Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – For cleaning a specific substrate or removing a specific...
Reexamination Certificate
2001-12-21
2003-12-02
Webb, Gregory E. (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, C510S212000, C134S002000, C134S003000, C134S013000, C134S042000, C252S079100
Reexamination Certificate
active
06656895
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a remover composition. More particularly, the present invention relates to a remover composition which removes a photoresist or residue generated in manufacturing a semiconductor.
2. Description of Related Art
Recently, formation of finer patterns of high precision is required due to increased concentration of integrated circuits, therefore, dry etching methods using a halogen-based gas are often used instead of conventional chemical etching methods, and further, ashing by oxygen plasma, ion injection and the like are conducted.
In such dry etching methods, ashing treatment and the like, a photoresist film is oxidized by a halogen-based etching gas, oxygen and the like, and changes from a film showing an organic property to a film showing an inorganic property, and changes into a film of poor solubility by an ion injection treatment.
Remover compositions are used for removing, photoresists and residues after dry etching remaining on the surface parts of wiring layers or insulation film layers, side wall parts of wiring layers or Via Holes, or bottom part of Via Holes, generated in forming wiring layers of a conductive metal and Via Hole.
As the remover composition, there is used, conventionally, a mixture of an organic alkali, inorganic alkali, organic acid, inorganic acid and polar organic solvent, or an aqueous solution thereof, and for example, JP-A No. 59-49539 discloses a remover composed of a 2-pyrrolidine compound and a dialkylsulfone compound, JP-A No. 4-350660 discloses a remover composed of 1,3-dimethyl-2-imidazolydinone and dimethylsulfoxide, JP-B No. 6-12455 discloses a remover composed of an alkanolamine, sulfone compound and glycol monoalkyl ether, and Japanese Patent No. 3048207 discloses a remover composed of (a) a nucleophilic amine such as hydroxylamine, hydrazine and the like, (b) an organic solvent, (c) a reducing agent such as catechol and the like, and (d) water, and the like.
With progress of size reduction of semiconductor elements, a problem of corrosion of a metal film used in a wiring layer also occurs in a process of removing a resist and a process of removing a residue after dry etching. When a metal film used in a wiring layer is corroded, resistance increases, leading to occurrence of problems such as increase in consumption power, heat generation from a semiconductor element, and the like.
However, the above-mentioned conventional releasing compositions have problems that ability of removing a resist and, a residue after dry etching is not sufficient, and corrosion of a metal film used in a wiring layer occurs, and the like.
Therefore, there is a desire for development of a remover composition having higher removing ability and does not easily cause corrosion of a metal film used in a wiring layer.
SUMMARY OF THE INVENTION
An object of the present invention is to solve the above-mentioned problems, and to provide a remover composition manifesting an extremely low corrosion property against materials such as an insulation film, metal film and the like constituting a semiconductor, and having a high ability of removing a photoresist and a residue generated in treating a semiconductor.
The present inventors have intensively studied a remover composition having no problems described above, and resultantly, found that a remover composition obtained by adding a cyclic urea compound having a specific structure manifests an extremely low corrosion property against materials such as an insulation film, metal film and the like, and has a high ability of removing a photoresist and a residue generated in treating a semiconductor element, and have completed the present invention.
Namely, the present invention relates to a remover composition comprising
(a) 100 parts by weight of a composition obtained by adding a cyclic urea compound to water, water-soluble organic solvent, or a mixture of water and water-soluble organic solvent so that the concentration of the cyclic urea compound is from 1 to 90% by weight,
wherein the cyclic urea compound is represented by the following general formula (I):
wherein, R
1
and R
2
each independently represent alkyl group which may be substituted, hydrogen atom, hydroxyl group, or carboxyl group, Z represents oxygen atom or sulfur atom,
(b) 0.1 to 150 parts by weight of an organic amine, and
(c) 0.001 to 100 parts by weight of a salt of an amine with an acid.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be explained in detail below.
The remover composition of the present invention is characterized in that it is obtained by addition of a cyclic urea compound of the general formula (I) so that the concentration thereof is from 1 to 90% by weight, or it contains a cyclic urea compound of the general formula (I) so that the concentration thereof is from 1 to 90% by weight. The addition amount or content of the cyclic urea compound is preferably from 10 to 60% by weight, particularly preferably from 10 to 40% by weight.
Specifically, the remover composition of the present invention is prepared by adding the above-mentioned cyclic urea compound to water and/or organic solvent, or contains the above-mentioned cyclic urea compound in water and/or organic solvent.
Namely, the remover composition of the present invention is characterized in that it is obtained by adding of a cyclic urea compound of the general formula (I) to water and/or water-soluble organic solvent so that the concentration thereof is from 1 to 90% by weight, or it contains a cyclic urea compound of the general formula (I) in water and/or water-soluble organic solvent so that the concentration thereof is from 1 to 90% by weight. The addition amount or content of the cyclic urea compound is preferably from 10 to 60% by weight, particularly preferably from 10 to 40% by weight.
When the concentration is less than 1% by weight, releasing property for a photoresist and etching residue is insufficient. On the other hand, when the concentration is over 90% by weight, releasing property for an etching residue is insufficient.
In a cyclic urea compound of the general formula (I) in the present invention, R
1
and R
2
each independently represent a hydrogen atom, hydroxyl group, carboxyl group or alkyl group optionally substituted. Z represents an oxygen atom or sulfur atom.
When R
1
and R
2
represent an alkyl group optionally substituted, groups of the following general formula (II):
—(CH
2
)
n
—X (II)
(wherein, n represents an integer of 1 or more. X represents a hydrogen atom, hydroxyl group, methoxy group or ethoxy group.) are listed for R
1
and R
2
each independently.
From the standpoint of sufficient ability for removing a photoresist and an etching residue, preferable R
1
and R
2
represent a hydrogen atom or an alkyl group optionally substituted of the general formula (II), n represents preferably 1 to 4, particularly preferably 1 to 2. Further, in view of raw material circumstances together, it is preferable that R
1
═R
2
.
Examples of the cyclic urea compound of the general formula (I) include 4,5-dihydroxy-2-imidazolidinone, 4,5-dihydroxy-1,3-dimethyl-2-imidazolidinone, 4,5-dihydroxy-1,3-bis(hydroxymethyl)-2-imidazolidinone, 4,5-dihydroxy-1,3-bis(methoxymethyl)-2-imidazolidinone, and the like.
Examples of the organic solvent in the present invention include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, t-butyl alcohol, pentanol, ethylene glycol, glycerin and the like; amides such as N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and the like; lactones such as &ggr;-butyrolactone and the like; esters such as propyl acetate, butyl acetate, butyl propionate, ethyl butyrate, butyl butryrate, methyl lactate, ethyl lactate and the like; ketones such as acetone, methyl ethyl ketone, acetylacetone, methyl butyl ketone, 3-pentanone, 2-heptanone and the like; ethers such as diethyl ether, dipropyl ether, dibutyl ether, oxirane, dioxane and the like; glycol
Birch & Stewart Kolasch & Birch, LLP
Sumitomo Chemical Company Limited
Webb Gregory E.
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