Photoresist stripping liquid composition for manufacturing display

Abstract

The present invention relates to a photoresist stripping solution composition for manufacturing a display, and more particularly, to an eco-friendly photoresist stripping solution composition for manufacturing a display, which uses a specific stripping promoter and an amine mixture having different boiling points, without using an aprotic amide-based organic solvent harmful to the environment and the human body, thereby having excellent photoresist removal ability.

Description

Technical Field

[0001] This invention relates to a photoresist stripping solution composition for manufacturing displays, and more specifically, to an environmentally friendly photoresist stripping solution composition for manufacturing displays, which uses a specific stripping accelerator and a mixture of amines with different boiling points, without using non-protic amide organic solvents that are harmful to the environment and human health, thereby exhibiting excellent photoresist removal capabilities. Background Technology

[0002] In display manufacturing, photolithography is used to form specified patterns of metal and oxide wiring on a substrate. This photolithography process mainly consists of various steps, including photolithography, dry or wet etching, ashing, and development. After coating the substrate with photoresist and performing exposure and development processes, a dry or wet etching process is performed to form the pattern on the substrate. In this case, any photoresist residue remaining on the metal and oxide wiring needs to be removed using a photoresist stripping solution.

[0003] Photoresist stripping solutions typically require strong stripping power, thus containing aprotic amide organic solvents as a main component. However, it is known that the waste liquid remaining after using stripping solutions containing such aprotic amide organic solvents has been found to have high total nitrogen (TN) levels, which are harmful to the environment and human health, making its disposal a major problem. Furthermore, with the increasing regulation of total nitrogen (TN) content in current industrial environments, there is an urgent need to replace photoresist stripping solutions with low total nitrogen (TN) content and strong stripping power.

[0004] The inventors discovered that by using a specific stripping accelerator and a mixture of amines with different boiling points in existing photoresist stripping compositions used for manufacturing displays, without using non-protic amide organic solvents that are harmful to the environment and human health, a photoresist stripping composition with excellent photoresist removal capability while reducing total nitrogen (TN) levels can be obtained, thus completing the present invention. Summary of the Invention

[0005] Technical issues The purpose of this invention is to provide a photoresist stripping solution composition for manufacturing displays, which solves the problems caused to human health and the environment when using aprotic amide organic solvents with high total nitrogen (TN) levels when waste liquid is generated after treatment.

[0006] Specifically, the present invention aims to provide a photoresist stripping solution composition for manufacturing displays, which uses a specific stripping promoter and a mixture of amines with different boiling points, thereby reducing the total nitrogen (TN) level while exhibiting stronger stripping power and superior metal corrosion resistance compared to the use of existing aprotic amide organic solvents.

[0007] Technical solution To achieve the above objectives, the present invention uses a specific stripping accelerator and a mixture of amines with different boiling points without using aprotic amide organic solvents, in order to reduce the total nitrogen (TN) level and have stronger stripping power and excellent metal corrosion resistance than existing photoresist stripping solutions.

[0008] Specifically, the photoresist stripping solution composition of the present invention is characterized by not using non-protic amide organic solvents such as N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N-methylformamide (NMF), dimethylpropionamide (DMPA), and dimethylacetamide (DMAC), which are harmful to the environment and human body.

[0009] In this invention, the theoretical calculation method for the total nitrogen level of the stripping solution is shown in Calculation Formula 1 and Calculation Formula 2 below. Specifically, Calculation Formula 1 can be used to calculate the theoretical nitrogen level per 1 mol of each substance in the stripping solution composition, and Calculation Formula 2 can be used to calculate the theoretical total nitrogen (TN) level of the entire stripping solution composition.

[0010] Formula 1:

[0011] Formula 2:

[0012] In a specific embodiment of the present invention, preferably, the theoretical total nitrogen (TN) level of the photoresist stripping solution composition for manufacturing displays of the present invention is less than 0.3.

