Cleaning and liquid contact with solids – Processes – For metallic – siliceous – or calcareous basework – including...
Reexamination Certificate
1999-02-22
2001-05-15
Gupta, Yogendra (Department: 1751)
Cleaning and liquid contact with solids
Processes
For metallic, siliceous, or calcareous basework, including...
C134S001300, C134S002000, C134S041000, C510S175000, C510S176000
Reexamination Certificate
active
06231677
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a photoresist stripping liquid composition, and more specifically relates to a photoresist stripping liquid composition for removing resist residues remaining after dry etching insulating films, wiring materials, capacitors and electrode materials in the manufacture of semiconductor devices.
BACKGROUND OF THE INVENTION
Dry etching is the most important technology for patterning insulating films, wiring materials, etc. in the manufacture of semiconductor devices. In the dry etching process a pattern is formed on a substrate, deposited by sputtering, CVD, spin coating, etc., by applying, exposing and developing a photoresist; after which the insulating film and the wiring pattern are formed by dry etching using a reactive gas and said photoresist as mask. After this patterning, ashing is performed, and the resist residues, which still remain in part after the photoresist used as mask has been removed by ashing, are typically removed by a stripping liquid.
However, the photoresist residues which remain after dry etching cannot be completely removed by the combination of an organic solvent with alkanolamine generally used as conventional stripping liquid (e.g., JP, A, 5-281753; U.S. Pat. No. 5,480,585). It is thought that the reason for this is that, together with the etched material, part of the resist residues remaining after ashing becomes inorganic. Therefore, stripping liquids containing fluorine compounds (JP, A, 7-201794; EP, A, 662705), hydroxylamine (U.S. Pat. No. 5,334,332) and quarternary ammonium compounds (JP, A, 8-262746; U.S. Pat. No. 5,567,574) have been proposed for removing photoresist residues after dry etching. However, since these stripping liquids corrode the wiring material, it is necessary to rinse with isopropyl alcohol or another organic solvent and to perform the treatment at a high temperature to remove resist residues completely.
Moreover, the impact of organic compounds on the environment has to be taken into consideration, since these stripping liquids are prepared from some 10% to 100% of organic compounds and since rinsing with organic solvents is also necessary.
On the other hand, together with the diversification of materials used for semiconductor devices in recent years, brought about by the use of new metallic materials such as barrier metals, ferroelectrics, etc. as wiring materials, etc., a diversification of the contents of the photoresist residue remaining after dry etching has also taken place. What is required of the removing liquid is that it be effective in removing photoresist residues and that it does not corrode the surrounding materials.
Also, the use of the before-mentioned fluorine compounds and inorganic acids is subject to limitation, since they possess the characteristic of etching lead zirconium titanate (PZT), which is a ferroelectric material. Moreover, removing methods using strongly alkaline liquids, such as tetramethylammoniumhydroxide (TMAH), etc., have also been proposed (JP, A, 8-222574); however, alkaline liquids cannot be used with titanium nitride, one of the barrier metals which is easily etched on the alkaline side, nor with hydrogen silsesquioxane (HSQ), which recently received much attention as interlayer insulating film because of its low dielectric constant, since there is the danger of film degradation (increase of the dielectric constant when the Si—H group changes to Si—OH). I.e., TMAH cannot be used with semiconductor devices in which PZT occurs together with titanium nitride or HSQ.
Thus, considering that the stripping liquids of the prior art are limited depending on their intended purpose, there is a need in the future for combining stripping liquids corresponding to the properties of the different materials used in the manufacturing processes of semiconductor devices. Therefore, when treating laminated films in which different materials are stacked, a different stripping liquid tank is required for each material; however, from the point of view of the manufacturing processes, production line planning and operating costs, this is a very negative factor.
Moreover, a related invention is mentioned in JP, A, 10-256210; however, the publication date of this application is Sep. 25, 1998, which is after the filing date of Feb. 27, 1998 of Japanese Patent Application Hei. 10-62031 which is the application on which the priority rights of the present application are based.
OBJECT OF THE INVENTION
Accordingly, the present invention provides a stripping liquid composition which is excellent for removing photoresist residues remaining after dry etching in the manufacturing processes of semiconductor devices using different metallic materials, does not corrode wiring materials, etc. and can be rinsed with water.
SUMMARY OF THE INVENTION
The inventors of the present invention, as a result of having made diligent efforts to achieve this object, accomplished the present invention by discovering that a stripping liquid comprising aliphatic polycarboxylic acids and their salts or aminopolycarboxylic acids and their salts on their own or in combination is excellent for removing photoresist residues, does not corrode metallic materials such as wiring materials, barrier metals, etc. and can be rinsed with water after treatment.
I.e., the present invention relates to the above-mentioned photoresist stripping liquid composition comprising, as active component, one or more polycarboxylic acids and/or their salts selected from the group consisting of aliphatic polycarboxylic acids and their salts as well as aminopolycarboxylic acids and their salts.
Through the present invention, it has been possible to provide a photoresist stripping liquid composition which is far more effective for removing photoresist residues remaining after dry etching than the stripping liquids of the prior art, does not corrode metallic materials and does not have an impact on the environment caused by organic solvents.
One embodiment of the present invention is a photoresist stripping liquid composition comprising, as active component, one or more aliphatic polycarboxylic acids and/or their salts selected from the group consisting of oxalic acid, malonic acid, tartaric acid, malic acid, succinic acid and citric acid.
Another embodiment of the present invention is a photoresist stripping liquid composition comprising, as active component, one or more aminopolycarboxylic acids and/or their salts selected from the group consisting of ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid diammonium salt or N-(2-hydroxyethyl)-N,N′,N′-ethylenediaminetriacetic acid.
Still another embodiment of the present invention relates to the use of a photoresist stripping liquid composition according to the present invention for removing resist residues from wiring material made of Al—Si—Cu or from ferroelectrics made of lead zirconium titanate (PZT).
Yet another embodiment of the present invention relates to the use of a photoresist stripping liquid composition according to the present invention for removing deposited polymers after ashing treatment.
One more embodiment of the present invention is one of the above-mentioned photoresist stripping liquid compositions not comprising any organic solvents.
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Ishikawa Norio
Mori Kiyoto
Suga Masanori
Darby & Darby
Gupta Yogendra
Kanto Kagaku Kabushiki Kaisha
Webb Gregory E.
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