KR102493785B1 - Stripper composition for removing photoresist and stripping method of photoresist using the same - Google Patents

Abstract

The present invention relates to a stripper composition used to remove a photoresist in a process of manufacturing an FPD (LCD, OLED) and a method using the same. Specifically, the stripper composition for removing photoresist according to the present invention can peel the photoresist in a short time even at a low temperature, and can peel without damaging the surface of the lower film, and at the same time, photoresist remains on the substrate after washing do not leave water

Description

Stripper composition for removing photoresist and method for removing photoresist using the same {Stripper composition for removing photoresist and stripping method of photoresist using the same}

The present invention relates to a stripper composition for removing a photoresist and a method for stripping a photoresist using the same.

In general, a microcircuit of a flat panel display (FPD) device such as LED or OLED is implemented through a photolithography process. The photolithography process includes 1) uniformly applying a photoresist to a conductive metal film or an insulating film formed on a substrate, 2) selective exposure and development to form a photoresist pattern, and 3) patterned photoresist. Using the film as a mask, wet or dry etch the conductive metal film or insulating film to transfer the fine circuit pattern to the lower photoresist layer, and then 4) remove the unnecessary photoresist layer with a stripper composition.

The photoresist stripper composition should be able to peel the photoresist in a short time even at a low temperature, minimize damage to the insulating layer and metal layer during the peeling process, and remove residues such as the photoresist and stripper composition peeled on the substrate after washing. should not be left behind

On the other hand, in recent years, as large-area display, ultra-miniaturization, and high resolution are required, it is actively proposed to use a copper (Cu) wiring pattern having excellent resistivity and electromigration characteristics. However, since the conventional stripper composition is highly corrosive to copper, when it is used as a release agent for copper wiring, the lower film containing copper is damaged, resulting in fine stains and residues.

Accordingly, attempts are being made to develop a stripper composition with less corrosion resistance to copper, such as by introducing an anti-corrosion additive, but the effect of preventing damage to copper is not sufficient, and the photoresist peeling performance is deteriorated, Even after cleaning is completed, there are limitations such as not being easily cleaned from the substrate surface.

That is, there is an urgent need for the development of a stripper composition having excellent peeling power and cleaning power for photoresist and excellent anti-corrosion effect for the lower film containing copper.

KR 10-2016-0114360 A KR 10-2017-0029285 A

The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a stripper composition for removing photoresist that has excellent peeling force for both photoresist and anti-corrosion ability for the lower film.

In addition, the present invention provides a method for stripping the photoresist using the stripper composition for removing the photoresist.

For the above purpose, the present invention provides a photoresist stripper composition comprising an amine compound represented by Formula 1 below.

[Formula 1]

(In Formula 1 above,

R ₁ and R ₂ are each independently hydrogen, (C1-C10)alkyl or hydroxy(C1-C10)alkyl;

L ₁ and L ₂ are each independently (C1-C12)alkylene, and -CH ₂ - of the alkylene of L ₁ and L ₂ may be replaced with -O-.)

The amine compound represented by Formula 1 according to an embodiment of the present invention may be represented by Formula 2, Formula 3 or Formula 4 below.

[Formula 2]

[Formula 3]

[Formula 4]

(In Chemical Formulas 2 to 4,

a, b, c, d, e and f are each independently an integer of 1 or 2.)

The stripper composition for removing the photoresist according to an embodiment of the present invention, the amine compound of Formula 1; aprotic polar organic solvent; and glycol-based compounds; can include

The aprotic polar organic solvent according to an embodiment of the present invention is N,N-dimethylpropionamide, N-methylformamide, dimethyl sulfoxide, dimethylacetamide, diethyl sulfoxide, dipropyl sulfoxide, sulfolane, It may include one or two or more selected from the group consisting of N-methylpyrrolidone, pyrrolidone, N-ethylpyrrolidone, dipropylene glycol monoethyl ether, and N, N'-dialkylcarboxamide. .