[0013] According to a specific embodiment of the present invention for achieving the above-mentioned objectives, the present invention provides a photoresist stripping liquid composition for manufacturing displays. The photoresist stripping liquid composition comprises: (a) 15–20% by weight of two amine compounds with different boiling points; (b) 45–60% by weight of protic polar organic solvents; (c) 5–10% by weight of cyclic alcohols; (d) 0.01–0.1% by weight of transition metal corrosion inhibitors; (e) 0.5 to 1% by weight of two peeling accelerators; and (f) The remaining ultrapure water, The two amine compounds with different boiling points are a combination of an amine with a boiling point less than 200°C and an amine with a boiling point above 200°C. The cyclic alcohol is selected from the group consisting of tetrahydrofurfuryl alcohol (THFA), furfuryl alcohol, and isopropylidenglycerol. The transition metal corrosion inhibitor is a heterocyclic compound containing a thiol group. The peeling accelerator is composed of compounds of chemical formula 1 and chemical formula 2. Do not use aprotic amide organic solvents. Chemical Formula 1:

[0014] In the chemical formula 1, R1 has C n H 2n+1 n is 3 to 8.

[0015] Chemical formula 2:

[0016] In a specific embodiment of the present invention, the amine with a boiling point less than 200°C is selected from the group consisting of monoethanolamine (MEA), monoisopropanolamine (MIPA), 2-(Methylamino)ethanol (NMEA), and 2-isopropylaminoethanol.

[0017] In a specific embodiment of the present invention, the amine with a boiling point above 200°C is selected from the group consisting of 1-(2-hydroxyethyl)piperidine (HEPD), methyl diethanolamine (MDEA), 1-(2-hydroxyethyl)piperazine (HEP) and 2-(2-aminoethoxy)ethanol (AEE).

[0018] In a specific embodiment of the present invention, the content of the two amine compounds with different boiling points is preferably 15 to 20% by weight, and the ratio of the amine with a boiling point less than 200°C to the amine with a boiling point above 200°C is preferably 2:1 by weight.

[0019] Furthermore, in a specific embodiment of the present invention, the ratio of the total amount of the two amine compounds with different boiling points to the content of the protic polar organic solvent is preferably 1:3 by weight. This is because when using two amine compounds with different boiling points, when the amine with the lower boiling point is partially consumed due to temperature and volatilization during operation, the amine with the higher boiling point can play an auxiliary role as a protic polar organic solvent.

[0020] In one specific embodiment of the present invention, the transition metal corrosion inhibitor is preferably a heterocyclic compound containing a thiol group, more preferably 2-mercapto-1-methylimidazole (MMI).

[0021] In one specific embodiment of the present invention, the stripping accelerator is a substance having the structure of the following chemical formula 1. Preferably, it is a combination of one of the following substances, such as propyl gallate, butyl gallate, octyl gallate, etc., and 1,3-diaminopropane-N,N,N',N''-tetraacetic acid (PDTA).

[0022] Chemical Formula 1:

[0023] In the chemical formula 1, R1 has C n H 2n+1 n is 3 to 8.

[0024] Specifically, more preferably, the compound of the above-mentioned chemical formula 1 is octyl gallate (OG) or propyl gallate (PG).

[0025] In a specific embodiment of the present invention, preferably, the proton-polar organic solvent is a solvent selected from the group consisting of ethylene glycol (EG), propylene glycol (PG), diethylene glycol monoethyl ether (EDG), diethylene glycol monobutyl ether (BDG), and diethylene glycol monomethyl ether (MDG).

[0026] In a specific embodiment of the present invention, preferably, the amount of the proton-polar organic solvent is 45-60% by weight of the total content of the composition, and the ratio of the total amount of the two amine compounds with different boiling points to the content of the proton-polar organic solvent is preferably 1:3 by weight.

[0027] In a specific embodiment of the present invention, the cyclic alcohol is selected from the group consisting of tetrahydrofurfuryl alcohol (THFA), furfuryl alcohol, and isopropylidenglycerol, preferably 5 to 10% by weight.

[0028] Invention Effects According to the present invention, a photoresist stripping solution composition for manufacturing displays is provided, which, without using aprotic amide organic solvents, uses a specific stripping promoter and a mixture of amines with different boiling points to reduce the total nitrogen (TN) level and has stronger stripping power and excellent metal corrosion resistance than existing photoresist stripping solutions.

