KR101679030B1 - Stripper composition of photoresist - Google Patents

Abstract

More particularly, the present invention relates to a composition for removing a resist, which comprises an imidazolidine-based compound having a cyclic amine structure, has excellent resist removing ability and is excellent in metal corrosion prevention effect, To a resist removing composition capable of minimizing corrosion of a metal wiring of a device.

Imidazolidine, resist, removal, metal corrosion, composition

Description

Stripper composition of photoresist < RTI ID = 0.0 >

The present invention relates to a composition for removing a resist used in a photo-lithography process, and more particularly, to a composition for removing a resist, which can minimize corrosion of a metal wiring when removing a resist patterning a metal wiring, And an excellent composition for removing a resist.

Resists (photoresists) are materials that are essential for photolithography processes, and these photolithography processes can be applied to integrated circuits (ICs), large scale integration (LSI) large scale integration (VLSI), and image forming devices such as a liquid crystal display (LCD) and a plasma display device (PDP).

However, after photo-lithography processing, the resist is removed at a high temperature by the remover solution, and as the resist is removed at such a high temperature, the underlying metal film may quickly corrode by the remover solution. That is, there is a problem that the degree of corrosion of the metal wiring is accelerated by the resist removing solution.

Resist removal solutions are disclosed in U.S. Patent No. 5,417,877 and U.S. Pat. No. 5,556,482 to prevent such metal wiring corrosion problems.

In this method, there is disclosed a method for preventing corrosion of copper used as a metal wiring by using a resist removing solution to which a corrosion inhibitor is added to a mixture of an amide material and an organic amine, wherein the organic amine includes monoethanolamine as a preferred amine I have specified. Further, it discloses an appropriate amount of the corrosion inhibitor, and it is suggested that the removal power of the photoresist film is lowered when the proper amount is exceeded.

In addition, in general, amines among constituents of the resist removal solution have been mainly used as monoethanolamine, methylethanolamine, and other primary or secondary amines.

However, such chain type amines have a disadvantage in that they have a low breaking point and have a severe compositional change, and after a certain period of time, it is inconvenient to replace the entire removal solution during the process due to the change in weight and composition due to volatilization.

Disclosure of Invention Technical Problem [8] The present invention provides a composition for removing a resist, which is capable of minimizing changes in composition due to volatilization and exhibiting excellent resist removal performance, in particular, minimizing corrosion of the underlying metal film.

In order to accomplish the above object, the present invention provides a resist stripper composition comprising an imidazolidine compound represented by the following formula (1) and a solvent.

[Chemical Formula 1]

R ₁ and R ₂ are each independently or simultaneously a linear or branched C 1 -C 5 alkyl, allyl, C 1 -C 5 alkylamino, C 1 -C 5 hydroxyalkyl, or C 1 -C 5 Lt; / RTI >

Wherein the resist-removing composition comprises 1 to 70% by weight of an imidazolidine-based compound represented by Formula 1; And the remainder of the solvent.

In the present invention, the solvent may be a protonic polar solvent, aprotic polar solvent or a mixture thereof.

Hereinafter, the present invention will be described in more detail.

When the solvent itself is used in combination with a specific cyclic amine having little influence on metal wiring corrosion in the composition for removing resist, it is possible to prevent the lower film from being corroded by the galvanic phenomenon with the upper metal film, Can be removed.

Therefore, the composition for removing resist according to the present invention is advantageous in that the metal wiring hardly corrodes in the step of removing the resist patterning the metal wiring, and the resist removing ability is excellent.

Such a resist-removing composition of the present invention includes a cyclic amine and a solvent. Wherein the cyclic amine is an imidazolidine compound represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently or simultaneously a straight or branched allyl, an alkyl having 1 to 5 carbon atoms, an alkylamino having 1 to 5 carbon atoms, a hydroxyalkyl (alkyl alcohol) having 1 to 5 carbon atoms, or Alkylphenyl having 1 to 5 carbon atoms.

The imidazolidine-based compound of formula (1) serves to remove the resist and does not exhibit corrosiveness, so that the resist-removing composition containing the imidazolidine-based compound may exhibit excellent properties. Particularly, according to the present invention, use of an imidazolidine compound having a substituent has an effect of enhancing the peeling efficiency because of high penetration effect.

In the present invention, at least one imidazolidine compound represented by the following formula (1) can be selected and used.