The glycol-based compound according to an embodiment of the present invention may be an alkylene glycol monoalkyl ether.

The alkylene glycol monoalkyl ether according to an embodiment of the present invention is ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl Ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether And it may include one or two or more selected from the group consisting of tripropylene glycol monobutyl ether.

The stripper composition for removing the photoresist according to an embodiment of the present invention may further include a corrosion inhibitor.

The corrosion inhibitor according to an embodiment of the present invention may include one or two or more selected from the group consisting of a benzimidazole-based compound, a triazole-based compound, and a tetrazole-based compound.

The triazole-based compound according to an embodiment of the present invention may include a compound represented by Formula 5 below.

[Formula 5]

The benzimidazole-based compound according to an embodiment of the present invention may include a compound represented by Formula 6 below.

[Formula 6]

Photoresist removal stripper composition according to an embodiment of the present invention is based on the total weight of the entire photoresist stripper composition, 30 to 60% by weight of an aprotic polar organic solvent, 20 to 60% by weight of a glycol-based compound, Formula 1 0.1 to 10% by weight of the compound and 0.005 to 0.6% by weight of the corrosion inhibitor.

In addition, the present invention comprises the steps of forming a photoresist pattern on the substrate on which the lower film is formed; patterning a lower layer with the photoresist pattern; And it provides a photoresist stripping method comprising the step of stripping the photoresist using the stripper composition for removing the photoresist.

The lower layer according to an embodiment of the present invention may include a metal layer including aluminum (Al), copper (Cu), molybdenum (Mo), titanium (Ti) or an alloy thereof; an insulating film of a silicon oxide film or a silicon nitride film; or a combination thereof.

The stripper composition according to the present invention has excellent anti-corrosion ability for the lower film and at the same time has a very excellent peeling force for the photoresist, so it may not leave stains and residues on the substrate after washing.

Specifically, since the photoresist can be peeled within a short time even at low temperature, the peeling speed can be further improved, and the solvency of the peeled photoresist is also excellent, so that no photoresist residue is left on the substrate after washing. At the same time, since the corrosion resistance of the insulating film and the metal film, which are the lower film, is excellent, only the photoresist can be selectively and quickly peeled off without causing stains or damage on the lower film.

Furthermore, the peeling force of the stripper composition according to the present invention can be maintained for a long period of time over time, and excellent solvency for the peeled photoresist can minimize defects such as filter clogging in the process. In addition, the stripper composition according to the present invention can be completely removed only by a washing process with ultrapure water, and does not remain on the substrate after washing.

Thus, the economics and efficiency of the process can be improved, and a highly reliable semiconductor device can be provided in a very economical way.

1 is a scanning electron microscope (SEM) photograph of a cross section of a specimen according to photoresist peel force evaluation of Example 1.
Figure 2 is a scanning electron microscope (SEM) picture of the specimen surface according to the evaluation of the lower film corrosion protection of Example 1.

Hereinafter, the present invention will be described in more detail. If there is no other definition in the technical terms and scientific terms used at this time, they have meanings commonly understood by those of ordinary skill in the art to which this invention belongs, and will unnecessarily obscure the gist of the present invention in the following description. Descriptions of possible known functions and configurations are omitted.

The singular form used herein may be intended to include the plural form as well, unless the context dictates otherwise.

Units used herein without special mention are based on weight, and as an example, the unit of % or ratio means weight% or weight ratio, and unless otherwise defined, weight% means that any one component of the entire composition is included in the composition. It means the weight percent occupied by

The term "comprises" in the present specification is an open description having the same meaning as expressions such as "comprises", "includes", "has" or "characterized by", elements not additionally listed, No materials or processes are excluded.

As used herein, the term "residue" may be by-products generated after etching or ashing from a substrate used in the semiconductor industry, and a contamination particle or contamination layer including organic or inorganic materials that may exist on the substrate after the process. may mean

Conventional stripper compositions have a problem in that the metal layer or the insulating layer is unnecessarily etched or causes surface damage of the metal layer. In order to solve this problem, a composition using various anti-corrosion additives has been proposed, but these additives have limitations such as degrading the peeling performance of the photoresist or not being easily washed from the substrate surface even after cleaning is completed.