[0029] The above composition does not use aprotic amide organic solvents, produces a low total nitrogen (TN) level, and when the waste liquid generated after use is treated, the total nitrogen (TN) level is as low as less than 0.3, thus exhibiting excellent water treatment performance in terms of environment, and further improving peeling force and excellent corrosion resistance. Attached Figure Description

[0030] Figure 1 These are microscope images used to evaluate the degree of corrosion in some embodiments and comparative examples of the present invention. Detailed Implementation

[0031] The embodiments of the present invention are provided to illustrate the invention more fully to those skilled in the art. The following embodiments can be modified in various ways, and the scope of the invention is not limited to the following embodiments. Rather, these embodiments are provided to make the invention more comprehensive and complete, and to convey the spirit of the invention more fully to those skilled in the art.

[0032] Furthermore, in the accompanying drawings, for ease of explanation and clarity, the thickness or size of each layer is exaggerated, and the same reference numerals in the drawings denote the same elements. As used in this specification, the term "and / or" includes any one or more of the listed items in all combinations.

[0033] The terminology used in this specification is for describing specific embodiments and is not intended to limit the invention. As used herein, singular expressions may include plural expressions unless explicitly indicated by the context. Furthermore, the terms "comprise" and / or "comprising" as used herein are intended to indicate the presence of the mentioned shapes, numbers, steps, actions, components, factors, and / or combinations thereof, but do not exclude the presence or addition of more than one other shape, number, action, component, factor, and / or combination.

[0034] The photoresist stripping solution for displays of the present invention does not use the aprotic amide organic solvents commonly used in the industry, but is composed of a mixture of amines with different boiling points, a stripping promoter, a cyclic alcohol, a protic polar organic solvent, a corrosion inhibitor, and the balance water.

[0035] The preferred embodiments of the present invention will now be described in detail.

[0036] As described above, a specific example of the photoresist stripping solution composition of the present invention comprises: (a) 15–20% by weight of two amine compounds with different boiling points; (b) 45–60% by weight of protic polar organic solvents; (c) 5–10% by weight of cyclic alcohols; (d) 0.01–0.1% by weight of transition metal corrosion inhibitors; (e) 0.5 to 1% by weight of two peeling accelerators; and (f) The remaining amount of ultrapure water.

[0037] The two amine compounds with different boiling points are a combination of an amine with a boiling point less than 200°C and an amine with a boiling point above 200°C.

[0038] The cyclic alcohol is selected from the group consisting of tetrahydrofurfuryl alcohol (THFA), furfuryl alcohol, and isopropylidenglycerol.

[0039] The transition metal corrosion inhibitor is a heterocyclic compound containing a thiol group.

[0040] The stripping accelerator is composed of compounds of chemical formula 1 and chemical formula 2.

[0041] Do not use aprotic amide organic solvents.

[0042] Chemical Formula 1:

[0043] In the chemical formula 1, R1 has C n H 2n+1 n is 3 to 8.

[0044] Chemical formula 2:

[0045] In one specific embodiment of the present invention, the photoresist stripping solution uses a mixture of amines with different boiling points. When the amines with lower boiling points volatilize due to prolonged heating, resulting in losses and performance degradation, the amines with higher boiling points do not volatilize and remain, thereby playing a role in assisting and maintaining the performance of the amines. The total amine content is 15-20% by weight, and the mixing ratio of the amines with lower boiling points to those with higher boiling points is maintained at 2:1 by weight. Excessive use of amines will make it difficult to prevent corrosion of metal wiring; therefore, an appropriate amine content is required.

[0046] In one specific embodiment of the present invention, during the photoresist stripping process, the amine in the photoresist stripping solution weakens the bonding force between photoresists by severing the bonding chains of the photoresist modified after exposure and etching, thereby playing a major role in the stripping of the modified photoresist. When such amines are lost, a decrease in stripping force occurs; therefore, a decrease in the stripping force of the photoresist can be prevented by using amines with high boiling points as an auxiliary agent.

