KR102414295B1 - Photoresist stripper composition - Google Patents

Abstract

The photoresist stripper composition of the present invention does not use N-methylformamide (NMF), N-methylpyrrolidone (NMP), which are harmful to the environment and human body, as a main solvent, Even after dry or wet etching, the denatured photoresist can be quickly peeled off, and foreign substances and stains do not remain on the substrate, thereby significantly increasing process efficiency.
In addition, there is an advantage that can significantly increase the efficiency of the process by minimizing the corrosion of the lower layer.

Description

Stripper composition for photoresist removal {PHOTORESIST STRIPPER COMPOSITION}

The present invention relates to a stripper composition for photoresist removal using an amine compound, a polar solvent, and a non-polar solvent that do not contain toxic substances harmful to the human body.

The photolithography process is a series of photographic processes in which a pattern designed for a mask is transferred onto a substrate on which a thin film to be processed is formed. The photolithography process is used to manufacture integrated circuits, highly integrated circuits, and the like.

In the photolithography process, a photoresist, which is a photosensitive material, is coated on a glass substrate on which a thin film is formed, and a mask is placed on the photoresist-coated substrate and exposed, and then the photoresist is developed. ) to form a photoresist pattern. The thin film may be, for example, a metal film, an insulating film, or the like. Using the photoresist pattern as a mask, wet or dry etching may be performed to transfer and etch the microcircuit pattern. Thereafter, the process proceeds to a process of removing the unnecessary photoresist pattern using a stripper, which is a composition for removing the photoresist pattern.

Among them, the photoresist removal solution used in the process of forming electrode circuits for displays and semiconductors should be able to remove the photoresist in a short time at a low temperature, and do not leave a photoresist residue on the substrate after washing. and at the same time, it should have the ability to peel without damage to the organic insulating film and the metal wiring. The photoresist stripper may basically include an organic compound such as an amine compound, an alkylene glycol alkyl ether compound, an aprotic polar solvent, and a corrosion inhibitor. Among the various stripper compositions as described above, an aprotic solvent such as N-methylformamide (NMF) and N-methylpyrrolidone (NMP) as the main solvent in consideration of peelability and corrosion properties has been mainly used (Korean Patent Publication No. 10-2011-0124955, Korean Patent Laid-Open No. 10-2014-0028962, Korean Patent Publication No. 10-2015-0102354, Korean Patent No. 10-0655108, etc.). Although these solvents have the advantage of having excellent peeling power, they have disadvantages that are harmful to the environment and the human body.

Republic of Korea Patent Publication No. 10-2011-0124955 Republic of Korea Patent Publication No. 10-2014-0028962 Republic of Korea Patent Publication No. 10-2015-0102354 Republic of Korea Patent Registration No. 10-0655108

In order to solve the above problems, an object of the present invention is to provide a stripper composition for photoresist removal that can improve the peeling speed even using solvents that are not harmful to the environment and the human body. More specifically, by using N-ethylformamide (NEF), it aims to develop a stripper composition for photoresist removal that is harmless to the environment and human body, and has excellent peeling power and minimizes corrosion of the lower layer.

Another object of the present invention is to provide a method for removing a photoresist using the above-described stripper composition for removing a photoresist.

In order to achieve the above object, the present invention is N-ethylformamide (NEF); amine compounds; And it relates to a stripper composition for removing a photoresist comprising a protic polar solvent.

According to an embodiment of the present invention, the photoresist removal solution composition may contain 10 to 80% by weight of N-ethylformamide, 1 to 30% by weight of an amine compound, and 10 to 80% by weight of a protic polar solvent. can

According to an embodiment of the present invention, the photoresist stripper composition further contains 1 to 30% by weight of ultrapure water or deionized water, 0.01 to 5% by weight of an additive, or 1 to 1 to ultrapure water or deionized water. 30% by weight and 0.01 to 5% by weight of additives may be further included.