Thus, the present invention is a novel amine compound having a very excellent peeling force for photoresist; aprotic polar organic solvent; glycol-based compounds; And it provides a photoresist stripper composition containing a corrosion inhibitor. As the stripper composition according to the present invention adopts the configuration combination as described above, it has the advantage of being excellent in both the corrosion protection ability for the lower film and the peeling force and cleaning power for the photoresist.

Hereinafter, the present invention will be specifically described.

The stripper composition for removing photoresist according to the present invention may include an amine compound represented by Formula 1 below.

[Formula 1]

(In Formula 1 above,

R ₁ and R ₂ are each independently hydrogen, (C1-C10)alkyl or hydroxy(C1-C10)alkyl;

L ₁ and L ₂ are each independently (C1-C12)alkylene, and -CH ₂ - of the alkylene of L ₁ and L ₂ may be replaced with -O-.)

According to an embodiment of the present invention, R ₁ and R ₂ are identical to each other and are preferably hydrogen or hydroxy (C1-C10)alkyl. The amine compound represented by Chemical Formula 1 according to an embodiment of the present invention is , More specifically, it may be represented by Formula 2, Formula 3 or Formula 4 below.

[Formula 2]

[Formula 3]

[Formula 4]

(In Chemical Formulas 2 to 4,

a, b, c, and d are each independently an integer of 1 to 5, and e and f are each independently an integer of 1 to 3.)

For example, in Formula 2, a to d may each independently be an integer of 1 to 3, and may be specifically 1 or 2.

For example, in Chemical Formula 3, a and b may each independently be an integer of 1 to 3, and may be specifically 1 or 2.

For example, in Chemical Formula 4, e and f may each independently be 1 or 2.

For example, in Formula 2, a to d may be identical to each other, a and b in Formula 3 may be identical to each other, and e and f in Formula 4 may be identical to each other.

The amine compound according to an embodiment of the present invention may be more preferably selected from Chemical Formula 2-1, Chemical Formula 3-1, or Chemical Formula 4-1, but is not limited thereto.

[Formula 2-1]

[Formula 3-1]

[Formula 4-1]

As the amine compound according to an embodiment of the present invention has the above structural characteristics, it can serve to dissolve and remove the bonding structure of the photoresist, and can implement a very excellent peeling force with respect to the photoresist. . Accordingly, it is possible to prevent the deterioration in economics and efficiency of the process caused by using an excessive amount of amine in the conventional stripper composition, and it is possible to significantly reduce the amount of waste liquid and the like. In addition, since the photoresist can be completely peeled off within a short time even at a low temperature, surface damage of the lower layer containing copper or the like can be minimized.

The amine compound according to an embodiment of the present invention may be included in 0.1 to 10% by weight, preferably 1 to 6% by weight, more preferably 2 to 5.5% by weight based on the total weight of the total stripper composition. there is.

In the above numerical range, the desired effect in the present invention, that is, excellent peeling and cleaning power for the photoresist, and remarkable corrosion prevention effect for the lower film containing copper are preferred in the present invention without compromising the stability of the composition. .

In addition, the amine compound may be used by mixing with an amine compound commonly used in the field, if necessary. As a non-limiting example thereof, diethanolamine, 2-aminoethoxy) -1-ethanol, aminoethylethanolamine, monomethanolamine, monoethanolamine, N-methylethylamine, 1-aminoisopropanol, methyldimethylamine, chain amine compounds such as diethylenetriamine and triethylenetetramine; and cyclic amine compounds such as 1-imidazolidine ethanol, amino ethyl piperazine and hydroxyethyl piperazine; etc. can be selected.

