JP2003015323A - Resist remover composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoresist remover capable of easily removing photoresist residue at a low temperature in a short time, capable of microfabrication in the removal without corroding inorganic substrates of various materials and capable of producing high-precision circuit wiring. SOLUTION: The photoresist remover composition comprises an organic base compound and an imine compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION Photoresists used in the use of lithography technology are widely used in integrated circuits such as IC and LSI, display devices such as LCD and EL devices, printed circuit boards, micromachines, DNA chips and the like. Used in the field. The present invention relates to a photoresist stripping composition used for stripping a photoresist from the surface of a material such as various substrates.

[0002]

2. Description of the Related Art Conventionally, an alkaline stripping agent has been used for removing photoresist. For example, a composition comprising an alkanolamine and dimethylsulfoxide, an alkanolamine, a composition comprising hydroxylamine, catechol and water, a composition comprising N-methyl-2-pyrrolidone and an alkanolamine compound are generally known. Photoresist strippers made of alkaline compounds are used in the photoresist stripping process, but in recent years their ability is low to respond to the miniaturization of semiconductor devices and liquid crystal display panel processes and short-time processing. Is desired. Further, in recent years, various materials have been used as materials for semiconductor integrated circuits and semiconductor elements of liquid crystal display devices, and photoresist stripping agents that do not corrode various inorganic substrates are required.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the stripping agent in the prior art, and to apply a photoresist film coated on an inorganic substrate or an inorganic substrate. The photoresist layer remaining after etching the photoresist film, or the photoresist residue remaining after etching the photoresist layer by ashing, can be easily peeled off at a low temperature in a short time, and at this time, the inorganic substrate made of various materials can be completely removed. It is an object of the present invention to provide a photoresist remover composition that can be processed finely without being corroded and can produce highly accurate circuit wiring.

[0004]

Means for Solving the Problems As a result of intensive investigations by the present inventors in order to achieve the above-mentioned object, the mask-formed photo remaining after etching the photoresist film coated on the inorganic substrate was found. Resist and resist residue, or resist residue remaining by ashing after etching can be easily peeled off in a short time, at which time fine processing is possible without corroding the wiring material, insulating film, etc. We have found a photoresist stripper composition consisting of an organic base compound and an imine compound that enables circuits.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The photoresist stripper composition of the present invention contains at least one imine compound.
The imine compound is a compound having a C = N imine structure, specifically, a compound having a structure represented by the following formula (1).

[0006]

[Chemical 2] (R ¹ = H, alkyl group, hydroxyalkyl group, aryl group, acyl group or alkoxyalkyl group, R ² = H, alkyl group, hydroxyalkyl group, aryl group, allyl group or alkoxyalkyl group, R ³ = H, It may be an alkyl group, a hydroxyalkyl group, an aminoalkyl group, an acyl group or an alkoxyalkyl group, and may have a cyclic structure in which R ² and R ³ are bonded.) In particular, R ^{2 in the} formula (1) is hydrogen and R ³ is H or 1 to 1 carbon atoms
The imine compound of 6 which is an alkyl group, a hydroxyalkyl group or an aminoalkyl group is preferable because it can be easily obtained and produced. Imine compounds can be readily prepared from the reaction of a carbonyl compound with an amine compound and are preferably used in the present invention. The imine compound made from a carbonyl compound and an amine compound can be used with or without isolation. The imine structure of the present invention has only to have one or more imine structures in the molecule, and it does not matter even if it has many imine structures. Specific examples of the imine compound used in the present invention include 1-propaneimine, ethaneimine, N-ethylidenemethylamine, N-ethylideneethylamine, N-ethylidenepropylamine, N-ethylidenebutylamine,
N-ethylideneethanolamine, N-ethylideneethoxyethanolamine, N-ethylideneethylenediamine,
N, N'-diethylideneethylenediamine, N-ethylidenediethylenetriamine, N, N ''-diethylidenediethylenetriamine, N-ethylidenetriethylenetetramine, N-
Propylidene ethanolamine, N-Propylidene methylamine, N-Propylidene ethylamine, N-Propylidene butylamine, N-Propylidene ethylenediamine, N,
N'-dipropylidene ethylenediamine, N-butylidene ethanolamine, N-butylidene methylamine, N-butylidene ethylamine, N-butylidene butylamine, N-butylidene ethylenediamine, N, N'-dibutylidene ethylenediamine, N -(1-hydroxypropyl-2-ene) ethanolamine, N- (1,3-dihydroxypropyl-2-ene)
Ethanolamine, N- (1,2-dihydroxypropyl-2-
En) ethanolamine, N- (2-hydroxycyclohexylidene) ethanolamine, N-benzylideneethanolamine, N-methylidenemethylamine, N-methylideneethylamine, N-methylidenepropylamine, N-methylidenebutylamine, N-methylideneethanolamine, N-methylideneethoxyethanolamine, N-methylideneethylenediamine, N, N'-dimethylideneethylenediamine, N-
Methylidenediethylenetriamine, N, N ''-Dimethylidenediethylenetriamine, N-methylideneformamide,
N-methylideneacetamide, N-methylidenepropylamide, N-ethylideneformamide, N-ethylideneacetamide, N-ethylidenepropylamide, N-propylideneformamide, N-propylideneacetamide, N-methylidenelactoamide, N- Examples thereof include ethylidene lactoamide. In the present invention, the imine compound is not limited to the above compounds and may have at least one imine structure in the molecule.

