TW202141206A - Photoresist stripper which has excellent storage stability while maintaining sufficient photoresist stripping performance - Google Patents

Abstract

The present invention provides a photoresist stripper having an excellent storage stability while maintaining sufficient photoresist stripping performances. The photoresist stripper of the present invention contains quaternary ammonium hydroxide (A), water (B) and an organic solvent (C). The organic solvent (C) is a mixture of the following organic solvents (C1), (C2) and (C3). For the organic solvent (C1), the polarity term (dP) of the Hansen solubility parameter is 15.0 or more and less than 21.0 and the hydrogen bond term (dH) is 6.0 or more and less than 14.0. For the organic solvent (C2), the polar term (dP) of the Hansen solubility parameter is 3.0 or more and less than 14.0 and the hydrogen bond term (dH) is 8.0 or more and less than 31.0. For the organic solvent (C3), the polarity term (dP) of the Hansen solubility parameter is 3.0 or more and less than 8.0 and the hydrogen bond term (dH) is 2.5 or more and less than 8.0. The content of the organic solvent (C1) is 15 to 80% by weight. The content of the organic solvent (C2) is 1 to 50% by weight. The content of the organic solvent (C3) is 3 to 50% by weight. The total content of the organic solvents (C1) to (C3) is 60 to 95% by weight. The photoresist stripper further comprises alkylene amine or alkanolamine (D). The organic solvent (C1) is dimethyl sulfoxide. The photoresist stripper is used for stripping a dry film resist. The quaternary ammonium hydroxide includes tetramethylammonium hydroxide (TMAH), trimethylethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, tripropyl (2-hydroxyethyl) ammonium hydroxide, or trimethyl (1-hydroxypropyl) ammonium hydroxide. The content of the quaternary ammonium hydroxide in the photoresist stripper of the present invention is preferably 0.5 to 20% by weight. The photoresist stripper also contains a corrosion inhibitor, a surfactant or a defoamer.

Description

Photoresist stripper

The present invention relates to a photoresist stripping liquid.

The semiconductor substrate or the like has an electrode structure implemented with fine wiring, and a photoresist is used in its manufacturing step. The electrode structure is manufactured, for example, by _{coating a photoresist on a conductive metal layer such as aluminum or an insulating film such as a SiO 2} film formed on a substrate, and performing exposure and development treatments to form a photoresist pattern. The patterned photoresist is used as a photomask to etch the conductive metal layer or insulating film to form fine wiring. After that, the unnecessary photoresist is removed with a photoresist stripper. For the photoresist stripping solution, in addition to the stripping performance of the photoresist, it also requires storage stability that does not produce solidification or precipitation at low temperatures.

Patent Document 1 discloses a photoresist stripping solution, which contains quaternary ammonium hydroxide as a strong base agent for stripping photoresist, and contains alkylene amine in order to dissolve the quaternary ammonium hydroxide in dimethyl sulfide , And polyols and/or glycol ethers with a molecular weight of less than 100. Although this stripping solution improves the storage stability at low temperatures, it is not sufficient. Moreover, the stripping performance of the photoresist is required to be further improved.

Patent Document 2 discloses that by mixing a plurality of organic solvents in the photoresist stripping solution, the stripping performance of the photoresist can be improved. However, it cannot be said that the storage stability of this peeling liquid at low temperature is sufficient. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. WO2017/065153 [Patent Document 2] JP 2007-254555 A

[The problem to be solved by the invention]

The object of the present invention is to provide a photoresist stripping solution that maintains sufficient photoresist stripping properties and is excellent in storage stability. [Technical means to solve the problem]

The inventors found that a photoresist stripping solution containing a specific organic solvent maintains sufficient photoresist stripping properties and is excellent in storage stability, thus completing the present invention.

That is, the present invention relates to a photoresist stripping liquid, which contains quaternary ammonium hydroxide (A), water (B) and organic solvent (C), and The organic solvent (C) is a mixture of the following organic solvents (C1), (C2) and (C3): For organic solvents (C1), the polarity term (dP) of the Hansen solubility parameter is 15.0 or more and less than 21.0, and the hydrogen bond term (dH) is 6.0 or more and less than 14.0; For organic solvents (C2), the polarity term (dP) of the Hansen solubility parameter is 3.0 or more and less than 14.0, and the hydrogen bond term (dH) is 8.0 or more and less than 31.0; For organic solvents (C3), the polarity term (dP) of the Hansen solubility parameter is 3.0 or more and less than 8.0, and the hydrogen bond term (dH) is 2.5 or more and less than 8.0.

