TWI743079B - Photoresist stripper composition - Google Patents

Abstract

Provided is a photoresist stripper composition capable of rapidly stripping a modified photoresist even after dry etching or wet etching without using, as a main solvent, N-methylformamide (NMF) or N-methylpyrrolidone (NMP), which is harmful to the environment and the human body, wherein foreign substances and stains do not remain on a substrate, and thus, process efficiency may be remarkably increased. In addition, it is possible to minimize corrosion of a lower film to remarkably increase the process efficiency.

Description

Photoresist stripper composition

The present invention relates to a photoresist stripping agent composition containing an amine compound, a polar solvent and a non-polar solvent and not containing toxic substances harmful to the human body.

The photo-etching process is a series of photo-processes in which a pattern designed in a mask is transferred to a substrate on which a thin film to be processed is formed. The photolithography process is used to manufacture integrated circuits, highly integrated circuits, etc.

In the photoetching process, a photoresist, which is a photosensitive material, is coated on a glass substrate with a thin film formed thereon, and a photomask is set and exposed on the substrate coated with a photoresist 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 can be used as a photomask to perform wet etching or dry etching to transfer and etch fine circuit patterns. Then, the unnecessary photoresist pattern is removed by using a release agent for removing the composition of the photoresist pattern.

In particular, the photoresist stripper composition used in the process of forming electrode circuits for displays and semiconductors should be able to peel off the photoresist in a short time at a low temperature, and should not leave the photoresist on the substrate after cleaning. the remains. At the same time, the photoresist stripper composition needs to have the ability to peel off without damaging the organic insulating film and the metal wiring. The photoresist stripper composition may basically include organic compounds, such as amine compounds, alkylene glycol alkyl ether compounds, aprotic polar solvents, and corrosion inhibitors. Considering the peeling ability and corrosiveness of various stripping agent compositions as described above, aprotic solvents such as N-methylformamide (NMF), N-methylpyrrolidone (N-methylpyrrolidone; NMP), etc. are mainly used as Main solvent (Korean Patent Publication No. 10-2011-0124955, Korean Patent Publication No. 10-2014-0028962, Korean Patent Publication No. 10-2015-0102354, Korean Patent Registration No. 10-0655108, etc.). These solvents have the advantage of excellent peeling force, but they are harmful to the environment and the human body. Therefore, there is still a continuing need to develop alternative solvents for replacing aprotic polar solvents.

[Prior Technical Literature]

[Patent Literature]

Patent Document 1: Korean Patent Publication No. 10-2011-0124955.

Patent Document 2: Korean Patent Publication No. 10-2014-0028962.

Patent Document 3: Korean Patent Publication No. 10-2015-0102354.

Patent Document 4: Korean Patent Registration No. 10-0655108.

One embodiment of the present invention relates to providing a photoresist stripper composition capable of improving the peeling speed by using a solvent that is harmless to the environment and the human body. More specifically, one embodiment of the present invention relates to the development of a photoresist stripper composition capable of including N-ethylformamide (NEF) which is harmless to the environment and the human body, has excellent peeling force, and can minimize the lower layer Corrosion of the lower film.

Another embodiment of the present invention relates to providing a method for stripping photoresist by using the photoresist stripper composition as described above.

In a general aspect, the photoresist stripper composition includes: N-ethylformamide (NEF); an amine compound; and a protic polar solvent.

The photoresist stripper composition may further include: 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 photoresist stripper composition may further include: 1 wt% to 30 wt% of ultrapure water or deionized water; or may further include 0.01 wt% to 5 wt% % By weight of additives; or may further include 1% to 30% by weight of ultrapure water or deionized water, and 0.01% to 5% by weight of additives.

The amine compound can be selected from monoethanolamine, monoisopropanolamine, imidazolidine ethanol (imidazolidine ethanol), 2-amino-1-propanol, aminoisopropanol, N-methylaminoethanol, 3-amino-1- Propanol, 4-amino-1-butanol, 2-(2-aminoethoxy)ethanol, diethanolamine, 1-(2-hydroxyethyl)piperazine, triethanolamine, 1-piperidineethanolamine, benzyl Any one or a mixture of two or more of the group consisting of benzyl piperazine and benzylamine.

The protic polar solvent can 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 monoethyl ether, and diethylene glycol monoethyl ether. Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, ethylene glycol propyl ether, ethylene glycol monobutyl ether and tetraethylhydrofuranol (tetraethyl hydrofuranol) hydrofurylalcohol) any one or a mixture of two or more of the group.