[0047] In one specific embodiment of the present invention, the stripping accelerator is preferably used in combination with compounds having structures such as chemical formula 1 and chemical formula 2. The terminal functional groups in the structure of each compound are ionized in the composition and exist in the form of a (-) charge. These ionized stripping accelerators undergo a chelation reaction by binding with metals and photoresists, thereby promoting the stripping effect of amines and improving the overall stripping force.

[0048] Furthermore, if the R group in Formula 1 is short, and the R group between N and N in Formula 2 is short, the reaction area is reduced due to the smaller molecular size of the peeling accelerator, making it difficult to obtain a peeling promotion effect. Specifically, when using peeling accelerators of Formula 1 and Formula 2, the total content of the peeling accelerator is preferably 0.1 to 1 weight percent or less. If the content of the peeling accelerator is less than 0.1 weight percent, the peeling force decreases significantly; if it is greater than 1 weight percent, it may exist in an undissolved state such as precipitation due to supersaturation in the composition.

[0049] In one specific embodiment of the present invention, the protic polar organic solvent used is one or more of the diols, which plays an auxiliary role in the stripping of photoresist. The diols help to fully mix the dissolved photoresist in the stripping solution, thereby helping to quickly remove residual stripping solution from the substrate surface during the cleaning process after the processing.

[0050] The diols that can be used in this invention have RO(CH2CH2O). n The general formula for H is used, where "R" refers to any one of straight-chain hydrocarbons, branched hydrocarbons, or cyclic hydrocarbons, and n is an integer greater than or equal to 1. Specifically, ethylene glycol (EG), propylene glycol (PG), diethylene glycol monoethyl ether (EDG), diethylene glycol monobutyl ether (BDG), and diethylene glycol monomethyl ether (MDG) are preferred, but not limited to these. Two or more of the above-mentioned glycols can be used in combination.

[0051] In one specific embodiment of the present invention, the content of the diol in the total composition is preferably 45-60% by weight. Preferably, it is in a 1:3 weight ratio with the amine compound described above.

[0052] In one specific embodiment of the invention, cyclic alcohols, like diols, are hydrophilic in the stripping solution, facilitating rapid removal from the substrate surface during the cleaning process. Specifically, tetrahydrofurfuryl alcohol (THFA), furfuryl alcohol, and isopropylidenglycerol are used. The content of the cyclic alcohols in the total composition is preferably 5 to 10% by weight.

[0053] In one specific embodiment of the invention, a transition metal corrosion inhibitor is used to prevent corrosion of metal wiring. The corrosion inhibitor is preferably a heterocyclic compound containing a thiol group, and more preferably, 2-mercapto-1-methylimidazole (MMI) is used.

[0054] The preferred content of the transition metal corrosion inhibitor in the total composition is 0.01 to 0.1% by weight. If the content of the corrosion inhibitor is too low, almost no corrosion protection effect on the metal wiring film will be observed; if the content of the corrosion inhibitor is too high, the photoresist stripping ability will be weakened. In the composition of the present invention, when using 0.1% by weight of corrosion inhibitor, it was confirmed that there were no abnormalities in corrosion protection and stripping ability. Furthermore, corrosion inhibitors are relatively expensive, so it is unnecessary to add an appropriate amount beyond the required amount. Specific Implementation The present invention will now be described in more detail through embodiments. These embodiments are merely illustrative of the invention, and it will be apparent to those skilled in the art that the scope of the invention is not to be construed as limited to these embodiments.

[0056] Example 1. Evaluation of the stripping and metal corrosion of modified photoresist The modified photoresist stripping ability was evaluated using the following method to compare the performance of the photoresist stripping solution composition of the present invention. The stripping solution composition of the present invention was prepared using two stripping accelerators and two amines with different boiling points, without using aprotic amide organic solvents. The specific components and contents are shown in Table 1 below. The components and contents of the composition prepared as a comparative example are shown in Table 2.

