KR20170099525A - Resist stripper composition - Google Patents

Abstract

The present invention relates to a resist stripping solution composition. More specifically, the present invention relates to a resist stripping solution composition which contains an imidazolidine-based compound represented by chemical formula 1 and an organic polar solvent, exhibits excellent resist stripping functions, and minimizes corrosiveness to metal films containing copper and aluminium. In the chemical formula 1, each substituent is the same as defined in the present specification.

Description

RESIST STRIPPER COMPOSITION [

The present invention relates to a resist stripping liquid composition that facilitates stripping of a resist attached to a substrate during a photoresist stripping process.

A photoresist is a chemical film that can form a fine pattern previously drawn on a photomask on a desired substrate by using a photochemical reaction by light. The photoresist is used as a polymer material applied to an exposure technique 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 manufacture a high-resolution flat panel display, a photolithography process for forming fine wirings on a substrate using such photoresist is generally used, which is a process of forming photoresist on a substrate by using thermal, mechanical, Applying a resist, exposing to light of a certain wavelength, and performing dry or wet etching.

In the fine patterning technique using a photoresist, the development of a new photoresist has become an important issue in the resist stripping solution. The photoresist should be removed by the resist stripper after the etching process, since the unnecessary photoresist layer after the etching process and the metal residue or deteriorated photoresist residue remaining on the substrate through the etching and washing processes are removed And it causes problems such as deterioration.

Therefore, it is required to have a high level of peeling property with respect to the removal force against the etching residue and the excellent peeling force against the deteriorated photoresist residue, specifically, the removal force against the etching residue generated after the dry etching process, . In particular, corrosion resistance to copper as well as aluminum is also required. In order to secure price competitiveness, economic efficiency such as improvement in peeling speed and increase in the number of processed substrates is also required.

In this regard, Korean Patent Registration No. 1008373 discloses a resist stripping liquid composition capable of improving the resist stripping ability by containing imidazolidine-based compounds having a specific formula and increasing the damping force against the photoresist lower film containing molybdenum . However, when the resist stripping solution composition is used, there is a possibility that the detergency against the metal film including copper and aluminum may be deteriorated.

Also, Korean Patent No. 1213735 discloses a resist stripping liquid composition which includes a cyclic amine, a stripping promoter, a corrosion inhibitor and the like to improve the resist stripping ability and increase the damping force against metal wiring. However, this may also result in insufficient resist peeling force and insufficient mechanical strength against metal film.

Korean Registered Patent No. 1008373 (2011.01.07, LG Chemical Co., Ltd.) Korean Registered Patent No. 1213735 (2012.12.12, Dongjin Semichem Co., Ltd.)

An object of the present invention is to provide a resist stripper composition which is excellent in the resist stripping effect in the resist stripping process and can minimize the corrosion of the metal film including copper and aluminum.

In order to achieve the above object, the resist stripper composition according to the present invention comprises a polar organic solvent and an imidazolidine compound represented by the following general formula (1).

[Chemical Formula 1]

(In the formula 1,

R ₁ and R ₂ are each independently alkylene having 1 to 3 carbon atoms.)

The resist stripping liquid composition according to the present invention includes the imidazolidine-based compound having a specific chemical formula, thereby facilitating the removal of the resist attached to the substrate during the resist stripping process and minimizing the corrosion to the metal film including copper and aluminum There is an effect that can be done.

Whenever a part is referred to as "including " an element in the present invention, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

Hereinafter, preferred embodiments of the present invention will be described in detail.

Imidazolidine-based compound

The resist stripping composition of the present invention comprises an imidazolidine-based compound represented by the following formula:

[Chemical Formula 1]

(In the formula 1,

R ₁ and R ₂ are each independently alkylene having 1 to 3 carbon atoms.

The imidazolidine-based compound of Chemical Formula 1 strongly penetrates into the polymer matrix of the modified or crosslinked resist under various process conditions such as dry or wet etching, ashing, or ion implant processing, The resist attached to the upper part of the substrate is easily removed by deforming the resist into amorphous polymer gel state by forming an empty space in the structurally weak part in the resist remaining on the substrate, . As a result, it is possible to rapidly remove a denatured or crosslinked resist in a small amount.

