KR20170088048A - Photoresist stripper composition - Google Patents

Abstract

A stripping liquor composition for removing a photoresist can quickly strip a denatured photoresist after dry-type or wet-type etching without using N-methylformamide (NMF) or N-methylpyrrolidone (NMP) harmful to environment and humans, and has an advantage of significantly increasing the efficiency of processes since foreign matters and stains do not remain on a substrate. In addition, the corrosion of a lower film is also minimized to significantly increase process efficiency.

Description

[0001] PHOTORESIST STRIPPER COMPOSITION [0002]

The present invention relates to a release liquid composition for removing a photoresist using an amine compound, a polar solvent, and a non-polar solvent which do not contain harmful toxic substances to human body.

The photolithography process is a series of photolithography processes in which a pattern designed in a mask is transferred onto a substrate on which a thin film to be processed is formed. Photolithography processes are used to fabricate 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, a mask is disposed and exposed on the substrate to which the photoresist is applied, 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. The photoresist pattern may be etched by wet or dry etching using the photoresist pattern as a mask to transfer and etch the fine circuit pattern. Then, the unnecessary photoresist pattern is removed by using a stripper as a composition for removing the photoresist pattern.

Among them, the remover for removing the photoresist used in the process of forming the electrode circuit for display and semiconductor must be able to peel the photoresist in a short time at a low temperature and leave the photoresist residue on the substrate after rinsing And at the same time have the ability to peel off without damaging the organic insulating film and the metal wiring. The removing solution for removing the photoresist may basically contain an organic compound such as an amine compound, an alkylene glycol alkyl ether compound, an aprotic polar solvent and a corrosion inhibitor. Considering the peelability and corrosiveness of the various peeling liquid compositions, the main solvent is a non-magnetic solvent such as N-methylformamide (NMF), N-methylpyrrolidone (NMP) (Korean Patent Publication No. 10-2011-0124955, Korean Patent Publication No. 10-2014-0028962, Korean Patent Publication No. 10-2015-0102354, Korean Patent No. 10-0655108, etc.). Although these solvents have an advantage of having excellent peeling force, they have disadvantages to the environment and the human body, and therefore, there is a continuing need to develop an alternative solvent for the aprotic polar solvent to replace them.

Korean Patent Publication No. 10-2011-0124955 Korean Patent Publication No. 10-2014-0028962 Korean Patent Publication No. 10-2015-0102354 Korean Patent No. 10-0655108

In order to solve the above problems, it is an object of the present invention to provide a peeling liquid composition for removing a photoresist which can improve the peeling speed even when using a solvent which is not harmful to the environment and human body. More specifically, it is an object of the present invention to develop a peeling liquid composition for removing photoresist which is harmless to the environment and human body using N-ethylformamide (NEF) and can minimize the peeling force and the lower film corrosion.

 Another object of the present invention is to provide a photoresist peeling method using the above-mentioned photoresist stripper composition for removal.

In order to accomplish the above object, the present invention provides a process for the preparation of N-ethylformamide (NEF); Amine compounds; And a protonic polar solvent for removing photoresist.

According to one embodiment of the present invention, the photoresist stripper solution composition comprises 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 protonic polar solvent .

According to an embodiment of the present invention, the detacking liquid composition for removing photoresist may further comprise 1 to 30% by weight of ultrapure water or deionized water, or may further contain 0.01 to 5% by weight of additives, 30% by weight, and 0.01 to 5% by weight of an additive.

According to an embodiment of the present invention, the amine compound may be at least one selected from the group consisting of monoethanolamine (MEA), monoisopropanolamine (MIPA), imidazolidine ethanol (IME), 2-amino-1-propanol, aminoisopropanol (AEE), 2- (2-aminoethoxy) -1-ethanol (AEE), 2- ), Diethanolamine (DEA), 1- (2-hydroethyl) piperazine (HEP), triethanolamine (TEA), 1-piperidineethanolamine (PPEtOH), benzylpiperazine Benzylamine), or a mixture of two or more thereof.

