Cleaning and liquid contact with solids – Processes – For metallic – siliceous – or calcareous basework – including...
Reexamination Certificate
1998-03-03
2002-08-13
Gulakowski, Randy (Department: 1746)
Cleaning and liquid contact with solids
Processes
For metallic, siliceous, or calcareous basework, including...
C510S176000
Reexamination Certificate
active
06432209
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is directed to a composition and method for removal of photoresist and photoresist residues from a substrate, such as a silicon wafer. Mixtures including hydroxylamine and a weak organic acid are used to strip hard to remove photoresist materials, such as photoresist residue which has been subjected to plasma etching and post-plasma ashing. The composition and method achieve improved strip rates while significantly reducing metal corrosion.
2. Brief Description of the Prior Art
Photoresist materials are commonly used as coating masks in the fabrication of integrated circuits. During the fabrication process, photoresist materials are applied to a substrate using various techniques known in the art. The substrate, now coated with photoresist materials, is then exposed to radiation, usually in the UV, e-beam or x-ray wave lengths. After exposure, the coated substrate is developed, leaving a defined pattern of photoresist materials on the substrate. The photoresist materials that remain on the substrate after developing are used to mask the substrate for further processing. After further processing, the photoresist materials are stripped from the substrate using a photoresist stripper. Further processing of the photoresist materials after developing, such as high temperature post-exposure bake, ion implantation and deep UV radiation hardening lead to highly cross-linked photoresist polymer materials which are extremely resistant to dissolution.
The need for plasma etching or reactive ion etching of the metal, oxide, and polysilicon layers has increased. As a result of plasma etching the masking photoresist leaves a substantially hardened organometallic sidewall polymer due to a complex reaction of metallic substrate with resist polymer and halogenated plasma gas molecules. Therefore, the need for post plasma polymer removers and photoresist strippers which work effectively without damaging desired features of the microcircuit has increased.
As semiconductor manufacturing has moved into sub-micron geometries, the need for photoresist and polymer removers which work effectively without damaging desired features of the circuit has increased. Since about 1990, mixtures of hydroxylamine with alkanolamines have been introduced to facilitate the removal of hardened photoresist polymer residues and for stripping. See U.S. Pat. Nos. 5,279,771; 5,334,332, 5,381,807; 5,419,779; and 5,482,566. The alkaline strippers mentioned above may be effective in removing hardened photoresist from substrates, however, in removing post-plasma etch cross-linked organometallic polymer residues from sub-micron geometries they cause undesirable side effects. The use of these alkaline strippers and polymer removers on microcircuit substrates containing metal films, particularly aluminum or various combinations or alloys of active metals such as aluminum or titanium with more electropositive metal such as copper or tungsten, has proven problematic, even without plasma treatment, because of metal corrosion. This problem has been addressed by employing intermediate rinses with non-alkaline organic solvents such as isopropyl alcohol, other alcohols, or glycols, but such rinses add to the expense and complexity of the manufacturing process. Moreover, hydroxylamine/alkanolamine mixtures in an aqueous media undergo thermal decomposition, generating an unstable product.
Schwartzkopf, U.S. Pat. No. 5,308,745, has addressed metal corrosion with photoresist stripper compositions containing stripping solvents such as n-methylpyrrolidinone, an alkaline amine such as an aminoalkanol, and a weak acid. However, these compositions are not effective for polymer removal.
At present, there is a trend toward use of 100% copper in metal layers. Since copper is more subject to corrosion than the metals previously used, the need has increased for a non-corrosive polymer and photoresist remover.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a photoresist stripper which is environmentally friendly, stable, and does not require intermediate rinses to avoid metal corrosion and which still effectively strips plasma treated or hardened photoresist and polymeric residues.
Another object of this invention is to provide a method for photoresist and polymer removal which can avoid oxygen ashing.
A further object of this invention is to provide such improved non-metal corroding stripper compositions without any undue adverse effect on strip rate of the photoresist for cross-linked or hardened photoresist.
Another object of this invention is to provide a photoresist stripper and post-plasma polymer remover that is stable, having extended bath life without any adverse effect of ambient temperature variations on stability and effectiveness of the stripping composition.
Another object of this invention is to provide a universally accepted photoresist stripper and post plasma polymer remover that does not contain any toxic additives such as catechol, works effectively on all post plasma etch processes independent of the dry etch equipment or the type of plasma gas used in processing, and is not corrosive to sensitive metal layers.
Briefly, the preferred embodiment of the present invention utilizes a mixture of hydroxylamine partially neutralized with a weak carboxylic acid and a biodegradable organic solvent such as an alkyl sulfoxide, a pyrrolidinone or a sulfone to remove hardened photoresist and photoresist residues from a substrate with reduced metal corrosion.
REFERENCES:
patent: 5279771 (1994-01-01), Lee
patent: 5308745 (1994-05-01), Schwartzkopf
patent: 5334332 (1994-08-01), Lee
patent: 5381807 (1995-01-01), Lee
patent: 5399464 (1995-03-01), Lee
patent: 5419779 (1995-05-01), Ward
patent: 5482566 (1996-01-01), Lee
patent: 5648324 (1997-07-01), Honda et al.
patent: 5665688 (1997-09-01), Honda et al.
patent: 5672577 (1997-09-01), Lee
patent: 5780406 (1998-07-01), Honda et al.
patent: 5792274 (1998-08-01), Tanabe et al.
patent: 5795702 (1998-08-01), Tanabe et al.
patent: 5902780 (1999-05-01), Lee
patent: 5911835 (1999-06-01), Lee et al.
patent: 5968848 (1999-10-01), Tanabe et al.
Jaffer David
Silicon Valley Chemlabs
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