JPH11271985A - Resist stripping composition and method of using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To remove a resist residue generated at the time of forming a wiring in a manufacturing process of a semiconductor element circuit or the like with high performance and to exhibit excellent Al corrosion protection. SOLUTION: 1,8-Diaza-bicyclo (5,4,
0) at least one of undecene-7 (DBU) and 1,5-diaza-bicyclo (4,3,0) nonene-5 (DBN), hydrogen fluoride, a water-soluble organic solvent, and water as main components Resist stripping composition. DBU and DB
0.1 to 30% by weight of at least one content of N,
The content of hydrogen fluoride is 0.1 to 10% by weight, the content of water-soluble organic solvent is 10 to 70% by weight, and the content of water is 10 to 8%.
9.8 wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a semiconductor integrated circuit,
Photoresist stripper composition used in the manufacture of semiconductor element circuits and the like of liquid crystal panels and methods of using the same, in detail,
The present invention relates to a photoresist stripping agent composition that improves both the performance of removing a resist residue generated when wiring is formed on a semiconductor substrate or a glass substrate for a liquid crystal and the aluminum corrosion protection of a substrate, and a method of using the same. .

[0002]

2. Description of the Related Art A stripping composition is used for stripping a photoresist used for manufacturing a semiconductor integrated circuit, a semiconductor element circuit of a liquid crystal panel, and the like. The manufacture of the semiconductor element circuit or the associated electrode unit is performed as follows. First, a metal film is laminated on a substrate such as silicon or glass by a method such as CVD or sputtering. A photoresist is coated on the upper surface, and a pattern is formed on the photoresist by processes such as exposure and development. The metal film is etched using the patterned photoresist as a mask. Thereafter, the unnecessary photoresist is stripped and removed using a stripping composition.
The element is formed by repeating the operation.

Conventionally, a single solvent such as an organic alkali, an inorganic alkali, an organic acid, an inorganic acid, and a polar solvent, a mixed solution thereof, or an aqueous solution thereof has been used as a release agent composition. Further, in order to remove a resist residue generated at the time of forming a wiring in a manufacturing process of a semiconductor element circuit or the like,
A resist stripping composition containing at least one of an alkylamine and an alkylammonium hydroxide, an organic solvent, and water is also well known.

Further, it is known that a mixture of hydrofluoric acid and various amines is effective for removing a resist residue generated during wiring formation in a semiconductor substrate manufacturing process or a liquid crystal glass substrate manufacturing process. For example, JP-A-8-20
No. 2052 describes a resist stripping composition containing hydrofluoric acid, ammonium fluoride, a water-soluble organic solvent and an anticorrosive. Also, Japanese Patent Application Laid-Open No. 9-1976
No. 81 describes a resist stripping solution composition containing a salt of hydrofluoric acid and a metal-free base, a water-soluble organic solvent and water, and having a hydrogen ion concentration (pH) of 5 to 8. Have been.

Japanese Patent Application Laid-Open No. Hei 7-201794 discloses that a protective deposition film formed in a semiconductor device manufacturing process is converted into an aqueous solution containing a quaternary ammonium salt and a fluorine compound or a quaternary ammonium salt and a fluorine compound. It is described that peeling is performed using a semiconductor device cleaning agent comprising an aqueous solution containing an organic solvent selected from amides, lactones, nitriles, alcohols, and esters. Also, JP-A-7-271056 discloses an organic carboxylic acid ammonium salt or an organic carboxylic acid amine salt,
And a photoresist stripper comprising an aqueous solution containing a fluorine compound. Further, Japanese Unexamined Patent Application Publication No. 9-6
JP 2013 describes a cleaning agent for semiconductor devices containing a fluorine compound and a betaine compound and at least one organic solvent selected from amides, lactones and alcohols.