Examples of the organic base compound used in the present invention include alkylamines, alkanolamines, polyamines, hydroxylamines, cyclic amines and quaternary ammonium. Specific compounds are exemplified below.
As alkylamine, methylamine, ethylamine,
n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine,
t-butylamine, pentylamine, 2-aminopentane, 3-aminopentane, 1-amino-2-methylbutane, 2-amino-2-methylbutane, 3-amino-2-
Methylbutane, 4-amino-2-methylbutane, hexylamine, 5-amino-2-methylpentane, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine , Primary alkylamines such as hexadecylamine, heptadecylamine and octadecylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine,
Dibutylamine, diisobutylamine, di-sec-butylamine, di-t-butylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine, methyl Isobutylamine, methyl-sec-butylamine, methyl-t-butylamine, methylamylamine, methylisoamylamine, ethylpropylamine, ethylisopropylamine, ethylbutylamine, ethylisobutylamine, ethyl-sec-butylamine, ethylamine, ethylisoamylamine, Secondary alkylamines such as propylbutylamine, propylisobutylamine, trimethylamine, triethylamine, Examples thereof include tertiary alkylamines such as tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine and methyldipropylamine.

Examples of the alkanolamine include ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, isopropanolamine, N-methylisopropanolamine and N.
-Ethylisopropanolamine, N-propylisopropanolamine, 2-aminopropan-1-ol,
N-methyl-2-amino-propan-1-ol, N-
Ethyl-2-amino-propan-1-ol, 1-aminopropan-3-ol, N-methyl-1-aminopropan-3-ol, N-ethyl-1-aminopropan-
3-ol, 1-aminobutan-2-ol, N-methyl-1-aminobutan-2-ol, N-ethyl-1-
Aminobutan-2-ol, 2-aminobutan-1-ol, N-methyl-2-aminobutan-1-ol, N-
Ethyl-2-aminobutan-1-ol, 3-aminobutan-1-ol, N-methyl-3-aminobutane-1
-Ol, N-ethyl-3-aminobutan-1-ol, 1-aminobutan-4-ol, N-methyl 1-aminobutan-4-ol, N-ethyl-1-aminobutan-4-ol, 1-amino- 2-methylpropane-2
-Ol, 2-amino-2-methylpropan-1-ol, 1-aminopentan-4-ol, 2-amino-4
-Methylpentan-1-ol, 2-aminohexane-
1-ol, 3-aminoheptan-4-ol, 1-aminooctane-2-ol, 5-aminooctane-4-
All, 1-aminopupan-2,3-diol, 2-aminopropane-1,3-diol, tris (oxymethyl) aminomethane, 1,2-diaminopropan-3-ol, 1,3-diaminopropane-2 -All, 2-
(2-aminoethoxy) ethanol and the like can be mentioned.