The additive may be a triazole compound.

The photoresist stripper composition of the present invention can quickly peel off the modified photoresist even after dry etching or wet etching, without using N-methylformamide (NMF) which is harmful to the environment and the human body Or N-methyl Pyrrolidone (NMP) is used as the main solvent, and foreign matter and stains will not remain on the substrate, so the process efficiency can be significantly improved.

In addition, the corrosion of the underlying film can be minimized to significantly improve the process efficiency.

Hereinafter, preferred embodiments of the photoresist stripper composition and methods of measuring its physical properties are described in detail. The present invention relates to a photoresist stripper composition for manufacturing displays and semiconductors. The present invention can be better understood by the following examples, and these examples are provided in an illustrative manner, but are not intended to limit the scope of protection defined in the scope of the patent application attached to the present invention.

The inventors of this case worked hard to develop a photoresist stripper composition that can improve the rate of photoresist removal without using N-methylformamide (NMF) or N-methylpyrrolidone (NMP), which is harmful to the human body, as the main It was found that when N-ethylformamide is used, the time spent in removing the photoresist can be reduced, and the retention of foreign matter and stains on the substrate can be minimized, thereby improving the process efficiency, and Complete the present invention.

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

The photoresist stripping agent composition according to the first aspect of the present invention includes N-ethylformamide; an amine compound; and a protic polar solvent.

The photoresist stripping agent composition according to the second aspect of the present invention includes N-ethylformamide; an amine compound; a protic polar solvent; and an additive.

The photoresist stripper composition according to the third aspect of the present invention includes N-ethylformamide; an amine compound; a protic polar solvent; and ultrapure water or deionized water.

The photoresist stripper composition according to the fourth aspect of the present invention includes N-ethylformamide; an amine compound; a protic polar solvent; an additive; and ultrapure water or deionized water.

The content of N-ethylformamide according to an exemplary embodiment of the present invention is not limited, but may be 10% by weight to 80% by weight. More preferably, the content may be about 15% to about 70% by weight. By including N-ethylformamide in the above-mentioned range, the peeling force can be improved to significantly reduce the photoresist removal time, and the corrosion of the underlying film 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 not significant, so it may take a long time to remove photoresist, foreign matter, stains, etc. that may remain on the substrate. In addition, when the content of N-ethylformamide is greater than 80% by weight, the underlying film may be corroded.

According to an exemplary embodiment of the present invention, the photoresist stripper composition may include an amine compound. The amine compound according to the exemplary embodiment of the present invention can improve the peeling force of the modified photoresist by combining N-ethylformamide.

The amine compound acts on the relatively weak part of the surface of the modified photoresist, thereby promoting 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 thereto. For example, the amine compound can be selected from the group consisting of monoethanolamine, monoisopropanolamine, imidazolium ethanol, 2-amino-1-propanol, aminoisopropanol, N-methylaminoethanol, 3-amino-1-propanol Alcohol, 4-amino-1-butanol, 2-(2-aminoethoxy)-1-ethanol, diethanolamine, 1-(2-hydroxyethyl)piperazine, triethanolamine, 1-piperidineethanolamine, Any one or a mixture of two or more of the group consisting of benzylpiperazine and benzylamine.

More preferably, selected from monoethanolamine, monoisopropanolamine, 2-(2-aminoethoxy)-1-ethanol, 1-piperidineethanolamine, diethanolamine, triethanolamine, N-methylaminoethanol, benzyl Piperazine, 1-(2-hydroxyethyl)piperazine, and benzylamine can be combined with N-ethylformamide, and thus the long-term storage stability of the composition can be further improved, and the peeling force can be further improved.

The amine compound according to the exemplary embodiment of the present invention, based on the total weight of the photoresist stripper composition, may have 1 wt% to 30 wt% content. More preferably, the content of the amine compound may be 3% to 25% by weight. By including the amine compound in the above range, the peeling force of the modified photoresist can be significantly improved.

When the content of the amine compound is less than 1% by weight, the peeling force to the modified photoresist is reduced, and therefore there is a risk of stains or foreign matter remaining on the substrate. When the content of the amine compound is more than 30% by weight, the aluminum wire and the copper wire under the photoresist may be corroded.

