KR20060024478A - Photoresist Stripper Composition - Google Patents

Abstract

The present invention relates to a photoresist stripper composition, and provides a photoresist stripper composition comprising a cyclic amine, a solvent, and a stripping accelerator. The present invention also provides a photoresist stripper composition comprising a cyclic amine, a solvent, a corrosion inhibitor and a stripping accelerator.

The photoresist stripper composition of the present invention is not only applied to the general process of applying isopropyl alcohol (hereinafter referred to as 'IPA') rinsing in the manufacture of LCD modules, but also to the metal wiring when applied to the recent process of omitting the IPA rinse process. In particular, the peeling force can be greatly improved without additional corrosion effects.

Photoresist stripper composition, improved peel strength

Description

Photoresist Stripper Composition {Composition for removing a photoresist}

The present invention is a three-component system comprising a cyclic amine for removing the photoresist used for forming the metal wiring, a two-component peeling solution containing a solvent or a corrosion inhibitor for preventing corrosion due to the galvanic effect in the composition. It is related with the peeling liquid composition for photoresist removal which can improve the peeling force of a peeling liquid composition by adding a peeling promoter to the above peeling liquid.

Photolithography process is used to form metal wiring in semiconductor devices such as integrated circuits (ICs), high integrated circuits (LSI), ultra high integrated circuits (VLSI), and liquid crystal displays (LCDs). It is done.

In order to remove the resist used in the photoresist process, a solution consisting of phenol and its derivatives, alkylbenzenesulfonic acid, and chloride-based organic solvents was used in the beginning of the industry. However, these peeling agents contained phenolic compounds and chlorine-based organic solvents, which are toxic, corrosive to the lower metal layer, difficult to treat the waste solution, and insoluble in water, making it difficult to avoid complicated rinsing processes after peeling.

In addition, the etching conditions of the metal and the oxide film are severe due to the miniaturization tendency of the metal wiring to be processed, thereby increasing the damage of the photoresist and deteriorating the resist. For this reason, even if treated with an organic solvent, since the resist remains on the substrate, a composition having a high peeling force is required so that there is no residue.

In order to improve this disadvantage, a water-soluble releasing agent composed of an organic amine and a solvent has been proposed and used.

In the case of a stripping solution composed of an organic amine and a solvent, it is known as a basic combination of stripping solutions currently used in most processes. However, the change of the metal wiring is being made at a rapid rate all the time and the change of the stripping liquid is required accordingly.

In addition, chain amines and cyclic amines are currently used in the liquid crystal display manufacturing process. Chained amines are strongly alkaline and can be strongly penetrated into the polymer matrix of the denatured or crosslinked resist under various process conditions such as dry or wet etching, ashing or ion implantation processes to break or weaken the bonds present in or between molecules. It has been used since the beginning of the industry to show a role of facilitating removal by liquid.

However, the miniaturization of the metal wiring has been required to improve the peeling force by promoting the modification of the photoresist by the etching process, and the change of the metal wiring used and the change of the metal wiring into the double or triple structure have the effect of corrosion on the wiring. It requires a minimum.

Therefore, cyclic amines have been proposed in order to minimize corrosion on the metal wirings of the existing chain-type amines, and corrosion inhibitors for preventing galvanic corrosion occurring in double or triple metal wirings rather than single film metal wirings are proposed. It is used.

However, the prior art has achieved a desired result in terms of corrosion protection, but there is no obvious improvement in terms of improvement of peeling force.

In order to solve the problems in the prior art as described above, it is an object of the present invention to provide a photoresist stripper composition which can promote the activation of the cyclic amine to achieve an improvement in the peel force.

Another object of the present invention is to provide a peeling liquid composition for removing photoresist that promotes activation of the cyclic amine, thereby improving peeling force and at the same time minimizing corrosion influence on metal wiring.

In order to achieve the above object, the present invention provides a peeling liquid composition for removing a resist comprising a cyclic amine, a solvent and a peeling accelerator.

The present invention also provides a peeling liquid composition for removing a resist containing a cyclic amine, a solvent, a corrosion inhibitor and a peeling accelerator.

The composition for removing a resist of the present invention may be included in an amount of 0.1 to 5 parts by weight of a peel force promoter based on 100 parts by weight of a composition containing 1 to 50% by weight of a cyclic amine and 50 to 99% by weight of a bipolar polar solvent. desirable.

In addition, the composition for removing a resist of the present invention is included in an amount of 0.1 to 10 parts by weight of an anticorrosive agent based on 100 parts by weight of a composition containing 1 to 50% by weight of a cyclic amine and 50 to 99% by weight of a protic polar solvent. And it is preferable to contain in the quantity of 0.1-5 weight part of peeling accelerators.