As the polyamine, ethylenediamine,
Propylenediamine, trimethylenediamine, tetramethylenediamine, 1,3-diaminobutane, 2,3-diaminobutane, pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylene. Diamine, N-methylethylenediamine, N, N-dimethylethylenediamine, trimethylethylenediamine, N
-Ethylethylenediamine, N, N-diethylethylenediamine, triethylethylenediamine, 1,2,3-
Examples include triaminopropane, hydrazine, tris (2-aminoethyl) amine, tetra (aminomethyl) methane, diethylenetriamine, triethylenetetramine, tetraethylpentamine, heptaethyleneoctamine, nonaethylenedecamine, diazabicycloundecene. To be

Examples of hydroxylamine include hydroxylamine, N-methylhydroxylamine, N-ethylhydroxylamine and N, N-diethylhydroxylamine.

Specific examples of the cyclic amine include pyrrole, 2-methylpyrrole, 3-methylpyrrole, 2-ethylpyrrole, 3-ethylpyrrole, 2,3-dimethylpyrrole, 2,4 dimethylpyrrole and 3,4. 4-dimethylpyrrole, 2,3,4-trimethylpyrrole, 2,3
5-trimethylpyrrole, 2-pyrroline, 3-pyrroline, pyrrolidine, 2-methylpyrrolidine, 3-methylpyrrolidine, pyrazole, imidazole, 1,2,3-triazole, 1,2,3,4-tetrazole, piperidine, 2 -Pipecoline, 3-Pipecoline, 4-Pipecoline, 2-4 Lupetidine, 2,6-Lupetidine, 3,5
-Lupetidine, piperazine, 2-methylpiperazine,
2,5-dimethylpiperazine, 2,6-methylpiperazine, morpholine and the like can be mentioned.

The quaternary ammonium includes tetramethylammonium hydroxide, tetraethylammonium hydroxysite, tetrapropylammonium hydroxysite, tetrabutylammonium hydroxysite,
Examples thereof include choline hydroxysite and acetylcholine hydroxysite. The amine used in the present invention is not limited to the above amines and is not limited as long as it is an organic base compound. Of the above amines, preferably, methylamine, ethylamine, propylamine, butylamine, ethanolamine, N-methylethanolamine,
N-ethylethanolamine, diethanolamine, isopropanolamine, 2- (2-aminoethoxy) ethanol, ethylenediamine, propylenediamine, butylenediamine, diethylenetriamine, piperazine and morpholine. These organic bases are used alone or in combination.

The resist stripper composition of the present invention may further contain an organic agent, if desired. The organic solvent used in the present invention is not particularly limited as long as it is miscible with the above-mentioned mixture of imine and organic base. It is preferably a water-soluble organic solvent. Examples include ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene. Glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether,
Ether-based solvents such as diethylene glycol dimethyl ether and dipropylene glycol dimethyl ether, formamide, monomethylformamide, dimethylformamide, monoethylformamide, diethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, N-methylpyrrolidone, N- Amide solvents such as ethylpyrrolidone, alcohol solvents such as methyl alcohol, ethyl alcohol, isopropanol, ethylene glycol, propylene glycol, sulfoxide solvents such as dimethyl sulfoxide, dimethyl sulfone, diethyl sulfone, bis (2-hydroxy sulfone, tetramethylene). Sulfone solvents such as sulfone, 1,3-dimethyl-2-imidazo Jin Won, 1,3-diethyl-2
Examples thereof include imidazolidinone-based solvents such as imidazolidinone and 1,3-diisopropyl-2-imidazolidinone, and lactone-based solvents such as γ-butyrolactone and δ-valerolactone. Among these, dimethyl sulfoxide, N,
N-dimethylformald, N, N-dimethylacetamide, N-methylpyrrolidone, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether,
Dipropylene glycol monobutyl ether and propylene glycol are easily available, have a high boiling point, and are easy to use.

Further, the resist stripper composition of the present invention may contain an anticorrosive agent if desired. The types of anticorrosion agents include phosphoric acid-based, carboxylic acid-based, oxime-based,
Examples include sugar alcohols, aromatic hydroxy compounds, and triazole compounds. Specifically, 1,2-propanediaminetetramethylenephosphonic acid, phosphoric acid such as hydroxyethanephosphonic acid, ethylenediaminetetraacetic acid, dihydroxyethylglycine, nitrilotriacetic acid, oxalic acid, citric acid, malic acid, tartaric acid Carboxylic acid-based compounds such as biviridine, tetraphenylporphyrin, phenanthroline, amine-based compounds such as 2,3-pyridinediol, oxime-based compounds such as dimethylglyoxime and diphenylglyoxime, phenylacetylene,
An acetylene-based anticorrosive such as 2,5-dimethyl-3-hexyne-2,5-diol can be used. Examples of sugar alcohols include sorbitol, xylitol, palatinit and the like.