The aprotic polar organic solvent according to an embodiment of the present invention is N,N-dimethylpropionamide, N-methylformamide, dimethyl sulfoxide, dimethylacetamide, diethyl sulfoxide, dipropyl sulfoxide, sulfolane, N-methylpyrrolidone, pyrrolidone, N-ethylpyrrolidone, dipropylene glycol monoethyl ether, and N, N'-dialkylcarboxamide; and the like, and one or two or more selected from these. It may be a mixed solvent, and it may be more preferable to use N,N-dimethylpropionamide or N-methylformamide without limitation.

The aprotic polar organic solvent according to an embodiment of the present invention may be included in 30 to 60% by weight, preferably 35 to 60% by weight, more preferably 40 to 58% by weight based on the total weight of the total composition. can be included

When the aprotic polar organic solvent is mixed with the amine compound and satisfies the numerical range as described above, a more remarkable effect can be realized. Specifically, the amine compound can be easily dissolved in the stripper composition, and the stripper composition is properly permeated onto the photoresist pattern and the lower film. Thus, it can serve to maximize the excellent peeling force and cleaning power of the stripper composition according to the present invention.

In addition, the stripper composition for removing photoresist according to an embodiment of the present invention may be used as a water-based stripper main composition by further including water in addition to the aprotic polar organic solvent described above. When water is optionally included, its content may be determined within an appropriate range among the content ranges of the aprotic organic solvent.

The glycol-based compound according to an embodiment of the present invention may be an alkylene glycol monoalkyl ether, and as a non-limiting example thereof, the alkylene glycol monoalkyl ether is ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene Glycol Monomethyl Ether, Propylene Glycol Monoethyl Ether, Propylene Glycol Monobutyl Ether, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monopropyl Ether, Diethylene Glycol Monobutyl Ether, Dipropylene Glycol Monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether , tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, and tripropylene glycol monobutyl ether, and the like, and may be one or two or more selected from these, but is not limited to di It may be more preferable to use ethylene glycol monomethyl ether or diethylene glycol monobutyl ether.

The one or more glycol-based compounds according to an embodiment of the present invention may be included in 20 to 60% by weight, preferably 30 to 60% by weight, more preferably 35 to 55% by weight based on the total weight of the composition can be included as

When the glycol-based compound satisfies the above-described numerical range, the surface tension of the stripper composition may be lowered to improve wettability (wettability) of the photoresist, and excellent peeling force for the cured or deteriorated photoresist as well as the peeled It can serve to improve the solvency of the photoresist. In addition, excellent compatibility between various organic materials present in the stripper composition according to the present invention can be imparted. Thus, the peeling force and cleaning force of the stripper composition according to the present invention can be maintained for a long time over time.

The corrosion inhibitor according to an embodiment of the present invention may be selected from the group consisting of a benzimidazole-based compound, a triazole-based compound, and a tetrazole-based compound.

The triazole-based compound according to an embodiment of the present invention may more preferably include a compound represented by Formula 5 below.

[Formula 5]

The benzimidazole-based compound according to an embodiment of the present invention may more preferably include a compound represented by Formula 6 below.

[Formula 6]

Using the corrosion inhibitor as described above, it is possible to effectively inhibit corrosion of the lower film while maintaining excellent peeling power of the stripper composition, and exhibit a synergistic effect with the amine compound (Formula 1) according to the present invention to maximize corrosion inhibitory effect can be implemented

The corrosion inhibitor according to an embodiment of the present invention may be included in 0.005 to 0.6% by weight, preferably 0.1 to 0.5% by weight, more preferably 0.2 to 0.4% by weight based on the total weight of the composition.

When the corrosion inhibitor satisfies the above-mentioned numerical range, it can produce a maximized corrosion inhibitory effect, and can be completely removed only by a washing process using ultrapure water, so that it does not adsorb or remain on the substrate after washing.

