JP3449651B2 - Resist stripper composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist stripping composition having high releasability, which is suitable for use in the production of semiconductor devices such as IC and LSI or liquid crystal panel devices. Regarding things.

[0002]

2. Description of the Related Art Semiconductor elements such as ICs and LSIs and liquid crystal panel elements are provided with a uniform photoresist on a conductive metal film such as aluminum, copper or aluminum alloy formed on a substrate or an insulating film such as a SiO ₂ film. After coating and exposing and developing it to form a resist pattern, the conductive metal film or insulating film is selectively etched using this pattern as a mask to form a fine circuit, and then an unnecessary resist layer is formed. It is manufactured by removing with a stripper.

As a stripping solution for removing the resist, an acidic stripping solution prepared by mixing an alkylbenzene sulfonic acid with a phenol compound or a chlorine solvent, or an alkaline stripping solution containing a water-soluble organic amine and various organic solvents has been used. It was Alkylbenzene sulfonic acid of the acidic stripping solution easily corrodes the conductive metal film of the substrate, the phenol compound of the compounding component is toxic, and the chlorine-based solvent causes environmental pollution. Workability, environmental problems, substrate However, the alkaline stripping solution containing water-soluble organic amines, especially monoethanolamine as an essential component has come to be widely used. Therefore, many studies have been made and various stripping solutions have been proposed. For example, US Pat. No. 4,617.
No. 251 describes (a) monoethanolamine, 2
Organic amines such as-(2-aminoethoxy) ethanol and (b) N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, carbitol acetate, methoxyacetoxypropane, etc. JP-A-62-49355 discloses a resist stripping solution comprising two components of an organic polar solvent of (a) an ethylene oxide adduct of alkanolamine such as monoethanolamine, diethanolamine, triethanolamine or ethylenediamine. Alkylene polyamine, (b) sulfone compounds such as sulfolane, (c) diethylene glycol monoethyl ether,
A stripping solution in which a glycol monoalkyl ether such as diethylene glycol monobutyl ether is blended in a specific ratio is disclosed in JP-A-63-208043 and 1,3-dimethyl-2-imidazolidinone and a water-soluble solution of monoethanolamine, diethanolamine and the like. A water-soluble stripping solution for a positive resist containing a hydrophilic organic amine is disclosed in JP-A-63-23.
1343 discloses (a) amines such as monoethanolamine, ethylenediamine, piperidine, and benzylamine; (b) polar solvents such as dimethyl sulfoxide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; c) A resist pattern stripping solution comprising a surfactant is disclosed in JP-A-64-42653 as (a) dimethyl sulfoxide, (b) diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, γ-butyrolactone and 1,3. -Dimethyl-2-
At least one selected from imidazolidinone,
(C) A positive-type photoresist stripping agent in which a nitrogen-containing organic hydroxyl compound such as monoethanolamine is blended at a specific ratio has been proposed. These strippers have excellent properties such as safety, workability, resist strippability, ashing, strippability of resist films that have been abnormally hardened / deteriorated by ion implantation or plasma treatment, and corrosion resistance of conductive metal films. Show.

However, in the recent manufacturing of semiconductor devices and liquid crystal devices, the stripping solution is 110-130.
It occurs that it is used under severe conditions of being kept at a high temperature of ℃, and in the stripping solution containing the monoethanolamine as an essential component, if stripping treatment is performed under the above conditions, acetone or methyl ethyl ketone after the treatment, etc. Insoluble matter is deposited in the rinsing process with the polar solvent of, and adheres as fine particles on the conductive metal film, which greatly hinders the production of semiconductor devices and liquid crystal devices, and manufactures high quality devices with high yield. There was a problem that I could not do it. Also,
An alkaline stripping solution containing triethanolamine as an essential component, which does not use monoethanolamine, is disclosed in JP-A-4-3.
However, the stripping solution is inferior in stripping action, and it is difficult to form a fine pattern of 10 μm or less, so that it cannot be used for manufacturing advanced semiconductor devices and liquid crystal devices. Further, in JP-A-64-81949, (a) at least one selected from γ-butyrolactone, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone ( b) N-n-butylethanolamine,
A photoresist stripping solution containing amino alcohols such as diethylaminoethanol and 2-ethylaminoethanol and (c) water is further disclosed in JP-A-64-81950, in which (a) dimethyl sulfoxide and (b) Nn are used. −
Butyl ethanolamine, diethylamino ethanol,
A photoresist stripping solution containing amino alcohols such as 2-ethylamino ethanol and (c) water has been proposed. The compounding ratios of the components (a), (b), and (c) in JP-A-64-81949 and JP-A-64-81950 are 30 wt% or more of the component (a) and component 1 of the component (b). ˜50 wt% and component (c) 5-60 wt%,
Each of them has a drawback that it contains water and corrodes the conductive metal film.

