KR20150052942A - Resist stripper composition - Google Patents

Abstract

The present invention relates to a resist stripper composition, and more specifically, to a resist stripper composition which has low volatility and can significantly reduce an amount that a stripper volatilizes and disappears during the stripping process, and has excellent stripping power and resolving capability to resist polymers by comprising a compound of chemical formula 1 and an alkali compound.

Description

Resist stripper composition [

The present invention relates to a resist stripper composition.

Photoresist is a chemical film that can form a fine pattern pre-drawn on a photomask on a desired substrate by using photochemical reaction by light. It is used as a polymer material applied to exposure technology together with a photomask. Is directly recognized as a major factor in determining the ultimate resolution limit. In order to put the increasing degree of circuit integration into a semiconductor of limited size every year according to the so-called Moore's law (the theory that semiconductor density doubles every two years), the designed circuit must be patterned much smaller Increasing semiconductor density is inevitably demanding the development of new photoresists.

In order to produce a high-resolution flat panel display, a photolithography process for forming fine wiring on a substrate using such a photoresist is generally used. This is performed by applying a photoresist to a substrate using the thermal, mechanical, Followed by exposure to light of a certain wavelength and performing dry etching or wet etching.

In the fine patterning technique using a photoresist, a development that has been emphasized with respect to a new photoresist is a resist stripper (or a photoresist remover). The photoresist must be removed by a solvent called Stripper (or Photoresist Remover) after the etching process. This is because unnecessary photoresist layer after the etching process and etching of the metal residue or deteriorated photo This is because the resist residues cause problems such as a decrease in the yield of semiconductor production.

Accordingly, there is a demand for development of a peeling liquid having an ability to remove etching residues and an excellent peeling ability with respect to deteriorated photoresist residues.

In order to secure price competitiveness, economical efficiency such as increase in the number of processed substrates is also demanded. However, even in the case of a peeling liquid in which the resist dissolution power is excellent and the number of processed substrates is improved, the peeling liquid composition volatilizes and disappears during the peeling process time, It is required to develop a release liquid composition capable of preventing this.

Korean Patent Publication No. 2011-0130563 discloses a photoresist stripper composition.

Korean Patent Publication No. 2009-75516

It is an object of the present invention to provide a resist stripper composition having a remarkably low volatility.

An object of the present invention is to provide a resist stripping liquid composition which is excellent in peeling force and dissolving power against a resist polymer.

1. A resist stripping liquid composition comprising a compound represented by the following formula (1) and an alkaline compound:

[Chemical Formula 1]

(Wherein R < ₁ > and R < ₂ > are each independently a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms which is substituted or unsubstituted with a halogen atom or a hydroxyl group).

2. The resist stripping composition according to 1 above, wherein the compound of Formula 1 is contained in an amount of 1 to 98% by weight based on the total weight of the composition.

3. The resist composition according to item 1, wherein the alkali compound is at least one selected from the group consisting of KOH, NaOH, tetramethylammonium hydroxide, tetraethylammonium hydroxide, ammonia, carbonate compounds, phosphate compounds, / RTI >

4. The resist stripper composition according to 1 above, wherein the alkali compound is contained in an amount of 0.1 to 30% by weight based on the total weight of the stripper composition.

5. The resist stripping composition according to 1 above, further comprising a water-soluble polar solvent.

The resist stripper composition of the present invention has low volatility and can significantly reduce the amount of volatilization of the stripper liquid during the stripper process.

In addition, the resist stripping composition of the present invention is excellent in the peeling force and dissolving power for the resist polymer.

The present invention relates to a resist stripping composition which is low in volatility and which can significantly reduce the amount of volatilization and disappearance of the stripping solution during peeling, and which has excellent peeling power and dissolving power against the resist polymer .

Hereinafter, the present invention will be described in detail.

The resist stripping composition of the present invention comprises a compound represented by the following formula

[Chemical Formula 1]

(Wherein R < ₁ > and R < ₂ > are each independently a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms which is substituted or unsubstituted with a halogen atom or a hydroxyl group).

Since the compound of formula (1) has a high boiling point, it is possible to prevent the peeling liquid composition from volatilizing and disappearing during the peeling process, thereby improving the process yield.

Further, the resist is excellent in the ability to dissolve the polymer, and since it is water-soluble, it is not washed away in the rinsing step after the peeling step and remains on the substrate.

That is, the resist stripper composition of the present invention contains the compound of formula (1), whereby an excellent dissolving power and a remarkably low volatilization amount can be secured at the same time.

The content of the compound of the formula (1) is not particularly limited within the scope of its function, and may be, for example, 1 to 98% by weight based on the total weight of the release liquid composition. It is possible to maximize the effect of improving the resist solubility and reducing the volatilization amount within the above range. From such a viewpoint, it is preferably contained in an amount of 50 to 98% by weight.

The resist stripping liquid composition of the present invention further comprises an alkaline compound.

The alkaline compound strongly penetrates into the polymer matrix of the resist or crosslinked resist 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.

