KR20150122956A - Resist stripper composition - Google Patents

Abstract

The present invention relates to a stripper composition and, more specifically, to a resist stripper composition having excellent resist removing functions, which includes a compound of chemical formula 1 or chemical formula 2, and minimizes corrosion of metal wires in a peeling process. In the chemical formula 1 and chemical formula 2, R is respectively one or more functional groups selected from the group consisting of hydrogen, a C1-10 alkyl group, a cycloalkyl group, an alkoxyalkyl group, a hydroxyl group, a hydroxyl alkyl group, an amine group, an aminoalkyl group, an aryl group, and an arylalkyl group.

Description

RESIST STRIPPER COMPOSITION [

The present invention relates to a resist stripper composition, and more particularly, to a resist stripper composition capable of minimizing corrosion of a metal wiring in a stripping process and having excellent resist removing ability.

In recent years, efforts have been made to increase the number of pixels per unit area as the demand for high resolution implementation of flat panel displays increases. In accordance with this trend, reduction of the wiring width is required, and in order to cope with this, the dry etching process has been introduced, and the process conditions have become increasingly severe. In addition, due to the enlargement of the flat panel display device, an increase in the signal speed in the wiring is also required, and wiring materials such as molybdenum and copper have been put to practical use. Accordingly, the required performance of the stripping solution used in the stripping process, which is a resist stripping process, is increasing.

Concretely, it is required to have a corrosion preventing ability against metals such as aluminum, copper, and silver, while retaining a considerable level of peeling force for metal wiring. The peeling step for removing the resist is performed by a peeling liquid at a high temperature. Since corrosion of metal wiring under the resist can be accelerated by such a high-temperature peeling liquid, a resist peeling solution Research is required.

Korea Patent Publication No. 2011-0068483

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resist stripper composition which can minimize the corrosion of metal wiring in a stripping process and has excellent resist removal properties.

According to an aspect of the present invention,

There is provided a resist stripper composition comprising at least one compound selected from compounds represented by the following general formulas (1) and (2).

[Chemical Formula 1]

(2)

R in the formulas (1) and (2) each represents a hydrogen atom, a C1-C10 alkyl group, a cycloalkyl group, an alkoxyalkyl group, a hydroxyl group, a hydroxyalkyl group, an amine group, an aminoalkyl group, an aryl group and an arylalkyl group Or more functional group.

The resist stripper composition of the present invention has an excellent resist removing effect and can completely remove resist residues and can provide an effect of minimizing the corrosion of the metal wiring caused in the stripping process.

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

The present invention

There is provided a resist stripper composition comprising at least one compound selected from compounds represented by the following general formulas (1) and (2).

[Chemical Formula 1]

(2)

R in the formulas (1) and (2) each represents a hydrogen atom, a C1-C10 alkyl group, a cycloalkyl group, an alkoxyalkyl group, a hydroxyl group, a hydroxyalkyl group, an amine group, an aminoalkyl group, an aryl group and an arylalkyl group Or more functional group.

(A) a compound represented by the formula To 2  The compounds to be displayed

The compounds represented by the formulas (1) and (2) serve to dissolve or swell the resist so that the resist can be easily removed from the substrate. Further, it is possible to minimize the corrosion of metal wiring including copper or aluminum, thereby minimizing the corrosion of metal wiring.

The compounds represented by the general formulas (1) and (2) are preferably selected from the group consisting of hexahydropyridazine, 1-methylpiperidazine, 2-hexahydropyridazin-1-yl-ethanol, hexahydropyrimidine, Methyl-hexahydropyrimidine, 1-ethyl-hexahydropyrimidine, 1- (3- (4-methylpiperazin-1- Aminopropyl) hexahydropyrimidine, 1-isopropylhexahydropyrimidine, 1-t-butyl-hexahydropyrimidine, 1-n-butylhexahydropyrimidine, 1-cyclohexylhexahydropyrimidine and N- -Hexahydropyrimidine, and the like can be used.

The compounds represented by Chemical Formulas 1 and 2 may be contained in an amount of 0.1 to 30% by weight based on the total weight of the resist stripping composition. If the chemical formula is less than 0.1% by weight, the compounding ability of the resist stripping composition may be insufficient. . On the other hand, if it exceeds 30% by weight, the amount of the organic solvent may decrease, which may affect the role of the rinsing and the ability to increase the number of sheets.

(B) an organic solvent

The resist stripper composition may further include an organic solvent. At this time, the organic solvent may be either a protonic polar solvent or an aprotic polar solvent, either alone or as a mixed solvent thereof.