According to an embodiment of the present invention, the protonic polar solvent may be selected from the group consisting of dimethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, monopropyl ether, monopropyl ether, 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 tetraethyl hardro And may be any one or a mixture of two or more selected from Tetra ethylhydro furyl alcohol.

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

The detachment liquid composition for removing photoresist of the present invention can be used for removing photoresist without using N-methylforamide (NMF) or N-methylpyrrolidone (NMP) The modified photoresist can be quickly peeled off even after dry or wet etching, and foreign matter and unevenness remain on the substrate, which is advantageous in that the efficiency of the process can be remarkably increased.

In addition, the lower film corrosion is also minimized and the process efficiency can be significantly increased.

Hereinafter, a preferred embodiment and a method for measuring a physical property of a peeling liquid composition for removing a photoresist will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a release liquid composition for removing a photoresist used in the manufacture of displays and semiconductors, which can be better understood by the following examples, the following examples are for the purpose of illustration of the present invention, It is not intended to limit the scope of protection defined by the claims.

      The inventors of the present invention have found that it is possible to improve the removal rate of the photoresist without using N-methylforamide (NMF) or N-methylpyrrolidone (NMP) As a result of research to develop a releasing solution composition capable of reducing the time consumed for photoresist removal by using N-ethylformamide and minimizing the residue of foreign matter and stains on the substrate, And the present invention has been completed.

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

A first aspect of the present invention is a process for the preparation of a compound of formula Amine compounds; And a protonic polar solvent.

A second aspect of the present invention is a process for the preparation of a compound of formula Amine compounds; Lt; / RTI > solvents and additives.

A third aspect of the present invention is a process for the preparation of a compound of formula Amine compounds; Lt; / RTI > polar solvent and ultrapure water or deionized water.

A fourth aspect of the present invention is a process for the preparation of a compound of formula Amine compounds; Protic polar solvents, additives, and ultrapure water or deionized water.

The content of N-ethylformamide according to an embodiment of the present invention is not limited, but may be 10 to 80% by weight. And more preferably 15 to 70% by weight. By including it in the above-mentioned range, the peeling force can be improved, the time for removing the photoresist can be remarkably shortened, and the lower film corrosion can be minimized.

When the content of the above-mentioned N-ethylformamide is less than 10% by weight, the improvement of the peeling force is insignificant, and it takes a long time to remove the photoresist, and foreign matters and stains may remain on the substrate. If it exceeds 80% by weight, the lower film may be corroded.

 According to one embodiment of the present invention, the release liquid composition for removing the photoresist of the present invention may contain an amine compound. The amine compound according to an embodiment of the present invention can further improve the peeling force of the photoresist modified by the N-ethylformamide combination.

The amine compound acts on a relatively weak part of the surface of the modified photoresist, thereby facilitating the penetration of the solvent component.

The amine compound of the present invention is a compound well known in the art and is not limited. For example, monoethanolamine (MEA), monoisopropanolamine (MIPA), imidazolidine ethanol (IME), 2-amino-1-propanol, aminoisopropanol (AIP), N-methylaminoethanol Amino-1-butanol, aminoethoxyethanol (AEE), 2- (2-aminoethoxy) -1-ethanol (AEE), diethanolamine (DEA) One or two selected from 1- (2-hydroxyethyl) piperazine (HEP), triethanolamine (TEA), 1- piperidineethanolamine (PPEtOH), benzylpiperazine (BP) and benzylamine The above mixture can be selected.

The amine compound according to an embodiment of the present invention may contain 1 to 30% by weight based on the total weight of the photoresist stripper solution composition. And more preferably 3 to 25% by weight. By including it in the above-mentioned range, the peeling force against the denatured photoresist can be remarkably improved.

If the content of the amine compound is less than 1% by weight, peeling force against the denatured photoresist may decrease to cause stains or foreign matter to remain on the substrate. If the content exceeds 30% by weight, aluminum and copper wires There is a risk of corrosion of the substrate.