According to an embodiment of the present invention, the amine compound is monoethanolamine (MEA), monoisopropanolamine (MIPA), imidazolidine ethanol (IME), 2-amino-1-propanol, aminoisopropanol (AIP), N-methylaminoethanol (N-MAE), 3-amino-1-propanol, 4-amino-1-butanol, aminoethoxyethanol (AEE), 2-(2-aminoethoxy)-1-ethanol (AEE) ), diethanolamine (DEA), 1- (2-hydroethyl) piperazine (HEP), triethanol amine (TEA), 1-piperidineethanolamine (PPEtOH), benzyl piperazine (BP) and benzylamine ( Benzylamine) may be any one selected from or a mixture of two or more.

According to an embodiment of the present invention, the protic polar solvent is dimethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether (diethylene glycol). monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether ( dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, ethylene glycol propyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether Glycol Monobutyl Ether) and tetraethylhydro furylalcohol (Tetra ethylhydro furylalcohol) may be any one or a mixture of two or more selected from.

According to an embodiment of the present invention, the additive may be a triazole compound.

The stripper composition for photoresist removal of the present invention does not use N-methylformamide (N-methylforamide; NMF), N-methylpyrrolidone (NMP), which are harmful to the environment and human body, as a main solvent, Even after dry or wet etching, the denatured photoresist can be quickly peeled off, and foreign substances and stains do not remain on the substrate, thereby significantly increasing the efficiency of the process.

In addition, there is an advantage that can significantly increase the efficiency of the process by minimizing the corrosion of the lower layer.

Hereinafter, a preferred embodiment and a method for measuring physical properties of the stripper composition for photoresist removal will be described in detail. The present invention relates to a stripper composition for photoresist removal used in the manufacture of displays and semiconductors, and may be better understood by the following examples, which are for illustrative purposes of the present invention, It is not intended to limit the scope of protection defined by the claims.

The inventors of the present invention can improve the removal rate of photoresist without using N-methylformamide (NMF), N-methylpyrrolidone (NMP), which are harmful to the human body, as a main solvent. As a result of research to develop a stripper composition that can The present invention was completed by finding that it can be done.

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

A first aspect of the present invention is N-ethylformamide; amine compounds; and protic polar solvents.

A second aspect of the present invention is N-ethylformamide; amine compounds; protic polar solvents and additives.

A third aspect of the present invention is N-ethylformamide; amine compounds; protic polar solvents and ultrapure or deionized water.

A fourth aspect of the present invention is N-ethylformamide; amine compounds; protic polar solvents, additives and ultrapure or deionized water.

The content of N-ethylformamide according to an embodiment of the present invention is not limited, but may be included in an amount of 10 to 80% by weight. More preferably, it may contain 15 to 70% by weight. By including in the above range, it is possible to significantly shorten the photoresist removal time by improving the peeling force, and to minimize corrosion of the lower layer.

When the above-mentioned content of N-ethylformamide is less than 10% by weight, the improvement in peeling force is insignificant, so it takes a long time to remove the photoresist, and foreign substances and stains may remain on the substrate. In addition, when it exceeds 80% by weight, there is a risk that the lower film may be corroded.

According to an embodiment of the present invention, the photoresist stripper composition of the present invention may include an amine compound. The amine compound according to an embodiment of the present invention may further improve the peeling force of the photoresist modified with the N-ethylformamide combination.

The amine compound may serve to facilitate penetration of the solvent component by acting on a relatively weak portion of the surface of the modified photoresist.

The amine compounds of the present invention are obviously known in the art and are not limited thereto. For example, monoethanolamine (MEA), monoisopropanolamine (MIPA), imidazolidine ethanol (IME), 2-amino-1-propanol, aminoisopropanol (AIP), N-methylaminoethanol (N-MAE) ), 3-amino-1-propanol, 4-amino-1-butanol, aminoethoxyethanol (AEE), 2-(2-aminoethoxy)-1-ethanol (AEE), diethanolamine (DEA), One or two selected from 1-(2-hydroethyl)piperazine (HEP), triethanolamine (TEA), 1-piperidineethanolamine (PPEtOH), benzyl piperazine (BP) and benzyl amine (BA) A mixture of the above may be selected.

The amine compound according to an embodiment of the present invention may be included in an amount of 1 to 30 wt% based on the total weight of the photoresist stripper composition. More preferably, it may contain 3 to 25% by weight. By being included in the above range, it is possible to significantly improve the peeling force for the modified photoresist.