The content of the organic solvent (C1) is preferably 15 to 80% by weight.

The content of the organic solvent (C2) is preferably 1 to 50% by weight.

The content of the organic solvent (C3) is preferably 3-50% by weight.

The total content of the organic solvents (C1) to (C3) is preferably 60 to 95% by weight.

The photoresist stripping liquid preferably further contains an alkyleneamine or an alkanolamine (D).

(D) The component is preferably an alkanolamine.

The organic solvent (C1) is preferably dimethyl sulfoxide.

The photoresist stripping liquid is preferably used for stripping dry film photoresist. [Effects of the invention]

In addition to the quaternary ammonium hydroxide (A) and water (B), the photoresist stripping solution of the present invention also contains a mixture of specific organic solvents (C1) to (C3), so that sufficient photoresist stripping properties are maintained, and Storage stability is also excellent.

＜＜Photoresist stripping liquid＞＞ The photoresist stripping liquid of the present invention contains quaternary ammonium hydroxide (A), water (B) and organic solvent (C), and is characterized in that the organic solvent (C) is the following organic solvents (C1), (C2) and (C3) Mixture: (C1) Organic solvents with the polarity term (dP) of the Hansen solubility parameter above 15.0 and below 21.0, and the hydrogen bonding term (dH) above 6.0 but below 14.0; (C2) Organic solvents with the polarity term (dP) of the Hansen solubility parameter above 3.0 and below 14.0, and the hydrogen bond term (dH) above 8.0 but below 31.0; (C3) An organic solvent whose polarity term (dP) of the Hansen solubility parameter is 3.0 or more and less than 8.0, and the hydrogen bond term (dH) is 2.5 or more and less than 8.0.

＜(A) Quaternary ammonium hydroxide＞ As the quaternary ammonium hydroxide, for example, a compound represented by the following general formula (1) can be used.

In the general formula (1), R ¹ to R ⁴ represent an alkyl group having 1 to 12 carbon atoms, a hydroxy-substituted alkyl group, or an aromatic-substituted alkyl group, and these may be the same or different.

Specific examples of quaternary ammonium hydroxide include: tetramethylammonium hydroxide (TMAH), trimethylethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, hydrogen Tetraethylammonium oxide, tetrapropylammonium hydroxide, trimethyl(2-hydroxyethyl)ammonium hydroxide, tripropyl(2-hydroxyethyl)ammonium hydroxide, trimethyl(1-hydroxyethyl)ammonium hydroxide Propyl)ammonium and the like. These may be used alone, or two or more of them may be used in combination. Among them, from the viewpoint of photoresist peeling properties, tetramethylammonium hydroxide, trimethylethylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide are preferred. Furthermore, in terms of having the smallest molecular weight, increasing the molar concentration per unit weight, and effectively exerting its effect, tetramethylammonium hydroxide is more preferable.

In the photoresist stripping solution of the present invention, the content of quaternary ammonium hydroxide is not particularly limited, and is preferably 0.5 to 20% by weight, more preferably 0.8 to 8% by weight, and still more preferably 1 to 5%. If the content of quaternary ammonium hydroxide is less than 0.5% by weight, the photoresist peelability may decrease, and if it exceeds 20% by weight, the metal corrosivity may increase.

＜(B) Water＞ The water system is used to dissolve and blend the quaternary ammonium hydroxide. The content of water is not particularly limited, but from the viewpoint of photoresist releasability, it is preferably 30% by weight or less, and from the viewpoint of negative photoresist releasability, it is preferably 20% by weight or less. In particular, when the photoresist stripping solution of the present invention containing the following alkylene amine or alkanolamine (D) is used to strip negative dry film photoresist, the water content is more preferably 10% by weight or less , More preferably 1 to 10% by weight, particularly preferably 2 to 6% by weight. If the water content is less than 1% by weight, the solubility of quaternary ammonium hydroxide may decrease, and if it exceeds 10% by weight, the releasability of the negative dry film photoresist may decrease. On the other hand, when the photoresist stripping liquid of the present invention that does not contain alkyleneamine or alkanolamine (D) is used to strip negative dry film photoresist, the water content is more preferably 2-15 weight %, more preferably 4 to 10% by weight. If the water content is less than 2% by weight, the solubility of quaternary ammonium hydroxide may decrease, and if it exceeds 15% by weight, the releasability of the negative dry film photoresist may decrease.