[0005]

In view of the current situation,
As a result of intensive studies by the present inventors, the use of a solution consisting of an N-alkylalkanolamine and a specific organic solvent as a stripping solution eliminates the deposition of insoluble matter even under severe stripping treatment at high temperature. The inventors have completed the present invention by finding that a resist stripping composition having less adhesion of fine particles to a substrate can be obtained.

That is, the present invention provides a resist stripping composition which has no workability and safety problems, can be used for both positive and negative resists, and has high strippability and corrosion prevention. To aim.

It is another object of the present invention to provide a resist stripping composition which hardly causes fine particles to adhere to a substrate even under severe use conditions.

[0008]

Means for Solving the Problems The present invention which achieves the above objects comprises (a) N-alkylalkanolamines 50 to 9:
The present invention relates to a resist stripping composition, which contains 0% by weight and (b) at least one selected from dimethyl sulfoxide and N-methyl-2-pyrrolidone.

As described above, the stripping solution composition of the present invention contains (a) an N-alkylalkanolamine as an essential component, and contains (b) at least one selected from dimethyl sulfoxide and N-methyl-2-pyrrolidone. It is a stripping composition having improved heat stability. The stripper composition further comprises (c) an aromatic hydroxy compound,
(D) Carboxyl group-containing organic compound and its anhydride,
Also, the compounding agent of the (e) triazole compound may be contained alone or in combination of two or more kinds. The addition of this compounding agent further improves the peeling property, the peeling stability, and the anticorrosion property, particularly the anticorrosion property in the rinse treatment with water. Further, other additives such as a surfactant may be added within the range that does not deteriorate the stripping solution composition of the present invention.

The above-mentioned component (a) is a compound having peelability and performance of not adhering fine particles to a substrate under severe use conditions in the stripping solution composition of the present invention. -Methylethanolamine, N-ethylethanolamine, N-propylethanolamine and the like can be mentioned, with N-methylethanolamine and N-ethylethanolamine being particularly preferred.

The above-mentioned component (b) has excellent miscibility with the component (a), and when mixed with the component (a), it contributes to corrosion prevention.

As the component (c) of the compounding agent, cresol, xylenol, pyrocatechol, resorcinol,
Hydroquinone, pyrogallol, 1,2,4-benzenetriol, salicyl alcohol, 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, 3,5-dihydroxybenzoic acid and the like can be mentioned, and among them, pyrocatechol is preferable. These compounds can be blended alone or in combination of two or more.

The component (d) of the compounding agent is an organic carboxylic acid or an acid anhydride thereof, and specific examples include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, Succinic acid, glutaric acid, maleic acid, fumaric acid, benzoic acid, phthalic acid, 1,2,3-benzenetricarboxylic acid, glycolic acid, lactic acid, malic acid, citric acid, acetic anhydride, phthalic anhydride, maleic anhydride, Examples thereof include succinic anhydride and salicylic acid. Preferred carboxyl group-containing organic compounds include formic acid, phthalic acid, benzoic acid, phthalic anhydride, and salicylic acid, and phthalic acid, phthalic anhydride, and salicylic acid are particularly preferable. These compounds can be blended alone or in combination of two or more.

Further, as the component (e) of the compounding agent,
For example, benzotriazole, o-tolyltriazole,
Examples thereof include m-tolyltriazole, p-tolyltriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, nitrobenzotriazole, dihydroxypropylbenzotriazole and the like, of which benzotriazole is preferable. These compounds can be blended alone or in combination of two or more. By adding these compounding agents in addition to the components (a) and (b), the releasability, the releasability, and the anticorrosive property are further improved. Therefore, they can be used in an appropriate combination according to the resist composition used, the stripping conditions such as stripping temperature, the conditions for forming a resist-altered film by ashing, ion implantation, plasma treatment, or the like, or the subsequent rinse treatment conditions. Especially when performing a rinse rinse after the peeling treatment,
It is preferable to use such a compounding agent because the substrate is easily corroded.