In addition, the resist removal composition of the present invention comprises in an amount of 0.1 to 5 parts by weight of a peeling accelerator with respect to 100 parts by weight of a composition containing 1 to 50% by weight of a cyclic amine and 50 to 99% by weight of an aprotic polar solvent. It is preferable.

In addition, the resist removal composition of the present invention comprises in an amount of 0.1 to 10 parts by weight of a corrosion inhibitor with respect to 100 parts by weight of a composition containing 1 to 50% by weight of a cyclic amine, and 50 to 99% by weight of an aprotic polar solvent. It is preferable to contain in the quantity of 0.1-5 weight part of peeling accelerators.

In addition, the resist removal composition of the present invention is peeled with respect to 100 parts by weight of a composition containing 1 to 50% by weight of the cyclic amine, and 10 to 80% by weight of the protic polar solvent and 15 to 75% by weight of the aprotic polar solvent. It is preferably included in an amount of 0.1 to 5 parts by weight of the accelerator.

In addition, the resist removal composition of the present invention is corroded to 100 parts by weight of the composition comprising 1 to 50% by weight of the cyclic amine, and 10 to 80% by weight of the protic polar solvent and 15 to 75% by weight of the aprotic polar solvent. It is preferably included in an amount of 0.1 to 10 parts by weight of the inhibitor and in an amount of 0.1 to 5 parts by weight of the release accelerator.

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

The present invention relates to a photoresist stripper composition, to provide a photoresist stripper composition comprising a small amount of a peeling accelerator for increasing the peeling force on a resist in a stripper solution composed of a cyclic amine and a solvent. In addition, the present invention includes a small amount of a peeling accelerator to increase the peeling force to the resist in a three-component or more composition containing a corrosion inhibitor for minimizing corrosion to the metallization patterned in the peeling solution consisting of a cyclic amine, a solvent. It provides the photoresist stripping liquid composition. The present invention improves the removal ability of the cyclic amine by adding a small amount of a peeling accelerator to the stripper composition, and at the same time maintains the corrosion characteristics of the metal wiring of the cyclic amine.

The cyclic amine used in the present invention has the characteristics of improving the corrosion characteristics of the metal wirings of the chain amine and improving the stability of the process due to the high boiling point.

The cyclic amine is 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) methylpiperazine, N- (3-aminopropyl) mol Porin, 2-methylpiperazine, 1-methylpiperazine, 1-amino-4-methylpiperazine, 1-benzyl piperazine, 1-phenylpiperazine, etc., which may be used alone or in combination of two or more thereof. .

In the present invention, the content of the cyclic amine is most preferably used in an amount of 1 to 50% by weight based on the total amount of the amine and the solvent when two or more selected from the compounds. At this time, if the content of the amine is less than 1% by weight, there is a problem that the resist removal performance is lowered, and when the content of the amine exceeds 50% by weight, the corrosion may be severe.

In addition, the solvent used in the present invention is preferably a protic polar solvent, an aprotic polar solvent or a mixture thereof.

In the present invention, when the process of removing the resist under high temperature conditions, the quantum polar solvent does not easily volatilize due to the high boiling point so that the performance of the stripping solution can be continuously maintained by maintaining the composition ratio of the initial stripping solution. Do it. In addition, under high temperature conditions, the surface force of the lower film of the resist is lowered to facilitate removal. Low freezing point and high flash point can also be advantageous in terms of storage stability.

These proton polar solvents can be mixed with amines and have almost infinite solubility with water. Examples of diethylene glycol monoalkyl ethers include diethylene glycol methyl ether, diethylene glycol ethyl ether, and diethylene glycol butyl ether. It can be used alone or in combination of one or more.

In the present invention, the content of the quantum polar solvent in the case of a two-component composition, it is preferable to use 50 to 99% by weight relative to the total amount of the amine and the solvent, when the content is less than 50% by weight relative amine content This increases the corrosion, and if it exceeds 99% by weight, the removal performance is reduced. In addition, in the case of three-component or more composition, the content of the protic polar solvent is preferably used in an amount of 10 to 80% by weight based on the total amount of the amine and the solvent, and when the content is less than 10% by weight, the polar solvent and the amine are relatively unprotonated. As the weight percent of the compound increases, corrosion of the metal wiring becomes severe, and the ability to dissolve the polymer gelled by the amine compound and the aprotic polar solvent is insufficient, resulting in the ability to remove the resist, which is lower than 80 wt%. If there is a relatively low weight percent of the aprotic polar solvent, there is a problem that the ability to remove the resist falls.