More preferably, the imidazolidine-based compound is a compound wherein R ₁ and R ₂ in Formula (1) are each independently a hydroxyalkyl having 1 to 5 carbon atoms. For example, the imidazolidine-based compound may be selected from the group consisting of imidazolidinemethanol, 1-hydroxymethyl imidazolidine, imidazolidineethanol, 1-hydroxyethyl imidazolidine, Imidazolidinedimethanol, imidazolidinediethanol, 1,3-dihydroxyethyl imidazolidine), imidazolidinepropanol ((methoxycarbonyl) imidazolidinedimethanol, imidazolidinedimethanol, imidazolidine propanol, 1-hydroxypropyl imidazolidine), imidazolidinedipropanol, 1,3-dihydroxypropylimidazolidine, imidazolidinebuthanol, 1-hydroxybutyl imide At least one selected from the group consisting of imidazolidinedibutanol and imidazolidinedibuthanol may be used. More preferably, the imidazolidine compound may be a compound in which R ₁ and R ₂ are independently or simultaneously a hydroxyalkyl (alkyl alcohol) group having 1 to 5 carbon atoms in Formula 1, This is because the gypsum is more effective in peeling off resist or metallic foreign matter.

At this time, the resist stripping composition of the present invention may use a protonic polar aprotic solvent and aprotic polar aprotic solvent, either singly or in combination, as a solvent. Therefore, the resist-removing composition of the present invention can be composed of two-component system or three-component system.

As a preferable example, the resist-removing composition of the present invention may be a two-component composition comprising the imidazolidine-based compound of Formula 1 and a protonic polar solvent.

The resist-removing composition of the present invention may be a two-component composition comprising the imidazolidine-based compound of Formula 1 and an aprotic polar solvent.

In addition, the resist-removing composition of the present invention may be a three-component composition comprising the imidazolidine-based compound of Formula 1, a protonic polar solvent, and an aprotic polar solvent.

The protonic polar solvent used in the present invention is one in which volatilization does not occur easily due to a high boiling point when the resist removal process is carried out under high temperature conditions. This is because the performance of the exfoliation solution is maintained As shown in FIG. Also, under a high temperature condition, the surface force against the lower film quality of the resist is lowered to facilitate removal. Low freezing point and high ignition point can be advantageous in terms of storage stability.

Such a protonic polar solvent is preferably an ether alcohol which can be mixed with the compound of formula (1) and has almost no solubility with water, and it is preferable to use a glycol ether compound. More preferably, An ether alcohol having an alkyl group of 1 to 5 may be used. More specifically, the quantum solvent may include ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether Propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, diethylene glycol methyl ether, Diethyleneglycol ethyl ether, diethyleneglycol ethyl ether, diethyleneglycol propyl ether, diethyleneglycol butyl ether, dipropylene glycol methyl ether, , Dipropylene glycol Butyl ether and the like, (dipropylene glycol ethyl ether), dipropylene glycol propyl ether (dipropylene glycol propyl ether), these may be used alone or mixed with one or more selected.

In the present invention, the aprotic polar solvent serves to dissolve the polymer gel lump separated by the compound of Formula 1 finely at a unit molecular level. In particular, it is possible to prevent the phenomenon of poor resist reattachment caused mainly in the cleaning process. Examples of the aprotic polar solvent include dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAc), N-methylformamide -Dimethylimidazole, -butyrolactone, sulfolane, etc. These may be used singly or in admixture.

In the present invention, the imidazolidine-based compound of Formula 1 may be contained in an amount of 1 to 70% by weight, more preferably 1 to 30% by weight based on the composition for removing the entire resist. At this time, if the content of the imidazolidine-based compound of Formula 1 is less than 1 wt%, there is a problem that the resist is difficult to remove. If the content of the imidazolidine-based compound is excessively large, corrosion to the lower film may occur.

The solvent may be contained in an amount of 1 to 70% by weight, more preferably 1 to 30% by weight, based on the entire resist composition.

In the present invention, when a three-component system is formed by using a mixture of a protonic polar solvent and an aprotic polar solvent, the protonic polar solvent and the aprotic polar solvent preferably have a ratio of 1:99 to 30 : 70 by weight.

As a more preferable example, in the composition for removing resist according to the present invention, in the case of a three-component system, 1 to 30% by weight of an imidazolidine compound, 10 to 65% by weight of an aprotic polar solvent and the balance of a protonic polar solvent . ≪ / RTI > Preferably, the composition for removing resist may be a composition comprising 1 to 30% by weight of an imidazolidine compound, 10 to 65% by weight of a protonic polar solvent and 10 to 65% by weight of aprotic polar solvent.

Further, in the case of the present invention, monoethanolamine (MEA), 2- (2-aminoethoxyethanol) (AEE), 1- (2-hydroxyethyl) piperazine (HEP) 2-methylpiperazine, 1-methylpiperazine, 1-amino-4-methyl (1-aminoethyl) piperazine, 1- Piperazine, piperazine, 1-benzylpiperazine, and 1-phenylpiperazine. The term " cyclic amine " In the case of the chain type amine or the cyclic amine, a synergistic effect can be obtained by enhancing the resist removing power by being included in the resist removing composition. In this case, the content of the chain amine or the cyclic amine may be 1 to 20 parts by weight based on 100 parts by weight of the sum of the imidazolidine compound and the solvent.