When the content of the amine compound is less than 1% by weight, the peeling force for the modified photoresist is lowered, and there is a risk that stains or foreign substances may remain on the substrate. There is a risk of corrosion of

In the case of the protic polar solvent, although it is not limited to a protic polar solvent clearly known in the art, for example, dimethylene glycol monoethyl ether, diethylene glycol monoethyl ether (diethylene) glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether (dipropylene glycol monoethyl ether), dipropylene glycol monopropyl ether (dipropylene glycol monopropyl ether), dipropylene glycol monobutyl ether (dipropylene glycol monobutyl ether), ethylene glycol propyl ether (Ethylene Glycol Propyl Ether), ethylene glycol monobutyl ether ( Any one or a mixture of two or more selected from Ethylene Glycol Monobutyl Ether, Diethylene Glycol Monobutyl Ether, and Tetra ethylhydro furylalcohol may be selected, but is not limited thereto .

More preferably, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether (diethylene) One or two or more types may be selected from glycol monobutyl ether) and tetraethylhydro furylalcohol.

The protic polar solvent according to an embodiment of the present invention may be included in an amount of 10 to 80% by weight based on the total weight of the photoresist stripper composition. More preferably, it may contain 25 to 78% by weight. By being included in the above range, it is possible to significantly improve the peeling force for the modified photoresist.

When the content of the protic polar solvent is less than 10% by weight, the peeling force for the modified photoresist is lowered, and there is a risk that stains or foreign substances may remain on the substrate. A problem may arise that increases the damage to the

Since the stripper composition for photoresist removal of the present invention may be a well-known aqueous or non-aqueous composition in this field in addition to the above components, ultrapure water or deionized water is added within the range that does not impair the physical properties of the photoresist stripper composition. may include More specifically, 1 to 30% by weight, more preferably 2 to 5% by weight, but may include, but is not limited thereto.

In addition, the photoresist stripper composition of the present invention may further include one or more other additives, if necessary, in addition to the above components. For example, it may be a triazole compound as a corrosion inhibitor. The triazole compound is not limited as long as it is a compound clearly known in the art, and specifically, benzotriazole, tolytriazole, carboxybenzotriazole, 1-hydroxylbenzotriazole, nitrobenzotriazole, dihydro Loxylpropylbenzotriazole and the like may be exemplified, but are not limited thereto.

In the stripper composition for removing the photoresist, the triazole compound may include 0.01 to 5% by weight, more preferably 0.1 to 0.5% by weight, but is not limited thereto.

In addition, according to another embodiment of the present invention, it is possible to provide a method of stripping a photoresist by treating the stripper composition for removing the photoresist.

In the method of removing the photoresist, the substrate is etched by using the photoresist pattern formed on the organic insulating film, the metal wiring, or the substrate including the metal wiring and the inorganic material layer as a mask, and the photoresist removal solution composition is used to remove the photoresist. (stripping) may include a step.

A method of peeling a photoresist from a substrate engraved with a microcircuit pattern using a stripper composition for photoresists according to an embodiment of the present invention involves dipping several sheets of a substrate to be peeled into a large amount of stripper at the same time. Both the dip method and the single-wafer method in which the photoresist is removed by spraying (spraying) the stripper on the substrate one by one may be used, but the present invention is not limited thereto.

As the type of photoresist that can be removed using the photoresist stripper composition of the present invention, for example, a positive type photoresist, a negative type photoresist, and a positive type/negative type photoresist (dual tone photoresist) are selected. The photoresist may include, but is not limited to, a photoresist that can be particularly effectively applied to a photoresist composed of a photoactive compound including a novolac-based phenol resin and diazonaphthoquinone.

The metal wiring to which the photoresist stripper composition can be applied may include, for example, an Au/Al/Ni/Cr quadruple film and Cu/dissimilar metal alloy, silver or a silver alloy as a lower layer, and the like. , but is not limited thereto.

Meanwhile, according to another embodiment of the present invention, it is possible to provide a liquid crystal display device or a semiconductor device manufactured by treating the photoresist removing solution composition.

In particular, the present invention can provide a liquid crystal display device or a semiconductor device manufactured by a conventional method including the above-described peeling method.