Specific examples of the aromatic hydroxy compound include phenol, cresol, xylenol, pyrocatechol, t-butylcatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, salicyl alcohol and p-hydroxybenzyl alcohol. , O-hydroxybenzyl alcohol, p-hydroxyphenethyl alcohol, p-aminophenol,
m-aminophenol, diaminophenol, aminoresorcinol, p-hydroxybenzoic acid, o-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid,
Examples include 3,5-dihydroxybenzoic acid and gallic acid. In addition, trizole compounds such as benzotriazole, aminotriazole, and aminotetrazole are listed as anticorrosion agents. These compounds can be blended alone or in combination of two or more.

In the present invention, the concentration of the imine compound is used in the range of organic base compound / imine compound (weight ratio) = 0.0001 to 10,000, preferably 0.005 to 200, relative to the organic base compound. The organic base compound is 0.1 to 9 in the entire composition.
It is used in a concentration of 9.99% by weight, preferably in the range of 5 to 95% by weight. In the present invention, the use of the organic solvent is not limited, but the concentration may be determined in consideration of the viscosity, specific gravity or etching of the composition, ashing conditions and the like. When used, it can be used at a concentration of 0 to 90% by weight. In the composition of the present invention, the addition amount of the anticorrosive agent is not specified,
It is 0 to 30% by weight, preferably 15% by weight or less of the whole composition. The use of water in the present invention is not limited, but the concentration may be determined in consideration of etching and ashing conditions. Most are used in the range of 0 to 50% by weight.

The temperature at the time of producing a semiconductor element by stripping the resist using the resist stripper composition of the present invention is usually in the range of normal temperature to 150 ° C., but especially at a low temperature of 70 ° C. or lower. Peeling is possible, and it is preferable to carry out at a temperature as low as possible in consideration of the attack on the material.
The inorganic substrate used in the present invention includes silicon, amorphous silicon, polysilicon, silicon oxide film, silicon nitride film, copper and copper alloys, aluminum, aluminum alloys, gold, platinum, silver, titanium, titanium-tungsten. ,
Titanium nitride, tungsten, tantalum, tantalum compounds, chromium, chromium oxide, chromium alloys, semiconductor wiring materials such as ITO (indium oxide), or compound semiconductors such as gallium-arsenic, gallium-phosphorus, indium-phosphorus, etc. Dielectric materials such as strontium-bismuth-tantalum, and glass substrates for LCDs are used.

In the method for manufacturing a semiconductor element of the present invention, after removing an unnecessary portion of the conductive thin film formed with a resist with a predetermined pattern by etching, the resist is removed with the above-mentioned stripping solution. If desired, ashing treatment may be performed, and then the residue generated by etching may be removed by the above-described stripping solution. The ashing process referred to here is, for example, a process of removing a resist made of an organic polymer as CO and CO ₂ by a combustion reaction with oxygen plasma generated in plasma. As a rinsing method after using the photoresist stripping agent of the present invention, an organic solvent such as alcohol may be used, or rinsing may be performed with water, and there is no particular limitation.

[0019]

EXAMPLES The present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples.

Production Example The production method of ethylidene butylamine will be described below as one of the production examples of general imine compounds. Butylamine 0.50mol and 90% acetaldehyde 0.61m
were mixed below 20 ° C. To this was added KOH in large excess. The oil separated into two layers was subjected to simple distillation. It was identified as ethylidene butylamine by NMR and used for the experiment.

Examples 1 to 9 and Comparative Examples 1 and 2 Next, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to these examples.
In this embodiment, a PFR-type substrate is used for a substrate having a tantalum / glass structure.
After applying 790 resist, development was performed. After that, a circuit was formed through a dry etching process using a fluorine compound. Using this substrate, the resist peeling property was tested. The above substrate was immersed in the composition liquid at 40 ° C. After a predetermined time, the substrate was taken out, rinsed with water, blown with nitrogen gas and dried, and then observed with an optical microscope. The time required for resist stripping was measured. The results are shown in Table 1 below.