[0057] More specifically, a glass substrate with metal film wiring having retained photoresist after etching was prepared by heat treatment at 170°C on a hot plate. The prepared stripping solution composition was maintained at a set temperature, and the prepared substrate was immersed in the stripping solution composition. The stripping force was evaluated by the degree of removal of the modified photoresist. Furthermore, the stripping solution composition was maintained at the set temperature, and a glass substrate with metal film wiring that had not undergone heat treatment was immersed for the same amount of time to evaluate the corrosion under the wiring film.

[0058] The experimental results are shown in Table 3, and a portion of the results are selected for presentation. Figure 1 middle.

[0059] Modified photoresist peel strength: ◎: The modified photoresist is removed within 90 seconds; ○: The modified photoresist is removed within 120 seconds; △: The modified photoresist is removed within 180 seconds; X: The modified photoresist could not be removed within 240°.

[0060] Degree of corrosion at the bottom of the metal wiring: ◎: No corrosion was observed under the metal wiring; △: Corrosion at the bottom of the metal wiring was observed to be less than approximately 300 nm; X: Corrosion of approximately 300 nm or more was observed in the lower part of the metal wiring.

[0061] The compounds used in this invention are abbreviated as follows: MEA: Monoethanolamine (Mone Ethanol Amine); NMEA: 2-(Methylamino)Ethanol; MIPA: Monoisopropanol Amine; HEPD: 1-(2-Hydroxyethtyl)piperidine; AEE: 2-(2-Aminoethoxy)Ethanol; MDEA: Methyl diethanolamine; THFA: Tetrahydrofurfuryl alcohol; NMF: N-methylformamide; NMP: N-methylpyrrolidone; DMAC: Dimethylacetamide; EDG: Diethylene Glycol Monoethyl Ether; OG: Octyl Gallate; PG: Propyl gallate; MG: Methyl Gallate; PDTA: 1,3-Diaminopropane-N,N,N',N''-tetraacetic acid. EDTA: Ethylenediaminetetraacetic acid. MMI: 2-Mercapto-1-Methylimidazole;

[0062]

[0063]

[0064] As shown in Tables 1 and 2, the high total nitrogen (TN) value was calculated when using aprotic amide organic solvents. The results in Table 3 confirm that the modified photoresist of the composition of the present invention, which does not use aprotic amide organic solvents, exhibits improved peel strength and corrosion resistance.

[0065] Specifically, comparing Example 1 and Comparative Example 8, it can be seen that Example 1, as the composition of the present invention without the use of aprotic amide organic solvents, exhibits relatively superior peel strength and good corrosion resistance. Furthermore, when the ratio of amine mixtures with different boiling points is 2:1, the peel strength and corrosion resistance are improved compared to the cases where the ratio of amine mixtures is 1:1 (Comparative Example 10) or 1:2 (Comparative Example 9).

[0066] In Tables 1 and 2, the results compared with the composition (Comparative Example 21 and Comparative Example 22) in which the ratio of amine mixture to protic polar organic solvent was 1:3 (without amine mixture) show that the peeling force and corrosion resistance also decreased.

[0067] In Tables 1 and 2, comparisons were made between combinations using the same amount of amine. Referring to Examples 1, 9, 2, and 17, it can be seen that, compared to the case of using aprotic amide organic solvents and using only one amine, the peeling force and corrosion resistance of the compositions using amines with different boiling points, without using aprotic amide organic solvents, and using peeling accelerators are improved.

[0068] In Tables 1 and 2, Comparative Examples 4 and 5, which used only one of the two stripping accelerators, were compared with Example 1. It can be seen that there was no difference in corrosion resistance, but the photoresist stripping force decreased. As shown in Example 1, when a combination of two stripping accelerators was used, an increased stripping promotion effect was confirmed.

[0069] like Figure 1As shown in Tables 1 and 2, comparative example 11, which uses methyl gallate (MG) with R=1 in Formula 1, and comparative example 12, which uses ethylene diaminetetraacetic acid (EDTA), which is similar to Formula 2 but has one less R group between N and N, exhibits bottom etching. However, in example 1, which uses octyl gallate (OG), and example 12, which uses 1,3-diaminopropane-N,N,N',N''-tetraacetic acid (PDTA), excellent photoresist peel strength and corrosion resistance are confirmed.