Hereinafter, preferred embodiments and methods for measuring physical properties of the stripper composition for photoresist removal of the present invention will be described in detail.

physical property measurement

One) photoresist Peel rate evaluation

In order to evaluate the photoresist stripping performance of the stripper composition for photoresist removal prepared as shown in Table 1 below, the photoresist composition was applied to a thickness of 1.5 μm on a glass substrate, and then at 160° C. and 170° C. for 10 minutes, respectively. A test specimen was prepared by performing a hard bake (H/B). The time required for the photoresist to be completely peeled off by the stripper under the spray pressure condition of 0.4 kgf was measured using a single-wafer spray-type stripping equipment maintained at a temperature of 60° C., and the evaluation results are shown in Table 2 below.

2) Insulation film damage evaluation

A test specimen was prepared by applying a photoresist composition to a glass substrate to a thickness of 1.5 μm and then performing hard bake at 160° C. and 170° C. for 10 minutes, respectively. After the photoresist is completely peeled off by the stripper under the spray pressure condition of 0.4kgf using a single-wafer spray-type peeling equipment maintained at a temperature of 60°C, the dried specimen is examined under an optical microscope at 200x magnification and FE- at 10K to 50K magnification. The degree of damage to the insulating film was confirmed by SEM. After confirmation, depending on the degree of damage to the insulating film, if there was no damage to the insulating film, it was described as “good”, and if damage to the insulating film was found, it was described as “poor”.

[Examples and Comparative Examples]

A stripper composition for photoresist removal was prepared by mixing the components and compositions shown in Table 1 below. At this time, the mixing was carried out at room temperature, and after mixing for at least 1 hour to be sufficiently dissolved, it was used by filtering with a Teflon filter (PTFA) having a pore size of 1 μm.

division menstruum amine aprotic polar solvent deionized water additive weight% weight% weight% weight% weight% ingredient content ingredient content ingredient content content ingredient content Example 1 NEF 30 MEA 7 MDG 60 3 - - Example 2 NEF 35 MEA 10 BDG 50 5 - - Example 3 NEF 50 MIPA 5 EDG/BDG 20/20.5 4.5 - - Example 4 NEF 55 PPEtOH 5 MDG 40 _ - - Example 5 NEF 40 AEE 7 EDG 53 - _ _ Example 6 NEF 40 DEA 3 MDG/EDG 20/37 - - - Example 7 NEF 50 TEA 5 EDG 45 - - - Example 8 NEF 45 MEA 7 MDG 48 - - - Example 9 NEF 50 NMEA 5 EDG 44.9 - TT 0.1 Example 10 NEF 30 MIPA 20 MDG 47.5 2.5 - - Example 11 NEF 35 MEA 10 BDG 55 - - - Example 12 NEF 25 MIPA 10 MDG 65 - - - Example 13 NEF 50 AEE 5 BDG 45 - - - Example 14 NEF 35 AEE 25 EDG 40 - - - Example 15 NEF 65 BP 10 EDG 25 - - - Example 16 NEF 70 HEP 5 MDG 25 - - - Example 17 NEF 15 HEP 7 EDG 78 - - - Example 18 NEF 50 BA 10 EDG 40 - - - Comparative Example 1 THFA 40 MEA 22 MDG/EDG 18/20 - - - Comparative Example 2 NEF 45 MEA - MDG 55 - - - Comparative Example 3 NMPA 40 MEA 3 BDG/EDG 27/30 - - - Comparative Example 4 THFA 50 MEA 10 BDG 39.9 - CHDM 0.1 Comparative Example 5 NEF 45 MEA 55 MDG - - - - Comparative Example 6 NEF 85 NMEA 5 EDG 10 - - - Comparative Example 7 NEF 5 MEA 32 MDG 63 - - -