In addition, the imidazolidine-based compound can minimize the corrosiveness to metal films including copper and aluminum.

Preferred examples of the imidazolidine-based compound of Formula 1 include imidazolidine ethoxyethanol, imidazolidine methoxymethanol, imidazolidine butoxybutanol, imidazolidine methoxyethanol, and the like. no.

The content of the imidazolidine-based compound of formula (1) is not particularly limited within a range that can fulfill its function, and may be included in an amount of 0.1 to 30% by weight based on 100% by weight of the total amount of the resist stripper composition have. If the content of the imidazolidine compound of the formula 1 is less than 0.1% by weight, the effect of increasing the peeling force is insignificant. If the content of the imidazolidine compound exceeds 30% by weight, the effect of increasing the peeling force is insufficient, May be relatively decreased and the solubility of the composition in the resist may be lowered.

Polar organic solvent

The resist stripping solution composition in the present invention includes a polar organic solvent.

The polar organic solvent dissolves the gelled resist polymer and allows the stripping liquid to be easily removed in the deionized water rinsing step after the resist stripping process to minimize re-adsorption and re-adhesion of the stripping liquid and dissolved resist.

Examples of the polar organic solvent include a protonic polar solvent and aprotic polar solvent, which may be used alone or as a mixture of two or more.

Preferred 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 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, polypropylene glycol, polyethylene Alkylene glycol monoalkyl ethers such as glycol monomethyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate Sites, and the like tetra-hydroperoxide furyl alcohol, and these can be used singly or in combination of two or more kinds.

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 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; N, N-dimethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N - (2-hydroxyethyl) acetamide, N, N-dimethylpropionamide, 3-methoxy-N, N dimethylpropionamide, 3- Amide compounds such as 3-butoxy-N, N-dimethylpropionamide, etc. These may be used alone or in admixture of two or more.

The boiling point of the polar organic solvent is not particularly limited, but it is preferable to use a polar organic solvent having a boiling point of 150 to 300 ° C for an appropriate peeling force. The polar organic solvent may further be added according to the performance required in the peeling process.

The content of the polar organic solvent is not limited within a range that can fulfill its function. For example, the amount of the polar organic solvent may be 70 to 99.9% by weight based on 100% by weight of the resist stripper composition. If the content is less than 70% by weight, the solubility of the resist may be lowered. If the content is more than 99.9% by weight, the content of the imidazolidine compound of the formula (1) may be decreased to deteriorate the peeling force for the resist.

Basic compound

The resist stripping composition of the present invention may further contain a basic compound.

The basic compound penetrates strongly into the polymer matrix of the degraded or crosslinked resist to break bonds existing in the molecule or between the molecules and forms voids in the structurally weak portions in the resist remaining on the substrate, So that the resist attached to the upper portion of the substrate can be easily removed by deforming into a polymer gel mass state. Therefore, when it is used together with the imidazolidine compound of the formula (1), the peeling force against the resist can be further improved.

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

Specific examples of the carbonate compound include sodium carbonate, sodium bicarbonate, 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 ), potassium monohydrogenphosphate (K ₂ HPO ₄ ), potassium dihydrogenphosphate (KH ₂ PO ₄ ), sodium phosphate (Na ₃ PO ₄ ), sodium monohydrogenphosphate (Na ₂ HPO ₄ ) 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 preferably 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 Alkoxyamine preferably having an alkoxy group having 1 to 6 carbon atoms; Hydroxylamines such as diethylhydroxylamine, dipropylhydroxylamine and N-ethyl-N-methylhydroxylamine; 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 the like, and the like.

The content of the basic compound is not particularly limited within a range capable of functioning, and may be, for example, 0.1 to 20% by weight based on 100% by weight of the resist stripper composition. If the content of the basic compound is less than 0.1% by weight, the effect of improving the resist peeling force may be insignificant. If the content is more than 20% by weight, rapid corrosion rate improvement may be caused on metal wiring made of aluminum or aluminum alloy and copper or copper alloy.

Corrosion inhibitor

The resist stripping composition of the present invention may further comprise a corrosion inhibitor.

The corrosion inhibitor may be used in combination with the imidazolidine-based compound of formula (I) to further improve the antifungal ability.