In the present invention, the aprotic polar solvent functions to dissolve the polymer gel mass separated by the amine compound at a unit molecular level. In particular, it is possible to prevent the resist re-adhesive defect mainly caused in the cleaning process. As the aprotic polar solvent, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylimidazole, γ-butyro Lactone, sulfolane and the like, these may be used alone or in combination of one or more.

In the present invention, when the content of the aprotic polar solvent is a two-component composition, it is preferable to use 50 to 99% by weight based on the total amount of the amine and the solvent, and if the content is less than 50% by weight, the content of the amine is relatively Corrosion is increased, and when it exceeds 99 weight%, resist removal performance falls. In addition, in the case of three-component or more composition, the content of the aprotic polar solvent is preferably used in an amount of 10 to 80% by weight, more preferably 15 to 70% by weight, based on 10% by weight, based on the total amount of the amine and the solvent. If it is less than%, there is a problem that the resist removal ability is lowered, and if it exceeds 80% by weight, the corrosion of metal wiring is severe, and the weight removal rate of glycol ether, which is a relatively bipolar polar solvent, is reduced, resulting in poor resist removal ability and cleaning ability. have.

The corrosion inhibitor is effective to prevent corrosion by using a compound containing an element such as -N-, -S-, -O- with a non-covalent electron pair, especially in the case of -OH, -SH group Excellent corrosion protection by chemical adsorption.

Corrosion inhibitors in the present invention include compounds of mercapto compounds such as alkyl gallate compounds having an alkyl group of C ₁ to C ₁₂ , mercaptobenzimidazole, mercaptomethylimidazole, etc .; And triazole compounds such as tolytriazole, benzotriazole, and carboxylic benzotriazole.

In the present invention, the amount of the corrosion inhibitor may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total composition of the amine and the solvent. In this case, if the content is less than 0.1 parts by weight, corrosion may occur in the metal wiring. If the content is more than 10 parts by weight, the peeling force may be reduced and the surface may be changed.

The peeling accelerator has a feature of increasing the activation of the peeling liquid compositions and at the same time maintaining the phenomenon of corrosion protection against metal wiring.

The peeling accelerator in the present invention can be used by selecting one or more from the group consisting of compounds represented by the following formula (1), (2), and (3).

[Formula 1]

[Formula 2]

[Formula 3]

(In Formulas 1 and 2, R is an alkyl group having 1 to 4 carbon atoms, and R 'is an alkyl group having 1 to 10 carbon atoms or hydroxy alkyl (alkyl alcohol).)

The photoresist stripper composition for removing the photoresist of the present invention has a very good removal force for removing a resist when used in a photolithography process including a stripping accelerator, and minimizes corrosion of the patterned metal wiring as well as an excellent stripping force when the corrosion inhibitor is included. can do.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, an Example is for illustrating this invention and is not limited only to these.

EXAMPLE

Corrosion and peelability tests for evaluating the photoresist stripper composition of the present invention having the composition shown in Table 1 below were used.

a) peel test                     

A test was conducted to confirm the pattern of peeling force that changes when a peeling accelerator is added to the photoresist stripper composition.

To test the removal efficiency of the photoresist stripper composition, a commonly used forge type resist composition (DTFR-3650B, Dongjin Semichem Chem) was spin coated on bare glass at 2500 rpm and a hot plate Heat treatment was carried out at 100 ° C. for 90 sec. The coating film thickness of 1.5 µm was measured in nanometer units, and then the wafer was heat-treated at 170 ° C. for 20 minutes after exposure and development to obtain a resist film. This wafer was immersed in the peeling solution described in the Example and the comparative example, maintaining the peeling solution temperature at 70 degreeC, and peeling performance was evaluated based on the following evaluation criteria. Immersion was carried out immediately after preparation and after 24 hours of volatilization at 70 ° C. to evaluate the peeling performance.

◎…. Removed within 2 minutes after sleeping

○…. Removed within 3 minutes after sleeping

Δ. Removed within 4 minutes after sleeping

×… Can't be removed within 6 minutes after sleeping

The positive-type resist composition used here consists of an alkali-soluble resin as a film formation component, a quinone diazide type compound as a photosensitive component, and the organic solvent which can dissolve these.

As the alkali-soluble resin, a novolak resin was synthesized by condensation of a mixture of formaldehyde and cresol isomer under an acid catalyst. The proportion of cresol isomers in the cresol isomer mixture was 60 wt% for m-cresol and 40 wt% for p-cresol.                     