In the case of the protonic polar solvent, it is not limited to the protonic polar solvent well known in the art, but for example, dimethylethylene glycol monoethyl ether, diethylene glycol monoethyl ether 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 monobutyl ether, ethylene glycol propyl ether, ethylene glycol monobutyl ether (ethylene glycol monoethyl ether), ethylene glycol monobutyl ether Ethylene Glycol Monobutyl Ether), diethylene glycol monobut But is not limited to, any one or a mixture of two or more selected from diethylene glycol monobutyl ether and tetraethylhydrofuryl alcohol.

More preferred are diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, glycol monobutyl ether, and tetraethylhydrofuryl alcohol may be selected from one or more of them.

The protonic polar solvent according to an embodiment of the present invention may contain 10 to 80% by weight, based on the total weight of the photoresist stripper solution composition. More preferably from 25 to 78% by weight. By including it in the above-mentioned range, the peeling force against the denatured photoresist can be remarkably improved.

If the content of the proton-polar solvent is less than 10% by weight, the peeling force against the denatured photoresist may be lowered, and stains or foreign matter may remain on the substrate. If the content exceeds 80% by weight, There is a problem in that the damage to the surface of the substrate is increased.

Since the detacking liquid composition for removing the photoresist of the present invention may be a water-based or non-aqueous composition well known in the art in addition to the above components, ultrapure water or deionized water may be added within a range that does not impair the physical properties of the photoresist stripper liquid composition. . More specifically from 1 to 30% by weight, and more preferably from 2 to 5% by weight.

In addition to the above components, the release liquid composition for removing photoresist of the present invention may further contain at least one kind of other additives as needed. 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 well known in the art, and specifically includes benzotriazole, tolythriazole, carboxybenzotriazole, 1-hydroxylbenzotriazole, nitrobenzotriazole, dihydro Propylbenzotriazole, and the like, but are not limited thereto.

In the photoresist stripper composition, 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.

According to still another embodiment of the present invention, there can be provided a photoresist peeling method for treating the photoresist stripper composition for removing the photoresist.

The photoresist stripping method is a method in which a substrate is etched using a photoresist pattern formed on an organic insulating film, a metal wiring, or a substrate including a metal wiring and an inorganic material layer as a mask, and stripping.

The method of peeling the photoresist from the substrate on which the fine circuit pattern is formed using the photoresist peeling liquid composition according to an embodiment of the present invention is a method of dipping a substrate to be peeled into a large amount of the peeling liquid at the same time But not limited to, a dipping method and a single-wafer method in which a photoresist is removed by spraying (spraying) a stripping liquid onto a substrate.

Examples of the type of the photoresist that can be peeled off using the photoresist stripper composition of the present invention include a positive photoresist, a negative photoresist, and a positive / negative dual tone photoresist The photoresist, which is particularly effective and can be applied, may be a photoresist composed of a photoactive compound containing a novolac-based phenol resin and a diazonaphthoquinone.

The metal wiring to which the photoresist removing liquid composition can be applied may include, for example, a Au / Al / Ni / Cr semi-conductor film and a Cu / dissimilar metal alloy, silver or silver alloy as the lower film , But is not limited thereto.

According to another embodiment of the present invention, there can be provided a liquid crystal display device or a semiconductor device manufactured by processing the photoresist stripping liquid composition for removing the photoresist.

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 separation method.

Best Mode for Carrying Out the Invention Hereinafter, a preferred embodiment and a physical property measuring method of the peeling liquid composition for removing the photoresist of the present invention will be described in detail.

Property measurement

One) Photoresist  Peel rate evaluation

To evaluate the photoresist peeling performance of the photoresist stripper composition for removing photoresist prepared as shown in Table 1 below, a photoresist composition was applied to a glass substrate at a thickness of 1.5 탆, and then dried at 160 캜 and 170 캜 for 10 minutes Experimental specimens were prepared by hard bake (H / B). The time taken for the photoresist to be completely peeled off by the peeling liquid under the spray pressure of 0.4 kgf was measured using a single-wafer spray type peeling apparatus in which the temperature was maintained at 60 캜. The evaluation results are shown in Table 2 below.