Accordingly, the stripper composition for removing photoresist according to the present invention is a mixture of the amine compound, the aprotic polar organic solvent, the glycol-based compound and the corrosion inhibitor in a specific ratio as described above, thereby improving the peeling power, cleaning power and anti-corrosion power. can make it Specifically, the photoresist can be completely peeled off within a short time even at low temperatures, and the solvency of the peeled photoresist is also excellent, so that no photoresist residue is left on the substrate after washing. At the same time, since the corrosion resistance of the insulating film and the metal film, which are the lower film, is excellent, only the photoresist can be selectively and quickly peeled off without leaving stains or damage on the lower film. Furthermore, the peeling force of the stripper composition according to the present invention can be maintained for a long period of time over time, and excellent solvency for the peeled photoresist can minimize defects such as filter clogging in the process. In addition, the stripper composition according to the present invention can be completely removed only by a washing process with ultrapure water, and does not adsorb and remain on the substrate after washing.

Thus, it is possible to improve the economics and efficiency of the process, and to provide a highly reliable FPD (LCD, OLED) device in a very economical way.

In addition, the present invention provides a method for stripping the photoresist using the above-described stripper composition for removing the photoresist.

A photoresist peeling method according to an embodiment of the present invention includes forming a photoresist pattern on a substrate on which a lower film is formed; patterning a lower layer with the photoresist pattern; And it may include the step of stripping the photoresist using the photoresist stripper composition for removal.

Specifically, the method of removing the photoresist is to etch the substrate using a photoresist pattern formed on a substrate including an insulating film, a metal film, or a lower film of a combination thereof as a mask, and the photoresist with a stripper composition for removing the photoresist. It may include a stripping step of peeling off.

The insulating film according to an embodiment of the present invention is not limited as long as it is a conventional one, and a non-limiting example thereof may include a silicon oxide film or a silicon nitride film.

The metal film according to an embodiment of the present invention is not limited as long as it is also conventional, and a non-limiting example thereof is a metal film including a metal selected from aluminum (Al), copper (Cu), and molybdenum (Mo). Or an alloy film etc. are mentioned.

In the photoresist peeling method according to an embodiment of the present invention, first, a photoresist pattern may be formed on a substrate on which a lower layer to be patterned is formed through a photolithography process. Thereafter, after patterning the lower film using the photoresist pattern as a mask, the photoresist may be stripped using a stripper composition for removing the photoresist. In the above process, since the formation of the photoresist pattern and the patterning process of the lower layer may follow a conventional semiconductor device manufacturing method, further description thereof will be omitted.

On the other hand, in stripping the photoresist using the photoresist stripper composition for removing the photoresist, first, the stripper composition is treated on the substrate on which the photoresist pattern remains, and a washing step and a drying step may be performed with ultrapure water. In addition, after treating the stripper composition, a step of washing using an alkaline buffer solution may be further included.

In the step of peeling the photoresist from the substrate on which the microcircuit pattern is engraved using the photoresist stripper composition according to an embodiment of the present invention, several substrates to be peeled are simultaneously immersed in a large amount of the stripper composition Both the dip method and the sheet method of removing the photoresist by spraying the stripper composition on the substrate one by one can be used, and the method is not limited thereto.

In the peeling method of the photoresist according to an embodiment of the present invention, when the stripper composition is employed in a dip method, the step of peeling the photoresist may be performed in the range of 25 to 70 °C. Specifically, the step may be performed in the range of 30 to 65 ℃, or 40 to 60 ℃ range. That is, according to the present invention, excellent photoresist peeling and cleaning power can be implemented without damaging the lower film even under mild temperature conditions. In addition, the step may be performed for 30 seconds to 10 minutes, 30 seconds to 5 minutes, or 30 seconds to 1 minute under the above-described temperature conditions. That is, according to the present invention, excellent peeling performance can be implemented within a very short time even under the above mild temperature conditions.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the following Examples and Comparative Examples are only one example for explaining the present invention in more detail, and the present invention is not limited by the following Examples and Comparative Examples.