As the quinone diazide compound as the photosensitive component, 2,3,4,4-tetrahydroxybenzophenone and 1,2-naphthoquinone diazide-5-sulfonyl chloride are esterified in the presence of a triethylamine catalyst. 2,3,4,4-detrahydroluxbenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester was synthesized and used.

20 g of the novolak resin and 5 g of the photosensitive compound synthesized above were dissolved in 75 g of ethylene glycol monoethyl ether acetate, and filtered through a 0.2 µm filter to obtain a positive photosensitive resist composition.

Composition (part by weight) of the stripping solution evaluation Amine Polar solvent Glycol ether Corrosion inhibitor Peeling force promoter Peelability Kinds amount Kinds amount Kinds amount Kinds amount Kinds amount ◎       Example One HEP 5 NMP 35 DEGBE 60 MG One ADD-1 0.5 ◎ 2 AEP 5 NMP 35 DEGBE 60 MG One ADD-1 0.5 ◎ 3 BP 10 DMSO 30 DEGBE 60 MG One ADD-1 One ◎ 4 PP 10 DMAc 30 DEGBE 60 MG 0.5 ADD-2 3 ◎ 5 HEP 20 DMSO 30 DEGBE 50 MG 0.5 ADD-2 0.1 ◎ 6 AEP 20 DMAc 30 DEGBE 50 MG 0.5 ADD-2 0.1 ◎ 7 BP 20 NMP 30 DEGBE 50 MMB 0.5 ADD-3 One ◎ 8 PP 20 NMP 30 DEGBE 50 MMB 0.5 ADD-3 3 ◎ 9 HEP 10 DMSO 30 DEGBE 60 ADD-1 0.5 ◎ 10 AEP 10 DMAc 30 DEGBE 60 ADD-1 0.5 ◎ 11 BP 10 NMP 30 DEGBE 60 ADD-1 3 ◎ 12 PP 10 NMP 30 DEGBE 60 ADD-2 5 ◎ 13 HEP 10 NMP 30 DEGEE 60 ADD-2 0.1 ◎ 14 AEP 10 NMP 30 DEGEE 60 ADD-2 0.1 ◎ 15 BP 10 NMP 30 DEGEE 60 ADD-3 5 ◎ 16 PP 10 NMP 30 DEGEE 60 ADD-3 5 ◎ 17 HEP 20 NMP 80 MG One ADD-1 0.5 ◎ 18 AEP 20 NMP 80 MG One ADD-2 0.5 ◎ 19 HEP 20 NMP 80 ADD-2 0.1 ◎ 20 AEP 20 NMP 80 ADD-2 0.1 ◎ 21 HEP 30 DEGBE 70 MG 0.5 ADD-1 0.5 ◎ 22 AEP 30 DEGBE 70 MG 0.5 ADD-3 0.5 ◎ 23 HEP 40 DEGBE 60 ADD-2 0.1 ◎ 24 AEP 40 DEGBE 60 ADD-3 0.1 ◎   Comparative Example One HEP 10 NMP 30 DEGBE 60 MG One × 2 AEP 10 NMP 30 DEGBE 60 MG One △ 3 BP 10 DMSO 30 DEGBE 60 MG One × 4 PP 10 DMAc 30 DEGBE 60 MG 0.5 × 5 HEP 20 DMSO 30 DEGBE 50 MG 0.5 ○ 6 AEP 20 DMAc 30 DEGBE 50 MG 0.5 △ 7 BP 40 NMP 10 DEGBE 50 MG 0.5 × 8 PP 40 NMP 30 DEGBE 30 MG 0.5 × 9 MEA 10 NMP 30 DEGBE 60 △ 10 MIPA 10 NMP 30 DEGBE 60 × 11 NMEA 10 NMP 30 DEGBE 60 △ 12 AEE 10 NMP 30 DEGBE 60 ×

Note) The evaluation of the corrosiveness is a comparison between before and after the addition of the peel force promoter, so the evaluation of the comparative example is not shown. Abbreviations in the table are as follows.

MEA: Monoethanolamine                     

NMEA: N-methylethanolamine

MIPA: Methylisopropylamine (1-Amino-2-propanol)

AEE: 2- (2-aminoethoxyethanol) (2- (2-Aminoethoxy) ethanol)

HEP: 1- (2-hydroxyethyl) piperazine (1- (2-Hydroxyethyl) piperazine)

AEP: 1- (2-aminoethyl) piperazine (1- (2-Aminoethyl) piperazine)

PP: Phenyl piperazine

BP: Benzyl piperazine

DEGBE: Diethyleneglycolethylether

DEGEE: Diethyleneglycolethylether

NMP: N-methyl-pyrrolydone

DMSO: Dimethylsulfoxide

DMAc: Dimethylacetamide

MG: Methyl gallate

MMB: Mercapto methyl benzimidazole

ADD-1: Chemical represented by Chemical Formula 1

ADD-2: Chemical represented by Chemical Formula 2

ADD-3: Chemical represented by Chemical Formula 3

The peeling liquid composition for removing photoresist according to the present invention is excellent in removing the resist, and at the same time, it is effective to completely remove and clean the resist without corrosion of unwanted metal wires generated during the process. Small changes can ensure process stability.