Therefore, the alkali compound is used together with the compound of the formula (I) so that the release liquid composition of the present invention has remarkably excellent resist dissolution and peeling power.

The alkali compound is not particularly limited as long as it has a good peeling force against the resist polymer, and examples thereof include KOH, NaOH, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), ammonia, Phosphate compounds, amine compounds, and the like. These may be used alone or in combination of two or more.

Specific examples of the carbonate compound include sodium carbonate, sodium chloride, potassium carbonate, potassium bicarbonate, lithium carbonate, calcium carbonate, magnesium carbonate, sodium hydrogencarbonate, calcium hydrogen carbonate and the like.

Specific examples of the phosphate compound include ammonium phosphate ((NH ₄ ) ₃ PO ₄ ), ammonium monohydrogen phosphate ((NH ₄ ) ₂ HPO ₄ ), ammonium dihydrogen phosphate (NH ₄ H ₂ PO ₄ ) K ₃ PO _4), hydrogen phosphate and potassium (K ₂ HPO _4), potassium dihydrogen phosphate (KH ₂ PO _4), sodium phosphate (Na ₃ PO _4), hydrogen phosphate, sodium (Na ₂ HPO _4), phosphoric acid Sodium hydride (NaH ₂ PO ₄ ), and the like.

Specific examples of the amine compound include primary amines such as methylamine, ethylamine, monoisopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine and pentylamine; Examples of the secondary amine such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine and methylisobutylamine Amine; Tertiary amines such as diethylhydroxyamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine and methyldipropylamine; But are not limited to, choline, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, Amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, Alkanolamines having a hydroxyalkyl group having 1 to 6 carbon atoms such as 4-amino-1-butanol and dibutanolamine; (Methoxymethyl) dimethylamine, (methoxymethyl) dimethylamine, (butoxymethyl) dimethylamine, (isobutoxymethyl) dimethylamine, (methoxymethyl) diethanolamine (Methoxymethyl) aminoethanol, methyl (butoxymethyl) aminoethanol, 2- (2-aminoethoxy) ethanol and the like An alkoxyamine having an alkoxy group having 1 to 6 carbon atoms; 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- Methylpiperazine, 1-amino-4-methylpiperazine, 1-benzylpiperazine, 1-phenylpiperazine, N-methylmorpholine, 4-ethylmorpholine, N-formylmorpholine, N - (2-hydroxyethyl) morpholine, N- (3-hydroxypropyl) morpholine, and other cyclic amines having a ring of 3 to 6 carbon atoms. These may be used alone or in combination of two or more.

The content of the alkali compound is not particularly limited within a range capable of performing the function, and may be, for example, 0.1 to 30% by weight, preferably 5 to 20% by weight, of the total weight of the release liquid composition have. If it is less than 0.1% by weight, the resist peeling force may be lowered, and if it exceeds 30% by weight, rapid corrosion rate increase is caused on metal wiring made of aluminum or aluminum alloy and copper or copper alloy.

Within the scope of the present invention, the resist stripping composition of the present invention may further contain a residual amount of a water-soluble polar solvent.

The water-soluble polar solvent dissolves the gelled resist polymer, and the peeling liquid can be easily removed in the rinsing step after the peeling step, thereby minimizing the re-adsorption and re-adhesion of the peeling liquid and the dissolved resist.

It is preferred that the water-soluble polar solvent is not too high or low in boiling point for proper peeling power.

Examples of the water-soluble polar solvent include a proton-polar solvent and a non-proton-polar solvent in which a polyhydric alcohol is excluded, and these solvents may be used alone or in combination of two or more.

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, diethylene Ethylene glycol monomethyl ether, 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 glycol Alkylene glycol monoalkyl ethers having an alkylene group of 1 to 10 carbon atoms such as monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether; Tetrahydrofurfuryl alcohol, etc. These may be used alone or in combination of two or more.

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 dimethylsulfoxide (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; N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, 3-methoxypyridine, N, N-dimethylformamide, Amide compounds such as N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide, They may be used alone or in combination of two or more.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Example  And Comparative Example

A resist stripping liquid composition containing the composition and the content shown in Table 1 below was prepared.

division (1)
compound
(NMFA) Alkaline compound
(B) Water soluble polar solvent
(C) Weight portion ingredient Weight portion ingredient Weight portion Example 1 90 MEA 5 EDG 5 Example 2 80 AEE 5 EDG 15 Example 3 75 MDEA 5 NMP 20 Example 4 80 HEP 5 NMF 15 Example 5 80 TMAH 5 EDG 15 Example 6 68 MDEA 5 NMP 27 Example 7 30 MEA 15 EDG 55 Comparative Example 1 90 - - EDG 10 Comparative Example 2 - MEA 5 NMF 95 Comparative Example 3 - MEA 5 DMAc 95 Comparative Example 4 - MEA 5 NMP 95 Comparative Example 5 - AEE 5 EDG /
NPF 15 /
80