The organic solvent of the present invention further increases the dissolution rate of the photoresist which is swollen and dispersed by the solvent, and helps the rinse force to be strengthened in the DI rinse process used after the exfoliation solution is cleaned. It helps to rinse the dispersed photoresist cleanly with the DI water after the peeling process, so it can shorten the DI rinse process time, eliminate the remaining foreign matter, and help the yield. One of the problems that may appear in metal film quality is that the problem related to staining can be solved because it is cleanly removed from the DI rinse process when a quantitative polar solvent is added in relation to the stain.

The organic solvent of the present invention is preferably a mixture of a protonic polar solvent and aprotic polar solvent or a mixture of a protonic polar solvent and aprotic polar solvent.

Preferable examples of the protonic polar solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, di Ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene Alkylene glycol monoalkyl ethers such as glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether, and triethylene glycol methyl butyl ether. These may be used alone or in combination of two or more selected from the group consisting of 1 The species may be used singly or two or more species may be used together.

On the other hand, the aprotic polar solvent serves to dissolve the resist polymer gelled by the alkali-based compound and smoothly disperses the photoresist to solvation. As an organic solvent highly effective in dissolving a photoresist, it is a component which improves the peeling performance by accelerating the penetration of the organic amine compound into the solidified photoresist in a short time. In addition, it facilitates the removal of the peeling liquid by the water during the rinsing of the deionized water after the peeling of the resist, thereby minimizing the re-adsorption / reattaching of the peeling liquid and the dissolved resist. It is preferable that the water-soluble polar solvent is not too high or low in boiling point for proper peeling force, and may be mixed and used.

Preferable examples of the aprotic polar solvent include pyrrolidone compounds such as N-methylpyrrolidone (NMP) and N-ethylpyrrolidone; Imidazolidinone compounds such as 1,3-dimethyl-2-imidazolidinone and 1,3-dipropyl-2-imidazolidinone; lactone compounds such as? -butyrolactone; Sulfoxide compounds such as dimethyl sulfoxide (DMSO) and sulfolane; Phosphate compounds such as triethyl phosphate, tributyl phosphate and the like; Carbonate compounds such as dimethyl carbonate, ethylene carbonate, and the like; But are not limited to, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N- (2-hydroxyethyl) Amide compounds such as N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide, These can be used alone or in admixture of two or more.

The content of the organic solvent of the present invention is preferably 70 to 99.9% by weight based on the total weight of the entire composition, and if it is less than 70% by weight, the ability to contain dissolved photoresist in the solution is poor, . On the other hand, when the content exceeds 99.9% by weight, the content of the other components is decreased, which affects the damage and peeling force.

In the present invention, when a three-component system comprising a pyrazolidine-based compound represented by the general formula (1) is prepared by using a mixture of a protonic polar solvent and an aprotic polar solvent, the protonic polar solvent and the aprotic polar solvent have a ratio of 1 : 99 to 30:70 by weight.

(C) amine

The resist stripping composition may further include an amine. The amines can penetrate the polymer matrix of the modified or crosslinked resist strongly under various process conditions such as dry or wet etching, ashing or ion implant processing, It serves to break the bond. An empty space is formed in a structurally weak portion in the resist remaining on the substrate, thereby deforming the resist into an amorphous polymer gel mass state so that the resist attached on the substrate can be easily removed.

The amines are preferably alkanolamines, piperazines and alkylamines, more preferably monoethanolamine, diethanolamine, diglycolamine, triethanolamine, monoisopropanolamine, N-methylethanolamine, N-methyl- Diethanolamine, dimethyl ethanolamine, 2- (2-aminoethoxyethanol), 1- (2-hydroxyethyl) piperazine, 1- Methylpiperazine, 1-amino-4-methylpiperazine, 1-benzylpiperazine, 1-phenylpiperazine, Diethylamine, methylethylamine, and the like.

The amine may be used in an amount of 0.5 to 20 wt%, more preferably 1 to 5 wt%, based on the total weight of the resist stripper composition.

(D) Corrective agent

The resist stripping composition may further include a rust preventive agent. The anticorrosion agent may be included in the resist stripper composition to prevent corrosion of the metal wiring.