Claims (17)

A peeling liquid composition for removing a resist comprising a cyclic amine, a solvent and a peeling accelerator. A peeling liquid composition for removing a resist comprising a cyclic amine, a solvent, a corrosion inhibitor, and a peeling accelerator. 3. The cyclic amine according to claim 1 or 2, wherein the cyclic amine is 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) methylpiperazine , N- (3-aminopropyl) morpholine, 2-methylpiperazine, 1-methylpiperazine, 1-amino-4-methylpiperazine, 1-benzyl piperazine, and 1-phenyl piperazine A stripper liquid composition for removing a resist that is selected from one or more kinds. The stripper composition of claim 1 or 2, wherein the content of the amine is in an amount of 1 to 50% by weight based on the total amount of the amine and the solvent. The stripper composition for removing a resist according to claim 1 or 2, wherein the solvent is a proton polar solvent, an aprotic polar solvent or a mixture thereof. The method of claim 5, wherein the proton polar solvent is ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, and diethylene glycol propyl. A stripper composition for removing a resist, which is a glycol ether compound selected from the group consisting of ethers. The method of claim 5, wherein the aprotic polar solvent is N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide and N, N-dimethylimidazole. , (gamma) -butyrolactone, and sulfolane, wherein the stripper composition for removing a resist is selected from at least one member. 3. The stripper composition of claim 2, wherein the corrosion inhibitor is selected from the group consisting of triazole compounds, mercapto compounds, alkyl gallate compounds, and mixtures thereof. 3. The stripper composition of claim 2, wherein the corrosion inhibitor is present in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total composition of the amine and the solvent. The peeling liquid composition for removing a resist according to claim 1 or 2, wherein the peeling accelerator is selected from the group consisting of compounds represented by the following general formulas (1), (2), and (3). [Formula 1]

[Formula 2]

[Formula 3]

(In the formulas (1) and (2), R is an alkyl group having 1 to 4 carbon atoms, and R 'is an alkyl group having 1 to 10 carbon atoms or hydroxy alkyl (alkyl alcohol).) The peeling liquid composition for removing a resist according to claim 1 or 2, wherein the peeling accelerator is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total composition of the amine and the solvent. The method of claim 1, A peeling liquid composition for removing a resist comprising 0.01 to 10 parts by weight of a peeling accelerator with respect to 100 parts by weight of a composition containing 1 to 50% by weight of a cyclic amine and 50 to 99% by weight of a protic polar solvent. The method of claim 2, Stripping solution for removing a resist containing 0.1 to 10 parts by weight of a corrosion inhibitor and 0.01 to 10 parts by weight of a peeling accelerator with respect to 100 parts by weight of a composition containing 1 to 50% by weight of a cyclic amine and 50 to 99% by weight of a protic polar solvent. Composition. The method of claim 1, A peeling liquid composition for removing a resist comprising 0.01 to 10 parts by weight of a peel accelerator with respect to 100 parts by weight of a composition containing 1 to 50% by weight of a cyclic amine and 50 to 99% by weight of an aprotic polar solvent. The method of claim 2, Stripping solution for removing a resist comprising 0.1 to 10 parts by weight of a corrosion inhibitor and 0.01 to 10 parts by weight of a peeling accelerator with respect to 100 parts by weight of a composition containing 1 to 50% by weight of a cyclic amine and 50 to 99% by weight of an aprotic polar solvent. Composition. The method of claim 1, A resist removal composition comprising 0.01 to 10 parts by weight of a peeling accelerator with respect to 100 parts by weight of a composition containing 1 to 50% by weight of a cyclic amine, 10 to 80% by weight of a protic polar solvent, and 15 to 70% by weight of an aprotic polar solvent. . The method of claim 2, 0.1 to 10 parts by weight of a corrosion inhibitor and 0.01 to 10 parts by weight of a corrosion inhibitor, based on 100 parts by weight of the composition including 5 to 30% by weight of a cyclic amine, 10 to 80% by weight of aprotic polar solvent, and 15 to 70% by weight of an aprotic polar solvent. A resist removal composition comprising a weight part.