[Production Example]

Preparation of amine compound (WJEA)

Under a nitrogen atmosphere, diethanolamine (20 g, 0.19 mol) and 200 ml of methanol were added to a three-necked flask and dissolved by stirring at room temperature (25 ° C), followed by formaldehyde solution (37 wt% in H ₂ O) 7.7 g ( 0.095 mol) was slowly added dropwise over 30 minutes. After completion of the dropwise addition, the mixed solution was further stirred for 4 hours under a 50° C. temperature condition and a refluxing nitrogen atmosphere. After completion of the reaction, after washing with distilled water and ethyl acetate, the organic layer was dried with MgSO ₄ and the solvent was removed by distillation under reduced pressure. Thereafter, 52% of the amine compound (WJEA) was obtained by purification using silica gel column chromatography hexane/ethyl acetate = 3:1 (vol:vol), and the production of WJEA was confirmed through ¹ H-NMR.

HRMS(EI): m/z calculated for C9H22N2O4 222.16

Preparation of amine compounds (MNA)

In the preparation example of the amine compound (WJEA), 37% of the amine compound (MNA) was obtained using the same method except that 2-aminoethanol was used instead of diethanolamine, and the MNA was obtained through ¹ H-NMR. Manufacturing was confirmed.

HRMS (EI): m/z calculated for C5H14N2O2 134.11

Preparation of amine compound (WJEA300)

In the preparation example of the amine compound (WJEA), 37% of the amine compound (MNA) was obtained using the same method except that 2,2-(aminoethoxy)ethanol was used instead of diethanolamine, and ¹ H - Manufacturing of WJEA300 was confirmed through NMR.

HRMS(EI): m/z calculated for C9H22N2O4 222.16

[Examples 1 to 12 and Comparative Example 1 and Comparative Example 2]

After mixing in the composition ratio shown in Table 1, stirring at room temperature (25 ℃) at a speed of 500rpm for 30 minutes to prepare a photoresist stripper composition for removal.

Furtherance
(content, wt%) amine compounds aprotic
polar organic solvent glycolic compounds corrosion inhibitor WJEA MNA WJEA
300 IME DEF NMF MDG BDG One 2 Example 1 2 45 29 23.7 0.2 0.05 Example 2 2.5 45 29 23.7 0.2 0.05 Example 3 3 45 28 23.7 0.2 0.05 Example 4 3.5 45 27.5 23.7 0.2 0.05 Example 5 4 50 25 20.7 0.2 0.1 Example 6 4 44 25.4 25.5 0.2 0.05 Example 7 4 50 45.7 0.2 0.1 Example 8 4 48.4 5 42.3 0.2 0.1 Example 9 4 45 23.7 27 0.2 0.1 Example 10 5.5 50 20 24.2 0.2 0.1 Example 11 4.5 56 39.2 0.2 0.1 Example 12 2 45 29 23.7 0.2 0.05 Comparative Example 1 4.5 55 40.2 0.2 0.1 Comparative Example 2 4.5 56 39.2 0.2 0.1 [abbreviation]
IME: imidazolyl-4-ethanol
DEF: N,N-diethylformamide
NMF: N-methylformamide
MDG: Diethylene glycol monomethyl ether
BDG: diethylene glycol monobutyl ether
Corrosion inhibitor 1: 2,2'-[(methyl-1H-benzotriazol-1yl)methyl]imino]bisethanol
Corrosion inhibitor 2: 1H-Benzimidazole

Photoresist peel force evaluation

With respect to the stripper composition prepared in the above Examples and Comparative Examples, photoresist stripping performance was evaluated. After applying a photoresist using a spin coater on a silicon wafer on which a Cu/Ti double film is deposited, hard baking is performed at 110 ° C, 120 ° C, 130 ° C, 140 ° C, and 150 ° C for 100 to 150 seconds, respectively, to about 1.2 A photoresist film was formed to a thickness of 2.1 μm to 2.1 μm. Subsequently, a specimen was prepared by cutting the wafer on which the photoresist was formed into a size of 10 mm x 150 mm x 150 mm. The photoresist was removed by immersing the specimen in each stripper composition at 50 °C for 1 minute. The evaluation sample from which the photoresist was removed was washed with ultrapure water and then dried with nitrogen.