Specific examples of the anticorrosive agent include benzotriazole, tolythriazole, methyltolytriazole, 2,2 '- [[[benzotriazole] methyl] imino] bisethanol, 2,2'- Methyl] imino] bis methanol, 2,2 '- [[[ethyl-1-hydrogen benzotriazol-1-yl] methyl] Ethanol, 2,2 '- [[[methyl-1-hydrogen-benzotriazol-1-yl] methyl] imino] Yl] methyl] imino] bismethylamine, 2,2 '- [[[aminomethyl] 1 hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol;

Quinone compounds such as 1,2-benzoquinone, 1,4-benzoquinone, 1,4-naphthoquinone, and anthraquinone;

Sugar alcohols such as mannitol, xylitol and sorbitol;

Alkyl gallates such as catechol, pyrogallol, methyl gallate, propyl gallate, dodecyl galeate, octyl galeate and gallic acid; And

Maleic amide esters, maleic amide esters, maleic amide esters, fumaric amide esters, oxalic amide esters, malonic amide esters, glutaric amide esters, acetic amide esters, lactic amide esters, And organic acid amide esters such as tartaric acid esters, tartaric acid esters, tartaric acid esters, tartaric acid esters, tartaric acid esters, tartaric acid esters, tartaric acid esters, tartaric acid esters, tartaric acid esters, tartaric acid esters and tartaric acid esters.

The anticorrosive agent may be used at a conventional level, for example, 0.1 to 5% by weight based on the total weight of the resist stripper solution.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the following examples and comparative examples are provided for illustrating the present invention, and the scope of the present invention is not limited by the following examples and comparative examples.

< Example  1 to 12 and Comparative Example  1 to 4>

The resist stripper composition was prepared based on the components and contents shown in Table 1 below.

                                              (Unit: wt%) The compound (A) of the formula (1) or (2) Organic solvent (B) Amines (C) The anti-corrosion agent (D) Kinds content Kinds content Kinds content Kinds content Example 1 a-1 5 NMP 95 Example 2 a-1 10 NMP 90 Example 3 a-1 5 BDG 93 DGA 2 Example 4 a-1 10 DMSO 90 Example 5 a-1 9 THFA 88.5 DGA 2 BTA 0.5 Example 6 a-2 15 NMP 85 Example 7 a-2 10 NMF 90 Example 8 a-2 7 BDG 92.5 BTA 0.5 Example 9 a-2 5 NMP 93 DGA 2 Example 10 a-2 8 NMP 90.5 DGA One BTA 0.5 Example 11 a-1 5 DMSO 92.5 DGA 2 BTA 0.5 Example 12 a-1 5 NMF 91.5 HEP 3 BTA 0.5 Comparative Example 1 NMP 100 Comparative Example 2 a-3 2 NMP 98 Comparative Example 3 a-3 2 NMP 95 DGA 3 Comparative Example 4 NMP 95 DGA 5

&Lt; Compound (A) of formula (1) or (2)

a-1: 2-Tetrahydropyrimidin-1-yl-ethanol

a-2: 1-Ethylhexahydropyrimidine

a-3: pyrazine

&Lt; Solvent (B) >

DMSO: dimethylsulfoxide

NMP: N-methylpyrrolidone

NMF: N-methylformamide

BDG: butyl diglycol (diethylene glycol monobutyl ether)

THFA: tetrahydroperfuryl alcohol

&Lt; Amine (C) >

DGA: diglycolamine

HEP: 1- (2-hydroxyethyl) piperazine

<Anti-Corrective Agent (D)>

BTA: benzotriazole

Experimental Example  One. Resist Peeling liquid  Of the composition Peelability  evaluation

The following experiments were conducted to evaluate the resist stripping properties of the resist stripper compositions of Examples 1 to 12 and Comparative Examples 1 to 4.

Specimens (size 20 mm x 20 mm) attached to copper (Cu) metal wirings and insulating films were used in the experiment for altered photoresist residues and polymer residues generated after plasma etching or high temperature ashing.

The specimen having the Cu metal wiring in the SiO ₂ insulating film was immersed in each of the peeling liquids having the temperature of 65 ° C (Examples 1 to 12 and Comparative Examples 1 to 4) for 20 minutes. Then, the specimen was taken out from the peeling solution, rinsed with ultra-pure water for 1 minute, and dried using nitrogen gas.

Then, using a scanning electron microscope, the SiO ₂ insulating film was evaluated for the peelability of the photoresist residue remaining after dry etching or high-temperature ashing from the substrate having the Cu metal wiring. The results are shown in Table 2 below.

[Evaluation criteria for peelability]

◎: Very good

○: Good

DELTA: presence of some residues

X: Residual can not be removed

Experimental Example  2. Resist Peeling liquid  Of the composition Improvisation  evaluation

In order to evaluate the corrosion resistance of the resist stripper compositions of Examples 1 to 12 and Comparative Examples 1 to 4, the following experiment was conducted.

