Semiconductor process residue removal composition and process

Details Semiconductor process residue removal composition and process Semiconductor process residue removal composition and process

2002-06-06

2004-11-30

Webb, Gregory (Department: 1751)

Cleaning compositions for solid surfaces, auxiliary compositions

Cleaning compositions or processes of preparing

For cleaning a specific substrate or removing a specific...

C510S175000, C510S245000, C510S255000, C134S001300, C134S002000, C134S038000, C134S040000

Reexamination Certificate

active

06825156

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates generally to a cleaning composition and process for removal of organic, organometallic, and/or metallic residues from semiconductor substrates, and also to a composition which can be used to apply controlled and predetermined etch rates on selected metal substrates. More particularly, the present invention relates to compositions including 2-carbon atom linkage alkanolamines, in particular 2-(2-aminoethylamino)-ethanol (AEEA), which are useful for removing semiconductor device fabrication residues and in some embodiments a small predetermined amount of substrate from semiconductor-type substrates. The invention also includes the processes of using the compositions of the present invention to clean and/or etch substrates particularly containing exposed aluminum, titanium, copper, tungsten, and/or alloys thereof.
BACKGROUND OF THE INVENTION
As integrated circuit manufacturing has become more complex and the dimensions of circuit elements fabricated on silicon or other semiconductor wafers have become smaller, continued improvement in techniques used to remove residues formed from such materials has been required. Resists, used to mask substrates such that patterned material can be added, need to be removed from substrates.
Many formulations have been developed to remove both positive and negative resist. A resist includes polymeric material, which may be crosslinked or hardened by baking. Therefore, a simple combination of solvents will often remove resists, though time and temperature constraints in the manufacturing process have in general moved the industry to slightly more aggressive compounds.
Early compositions used for removing photoresists and other substrate layers have, for the most part, been highly flammable. In addition, reactive solvent mixtures can exhibit an undesirable degree of toxicity and are generally hazardous to both humans and the environment. Moreover, these compositions are not only toxic, but their disposal is costly, since they must be disposed of as a hazardous waste. In addition, these prior art compositions generally have a severely limited bath life and, for the most part, are not recyclable or reusable.
U.S. Pat. No. 4,617,251 to Sizensky, which issued on Oct. 14, 1986, describes a solution for removing polymeric resists that contains from 2 to 98% of an organic polar solvent and from 2 to 98% of an amine, particularly AEEA, 2-(2-aminothothoxy)-ethanol (DGA), or a mixture thereof. The patent teaches that the formulation is effective even on baked resists which have been exposed to temperatures of up to 200° C. for up to 30 minutes. The patent suggests that up to 50% of water or more can be added, and also that wetting agents and surfactants can be added.
Other prior art compositions for removing photoresists include inorganic alkalis in water, and polar organic solvents for positive photoresists. Polar organic solvents are used generally at temperatures below 50° C. Mixtures of alkanolamines in water can be used for most types of resists.
Additionally, because many of the toxic components of such compositions are highly volatile and subject to unduly high evaporation rates, the compositions require special human and environmental safety precautions to be taken during storage and use of said compositions.
The resists may in some locations be altered, for example by etching, into various compounds, which incorporate the altered resist, as well as some usually altered substrate. For example, oxygen plasma oxidation is often used for removal of resists or other polymeric materials after their use, during the fabrication process has been completed. Such high energy processes typically result in the formation of organometallic and other residues, for example metal oxides, on sidewalls of the structures being formed in the fabrication process. Other etching, including the use of directed energy and/or chemical etching, leave different types of residue, for example organometallic compounds and/or metal fluorides. Finally, direct layer deposition using convertible organometallic compounds, which may or may not require etching to form a pattern, may leave yet other types of residues. These residues must be removed without substantially altering the underlying substrate.
U.S. Pat. No. 6,372,050 teaches a composition for cleaning residue from a substrate that contains 5 to 50% of a solvent selected from a particular group that includes M-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide, and many others; 10 to 90% of an alkanolamine selected from diethyleneglycolamine (DGA), monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), AEEA, and mixtures thereof; from 0.1 to 10% of a carboxylic acid selected from formic acid, acetic acid, phthalic acid, salicylic acid, oxalic acid, and many others; and 1 to 40% water.
A variety of metal and other layers are commonly employed in integrated circuit fabrication, including aluminum, aluminum/silicon/copper, copper, titanium, titanium nitride, titanium/tungsten, tungsten, silicon oxide, polysilicon crystal, and the like. The use of such different layers results in the formation of different organometallic residues in the high energy processes. Further, there is almost always at least two, but in some cases there may be more than two substrate types on an outer layer to be cleaned. A cleaning composition is often designed to be compatible with a single substrate exposed to the cleaning composition.
A variety of residue removal compositions and processes suitable for integrated circuit fabrication have been developed and marketed by EKC Technology, Inc. (hereinafter “EKC”), the assignee of the present application. Some of these compositions and processes are also useful for removing photoresist, polyimide, or other polymeric layers from substrates in integrated circuit fabrication, and EKC has also developed a variety of compositions and processes specifically for removing such polymeric layers from substrates in integrated circuit fabrication. Additionally, EKC has developed a variety of compositions and processes to selectively remove specific substrate compositions from a substrate surface at a controlled rate. Such compositions and processes are disclosed in the following commonly assigned issued patents:
U.S. Pat. No. 6,367,486 to Lee et al., which issued on Apr. 9, 2002, entitled Ethylenediaminetetraacetic acid or its ammonium salt semiconductor process residue removal process;
U.S. Pat. No. 6,313,039 to Small et al., which issued on Nov. 6, 2001, entitled Chemical mechanical polishing composition and process;
U.S. Pat. No. 6,276,372 to Lee, which issued on Aug. 21, 2001, entitled Process using hydroxylamine-gallic acid composition;
U.S. Pat. No. 6,251,150 to Small et al., which issued on Jun. 26, 2001, entitled Slurry composition and method of chemical mechanical polishing using same;
U.S. Pat. No. 6,248,704 to Small et al., which issued on Jun. 19, 2001, entitled Compositions for cleaning organic and plasma etched residues for semiconductors devices;
U.S. Pat. No. 6,242,400 to Lee, which issued on Jun. 5, 2001, entitled Method of stripping resists from substrates using hydroxylamine and alkanolamine;
U.S. Pat. No. 6,235,693 to Cheng et al., which issued on May 22, 2001, entitled Lactam compositions for cleaning organic and plasma etched residues for semiconductor devices;
U.S. Pat. Nos. 6,187,730 and 6,221,818, both to Lee, which issued on Feb. 13, 2001 and on Apr. 24, 2001, respectively, entitled Hydroxylamine-gallic compound composition and process;
U.S. Pat. No. 6,156,661 to Small, which issued on Dec. 5, 2000, entitled Post clean treatment;
U.S. Pat. No. 6,140,287 to Lee, which issued on Oct. 31, 2000, entitled Cleaning compositions for removing etching residue and method of using;
U.S. Pat. No. 6,121,217 to Lee, which issued on Sep. 19, 2000, entitled Alkanolamine semiconductor process residue removal composition and process;
U.S. Pat. No. 6,117,783 to Small et al., which issued on Sep. 12, 2000, entitled Chemical m

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