＜(C) Organic solvent＞ The organic solvent (C) is a mixture of organic solvents (C1), (C2) and (C3). Organic solvents (C1) ~ (C3) are solvents that fully meet the specific Hansen solubility parameters. Furthermore, the Hansen solubility parameter represents the Hildebrand solubility parameter by three parameters: dispersion term dD, polar term dP, and hydrogen bond term dH. Dispersion term dD, polar term dP, and hydrogen bond term dH are inherent physical property values of substances, for example, as shown in "Hansen Solubility Parameters: A User's Handbook, HSPiP 3rd Edition ver.3.0.20". Furthermore, the hydrogen bond term dH can be calculated using the neural network method, namely the Y-MB method, in addition to the value described in the above-mentioned literature.

The total content of the organic solvents (C1) to (C3) relative to the entire photoresist stripping liquid is not particularly limited. From the viewpoint of the balance between photoresist stripping properties and storage stability, it is preferably 60 to 95% by weight, and more It is preferably 80 to 95% by weight, and more preferably 85 to 95% by weight. If it is less than 60% by weight, the ratio of quaternary ammonium hydroxide or water may increase and metal corrosion may occur. If it exceeds 95% by weight, the releasability may become insufficient.

＜Organic solvent (C1)＞ The polarity term (dP) of the Hansen solubility parameter of the organic solvent (C1) is 15.0 or more and less than 21.0, and the hydrogen bond term (dH) is 6.0 or more and less than 14.0. The polar term (dP) is preferably 15.5-20, more preferably 16-20. If the polarity term (dP) is less than 15.0, the releasability tends to become insufficient, and if it is 21.0 or more, the storage stability tends to become insufficient. The hydrogen bond term (dH) is preferably 6-13, more preferably 7-12. If the hydrogen bond term (dH) is less than 6.0, the storage stability tends to become insufficient, and if it is 14.0 or more, the releasability tends to become insufficient.

The dispersion term (dD) of the Hansen solubility parameter of the organic solvent (C1) is not particularly limited, and is preferably 15-21, more preferably 17-21. If it is less than 15 or more than 21, peelability may become insufficient.

As specific examples of the organic solvent (C1), dimethyl sulfene, cyclobutane, dimethyl sulfide, 2-pyrrolidone, γ-butyrolactone, etc. may be mentioned. These solvents may be used alone, or two or more of them may be mixed and used.

The content of the organic solvent (C1) relative to the entire photoresist stripping liquid is not particularly limited, but is preferably 15 to 80% by weight, more preferably 50 to 80% by weight, and still more preferably 50 to 78% by weight. If it is less than 15% by weight or more than 80% by weight, the photoresist releasability may become insufficient.

＜Organic solvent (C2)＞ The polarity term (dP) of the Hansen solubility parameter of the organic solvent (C2) is 3.0 or more and less than 14.0, and the hydrogen bond term (dH) is 8.0 or more and less than 31.0. The polar term (dP) is preferably 3.5-13, more preferably 4-13. If the polarity term (dP) is less than 3.0, the releasability tends to become insufficient, and if it is 14.0 or more, the storage stability tends to become insufficient. The hydrogen bond term (dH) is preferably 8.5-30, more preferably 9-30. If the hydrogen bond term (dH) is less than 8.0, the storage stability tends to become insufficient, and if it is 31.0 or more, the releasability tends to become insufficient.

The dispersion term (dD) of the Hansen solubility parameter of the organic solvent (C2) is not particularly limited, but is preferably 10-25, more preferably 14-20. If it is less than 10, peelability may become insufficient, and if it exceeds 25, storage stability may become insufficient.

Specific examples of the organic solvent (C2) include: polyols such as glycerol; methoxybutanol such as 1-butoxy-2-propanol and 3-methoxy-3-methylbutanol. Alcohols; glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol; ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol hexane Ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol hexyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol hexyl ether, dipropylene glycol methyl ether, two Propylene glycol ethyl ether, dipropylene glycol butyl ether, dipropylene glycol hexyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol butyl ether, triethylene glycol hexyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, three Glycol monoethers such as propylene glycol butyl ether and tripropylene glycol hexyl ether. These solvents may be used alone, or two or more of them may be mixed and used.

Among the above examples, as the organic solvent (C2), polyols, methoxybutanols, and diols are preferred in terms of exerting an effect when added in a small amount.

The content of the organic solvent (C2) relative to the entire photoresist stripping liquid is not particularly limited, but is preferably 1 to 50% by weight, more preferably 2 to 30% by weight. If it is less than 1% by weight, the storage stability may become insufficient, and if it exceeds 50% by weight, the photoresist peelability may become insufficient.