[0006]

SUMMARY OF THE INVENTION A resist stripping composition is excellent in resist residue removal properties, and can favorably prevent corrosion of a conductive metal film such as aluminum or an aluminum alloy formed on a substrate. Is required. However, in a resist stripping composition comprising an amine, hydrogen fluoride, a water-soluble organic solvent, and water, even when the amine described in the above publication is used as the amine, both the residue removal property and the aluminum corrosion protection property are satisfied. (See Comparative Examples 1 to 32, Tables 2 and 3 below), but 1,8-diaza-bicyclo (5,4,0) undecene-7 (hereinafter sometimes referred to as DBU) as an amine. ) Or 1,
When 5-diaza-bicyclo (4,3,0) nonene-5 (hereinafter sometimes referred to as DBN) is used, a remarkably excellent effect can be obtained, that is, residue removal and aluminum corrosion prevention. The present inventor has found that both properties can be satisfied.

SUMMARY OF THE INVENTION The present invention has been made based on the above findings, and it is an object of the present invention to remove a resist residue generated at the time of forming a wiring in a manufacturing process of a semiconductor device circuit or the like with high performance and simultaneously remove aluminum residue on a substrate. And a method for using the same.

[0008]

In order to achieve the above object, a resist stripping composition of the present invention comprises 1,8-diaza-bicyclo (5,4,0) undecene-7 (DBU).
And 1,5-diaza-bicyclo (4,3,0) nonene-
5 (DBN) and hydrogen fluoride (H
F), a water-soluble organic solvent, and water. In the resist stripping composition of the present invention, a commercially available hydrofluoric acid which is an aqueous solution of 50 to 60% by weight of hydrogen fluoride may be used instead of hydrogen fluoride. In some cases, additives such as an anticorrosive may be added.

In the above resist stripping composition,
1,8-diaza-bicyclo (5,4,0) undecene-
7 (DBU) and 1,5-diaza-bicyclo (4,3
0) The content of at least one of nonene-5 (DBN) is 0.1 to 30 wt%, preferably 0.1 to 5.0 wt%.
%, The content of hydrogen fluoride is 0.1 to 10% by weight, preferably 0.1 to 5.0% by weight, and the content of the water-soluble organic solvent is 10%.
The content of water is from 10 to 89.8% by weight, preferably from 50 to 80% by weight. When the content of DBU or DBN and hydrogen fluoride is less than the above range, the removability of the residue decreases, and when the content exceeds the above range, metals, particularly Al and Al-
It is not preferable because it corrodes metals such as Si and Al-Si-Cu. Further, when the content of the water-soluble organic solvent is less than the above range, the peeling of the organic film is insufficient, and when the content exceeds the above range, the content of other components is reduced, so that the removability of the residue is reduced. descend. When the water content is less than the above range, the removability of the residue is insufficient, and when the water content is more than the above range, metals, particularly Al and Al-S which are easily corroded.
It is not preferable because it corrodes metals such as i and Al-Si-Cu.

The water-soluble organic solvent used in the resist stripping composition of the present invention may be any organic solvent that is miscible with hydrofluoric acid, and may be any water-soluble organic solvent used in conventional organic amine stripping solutions. Solvents can be used. Examples of the water-soluble organic solvent include sulfoxides such as dimethyl sulfoxide, sulfones such as dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone and tetramethylene sulfone, N, N-dimethylformamide, N-methylformamide, Amides such as N, N-dimethylacetamide, N-methylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-
2-pyrrolidone, N-propyl-2-pyrrolidone, N-
Lactams such as hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl- Imidazolidinones such as 2-imidazolidinone, lactones such as γ-butyrolactone and δ-valerolactone, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate; Ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl Glycol: BDG), triethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, allyl ethylene glycol, propylene glycol, propylene glycol monomethyl ether,
Propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethyl diethylene glycol diethyl ether, dipropylene glycol dimethyl ether And polymethyl alcohols such as 3-methyl-3-methoxy-butanol, methyl lactate, ethyl lactate, isopropyl lactate and butyl lactate, and derivatives thereof. Among them, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, diethylene glycol monobutyl ether ( Butyldiglycol: BDG),
Propylene glycol monomethyl ether is preferred because it has excellent resist residue removal properties and Al corrosion protection.

The method of using the resist stripping composition of the present invention is to remove the resist residue generated when wiring is formed on a semiconductor substrate or a glass substrate for liquid crystal by using the resist stripping composition of the present invention. It is characterized in that it is peeled off and removed.