[0070] Example 2. Comparative evaluation of the composition of the drug solution after being left exposed at high temperature The photoresist stripping composition of the present invention was placed in an open environment at high temperature to simulate long-term use. To compare whether the stripping force of the stripping composition on the modified photoresist changed after long-term use at high temperature, the following evaluation was conducted. The stripping composition of the present invention uses amines with different boiling points. The purpose is that when the composition is used in an open environment at high temperature for a long time, after the lower boiling point amine volatilizes, the higher boiling point amine assists in the stripping performance. To verify this, specific compositions were selected from Tables 1 and 2 for comparison.

[0071] More specifically, the photoresist stripper composition was heated to at least 10°C above the processing temperature, and then left exposed to the elements while maintaining the temperature. The composition was left exposed at this temperature for 72 hours, then cooled to the processing temperature, and the peel strength was evaluated. The substrate used in the evaluation was prepared in the same manner as the substrate used in the peel strength evaluation of Experimental Example 1.

[0072]

[0073] As shown in Table 4, when using amines with low boiling points alone, the amines in the composition volatilize after 72 hours, resulting in a decrease in peel strength. Conversely, when using amines with different boiling points, even if the low-boiling-point amines partially volatilize, the high-boiling-point amines remain, thus maintaining the peel strength.

[0074] This concludes the description of the present invention focusing on preferred embodiments. Those skilled in the art will understand that the present invention can be implemented in modified forms without departing from its essential characteristics.

Claims

1. A photoresist stripping solution composition for manufacturing displays, characterized in that, The photoresist stripping solution composition comprises: (a) 15–20% by weight of two amine compounds with different boiling points; (b) 45–60% by weight of protic polar organic solvents; (c) 5–10% by weight of cyclic alcohols; (d) 0.01–0.1% by weight of transition metal corrosion inhibitors; (e) 0.5 to 1% by weight of two peeling accelerators; as well as (f) The remaining amount of ultrapure water; The two amine compounds with different boiling points are a combination of an amine with a boiling point less than 200°C and an amine with a boiling point above 200°C. The cyclic alcohol is selected from the group consisting of tetrahydrofurfuryl alcohol, furfuryl alcohol, and acetone glycerol. The transition metal corrosion inhibitor is a heterocyclic compound containing a thiol group. The peeling accelerator is composed of compounds of chemical formula 1 and chemical formula 2. Do not use aprotic amide organic solvents. Chemical Formula 1: ， In the chemical formula 1, R1 has C n H 2n+1 n is 3 to 8. Chemical formula 2: 。 2. The photoresist stripping solution composition for manufacturing displays according to claim 1, characterized in that, The amine with a boiling point less than 200°C is selected from the group consisting of monoethanolamine, monoisopropanolamine, 2-methylaminoethanol and 2-isopropylaminoethanol.

3. The photoresist stripping solution composition for manufacturing displays according to claim 1, characterized in that, The amine with a boiling point above 200°C is selected from the group consisting of 1-(2-hydroxyethyl)piperidine, methyldiethanolamine, 1-(2-hydroxyethyl)piperazine and 2-(2-aminoethoxy)ethanol.

4. The photoresist stripping solution composition for manufacturing displays according to claim 1, characterized in that, In the two amine compounds with different boiling points, the weight ratio of the amine with a boiling point less than 200°C to the amine with a boiling point above 200°C is 2:

1.

5. The photoresist stripping solution composition for manufacturing displays according to claim 1, characterized in that, The total amount of the two amine compounds with different boiling points is in a weight ratio of 1:3 to the protic polar organic solvent.

6. The photoresist stripping solution composition for manufacturing displays according to claim 1, characterized in that, The transition metal corrosion inhibitor is 2-mercapto-1-methylimidazole.

7. The photoresist stripping solution composition for manufacturing displays according to claim 1, characterized in that, The compound of chemical formula 1 is octyl gallate or propyl gallate.

8. The photoresist stripping solution composition for manufacturing displays according to claim 1, characterized in that, The protic polar organic solvent is selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and diethylene glycol monomethyl ether.

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