The anticorrosion property evaluation was carried out in the same manner as in the peelability evaluation of Experimental Example 1 except that the evaluation of the peelability of the photoresist residue remained on the glass was changed to the evaluation of the anticorrosiveness of the metal wiring.

Then, the degree of the metal wiring was evaluated by dry etching or high-temperature etching from the substrate having the Cu metal wiring in the SiO ₂ insulating film using a scanning electron microscope. The results are shown in Table 2 below.

[Evaluation criteria for Cu etchability]

◎: No corrosion

○: almost no corrosion

Δ: Partial corrosion, surface roughness change

X: etch occurred

Peelability Cu anticorrosive Example 1 ○ ○ Example 2 ○ ○ Example 3 ◎ ○ Example 4 ○ ○ Example 5 ◎ ◎ Example 6 ○ ○ Example 7 ○ ○ Example 8 ○ ◎ Example 9 ◎ ○ Example 10 ◎ ◎ Example 11 ◎ ◎ Example 12 ◎ ◎ Comparative Example 1 X ◎ Comparative Example 2 △ ◎ Comparative Example 3 ◎ X Comparative Example 4 ◎ X

As shown in Table 2, it was confirmed that the resist stripper compositions of Examples 1 to 12, which are the resist stripper compositions of the present invention, not only had excellent peelability but also excellent corrosion resistance against metals including Cu. On the other hand, the resist stripper compositions of Comparative Examples 1 to 4, which do not contain at least one compound selected from the compounds represented by formulas (1) and (2) of the present invention, show inadequate results in at least one of the peelability and the corrosion resistance evaluation Respectively.

As described above, the resist stripper composition comprising at least one compound selected from the compounds represented by the general formulas (1) and (2) provided by the present invention has excellent resist strippability and metal corrosion resistance I could confirm.

Claims (11)

A resist stripper composition comprising at least one compound selected from the group consisting of compounds represented by the following formulas (1) and (2).

[Chemical Formula 1]

(2)
R in the formulas (1) and (2) each represents a hydrogen atom, a C1-C10 alkyl group, a cycloalkyl group, an alkoxyalkyl group, a hydroxyl group, a hydroxyalkyl group, an amine group, an aminoalkyl group, an aryl group and an arylalkyl group Or more functional group. The method according to claim 1,
Wherein the resist stripping liquid composition further comprises an organic solvent. The method of claim 2,
Wherein the organic solvent is a protonic polar solvent, an aprotic polar solvent, or a mixed solvent thereof. The method according to claim 1,
Amine. &Lt; / RTI &gt; The method according to claim 1,
Wherein the resist stripping liquid composition further comprises an anticorrosive agent. The method of claim 3,
Wherein the organic solvent is a mixed solvent in which the protonic polar solvent and the aprotic polar solvent are mixed in a weight ratio of 1:99 to 30:70. The method of claim 3,
Wherein the protonic polar solvent is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisoprene Propylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether , Propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, alkylene glycol monoalkyl ether, propylene glycol monomethyl ether acetate and tetrahydrofurfuryl alcohol And at least one selected from the group consisting of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl butyl ether and triethylene glycol methyl butyl ether. The resist stripping liquid composition comprising: The method of claim 3,
The aprotic polar solvent may be selected from the group consisting of N-methylpyrrolidone (NMP), N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, (DMSO), sulfolane, triethyl phosphate, tributyl phosphate, dimethyl carbonate, ethylene carbonate, formamide, N-methylformamide, N, Amide, N-methylacetamide, N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, 3-methoxy- ) -N, N-dimethylpropionamide, and 3-butoxy-N, N-dimethylpropionamide. The method according to claim 1,
And 0.1 to 30% by weight of at least one compound selected from the group consisting of compounds represented by formulas (1) and (2) based on the total weight of the resist stripper composition. The method of claim 2,
Wherein the resist stripper solution composition contains 70 to 99.9% by weight of an organic solvent based on the total weight of the resist stripper composition. The method according to claim 1,
The compounds represented by Formulas (1) and (2) are preferably selected from the group consisting of hexahydropyridazine, 1-methylpiperidazine, 2-hexahydropyridazin-1-yl-ethanol, hexahydropyrimidine, 1-ethyl-hexahydropyrimidine, 1-ethyl-hexahydropyrimidine, 1- (3,3-dihydropyrimidin- -Aminopropyl) hexahydropyrimidine, 1-isopropylhexahydropyrimidine, 1-t-butyl-hexahydropyrimidine, 1-n-butylhexahydropyrimidine, 1-cyclohexylhexahydropyrimidine, N- And benzyl-hexahydropyrimidine. The resist stripper composition according to claim 1,