[0012]

EXAMPLES Examples and comparative examples are shown below to further clarify the features of the present invention. Examples 1 to 9, Comparative Examples 1 to 32 TiN / Ti / TiN / Al-Cu on silicon oxide film
/ TiN film-coated substrate is dry-etched using Cl ₂ and BCl ₃ using a patterned resist as a mask, and subsequently, ashing is performed using oxygen and water to remove a resist residue generated on a wiring sidewall or an upper portion. It was an object. The object to be peeled was processed under the following peeling conditions. That is, this object to be peeled is shown in Table 1 (Examples 1 to 5).
9), Table 2 (Comparative Examples 1 to 16), Table 3 (Comparative Examples 17 to 3)
After immersion in the release agent composition prepared in the composition shown in 2) at 24 ° C. for 1 minute, immersion in pure water at 24 ° C. for 5 minutes, and further immersion in pure water at 24 ° C. for 5 minutes, Finally, the pure water was blown off with an air gun. The degree of residue removal and the degree of aluminum corrosion were observed with a scanning electron microscope (SEM), and the residue removal and aluminum corrosion protection were compared. The results are shown in Tables 1 to 3. In the column for residue removal in the table,
The mark ○ indicates “no residue”, the mark Δ indicates “residue has been removed but the residue remains before treatment”, and the mark “x” indicates “residue state before treatment”. Further, in the column of Al corrosion protection in the table, a circle indicates “no corrosion”, a triangle indicates “the wiring is thin”, and a cross indicates “the wiring is extremely thin”.

[0013]

[Table 1]

[0014]

[Table 2]

[0015]

[Table 3]

In the table, MEA is monoethanolamine, TMAH is tetramethylammonium hydroxide, DEA is diethylamine, EAE is ethylaminoethanol, DEAE is diethylaminoethanol,
MAE is methylaminoethanol, DMAE is dimethylaminoethanol, DBU is 1,8-diaza-bicyclo (5,4,0) undecene-7, and DBN is 1,5-diaza-bicyclo (4,3,0) nonene-. 5. BDG indicates butyl diglycol (diethylene glycol monobutyl ether). From the table, the release agent composition containing no DBU or DBN (Comparative Examples 1 to 32) shows the residue removal property and A
l Although there is a problem with any of the anticorrosion properties, DBU or DBN
It can be seen that the release agent composition containing any of the above is excellent in both the residue removal property and the Al corrosion protection property.

Next, an example of a method for using the release agent composition of the present invention will be described. A metal thin film is formed on a semiconductor substrate or a glass substrate for liquid crystal by CVD, sputtering, or the like. After a photoresist is applied on the upper surface, a pattern is formed by processes such as exposure and development. The metal thin film is etched using the patterned photoresist as a mask. Thereafter, the unnecessary photoresist is ashed, and the residue generated at that time is stripped / removed using the stripping agent composition of the present invention to manufacture a semiconductor element having wirings and the like formed thereon.

[0018]

As described above, the present invention has the following effects. (1) 1,8-diaza-bicyclo (5,4,0) undecene-7 (DBU) and 1,8-diaza-bicyclo (5,4,0) undecene-7 (DBU)
5-diaza-bicyclo (4,3,0) nonene-5 (DB
By including at least one of N), a resist residue generated at the time of forming a wiring in a manufacturing process of a semiconductor element circuit or the like can be removed with high performance, and corrosion of a metal thin film such as aluminum on a substrate can be improved. Can be prevented.

Claims (3)

[Claims] (1) 1,8-diaza-bicyclo (5,4,
0) at least one of undecene-7 and 1,5-diaza-bicyclo (4,3,0) nonene-5, hydrogen fluoride, a water-soluble organic solvent, and water as main components. Resist stripping composition. 2. A 1,8-diaza-bicyclo (5,4,
0) The content of at least one of undecene-7 and 1,5-diaza-bicyclo (4,3,0) nonene-5 is 0.1 to 30% by weight, and the content of hydrogen fluoride is 0.1 to 30%.
10 wt%, water-soluble organic solvent content is 10-70 wt%,
The resist stripping composition according to claim 1, wherein the water content is 10 to 89.8 wt%. 3. A resist stripping agent formed by forming a wiring on a semiconductor substrate or a liquid crystal glass substrate by using the resist stripping composition according to claim 1 or 2. To use the resist stripping composition.