2) Evaluation of insulation film damage

The photoresist composition was coated on the glass substrate to a thickness of 1.5 탆, and hard bake was performed at 160 캜 and 170 캜 for 10 minutes, respectively, to prepare test specimens. The photoresist was peeled off completely with a peeling liquid under a spraying pressure of 0.4 kgf using a single-leaf type spray-type peeling apparatus in which the temperature was maintained at 60 ° C. The dried specimens were observed under an optical microscope of 200 magnifications and FE- The degree of damage of the insulating film was confirmed by SEM. When the insulation film damage was found, it was described as "good" when there was no insulation film damage and "poor" when the insulation film damage was found.

[Examples and Comparative Examples]

The components and compositions shown in Table 1 below were mixed to prepare a photoresist peel solution composition for removing the photoresist. At this time, mixing was carried out at room temperature, and the mixture was mixed for 1 hour or more so as to be sufficiently dissolved, and then filtered using 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-piperidine Ethanol

DEA: diethanolamine

TEA: triethanolamine

NMEA: N-methylaminoethanol

BP: benzylpiperazine

HEP: 1- (2-Hydroethyl) piperazine

BA: benzylamine

<Non-polar magnetic polar solvent>

MDG: diethylene glycol monomethyl ether

BDG: diethylene glycol monobutyl ether

EDG: diethylene glycol monoethyl ether

<Additives>

CHIDM: 1,4-cyclohexanedimethanol

TT: Tolythriazole

division Peeling performance evaluation Organic insulating film
Damaged 160 ° C, H / B 170 ° C, 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 Bad Comparative Example 6 60 70 Bad Comparative Example 7 60 300 Bad

As shown in Table 2, it was confirmed that the peeling liquid composition for removing the photoresist according to the present invention is remarkably excellent in both the removal rate and the lower film corrosion. 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 occurs in the insulating film. And more preferably 15 to 70% by weight.

In the case of Comparative Examples 1 to 5, the time required for removing the photoresist at 160 ° C. and 170 ° C. was 50 seconds and 60 seconds, respectively, which was longer than that in Examples 5 to 6 times. Showed excessive use of amines to cause corrosion of the underlying film.

Accordingly, the photoresist stripper composition for removing photoresist according to the present invention can rapidly remove the photoresist without damaging the organic insulating film, and the efficiency and reliability of the process can be increased due to the removal of foreign matter and unevenness upon removal.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Accordingly, the above description should not be construed as limiting the scope of the present invention defined by the limits of the following claims.

Claims (5)

10 to 80% by weight of N-ethyl formamide, 1 to 30% by weight of an amine compound and 10 to 80% by weight of a protonic polar solvent. The method according to claim 1,
The photoresist stripper composition may further contain 1 to 30% by weight of ultrapure water or deionized water,
0.01 to 5% by weight of an additive,
1 to 30% by weight of ultrapure water or deionized water and 0.01 to 5% by weight of an additive. The method according to claim 1,
The amine compound may be at least one selected from the group consisting of monoethanolamine (MEA), monoisopropanolamine (MIPA), imidazolidine ethanol (IME), 2-amino-1-propanol, aminoisopropanol (AIP) Amino-1-butanol, aminoethoxyethanol (AEE), 2- (2-aminoethoxy) -1-ethanol (AEE), diethanolamine (DEA) One or two selected from 1- (2-hydroxyethyl) piperazine (HEP), triethanolamine (TEA), 1- piperidineethanolamine (PPEtOH), benzylpiperazine (BP) and benzylamine By weight based on the total weight of the photoresist composition. The method according to claim 1,
The protonic polar solvent may be selected from the group consisting of dimethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, Diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Dipropylene glycol monobutyl ether, ethylene glycoll propyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and tetraethyl Tetra ethylhydrofuryl alcohol wherein the photoresist-removing liquid composition is a mixture of one or more selected from the group consisting of polyvinyl alcohol, polyvinyl alcohol, and polyvinyl alcohol. 3. The method of claim 2,
Wherein the additive is a triazole compound.