The stripper composition of the present invention contains the above components in the following mixing ratios. That is,

In the case of a two-component system comprising (i) component (a) and component (b), component (a) is 50 to 90% by weight, preferably 60.
~ 90 wt%, component (b) 50 to 10 wt%, preferably 40 to 10 wt%;

In the case of a three-component system consisting of (ii) component (a), component (b) and component (c), (d) or (e), the two-component resist stripper of (i) is c),
1 to 20% by weight of component (d) or (e), preferably 1 to
10% by weight;

(Iii) In the case of a four-component system consisting of the component (a), the component (b) and the component (c) or the component (d) and the component (e), the two-component resist stripping solution of the component (i) is used. , (C)
Or (d) component 1 to 20% by weight, preferably 1 to 10% by weight, and component (e) component 0.2 to 5% by weight, preferably 0.5 to 2% by weight;

(Iv) (a) component, (b) component and (c)
In the case of a four-component system consisting of component and (d) component, 2 of (i)
1 to 20% by weight of the component (c), preferably 1 to 10% by weight, and (d) the components 1 to 2 in the component-based resist stripping solution.
0% by weight, preferably 1-10% by weight;

(V) In the case of a five-component system consisting of the components (a), (b), (c), (d) and (e),
In (i) the two-component resist stripper, (c) component 1 to
20% by weight, preferably 1-10% by weight, component (d) 1
-20% by weight, preferably 1-10% by weight, and (e)
0.2-5% by weight of components, preferably 0.5-2% by weight;

If the blending ratio deviates from the above range, the releasability, the peeling stability, the anticorrosiveness, etc. are deteriorated, so it is important to blend each component within the above range.

The stripping composition of the present invention is used by contacting it with a resist film formed on a substrate at a temperature of 60 to 130 ° C., especially at a temperature of 110 to 130 ° C. for a long time. For example, even if they are used in contact with each other for about 1 day, insoluble matter is less likely to precipitate in the rinsing step, so that they are less likely to become fine particles and adhere to the substrate, which is particularly effective for peeling treatment under severe conditions. .

Further, the resist stripping composition of the present invention is
It can be effectively used for resists that can be developed using an aqueous alkaline solution, including negative and positive type resists. Examples of the resist include (i) a positive resist containing a naphthoquinonediazide compound and a novolak resin, (ii) a compound that generates an acid upon exposure, a compound that decomposes with an acid and has an increased solubility in an alkaline aqueous solution, and an alkali-soluble resin. A positive resist containing (iii) a compound that generates an acid upon exposure, a positive resist containing an alkali-soluble resin having a group that is decomposed by an acid to increase the solubility in an alkaline aqueous solution, and (iv) an acid is generated by light. Examples thereof include, but are not limited to, a negative resist containing a compound generated, a crosslinking agent and an alkali-soluble resin.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0025]

【Example】

Examples 1 to 3 OFPR- which is a positive resist composed of a naphthoquinonediazide compound and a novolac resin on a silicon wafer.
Apply 800 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to a spinner and
Prebaking is performed at 10 ° C. for 90 seconds, and the film thickness is 1.
A 26 μm resist layer was formed. This resist layer is N
SR-1505G7E (manufactured by Nikon Corporation) was exposed through a mask pattern and developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution to form a resist pattern. Then, post baking was performed at 140 ° C. for 300 seconds.

A silicon wafer having the above resist pattern was immersed in a resist stripping composition having the composition shown in Table 1 and kept at 120 ° C. for 24 hours for 10 minutes,
A peeling process was performed. The stripped substrate was immersed in acetone for 3 minutes, rinsed, washed with water and dried. The number of fine particles adhering to the surface of the obtained silicon wafer was measured using a surface inspection device WIS-850 (manufactured by Canon Inc.). The results are shown in Table 1.

Separately, in order to examine the corrosion of the substrate by the stripping solution, a silicon wafer having an aluminum pattern of 10,000 Å was placed in a stripping solution having the composition shown in Table 1
After immersion at 0 ° C., the corrosion rate of the aluminum pattern was calculated from the immersion time (minutes) and the corrosion amount of aluminum (mÅ). This is defined as the corrosive rate A. In addition, as a compulsory test to examine the corrosion of the substrate during the rinse treatment with water, 1
A silicon wafer having an aluminum pattern of 10,000 Å was immersed in an aqueous solution containing 10% by weight of a stripping solution having the composition shown in Table 1 at 40 ° C. for 20 minutes to determine the corrosion rate of the aluminum pattern in the immersion time (minutes). Calculated from the corrosion amount of aluminum and aluminum (mÅ). This is defined as the corrosion rate B. The results are shown in Table 1.