(N-메틸포름아닐라이드)
MEA: 모노에탄올아민
AEE: 2-(2-아미노에틸아미노)-1-에탄올
MDEA: N-메틸디에탄올아민
HEP: 히드록시에틸 피페라진
EDG: 디에틸렌글리콜 모노에틸 에테르
NMP: N-메틸피롤리돈
NMF: N-메틸포름아마이드
DMAc: 디메틸아세트아마이드
NPF:

(N-페닐포름아닐라이드)NMFA:

(N-methylformanilide)
MEA: Monoethanolamine
AEE: 2- (2-aminoethylamino) -1-ethanol
MDEA: N-methyldiethanolamine
HEP: hydroxyethylpiperazine
EDG: diethylene glycol monoethyl ether
NMP: N-methylpyrrolidone
NMF: N-methylformamide
DMAc: dimethylacetamide
NPF:

(N-phenylformanilide)

Experimental Example  One. Resist Peel force  evaluation

Mo / Al and Cu / Ti layers were formed on the glass substrate by thin film sputtering. Subsequently, a photoresist (DWG-520, Dongwha Fine-Chem) pattern was formed, and a substrate on which a metal film was etched by a wet etching and a dry etching method was prepared.

The substrate was immersed in a resist stripping liquid composition at 50 DEG C for 1 minute, taken out, washed with pure water for 1 minute, and completely dried using nitrogen to remove pure water remaining on the substrate.

The removal performance of the modified or cured resist and dry etching residue of the substrate was observed with a scanning electron microscope (SEM, Hitachi S-4700), and the peeling force was evaluated according to the following criteria. The results are shown in Table 2 below.

<Evaluation Criteria>

⊚: very good (resist completely removed after dry and wet etching)

?: Good (no trace amount of denatured resist was removed by dry etching)

X: Bad (excess of resist after dry or wet etching is not removed)

Experimental Example  2. Resist solvency  Evaluation (number of processed / evaluated capacity)

5 parts by weight of a resist (DWG-520, Dongwu Fine-Chem) (a resist solidified by removing all the solvent through heat treatment at 130 DEG C for 3 days) solidified was added to 100 parts by weight of the exfoliant, &Lt; / RTI &gt; Thereafter, the remaining insoluble residue was filtered with a filter paper to measure its weight, and the solubility of the resist was determined. It can be determined that the higher the value, the higher the resist solubility and the higher the number of processed / treated capacities. The results are shown in Table 2 below.

Experimental Example  3. Exfoliation In process  Volatility evaluation

500 g of the release liquid composition was immersed in two 1000 ml beakers, and then placed in a thermostatic bath at 50 ° C and 60 ° C, respectively. Then, after 24 hours, the amount of the stripper solution remaining in the beaker was measured and the volatilization amount was calculated. The results are shown in Table 2 below.

division Peel force solvency(%) Volatiles (%) 50 ℃ 60 ° C Example 1 ◎ 98.3 6.5 8.4 Example 2 ◎ 97.8 7.2 9.5 Example 3 ◎ 97.6 7.1 10.5 Example 4 ◎ 95.6 7.1 9.8 Example 5 ◎ 95.2 7.4 10.9 Example 6 ◎ 94.4 6.8 8.4 Example 7 ◎ 95.6 8.2 15.2 Comparative Example 1 X 97.3 6.2 9.8 Comparative Example 2 X 95.8 13.2 21.5 Comparative Example 3 ◎ 96.2 19.5 41.2 Comparative Example 4 ◎ 96.2 10.8 19.2 Comparative Example 5 ◎ 70.1 7.1 8.2

Referring to Table 2, the peeling liquid compositions of Examples 1 to 7 were excellent in resist peeling force and dissolution ability. It was also confirmed that most of the peeling liquid remained volatilized even after being left in the thermostat for 24 hours, and the volatilization amount was remarkably low.

However, it was confirmed that the compositions of Comparative Examples 1 to 5 can not secure excellent peel strength, solubility and volatilization simultaneously.

Claims (5)

A resist stripping liquid composition comprising a compound represented by the following formula (1) and an alkaline compound:
[Chemical Formula 1]

(Wherein R &lt; ₁ &gt; and R &lt; ₂ &gt; are each independently a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms which is substituted or unsubstituted with a halogen atom or a hydroxyl group).
The resist stripper composition according to claim 1, wherein the compound of Formula 1 is contained in an amount of 1 to 98% by weight based on the total weight of the composition.
The resist stripping composition according to claim 1, wherein the alkaline compound is at least one selected from the group consisting of KOH, NaOH, tetramethylammonium hydroxide, tetraethylammonium hydroxide, ammonia, carbonate compound, phosphate compound and amine compound .
The resist stripper composition according to claim 1, wherein the alkali compound is contained in an amount of 0.1 to 30% by weight based on the total weight of the stripper composition.
The resist stripping composition according to claim 1, further comprising a water-soluble polar solvent.