[0022]

[Table 1] *) EA = ethanolamine, EBA = N-ethylidenebutylamine, DMAC = dimethylacetamide, EDA = ethylenediamine, EEA = N-ethylideneethanolamine, DGME = diethylene glycol monomethyl ether, BA = butylamine, DGBE = diethylene glycol monobutyl ether, M
EA = methylethanolamine, NMP = N-methylpyrrolidone, PA = 1-amino-2-propanol, EPA = N-ethylideneamino-2-propanol, PG = propylene glycol

Examples 10 to 16 and Comparative Examples 3 and 4 Dry etching was performed using the resist film as a mask to
FIG. 1 is a cross-sectional view of a semiconductor device in which an 1-alloy (Al-Cu) wiring body 5 is formed and further subjected to ashing treatment by oxygen plasma.
Shown in 1. In a semiconductor device, an oxide film 2 is formed on a silicon substrate 1, and an Al alloy 5 which is a wiring body is formed on the oxide film 2.
Are formed, and the resist residue 6 remains on the side wall. Note that titanium 3 and titanium nitride 4 are present as barrier metals. The semiconductor device of FIG. 1 was immersed in a release agent having the composition shown in Table 2 for a predetermined time, rinsed with ultrapure water, and then dried.
Observation was performed with an electron microscope (SEM). The results of evaluation of the peeled state of the photoresist film 4 and the side wall protective deposition film 5 and the corrosion state of the aluminum wiring body 3 are shown.
Shown in 2. The evaluation criteria by SEM observation are as follows. (Peelability) A: Completely removed. B: Almost completely removed. C: Residue was observed. (Corrosion) A: No corrosion was observed. B: Almost no corrosion was observed. C: crater-like or pit-like corrosion was observed.

[0024]

[Table 2] *) EA = ethanolamine, EBA = N-ethylidene butylamine, NMP = N-methylpyrrolidone, CA = catechol, DETA =
Diethylenetriamine, EEA = N-ethylideneethanolamine, DMSO = dimethylsulfoxide, MEA = methylethanolamine, BT = benzotriazole, BuCA = 4-t-butylcatechol, EDA = ethylenediamine, PA = 1-amino-2-propanol, DGME = Diethylene glycol monomethyl ether, DPME = Dipropylene glycol monomethyl ether, KA = Citric acid, AEE = Aminoethoxyethanol

[0025]

By using the resist remover composition of the present invention, the resist can be removed in a short time. Further, the wiring material can be peeled off without corrosion.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a semiconductor device after dry etching is performed by using a resist film as a mask to form an Al alloy wiring body and further ashing treatment is performed by oxygen plasma.

[Explanation of symbols]

1: Silicon substrate 2: Oxide film 3: Titanium 4: Titanium nitride 5: Al alloy 6: Resist residue

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroshi Yoshida             6-1, 1-1 Shinjuku, Katsushika-ku, Tokyo Mitsubishi tile             The Chemical Research Institute Tokyo Research Center F-term (reference) 2H096 AA25 AA26 AA27 LA03                 5F046 MA02

Claims (9)

[Claims] 1. A resist stripper composition comprising an organic base compound and an imine compound. 2. The resist stripper composition according to claim 1, wherein the imine compound is an imine compound having a structure represented by the following formula (1). [Chemical 1] (R ¹ = H, alkyl group, hydroxyalkyl group, aryl group, acyl group or alkoxyalkyl group, R ² = H, alkyl group, hydroxyalkyl group, aryl group, allyl group or alkoxyalkyl group, R ³ = H, It is an alkyl group, a hydroxyalkyl group, an aminoalkyl group, an acyl group or an alkoxyalkyl group, and may have a cyclic structure in which R ² and R ³ are bonded.) 3. The formula (1) wherein R ² is hydrogen, and R ³ is H or an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group or an aminoalkyl group.
The resist stripper composition described. 4. The resist stripper composition according to claim 1, wherein the imine compound is produced by a reaction of a carbonyl compound and an organic base compound. 5. The resist stripper composition according to claim 1, wherein the organic base compound is alkylamine, alkanolamine, polyamine, hydroxylamine, cyclic amine or quaternary ammonium. 6. The resist stripper composition according to claim 1, further comprising an organic solvent. 7. The method according to claim 1, further comprising an anticorrosive agent.
Item 5. A resist stripper composition according to item. 8. The anticorrosive agent is an aromatic hydroxy compound, a sugar alcohol compound or a triazole compound.
The resist stripper composition described. 9. The resist stripper composition according to claim 1, further comprising water.