Regarding the releasability of the resist film by the above-mentioned stripping solution composition, the same effect as that of the stripping solution containing monoethanolamine was obtained.

Examples 4 to 6 In the same manner as in Example 1 except that the rinse solution in Example 1 was replaced with methyl ethyl ketone and the stripping solution had the composition shown in Table 1, the number of fine particles adhering to the surface of the silicon wafer was determined. It was measured. Further, the corrosion rate A and the corrosion rate B were calculated in the same manner as in Example 1. The results are shown in Table 1.

The peelability of the resist film was almost the same as that of the stripping solution containing monoethanolamine.

Comparative Examples 1 to 3 In Example 1, the number of fine particles adhering to the surface of the silicon wafer was measured in the same manner as in Example 1 except that the stripping solution was changed to the composition shown in Comparative Examples 1 to 3 of Table 1. It was measured. Further, the corrosion rate A and the corrosion rate B were calculated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 4 to 6 In Example 4, the number of fine particles attached to the surface of the silicon wafer was determined in the same manner as in Example 4 except that the stripping solution was changed to the composition shown in Comparative Examples 4 to 6 in Table 1. It was measured. Further, the corrosion rate A and the corrosion rate B were calculated in the same manner as in Example 1. The results are shown in Table 1.

[0033]

[Table 1] Note) DMSO: dimethyl sulfoxide NMP: N-methyl-2-pyrrolidone

Examples 7 to 12 The number of fine particles adhering to the surface of a silicon wafer was measured in the same manner as in Example 1 except that the composition shown in Table 2 was used instead of the stripping solution. Further, the corrosion rate A and the corrosion rate B were examined in the same manner as in Example 1. The results are shown in Table 2.
Shown in.

The strippability of the resist film was almost the same as that of the stripping solution containing monoethanolamine.

[0036]

[Table 2] Note) DMSO: dimethyl sulfoxide NMP: N-methyl-2-pyrrolidone

Comparative Examples 7 to 12 The number of fine particles attached to the surface of a silicon wafer was measured in the same manner as in Example 1 except that the stripping solution was changed to the composition shown in Table 3. Further, the corrosion rate A and the corrosion rate B were examined in the same manner as in Example 1. The results are shown in Table 3.
Shown in.

[0038]

[Table 3] Note) DMSO: dimethyl sulfoxide NMP: N-methyl-2-pyrrolidone

As shown in Tables 1 and 2 above, in the stripping treatment using the resist stripping composition of the present invention, the number of fine particles adhering to the substrate after the rinsing treatment was as small as 100 or less, and the substrate was not corroded. On the other hand, as shown in Table 3, in the conventional stripping solution containing monoethanolamine as an essential component, the number of fine particles exceeded 2000 and the yield of device manufacturing was poor. Further, even when N-alkylalkanolamine was used, when water was used together, corrosion appeared on the substrate.

[0040]

The resist stripper composition of the present invention has excellent properties such as safety, strippability and corrosion resistance, and can sustain a stable stripping action even under severe stripping conditions. Since it does not corrode, high quality semiconductor devices and liquid crystal panel devices can be manufactured.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 64-81950 (JP, A) JP 64-81949 (JP, A) JP 4-289866 (JP, A) JP 4- 124668 (JP, A) JP-A-6-244099 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (4)

(57) [Claims] 1. (a) N-alkylalkanolamine 5
0-90% by weight and (b) dimethyl sulfoxide and N-
At least one selected from methyl-2-pyrrolidone 5
A stripper composition for resist , which contains 0 to 10% by weight and does not contain water . 2. The resist stripping composition according to claim 1, wherein the component (a) is N-methylethanolamine or N-ethylethanolamine. 3. (a) N-alkylalkanolamine 5
0-90% by weight, (b) dimethyl sulfoxide and N-
At least one selected from methyl-2-pyrrolidone 5
A resist stripping composition comprising 0 to 10% by weight of a resist stripping composition containing no water and further containing 1 to 20% by weight of a compounding agent. 4. The resist stripper according to claim 3, wherein the compounding agent is at least one selected from the group consisting of an aromatic hydroxy compound, a carboxyl group-containing organic compound and its anhydride, and a triazole compound. Liquid composition.