<solvent>

NEF: N-ethylformamide

THFA: tetraethylhydrofuryl alcohol

NMPA: N-methylpropionamide

NMF: N-methylformamide

<Amine>

MEA: monoethanolamine

MIPA: monoisopropanolamine

AEE: 2-(2-aminoethoxy)-1-ethanol

PPEtOH: 1-piperidineethanol

DEA: diethanolamine

TEA: triethanolamine

NMEA: N-methylaminoethanol

BP: Benzyl Piperazine

HEP: 1-(2-hydroethyl)piperazine

BA: Benzylamine

<Aprotic polar solvent>

MDG: diethylene glycol monomethyl ether

BDG: Diethylene glycol monobutyl ether

EDG: Diethylene glycol monoethyl ether

<Additives>

CHIDM: 1,4-cyclohexanedimethanol

TT: tolytriazole

division Peel Performance Evaluation organic insulating film
Whether damage 160℃, H/B 170℃, H/B Example 1 10 20 Good Example 2 10 20 Good Example 3 10 20 Good Example 4 10 20 Good Example 5 10 20 Good Example 6 10 20 Good Example 7 10 20 Good Example 8 10 20 Good Example 9 10 20 Good Example 10 10 20 Good Example 11 10 20 Good Example 12 10 20 Good Example 13 10 20 Good Example 14 10 20 Good Example 15 10 20 Good Example 16 10 20 Good Example 17 10 20 Good Example 18 10 20 Good Comparative Example 1 60 80 Good Comparative Example 2 60 120 Good Comparative Example 3 50 100 Good Comparative Example 4 60 80 Good Comparative Example 5 10 20 error Comparative Example 6 60 70 error Comparative Example 7 60 300 error

As shown in Table 2, it was confirmed that the stripper composition for photoresist removal according to the present invention was remarkably excellent in both the removal rate and the corrosion of the lower layer. As shown in Comparative Examples 6 and 7, when the content of N-ethylformamide is 85% by weight or 5% by weight, the removal rate is not improved and damage to the insulating film occurs, so 10 to 80% by weight, Even better, it was found that it is good to use 15 to 70% by weight.

In the case of Comparative Examples 1 to 5, the time required to remove the photoresist at 160 ° C. and 170 ° C. was 50 seconds and 60 seconds, which was about 5 to 6 times longer than that of Examples, and Comparative Example 5 showed that the amine was used in excess to cause corrosion of the lower layer.

Therefore, according to the stripper composition for photoresist removal according to the present invention, the photoresist can be quickly removed without damaging the organic insulating film, and foreign substances and stains are not left during removal, thereby increasing the efficiency and reliability of the process.

Although preferred embodiments of the present invention have been described above, it is clear that the present invention can use various changes and equivalents, and can be equally applied by appropriately modifying the above embodiments. Accordingly, the above description is not intended to limit the scope of the present invention, which is defined by the limits of the following claims.

Claims (5)

10 to 80% by weight of N-ethylformamide, 1 to 30% by weight of an amine compound, and 10 to 80% by weight of a protic polar solvent,
The amine compound is any one or a mixture of two or more selected from monoethanolamine (MEA), monoisopropanolamine (MIPA), diethanolamine (DEA) and triethanolamine (TEA). The method of claim 1,
The stripper composition for removing the photoresist further comprises 1 to 30% by weight of ultrapure water or deionized water,
Further comprising 0.01 to 5% by weight of an additive, or
1 to 30% by weight of ultrapure water or deionized water, and 0.01 to 5% by weight of an additive, the photoresist stripper composition further comprising. delete The method of claim 1,
The protic polar solvent is dimethylene glycol monoethyl ether (dimethylene glycol monoethyl ether), diethylene glycol monoethyl ether (diethylene glycol monoethyl ether), diethylene glycol monopropyl ether (diethylene glycol monopropyl ether), diethylene glycol monobutyl Ether (diethylene glycol monobutyl ether), dipropylene glycol monomethyl ether (dipropylene glycol monomethyl ether), dipropylene glycol monoethyl ether (dipropylene glycol monoethyl ether), dipropylene glycol monopropyl ether (dipropylene glycol monopropyl ether), dipropylene glycol Dipropylene glycol monobutyl ether, Ethylene Glycol Propyl Ether, Ethylene Glycol Monobutyl Ether, Diethylene Glycol Monobutyl Ether, and Tetra Ethyl Hard Any one or a mixture of two or more selected from furyl alcohol (Tetra ethylhydro furylalcohol), a photoresist stripper composition for removal. 3. The method of claim 2,
The additive is a stripper composition for removing a photoresist that is a triazole compound.