The kind of the above-mentioned corrosion inhibitor is not particularly limited, and a corrosion inhibitor known in the art may be used, and these may be used alone or in combination of two or more.

Specific examples of the corrosion inhibitor include monocarboxylic acids such as formic acid, acetic acid and propionic acid; Dicarboxylic acids such as acetic acid, malic acid, malonic acid, succinic acid, gluconic acid, adipic acid, pimelic acid, maleic acid, fumaric acid and glutaronic acid; Tricarboxylic acids such as trimellitic acid and tricarvaleric acid; Organic acids such as hydroxyacetic acid, lactic acid, salicylic acid, malic acid, tartaric acid, citric acid, gluconic acid and oxycarboxylic acid; 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, Organic acid amide esters such as tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, Benzotriazole, tolyltriazole, methyltolytriazole, 2,2 '- [[[benzotriazole] methyl] imino] bisethanol, 2,2' [[ Yl] methyl] imino] bisethanol, 2,2 '- [[[methyl (2-methoxyphenyl) -1-methyl] imino] biscarboxylic acid, 2 ' - [[methyl-hydrogen-benzotriazol- Yl] methyl] imino] bismethylamine and 2,2 '- [[[amine-1-hydrogen-benzotriazol- Methyl] imino] bis ethanol 4-methyl-1-hydrogen-benzotriazole, 6-methyl-4,5,6,7-tetrahydro- Methyl-4,5,6,7-tetrahydro-1H-benzo [1,2,3] triazole, 5-methyl-4,5,6,7-tetrahydro- , 3] triazole, 5,6-dimethyl-4,5,6,7-tetrahydro-1-hydrogen-benzo [1,2,3] triazole, 4,6-dimethyl- - tetrahydro-1 Small-benzo [l, 2,3] triazole and 5-methyl-1-hydrogen-azole compounds such as benzotriazole; 2,6-dimethylphenol, 2,4,6-trimethylphenol, 2,6-diethylphenol, 2,6-diethyl-4-methylphenol, 4-methylphenol, 2,6-di-t-butylphenol, 2,4,6-tri-t-butylphenol and 2,6- ; And the like.

The content of the corrosion inhibitor is not particularly limited and may be, for example, 0.001 to 5% by weight based on 100% by weight of the resist stripper composition. If the content of the corrosion inhibitor is less than 0.001% by weight, the effect of improving the performance may be insignificant. If the content of the corrosion inhibitor is more than 5% by weight, The resist peeling force and dissolution power may be inhibited.

It is to be understood that both the foregoing general description and the following detailed description 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. In the following Examples and Comparative Examples, "%" and "part" representing the content are by weight unless otherwise specified.

Examples and Comparative Examples

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

division Imidazolidine series
compound Polar organic solvent Basic compound Corrosion inhibitor ingredient weight% ingredient weight% ingredient weight% ingredient weight% Example 1 IMEE ^{1 )} 3 NMP ^{2 )} 97 - - - - Example 2 IMEE 3 NMF ^{3 )}
BDG ^{4 )} 67
30 - - - - Example 3 IMEE 3 NEF
EDG ^{5 )} 66
30 MDEA ^{6 )} One - - Example 4 IMEE 2 NMP
EDG 50
45.9 AEE ^{7 )} 2 TTA ^{10 )} 0.1 Comparative Example 1 - - NMP
EDG 70
30 - - - - Comparative Example 2 - - NMP
EDG 65
30 MEA ^{8 )} 5 - - Comparative Example 3 - - NMP
EDG 60
30 HEP ^{9 )} 10 - - Comparative Example 4 - - NMP
EDG 65
30 AEE 5 - - Comparative Example 5 IME ^{11 )} 3 NMP
EDG 67
30 - - - -
1) Imidazolidine ethoxyethanol
2) N-methylpyrrolidone
3) N-methylformamide
4) Diethylene glycol monobutyl ether
5) Diethylene glycol monoethyl ether
6) N-methyldiethanolamine
7) 2- (2-aminoethoxy) -1-ethanol
8) Monoethanolamine
9) N-Hydroxyethyl Piperazine
10) Tolyltriazole
11) Imidazolidine Ethanol

Experimental Example  One. Resist Peel force  evaluation

1.7 탆 of a photoresist (DWG-520, Dongwu Fine-Chem) was applied on a glass substrate, followed by hard bake at 170 캜 for 10 minutes.