In addition, the present invention may further comprise additives such as corrosion inhibitors and release promoters used in the resist stripper composition in a usual amount, and may contain, for example, 100 parts by weight of the sum of the imidazolinone compound and the solvent May be used in an amount of 0.1 to 5 parts by weight.

The resist stripper composition of the present invention can effectively remove the resist at a high temperature after the photolithography process but also prevent metal corrosion due to the galvanic phenomenon between the metal film on the lower part of each device and the upper film, It hardly causes corrosion. Therefore, it is suitable for use in a manufacturing process of a semiconductor element or a flat panel display element.

The composition for removing a resist according to the present invention has an excellent effect of removing a resist and has an effect of completely removing and cleaning the resist without any corrosion of unwanted metal wiring which occurs during the process. The process stability can be secured.

Best Mode for Carrying Out the Invention Hereinafter, the function and effect of the present invention will be described in more detail through specific examples of the present invention. It is to be understood, however, that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention.

<Experimental Example 1>

The resist removal performance for the single raw materials and the corrosion resistance of metals (aluminum, molybdenum, copper) were evaluated, and the results are shown in Table 1 below.

That is, in order to select a more suitable imidazolidine-based compound and a glycol ether-based solvent as a quantum-polar solvent, the following experiment was carried out.

First, to evaluate the corrosive force of the solvent on the metal, specimens having a thickness of about 2000 Å, aluminum, molybdenum, and copper deposited on the glass surface in order and applying resist and developing the film were used. (Specimen 1: size 100 mm X 100 mm)

Second, an n + a-Si: H active film specimen, which was dry etching gas, was used to evaluate the resist removal performance. After the chromium film was formed on the glass substrate, resist was applied and wet etched. : Size 100mm X 100mm) The adhesion of resist in chromium is maximized, and when the dry etching gas is applied, the resist is deformed and it is not easy to remove it as a remover, so it can be used as a test specimen for testing the resist removal power. The evaluation criteria are as follows.

(1) Evaluation Criteria for Metal Corrosion

◎ (No corrosion at all, no corrosion of 100% against the area of specimen 1)

○ (with some corrosion, if there is 20 ~ 30% corrosion on the area of specimen 1)

△ (severe corrosion, when there is 80 ~ 90% corrosion on the area of specimen 1)

X (fully eroded, 90 to 100% corrosion on the area of specimen 1)

(2) Evaluation criteria for resist removal

&Lt; / RTI &gt; &amp; cir &amp; &amp;bull; (complete removal of resist, 100% resist residue removed relative to area of specimen 2)

? (When there is a small amount of resist residue and 20 to 30% of resist residue exists in relation to the area of the test piece 2)

(When resist residue is excessive and 80 to 90% of the resist residue exists with respect to the area of the test piece 2)

× (no resist was removed at all, and a resist residue of 90 to 100% with respect to the area of the test piece 2 was present)

[Table 1]

(1) Evaluation of metal corrosion (2) Removal of resist
evaluation 30 minutes of immersion at 70 ℃ 70 ℃ for 1 minute compound aluminum molybdenum Copper Monomethanolamine × ○ × ◎ Imidazolidine &lt; / RTI &gt; ◎ ◎ ◎ ◎ Imidazolidine ethanol ◎ ◎ ◎ ◎

&Lt; Examples 1 to 4 and Comparative Examples 1 and 2 >

In order to evaluate the resist removal force and corrosion resistance for each metal wiring, a composition for removing resist was prepared by the composition and contents shown in Table 2 below.

Then, the performance of each resist stripping composition was evaluated using the test specimen used in Experimental Example 1, and the results are shown in Table 3. The evaluation criteria are the same as in Experimental Example 1 above.

[Table 2]

division Amine Quantum polar solvent Aprotic polar solvent Kinds content
(wt%) Kinds content
(wt%) Kinds content
(wt%) Example 1 Imidazolidine ethanol 5 Butyl diglycol 55 NMP 40 Example 2 Imidazolidine ethanol 20 Butyl diglycol 40 NMP 40 Example 3 Imidazolidinediethanol 5 Methyl diglycol 95 - - Example 4 Imidazolidinediethanol 20 - - DMSO 80 Comparative Example 1 Monoethanolamine 10 Butyl diglycol 50 NMP 40 Comparative Example 2 Monoethanolamine 20 Butyl diglycol 40 NMP 40 Comparative Example 3 Dimethylimidazolidinone 20 Butyl diglycol 40 NMP 40

