Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – For cleaning a specific substrate or removing a specific...
Reexamination Certificate
1999-11-16
2001-02-27
Del Cotto, Gregory N. (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
For cleaning a specific substrate or removing a specific...
C510S176000, C510S178000, C510S245000, C510S254000, C510S477000, C510S499000, C510S504000
Reexamination Certificate
active
06194366
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates generally to the field of post chemical-mechanical polishing (post-CMP) cleaning operations, and more specifically to post-CMP cleaning solutions for copper-containing microelectronic substrates.
BACKGROUND OF THE INVENTION
The present day fabrication of semiconductor devices is a complex, multi-step process. The CMP process is now a well established enabling technology used by most advanced semiconductor operations for planarization (or “polishing”) of various substrates for production of devices with design geometries less than 0.35 micron.
The CMP processes involve holding and rotating a thin, flat substrate of the semiconductor material against a wetted polishing surface under controlled chemical, pressure and temperature conditions. A chemical slurry containing a polishing agent, such as alumina or silica, is used as the abrasive material. In addition, the chemical slurry contains selected chemicals which etch various surfaces of the substrate during processing. The combination of mechanical and chemical removal of material during polishing results in superior planarization of the surface.
The CMP process, however, leaves contamination on the surfaces of the semiconductor substrate. This contamination is comprised of abrasive particles from the polishing slurry which may consist of alumina or silica, with reactive chemicals added to the polishing slurry. In addition, the contaminant layer may comprise reaction products of the polishing slurry and the polished surfaces. It is necessary to remove the contamination prior to subsequent processing of the semiconductor substrate in order to avoid degradation in device reliability and to avoid the introduction of defects which reduce the manufacturing process yield. Thus, post-CMP cleaning solutions have been developed to cleanse the substrate surface of CMP residuum.
Alkaline solutions based on ammonium hydroxide have been traditionally used in post-CMP cleaning applications. To date, most CMP applications have been directed to aluminum, tungsten, tantalum, and oxide-containing surfaces.
However, copper is increasingly becoming a material of choice in the production of interconnects in semiconductor fabrication. Copper is replacing aluminum as the metal of choice in such fabrication. Conventional post-CMP processes are inadequate for cleaning surfaces containing copper. Copper, copper oxide, and the slurry particles are the contaminants that exist on the copper-containing surface following this CMP process. The copper surface contamination diffuses quickly in silicon and silicon dioxide, and therefore, it must be removed from all wafer surfaces to prevent device failure.
Post-CMP cleaning solutions that are traditionally effective on alumina and silica-based CMP processes are not effective on copper-containing surfaces. Copper is easily damaged by these cleaning solutions. In addition, cleaning efficacy with the present post-CMP cleaning solutions has been proven unacceptable.
Nam, U.S. Pat. No. 5,863,344, discloses a cleaning solution for semiconductor devices containing tetramethyl ammonium hydroxide, acetic acid, and water. The solution preferably contains a volumetric ratio of acetic acid to tetramethyl ammonium hydroxide ranging from about 1 to about 50.
Ward, U.S. Pat. No. 5,597,420, discloses an aqueous stripping composition useful for cleaning organic and inorganic compounds from a substrate that will not corrode or dissolve metal circuitry in the substrate. The disclosed aqueous composition contains preferably 70 to 95 wt % monoethanolamine and a corrosion inhibitor at about 5 wt % such as catechol, pyrogallol or gallic acid.
Ward, U.S. Pat. No. 5,709,756, discloses a cleaning composition containing about 25 to 48 wt % hydroxylamine, 1 to 20 wt % ammonium fluoride, and water. The pH of the solution is greater that 8. The solution may further contain a corrosion inhibitor such as gallic acid, catechol, or pyrogallol.
Ilardi et al., U.S. Pat. No. 5,466,389, discloses an aqueous alkaline cleaning solution for cleaning microelectronic substrates. The cleaning solution contains a metal ion-free alkaline component such as a quaternary ammonium hydroxide (up to 25 wt %), a nonionic surfactant (up to 5 wt %), and a pH-adjusting component, such as acetic acid, to control the pH within the range of 8to 10.
There is a need for a post-CMP cleaning composition for copper-containing surfaces. Such a post-CMP cleaning composition must effectuate substantial particle removal from the target surface and prevent or substantially lessen corrosion of the copper-containing substrate. Such a post-CMP cleaning composition must also refrain from attacking the process equipment used in the post-CMP process. Such a post-CMP cleaning composition should also be economical, work effectively through a wide temperature range, and preferably contain chemical components of comparatively lower toxicity. Such a post-CMP cleaning composition should also be useful in cleaning operations following CMP processes utilizing alumina or silica-based slurries.
SUMMARY OF THE INVENTION
A cleaning solution for cleaning copper-containing microelectronic substrates comprises a quaternary ammonium hydroxide selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylethylammonium hydroxide, and combinations thereof; an organic amine selected from the group consisting of monoethanolamine, aminoethylethanolamine, -methylaminoethanol, aminoethoxyethanol, diethanolamine, triethanolamine, C
1
-C
5
alkanolamines, and combinations thereof; a corrosion inhibitor selected from the group consisting of gallic acid, catechol, pyrogallol, resorcinol, hydroquinone, benzotriazole, and combinations thereof; and water. The pH of the solution is greater than 10.
A cleaning solution for cleaning copper-containing microelectronic substrates comprises a) tetramethylammonium hydoxide, b) monoethanolamine, c) gallic acid, and deionized water. The pH of the solution is greater than 10. Preferably, tetramethylammonium hydroxide is in the cleaning solution in an amount in the range from about 0.15 wt % to about 1.25 wt %, monoethanolamine is in the solution in an amount in the range from about 0.4 wt % to about 2.25 wt %, and gallic acid is in the solution in an amount in the range from about 0.09 wt % to about 0.9 wt %.
A concentrate composition for a cleaning solution for cleaning copper-containing microelectronic substrates in also provided. The concentrate composition comprises tetramethylammonium hydroxide in an amount in the range from about 8.0 wt % to about 12.4 wt %, monoethanolamine in an amount in the range from about 14.4 wt % to about 27.8 wt %, gallic acid in an amount in the range from about 5.6 wt % to about 10.9 wt %, and the balance deionized water. A cleaning solution is provided comprising the concentrate in an amount in the range from about 1.5 wt % to about 12.5 wt % in the cleaning solution.
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Barnes Jeff
Hashemi Yassaman
Naghshineh Shahriar
Oldak Ewa B.
Del Cotto Gregory N.
ESC Inc.
Ratner & Prestia
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