The substrate was immersed in the resist stripping composition of Example and Comparative Example at 50 占 폚 at intervals of 30 seconds to evaluate the peeling force. The substrate was cleaned with pure water for 1 minute to remove residual peeling liquid, and the substrate was completely dried with nitrogen to remove pure water remaining on the substrate.

The substrate was visually inspected and the time for completely removing the resist was measured. The results are shown in Table 2 below.

The shorter the peeling time, the better the peeling effect.

Experimental Example  2. Metal wiring Revolution  evaluation

A substrate on which a metal film is etched by a wet etching and a dry etching method is formed on the organic substrate by forming a Mo / Al or Cu / Ti layer by a thin film sputtering method, forming a pattern of a photoresist (DWG-520, Dongwha FineChem) Respectively.

The substrate was immersed in the resist stripper solution composition of Example and Comparative Example at 50 占 폚 for 30 minutes, taken out, cleaned with pure water for 1 minute, and the substrate was completely dried with nitrogen to remove pure water remaining on the substrate.

Aeration force was observed with a scanning electron microscope (SEM, Hitachi S-4700) and evaluated according to the following criteria. The results are shown in Table 2 below.

<Evaluation Criteria>

&Amp; cir &amp;: Very good (no corrosion was observed on the surface and interface of metal wiring)

○: Good (fine corrosion is observed at the interface of metal wiring, but there is no problem in use as wiring)

DELTA: Normal (fine corrosion was observed on the surface and interface of metal wiring)

X: Defective (severe corrosion is observed on the surface and interface of metal wiring)

division Peeling time
(sec) Revolution Al Cu Example 1 30 ◎ ◎ Example 2 30 ◎ ◎ Example 3 30 ◎ ◎ Example 4 30 ◎ ◎ Comparative Example 1 ≥ 600 ◎ ◎ Comparative Example 2 180 X X Comparative Example 3 480 △ △ Comparative Example 4 300 △ X Comparative Example 5 30 △ X

With reference to Table 2, in the case of Examples 1 to 4 using the resist stripper composition containing the imidazolidine-based compound of the present invention, the resist stripper compositions containing the resist stripper solution compositions of Comparative Examples 1 to 5 The peeling speed was significantly higher than in the case of In addition, the corrosion resistance against copper and aluminum wiring was also excellent.

Specifically, when the resist stripping liquid composition containing no imidazolidine-based compound represented by Chemical Formula 1 in the present invention is used as in Comparative Examples 1 to 4, even if basic compounds such as amines are contained, It was confirmed that it was not possible.

As in Examples 1 to 4, when the resist stripping liquid composition containing the imidazolidine-based compound of Chemical Formula 1 was used and the imidazolidine-based compound represented by Chemical Formula 1 was used as in Comparative Example 5 It was confirmed that the resist stripping composition of the present invention exhibited a better antifungal effect.

Claims (6)

A polar organic solvent and an imidazolidine compound represented by the following formula (1):
[Chemical Formula 1]

(In the formula 1,
R ₁ and R ₂ are each independently alkylene having 1 to 3 carbon atoms. The method according to claim 1,
The imidazolidine-based compound
Is contained in an amount of 0.1 to 30% by weight based on 100% by weight of the total resist stripping solution composition. The method according to claim 1,
The polar organic solvent
Wherein the resist stripping liquid composition comprises 70 to 99.9% by weight based on 100% by weight of the total resist stripping composition. The method according to claim 1,
Wherein the resist stripping liquid composition further comprises at least one additive selected from the group consisting of a basic compound and a corrosion inhibitor. 5. The method of claim 4,
The basic compound
Is contained in an amount of 0.1 to 20% by weight based on 100% by weight of the total amount of the resist stripping solution composition. 5. The method of claim 4,
The corrosion inhibitor
Wherein the resist stripping liquid composition is contained in an amount of 0.001 to 5% by weight based on 100% by weight of the total resist stripping liquid composition.