In Table 2, butyl diglycol: diethylene glycol butyl ether

[Table 3]

division (1) Evaluation of metal corrosion (2) Evaluation of resist removal 30 minutes of immersion at 70 ℃ 70 ℃ for 1 minute aluminum molybdenum Copper Example One ◎ ◎ ◎ ◎ 2 ◎ ◎ ◎ ◎ 3 ◎ ◎ ◎ ◎ 4 ◎ ◎ ◎ ◎ Comparative Example One × ○ × ◎ 2 × △ × ◎ 3 ◎ ◎ ◎ ×

As can be seen from the results of Table 3, in comparison with Comparative Examples 1 and 2 in Examples 1 to 4 of the present invention, not only resist removal ability but also metal corrosion prevention effect is excellent.

On the other hand, Comparative Examples 1 and 2 showed a certain degree of resist removal performance, but it was found that metal corrosion was severe and thus it was not suitable for use as a resist remover. In addition, in Comparative Example 3, although the corrosion inhibiting ability against the metal was shown, the resist removal performance was lowered as the structure was slightly different from the imidazolidine based compound of the present invention.

&Lt; Examples 5 to 10 >

Using the compositions of Examples 1 to 4, a peeling liquid composition was prepared by adding a chain type or cyclic amine as shown in Table 4 below. These chain type or cyclic amines were added in the contents (parts by weight) shown in Table 4 below to 100 parts by weight of the compositions of Examples 1 to 4 above.

[Table 4]

division Composition content
(Parts by weight) Amine content
(Parts by weight) Example 5 Example 1 100 MEA 2 Example 6 Example 2 100 HEP 3 Example 7 Example 3 100 MEA 2 Example 8 Example 3 100 HEP One Example 9 Example 4 100 AEE One Example 10 Example 4 100 HEP 3

In Table 4, MEA: monoethanolamine, AEE: 2- (2-aminoethoxyethanol), HEP: 1- (2-hydroxyethyl)

The compositions of the resist stripping compositions of Examples 5 to 10 were evaluated for their performance using the specimen of Experimental Example 1, and the results are shown in Table 5 below.

[Table 5]

(1) Evaluation of metal corrosion (2) Evaluation of resist removal 30 minutes of immersion at 70 ℃ 70 ℃ for 1 minute aluminum molybdenum Copper Example 5 ◎ ◎ ◎ ◎ Example 6 ◎ ◎ ◎ ◎ Example 7 ◎ ◎ ◎ ◎ Example 8 ◎ ◎ ◎ ◎ Example 9 ◎ ◎ ◎ ◎ Example 10 ◎ ◎ ◎ ◎

The results of Table 5 also show that Examples 5 to 10 of the present invention further contain a chain amine or a cyclic amine in the composition for removing a resist, and have excellent metal corrosion inhibiting ability and resist removing ability by synergy effect .

Claims (11)

A resist stripper composition comprising an imidazolidine compound represented by the following formula (1) and a solvent. [Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently or simultaneously a hydroxyalkyl having 1 to 5 carbon atoms. The method according to claim 1, 1 to 70% by weight of an imidazolidine compound represented by the formula (1); And the remainder of the solvent. The method according to claim 1, 1 to 30% by weight of an imidazolidine compound represented by the formula (1); And the remainder of the solvent. The resist stripper composition of claim 1, wherein the solvent is a protonic polar solvent, an aprotic polar solvent, or a mixture thereof. 5. The resist stripper composition of claim 4, wherein the solvent comprises a quantitative polar solvent and an aprotic polar solvent in a weight ratio of 1:99 to 30:70. The resist stripper composition of claim 1, wherein said composition comprises from 1 to 30% by weight of an imidazolidine compound, from 10 to 65% by weight of a protonic polar solvent and from 10 to 65% by weight of an aprotic polar solvent. delete 5. The process of claim 4, wherein the protonic solvent is selected from the group consisting of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, Selected from the group consisting of ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol propyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether and dipropylene glycol propyl ether. Type resist stripper composition. 5. The method of claim 4 wherein the aprotic polar solvent is selected from the group consisting of dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methylformamide, N, -Butyrolactone and sulfolane. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The composition of claim 1 wherein the composition is selected from the group consisting of monoethanolamine, 2- (2-aminoethoxyethanol), 1- (2-hydroxyethyl) piperazine, 1- 2-methylpiperazine, 1-amino-4-methylpiperazine, 1-benzylpiperazine, and 1-amino- And 1-phenylpiperazine, in an amount of 1 to 20 parts by weight based on 100 parts by weight of the sum of the content of the imidazolidine-based compound and the solvent. The resist stripper composition according to claim 1, wherein the composition further comprises at least one additive selected from the group consisting of a corrosion inhibitor and a release promoter.