The protic polar solvent may be a protic polar solvent that is clearly known in the art, but it is not limited thereto. For example, it may be selected from the group consisting of dimethyl glycol monoethyl ether, diethylene glycol monoethyl ether, and diethyl ether. Glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, ethylene glycol propyl ether , Ethylene glycol monobutyl ether and tetraethylhydrofuranol, any one or a mixture of two or more of the group.

More preferably, the protic polar solvent may be selected from the group consisting of diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether and tetraethyl hydrogenated One or two or more of the group consisting of furanol.

More preferably, any one or two or more selected from diethylene glycol monobutyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether can be used When mixed with N-ethylformamide and an amine compound, the long-term storage stability of the composition can be further improved, and the peeling force can be further improved.

The protic polar solvent according to an exemplary embodiment of the present invention may have a content of 10% to 80% by weight based on the total weight of the photoresist stripper composition. More preferably, the content of the protic polar solvent may be 25% to 78% by weight. By including the protic polar solvent in the above range, the peeling force of the modified photoresist can be significantly improved.

When the content of the protic polar solvent is less than 10% by weight, the peeling force of the modified photoresist will be reduced, and therefore there may be a risk of stains or foreign matter remaining on the substrate. When the content of the protic polar solvent is greater than 80% by weight, the problem of damage to the organic insulating film under the common electrode may increase.

In addition to the above components, since the photoresist stripper composition of the present invention can be a water-based or non-aqueous composition well known in the art, the photoresist stripper composition is used in the photoresist stripper. The composition may further include ultrapure water or deionized water within the range where the physical properties of the composition are not hindered. More specifically, the ultrapure water or deionized water may have a content of 1% to 30% by weight, and more preferably, 2% to 5% by weight, but the content is not limited thereto.

In addition, in addition to the above-mentioned components, the photoresist release agent composition of the present invention may further include at least one other additive as required. For example, you can Triazole compounds are included as corrosion inhibitors. The triazole compound is not particularly limited as long as it is a compound known in the art, and specifically, it may include benzotriazole, tolyltriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, nitro Base benzotriazole, dihydroxypropyl benzotriazole, etc. More preferably, by using tolyltriazole, the long-term storage stability and anti-corrosion effect can be further improved, and the peeling force can be further improved.

The photoresist stripper composition may include the triazole compound in an amount of 0.01% to 5% by weight, and more preferably 0.1% to 0.5% by weight, but the content is not limited thereto.

According to another exemplary embodiment of the present invention, a method of stripping photoresist by processing the photoresist stripper composition can be provided.

The method of stripping photoresist may include etching the substrate by using a photoresist pattern formed on a substrate including an organic insulating film, a metal wiring, or a metal wiring and an inorganic material layer as a photomask, and using the photoresist stripper composition To peel off the photoresist.

The method of peeling the photoresist from the substrate on which the fine circuit pattern is formed by using the photoresist stripper composition according to the exemplary embodiment of the present invention may include two kinds of dipping method and single wafer method. The stripped multiple substrates are immersed in a large amount of stripper solution at the same time. The single-wafer method is to remove the light by spraying the stripper solution onto each substrate. Resistance, but it is not limited to this.

Examples of photoresists that can be stripped by using the photoresist stripper composition of the present invention may include positive photoresist, negative photoresist, and positive/negative dual dimming photoresist (positive/negative dual tone photoresist), and there are no restrictions on its components. However, a particularly and effectively applicable photoresist may be a photoresist composed of a photoactive compound including novolak-based phenol resin and diazonaphthoquinone.

The metal wiring to which the photoresist stripper composition can be applied may include, for example, Au/Al/Ni/Cr four-piece film, Cu/dissimilar metal alloy, silver or silver alloy as the underlying film, etc., but it is not limited thereto.

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

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

Hereinafter, a preferred embodiment of the photoresist stripper composition and a method of measuring its physical properties will be described in detail.

Measurement of physical properties

1) Evaluation of photoresist peeling speed

In order to evaluate the photoresist peeling performance of the photoresist stripper composition prepared as shown in Table 1 below, the photoresist composition was coated on a glass substrate with a thickness of 1.5 μm and hardened at 160°C and 170°C, respectively. Bake (H/B) for 10 minutes to prepare test samples. Using a single-wafer spray stripping device in which the temperature was maintained at 60°C, the time required for the photoresist to be completely stripped off by the stripper solution was measured under a spray pressure of 0.4 kgf. The evaluation results are shown in Table 2 below.