Thereafter, the dried specimen was checked for removal of the photoresist by EDS (surface qualitative analysis) of FE-SEM, and the results evaluated according to the following evaluation criteria are listed in Table 2 below.

◎:　 100% photoresist removed, no residue

○:　More than 80% to less than 100% of the photoresist is removed, leaving almost no residue

△: 　 More than 50% to less than 80% of the photoresist is removed and a significant amount remains

X: 　 Less than 50% of the photoresist is removed, leaving a rather large amount of photoresist

Evaluation of lower film corrosion protection

With respect to the stripper composition prepared in the above Examples and Comparative Examples, in order to evaluate the copper film corrosion resistance, the silicon wafer on which the Cu / Ti double film was deposited was cut into a size of 10 mm x 150 mm x 150 mm. 50 It was immersed for 18 hours at ℃. The specimen was washed with ultrapure water and dried with nitrogen.

Thereafter, the copper ion concentration change present in the stripper composition was measured through ICP-MS, and the degree of copper damage was confirmed by FE-SEM in the dried specimen, and the results are shown in Table 2 and FIG. 2.

Peel force evaluation over time

With respect to the stripper composition prepared in the Examples and Comparative Examples, the peeling performance according to the photoresist concentration was evaluated. The photoresist was heat-treated at 150° C. for 24 hours to remove all solvents to prepare a photoresist solid. The photoresist was removed by immersing the photoresist-coated specimen in a stripper composition in which the photoresist solid content was dissolved from 1% to 5% by weight at 50 °C for 1 minute. The evaluation sample from which the photoresist was removed was washed with ultrapure water and then dried with nitrogen.

Thereafter, the dried specimen was checked for removal of the photoresist by FE-SEM, and the results evaluated according to the following evaluation criteria are shown in Table 2 below.

◎:　 100% photoresist removed, no residue

○:　More than 80% to less than 100% of the photoresist is removed, leaving almost no residue

△: 　 More than 50% to less than 80% of the photoresist is removed and a significant amount remains

X: 　 Less than 50% of the photoresist is removed, leaving a rather large amount of photoresist

Peel force corrosion
prevention Peel force according to photoresist concentration 1% by weight 2% by weight 3% by weight 4% by weight 5% by weight Example 1 ◎ <10 ppb ◎ ◎ ◎ △ X Example 2 ◎ <10 ppb ◎ ◎ ◎ △ X Example 3 ◎ <10 ppb ◎ ◎ ◎ △ X Example 4 ◎ <10 ppb ◎ ◎ ◎ △ X Example 5 ◎ <10 ppb ◎ ◎ ◎ △ X Example 6 ◎ <10 ppb ◎ ◎ ◎ △ X Example 7 ◎ <10 ppb ◎ ◎ ◎ △ X Example 8 ◎ <10 ppb ◎ ◎ ◎ △ X Example 9 ◎ <10 ppb ◎ ◎ ◎ △ X Example 10 ◎ <10 ppb ◎ ◎ ◎ △ X Example 11 ◎ <10 ppb ◎ ◎ ◎ △ X Example 12 ◎ <10 ppb ◎ ◎ ◎ △ X Comparative Example 1 O >1000 ppb ○ ○ △ X X Comparative Example 2 O >1000 ppb ○ ○ △ X X

As shown in Table 2, the stripper composition for removing photoresist according to the present invention showed excellent peeling force against the photoresist, as well as remarkable corrosion protection against the lower film containing copper. In addition, the stripper composition according to the present invention can be completely removed only by a washing process with ultrapure water, leaving no residue on the substrate after washing.

Specifically, as a result of evaluating the photoresist peeling force of Examples 1 to 12, it was found that 100% of the photoresist was removed within a very short time and was completely washed without leaving a residue on the substrate. In addition, as shown in Figure 1, when the photoresist is peeled off with the stripper composition of Example 1 of the present invention, it can be confirmed that an excellent taper shape can be obtained because the undercut does not appear and the inclination of the two metal layers is appropriate.

