JP3449650B2 - Stripper composition for resist - 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 solution composition, and more specifically, a highly strippable resist stripping composition suitable for use in the production of semiconductor devices such as IC and LSI or liquid crystal panel devices. Liquid composition.

[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.
Although proposed in Japanese Patent Application Laid-Open No. 05653, the stripping solution has a drawback that it has a poor stripping action, it is difficult to form a fine pattern of 10 μm or less, and it cannot be used for manufacturing advanced semiconductor devices and liquid crystal devices.

[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. Found that a resist stripping composition having less adhesion of fine particles to a substrate can be obtained,
The present invention has been completed.

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

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 object comprises (a) an N-alkylalkanolamine and (b)
The present invention relates to a resist stripping composition containing at least one selected from 1,3-dimethyl-2-imidazolidinone and diethylene glycol monoalkyl ether.

As described above, the stripping solution composition of the present invention contains (a) N-alkylalkanolamine as an essential component, and (b) 1,3-dimethyl-2-imidazolidinone and diethylene glycol monoalkyl ether. It is a stripper composition having improved thermal stability, which contains at least one of the following: The stripper composition further contains (c) an aromatic hydroxy compound, (d) a carboxyl group-containing organic compound and its anhydride, and (e) a compounding agent of a triazole compound, alone or in combination of two or more kinds. be able to. By incorporating these compounding agents, the releasability, the release stability, and the anticorrosion property, especially the anticorrosion property in the rinse treatment with water, are further improved. 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.

Examples of the diethylene glycol monoalkyl ether as the component (b) include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and the like, with diethylene glycol monobutyl ether being particularly preferred. The component (b) of the present invention needs to be a water-soluble organic polar solvent miscible with the component (a). Such solvents are described in the above-mentioned prior art,
Among them, 1,3-dimethyl-2-imidazolidinone and diethylene glycol monoalkyl ether are preferable because they are inexpensive and easily available and have low toxicity and excellent safety.

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, specifically, 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, m
-Tolyltriazole, p-tolyltriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, nitrobenzotriazole, dihydroxypropylbenzotriazole and the like can be mentioned, and among them, 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 system resist stripper of (i) (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 comprising the components (a), (b) and (c) or (d) and (e), the two-component resist stripper of (i) To
1 to 20% by weight of the component (c) or (d), preferably 1 to
10% by weight, and 0.2 to 5% by weight of component (e),
Preferably 0.5-2% 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),
The component (c) component 1 is added to the two-component resist stripping solution of component (i).
-20% by weight, preferably 1-10% by weight, component (d) 1-20% by weight, preferably 1-10% by weight, and component (e) 0.2-5% by weight, 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 can be effectively used for resists which can be developed using an aqueous alkaline solution, including negative and positive resists. As the resist, (i) a positive type 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 to increase the solubility in an alkaline aqueous solution and a positive resist containing an alkali-soluble resin, and (iii) a compound that generates an acid upon exposure to an alkali aqueous solution that decomposes with an acid. Examples thereof include a positive resist containing an alkali-soluble resin having a group whose solubility is increased, and (iv) a negative resist containing a compound that generates an acid by light, a cross-linking agent and an alkali-soluble resin. It is not limited.

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, as a compulsory test for investigating the corrosion of the substrate during the rinse treatment with water, a silicon wafer having an aluminum pattern of 10,000 liters was used as an aqueous solution containing 10% by weight of a stripping solution having the composition shown in Table 1. The aluminum pattern was immersed for 20 minutes at 40 ° C., and the corrosion rate of the aluminum pattern was calculated from the immersion time (minutes) and the corrosion amount of aluminum (mÅ). The results are shown in Table 1.

Regarding the strippability of the resist film by the above stripping solution composition, the same effect as that of the stripping solution containing monoethanolamine was exhibited.

Examples 4 to 5 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, in the same manner as in Example 1, the corrosion of the substrate during the rinse treatment with water was examined. 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, in the same manner as in Example 1, the corrosion of the substrate during the rinse treatment with water was examined. The results are shown in Table 1.

Comparative Examples 4 to 5 In Example 4, the number of fine particles attached to the surface of the silicon wafer was measured in the same manner as in Example 4 except that the stripping solution was changed to the composition shown in Comparative Examples 4 to 5 in Table 1. It was measured. Further, in the same manner as in Example 1, the corrosion of the substrate during the rinse treatment with water was examined. The results are shown in Table 1.

[0034]

[Table 1] Note) DEMB: diethylene glycol monobutyl ether DMI: 1,3-dimethyl-2-imidazolidinone

Examples 6 to 11 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 stripping solution was changed to the composition shown in Table 2. Further, in the same manner as in Example 1, the corrosion of the substrate during the rinse treatment with water was examined. The results are shown in Table 2.

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

[0037]

[Table 2] Note) DEMB: diethylene glycol monobutyl ether DMI: 1,3-dimethyl-2-imidazolidinone

Comparative Examples 6 to 11 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 stripping solution was changed to the composition shown in Table 3. Further, in the same manner as in Example 1, the corrosion of the substrate during the rinse treatment with water was examined. The results are shown in Table 3.

[0039]

[Table 3] Note) DEMB: diethylene glycol monobutyl ether DMI: 1,3-dimethyl-2-imidazolidinone

As shown in Tables 1 and 2 above, in the stripping treatment using the resist stripping solution 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. 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 adhered over 2000. As is clear from Tables 1 and 2, the resist stripping solution composition of the present invention can stably perform the stripping action even in stripping treatment under severe conditions, and can manufacture a high quality device.

Further, in the stripping treatment using the resist stripping liquid composition to which the compounding agent was further added, the corrosion rate of the substrate was small at the time of the water rinse treatment, and the superiority to the case where the compounding agent was not added was confirmed. .

[0042]

EFFECTS OF THE INVENTION The resist stripper composition of the present invention has excellent properties such as safety, strippability, and corrosion resistance, and has a stable stripping action even under severe stripping conditions, and has a high quality. Semiconductor elements and liquid crystal panel elements can be manufactured.

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-7-160009 (JP, A) JP-A-7-253678 (JP, A) JP-A 64-81950 (JP, A) JP-A 64-- 81949 (JP, A) JP 57-165834 (JP, A) JP 4-289866 (JP, A) JP 64-42653 (JP, A) JP 63-50838 (JP, A) JP-A-4-124668 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (5)

(57) [Claims] 1. (a) N-alkylalkanolamine 5
Resist containing 0 to 90% by weight and (b) 50 to 10% by weight of at least one kind selected from 1,3-dimethyl-2-imidazolidinone and diethylene glycol monoalkyl ether , and containing no water Stripping liquid composition. 2. The resist stripping composition according to claim 1, wherein the component (a) is N-methylethanolamine or N-ethylethanolamine. 3. The stripping solution composition for resist according to claim 1, wherein the component (b) is diethylene glycol monobutyl ether. 4. (a) N-alkylalkanolamine 5
Compounding agent 1 to the resist stripping solution containing 0 to 90% by weight and (b) 50 to 10% by weight of at least one kind selected from 1,3-dimethyl-2-imidazolidinone and diethylene glycol monoalkyl ether. 20% by weight of a resist stripping composition. 5. The resist stripper according to claim 4, 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.