2) Assess the damage of the insulating film

Test samples were prepared by coating the photoresist composition on a glass substrate with a thickness of 1.5 μm and performing hard bake (H/B) at 160° C. and 170° C. for 10 minutes, respectively. Using a single-wafer spray peeling device in which the temperature is maintained at 60°C, the photoresist is completely peeled off with a release agent solution at a spray pressure of 0.4 kgf, and the sample is dried. The degree of damage to the insulating film of the dried sample was confirmed by an optical microscope at a magnification of 200 and an FE-SEM at a magnification of 10K to 50K. According to the degree of damage of the insulating film after confirmation, when the insulating film is not damaged, it is described as "good". When damage to the insulating film is found, it is described as "defective".

[Examples and comparative examples]

The components and compositions shown in Table 1 below were mixed to prepare a photoresist stripper composition. Here, mixing is performed at room temperature, and each mixture is mixed for 1 hour or more to fully dissolve, and then filtered using a Teflon filter (PTFA having a pore diameter of 1 μm).

[Solvent]

NEF: N-Ethyl Formamide

THFA: Tetraethyl Hydrofuranol

NMPA: N-Methylpropionamide

NMF: N-methylformamide

[amine]

MEA: Monoethanolamine

MIPA: Monoisopropanolamine

AEE: 2-(2-Aminoethoxy)ethanol

PPEtOH: 1-piperidine ethanol

DEA: Diethanolamine

TEA: Triethanolamine

NMEA: N-Methylaminoethanol

BP: Benzylpiperazine

HEP: 1-(2-hydroxyethyl)piperazine

BA: Benzylamine

[Proton Polar Solvent]

MDG: Diethylene glycol monomethyl ether

BDG: Diethylene glycol monobutyl ether

EDG: Diethylene glycol monoethyl ether

[additive]

CHIDM: 1,4-Cyclohexane dimethanol

TT: Tolyltriazole

As shown in Table 2, it can be confirmed that the photoresist stripper composition according to the present invention is significantly superior in both the removal rate and the minimization of the corrosion of the underlying film. In addition, it was confirmed that in the evaluation of long-term storage stability, the content of the release agent composition did not change, so the storage stability effect was excellent, and the loss due to evaporation during the manufacturing process was small. As shown in Comparative Example 6 and Comparative Example 7, when the content of N-ethylformamide was 85% by weight or 5% by weight, respectively, the removal rate was not improved, but the insulating film was damaged. Therefore, it can be understood that it is preferable to use 10% to 80% by weight, and more preferably 15% to 70% by weight of N-ethylformamide.

Shown in Comparative Example 1 to Comparative Example 5, at 160°C and 170 The time required to remove the photoresist at °C is 50 seconds and 60 seconds, respectively, which is about 5 to 6 times longer than the time required in their examples. In Comparative Example 5, excessive use of amine resulted in corrosion of the underlying film. Therefore, the photoresist stripper composition according to the present invention can quickly remove the photoresist without damaging the organic insulating film, and because no foreign matter and dirt are left when the photoresist is removed, the process efficiency and reliability are improved. sex.

As described above, although the preferred embodiments of the present invention are described, the present invention should be construed as including all changes, modifications and equivalents, so that it is obvious that the above exemplary embodiments can be used equivalently by appropriately modifying this invention. Therefore, the above description is not intended to limit the scope of the present invention defined by the limitation of the scope of the appended application.

Claims (4)

A photoresist stripper composition comprising: 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 photoresist stripping agent composition further comprises: i) 1% to 30% by weight of ultrapure water or deionized water; or ii) 0.01% to 5% by weight of additives; or iii) 1% to 30% by weight Wt% ultrapure water or deionized water and 0.01 wt% to 5 wt% additives. The photoresist stripper composition according to claim 1, wherein the amine compound is selected from the group consisting of monoethanolamine, monoisopropanolamine, imidazolium ethanol, 2-amino-1-propanol, aminoisopropanol, N- Methylaminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 2-(2-aminoethoxy)ethanol, diethanolamine, 1-(2-hydroxyethyl)piperazine, Any one or a mixture of two or more of the group consisting of triethanolamine, 1-piperidineethanolamine, benzylpiperazine, and benzylamine. The photoresist stripper composition according to claim 1, wherein the protic polar solvent is selected from the group consisting of dimethyl glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monoethyl ether. Ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, ethylene glycol propyl ether, ethylene glycol monobutyl ether And any one or a mixture of two or more of the group consisting of tetraethylhydrofuranol. The photoresist stripper composition according to claim 1, wherein the additive is a triazole compound.