copper diffusion barriers, there also remains a need in the art for thin films which can be useful as insulating materials, resist films, lubricating layer materials, and surface modification and sealing materials. Many varieties of dielectric or insulating materials have been employed in microelectronics devices. Silicon dioxide, silicon nitride, polyimides, and polyphenylene polymers are examples of materials which have been proposed for these applications. For example, U.S. Pat. No. 4,588,609 proposes one method of preparing polyparaphenylene polymer films by photochemical vapor deposition. These materials can be difficult to fabricate and process, and producing the necessary thin layers of these materials for use in microelectronics has been challenging.
There remains a need in the art for effective copper diffusion barriers and insulating materials. There further remains a need in the art for copper diffusion barriers which prevent the diffusion of copper atoms or ions at elevated temperatures. In addition, there remains a need in the art for copper diffusion barriers which can be fabricated as ultra-thin films. There also remains a need in the art for methods of producing polymer films for use in microelectronics applications. In one aspect, the present invention provides a copper diffusion barrier for use in electronics and microelectronics applications. The present invention also provides a method for producing thin polymer films on substrates for use in electronic, particularly microelectronic, devices.
SUMMARY OF THE INVENTION
As a first aspect, the present invention provides a copper diffusion barrier for a microelectronic device comprising a copper feature. The copper diffusion barrier comprises a crosslinked carbon-silicon polymer film having a thickness sufficient to attenuate the diffusion of copper atoms and copper ions from the copper feature.
As a second aspect, the present invention provides a microelectronic device comprising a copper feature and a copper diffusion barrier on a substrate. The copper diffusion barrier includes a crosslinked carbon-silicon polymer film, and prevents the diffusion of copper atoms and copper tons from the copper feature at temperatures of up to about 750 K.
As a third aspect, the present invention provides a method for producing a polymer film covalently bonded to a substrate. The method includes the steps of: a) adsorbing a plurality of vinyl silane monomers on the substrate; b) contacting the adsorbed vinyl silane monomers with gaseous polymerizable monomers selected from the group consisting of unsaturated hydrocarbon monomers, unsaturated halo-substituted hydrocarbon monomers, and combinations thereof; and c) polymerizing the polymerizable monomers on the adsorbed vinyl silane monomers. The polymerization of the polymerizable monomers produces the polymer film covalently bound to the substrate through the vinyl silane monomers.
As a fourth aspect, the present invention provides a microelectronic device including a substrate and a thin polymer film covalently bound thereto. The thin polymer film is covalently bound to the substrate through vinyl silane monomers.
These and other aspects of the present invention are described further in the detailed description and examples of the invention which follow.
REFERENCES:
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patent: 4925612 (1990-05-01), Waragai et al.
patent: 5164332 (1992-11-01), Kumar
patent: 5187639 (1993-02-01), Ogawa et al.
patent: 5288528 (1994-02-01), Blanchet-Fincher
Imahori, J. et al., “Diffusion barrier properties of TaC between Si and Cu,”Thin Solid Films, 301 142-148 (1997).
Helmann, D. et al., “Epitaxial growth of &bgr;-SIC thin films on a 6H-SIC substrate using the chemical solution deposition method,”Journal of Materials Research, Abstracts for Nov. 1997, vol. 12, No. 11, p. 60.
Bozso, F. et al., “Studies of SiC formation on Si(100) by chemical vapor deposition,”J. Appl. Phys. 57(8), Apr. 15, 1985, pp. 2771-2778.
Taylor, P.A., et al., “X-ray photoelectron spectroscopy study of Si-C film growth by chemical vapor deposition of ethylene on Si(100),”J. Appl. Phys. 65(3), Feb. 1, 1989.
Tillman, Nolan, et al., “Formation of Multilayers of Self-Assembly,” American Chemical Society, Langmuir, pp. 101-111 vol. 5, 1, 1989.
Wasserman, Stephen R., “Structure and Reactivity of Alkylsiloxane Monolayers Formed by Reaction of Alkyltrichlorosilanes on Silicon Substrates,” American Chemical Society, pp. 1074-1989.
Wiegand, B.C., et al., “Si-H Bond Activation on Cu: Reaction of Silane on Cu(111),”J. Phys. Chem. 97, pp. 11553-11562, 1993.
Tao, Y.-T., “Structural Comparison of Self-Assembled Monolayers ofn-Alkanoic Acids on the Surfaces of Silver, Copper, and Aluminum,”J. Phys. Chem. 115, pp. 4350-4358, 1993.
Lenhart, S.J., et al., “The Corrosion Resistance of an Aluminum Alloy Coated with Polysilazane-Derived Ceramics,”Science, vol. 45, No. 6, 1989.
Kurth, D.G., et al., “Monomolecular Layers and Thin Films of Silane Coupling Agents by Vapor-Phase Adsorption on Oxidized Aluminum,”J. Phys. Chem. 96, pp. 6707-6712, 1992.
Gates, S.M., “Decomposition mechanisms of SiHx species on Si(100)-(2×1) for x=2,3, and 4,”J. Phys. Chem. 93, pp. 7493-7503, 1990.
Dubois, L.H., et al., “The adsorption and thermal decomposition of trimethylamine alane on aluminum and silicon single crystal surfaces: kinetic and mechanistic studies,”Surface Science236 pp. 77-84, 1990.
Curson, N.J., et al., “Interaction of silane with Cu(111): Surface alloy and molecular chemisorbed phases,” The American Physical Society, Physical Review B, vol. 55, No
Nakarani D. S.
Townsend and Townsend / and Crew LLP
University of North Texas
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