In addition, as a result of evaluating the lower film corrosion resistance of Examples 1 to 12, there was almost no copper ion dissolved in the stripper composition, and as shown in FIG. 2, damage to the copper film was not observed even in the SEM measurement result. . In addition, it was confirmed that excellent peeling force for the photoresist could be maintained even when the photoresist solid content was dissolved up to 3% by weight.

That is, it can be seen that the stripper composition for removing photoresist according to the present invention has excellent peeling power, cleaning power, corrosion protection and peeling force over time.

On the other hand, in the case of Comparative Examples 1 and 2, which are stripper compositions that do not contain the amine compound (WJEA or MNA) according to the present invention, the peeling force to the photoresist was low, and as a result of evaluating the lower film corrosion resistance, a significant amount in the stripper composition Copper ions were observed, showing a significant difference in corrosion resistance to the lower film.

Claims (13)

A photoresist stripper composition comprising an amine compound represented by Formula 1 below.
[Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently hydrogen, (C1-C10)alkyl or hydroxy(C1-C10)alkyl;
L ₁ and L ₂ are each independently (C1-C12)alkylene, and -CH ₂ - of the alkylene of L ₁ and L ₂ may be replaced with -O-. According to claim 1,
The amine compound represented by Formula 1 is to be represented by Formula 2, Formula 3 or Formula 4, photoresist stripper composition for removal.
[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 2 to 4,
a, b, c, d, e and f are each independently an integer of 1 or 2. According to claim 1,
The photoresist stripper composition for removing, the amine compound of Formula 1; aprotic polar organic solvent; and glycol-based compounds; Containing, a photoresist stripper composition for removal. According to claim 3,
The aprotic polar organic solvent is N,N-dimethylpropionamide, N-methylformamide, dimethylsulfoxide, dimethylacetamide, diethylsulfoxide, dipropylsulfoxide, sulfolane, N-methylpyrrolidone, Rolidone, N- ethylpyrrolidone, dipropylene glycol monoethyl ether and N, N'-dialkyl carboxamide containing one or two or more selected from the group consisting of, a photoresist stripper composition for removal. According to claim 3,
The glycol-based compound is an alkylene glycol monoalkyl ether, photoresist stripper composition for removal. According to claim 5,
The alkylene glycol monoalkyl ether is ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol monomethyl Ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether and tripropylene glycol monobutyl ether Containing one or two or more selected from the group consisting of, photoresist stripper composition for removal. According to claim 3,
The stripper composition for removing the photoresist further comprises a corrosion inhibitor, a photoresist stripper composition for removing. According to claim 7,
The corrosion inhibitor is a benzimidazole-based compound, a triazole-based compound and a photoresist stripper composition comprising one or more selected from the group consisting of tetrazole-based compounds, including two or more. According to claim 8,
The triazole-based compound is a stripper composition for removing a photoresist comprising a compound of Formula 5 below.
[Formula 5]

According to claim 8,
The benzimidazole-based compound is a stripper composition for removing a photoresist comprising a compound of Formula 6 below.
[Formula 6]

According to claim 7,
Based on the total weight of the stripper composition for removing the entire photoresist, 30 to 60% by weight of an aprotic polar organic solvent, 20 to 60% by weight of a glycol compound, 0.1 to 10% by weight of the compound of Formula 1, 0.005 to 0.6% by weight of a corrosion inhibitor Contained as, photoresist stripper composition for removal. forming a photoresist pattern on the substrate on which the lower film is formed;
patterning a lower layer with the photoresist pattern; and
A photoresist stripping method comprising the step of stripping the photoresist using the photoresist stripper composition according to any one of claims 1 to 11. According to claim 12,
The lower layer may include a metal layer including aluminum (Al), copper (Cu), molybdenum (Mo), titanium (Ti), or an alloy thereof; an insulating film of a silicon oxide film or a silicon nitride film; Or a photoresist stripping method comprising a combination thereof.

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