＜Organic solvent (C3)＞ The polarity term (dP) of the Hansen solubility parameter of the organic solvent (C3) is 3.0 or more and less than 8.0, and the hydrogen bond term (dH) is more than 2.5 and less than 8.0. The polar term (dP) is preferably 4.0 to 7.5, more preferably 4.5 to 7.0. If the polarity term (dP) is less than 3.0, the releasability tends to become insufficient, and if it is 8.0 or more, the storage stability tends to become insufficient. The hydrogen bond term (dH) is preferably 3 to 7.5, more preferably 4.0 to 7.0. If the hydrogen bond term (dH) is less than 2.5, the releasability tends to become insufficient, and if it is 8.0 or more, the storage stability tends to become insufficient.

The dispersion term (dD) of the Hansen solubility parameter of the organic solvent (C3) is not particularly limited, and is preferably 10-20, more preferably 13-18. If it is less than 10, the storage stability may become insufficient, and if it exceeds 20, the storage stability may become insufficient.

Specific examples of the organic solvent (C3) include: ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol dimethyl ether, Ethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, Dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, ethylene glycol methyl ethyl ether, ethylene glycol methyl butyl ether, ethylene glycol methyl butyl ether, diethylene glycol methyl ethyl ether, diethyl Glycol methyl butyl ether, diethylene glycol methyl butyl ether, triethylene glycol methyl ethyl ether, triethylene glycol methyl butyl ether, triethylene glycol methyl butyl ether, propylene glycol methyl Ethyl ether, propylene glycol methyl butyl ether, propylene glycol methyl butyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl butyl ether, dipropylene glycol methyl butyl ether, tripropylene glycol methyl ethyl ether , Tripropylene glycol methyl butyl ether, tripropylene glycol methyl butyl ether and other glycol diethers. These solvents may be used alone, or two or more of them may be mixed and used.

Among the above examples, as the organic solvent (C3), dimethyl ethers are preferred in terms of good releasability.

The content of the organic solvent (C3) relative to the entire photoresist stripping liquid is not particularly limited, but is preferably 3 to 50% by weight, more preferably 5 to 40% by weight. If it is less than 3% by weight, the storage stability may become insufficient, and if it exceeds 50% by weight, the releasability may become insufficient.

＜Optional ingredients＞ The photoresist peeling liquid of this invention may contain other arbitrary components in addition to the said (A)-(C) component. As optional components, alkylene amines or alkanol amines (D), corrosion inhibitors, organic solvents other than component (C), surfactants, defoamers, etc. may be mentioned.

When the photoresist stripper contains alkyleneamine or alkanolamine (D), the alkyleneamine or alkanolamine (D) functions as a dissolving agent for quaternary ammonium hydroxide.

The alkylene amine is not particularly limited, and a compound represented by the following general formula (2) can be used.

（通式（2）中，m、n表示1～5之整數。R⁵ 、R⁶ 分別獨立地表示氫原子或碳數1～3之烷基。於有複數個R⁵ 、R⁶ 之情形時，分別可相同，亦可不同）

(In the general formula (2), m and n represent an integer of 1 to 5. R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group with 1 to 3 carbon atoms. When there are plural R ⁵ and R ⁶ , They can be the same or different)

（通式（3）中，n表示1～5之整數）Specific examples of alkylene amines include: ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA) ) Ethyleneamine represented by the following general formula (3); Propylenediamine, etc. Among them, from the viewpoint of the absorption of carbon dioxide, ethylene amine represented by the following general formula (3) is preferred, poly ethylene amine with n=2 or more is more preferred, and triethyl amine is more preferred. Tetraamine, tetraethylenepentamine. These alkylene amines may be used alone or in combination of two or more kinds.

(In the general formula (3), n represents an integer from 1 to 5)

Specific examples of alkanolamines include monoethanolamine (MEA), N-methylethanolamine (MMA), monomethyldiethanolamine (MDA), and triethanolamine (TEA). Among them, from the viewpoint of storage stability, monoethanolamine is preferred.

When the alkylene amine or alkanolamine (D) is blended in the photoresist stripping solution of the present invention, the content is not particularly limited, but is preferably 0.5 to 25% by weight, more preferably 1 to 20% by weight %. If the content of alkyleneamine or alkanolamine (D) is less than 0.5% by weight, the stability may decrease over time, and if it exceeds 25% by weight, the photoresist peelability may decrease. In addition, from the viewpoint of stability over time, the content of alkyleneamine or alkanolamine (D) is preferably 10 parts by weight or more with respect to 100 parts by weight of quaternary ammonium hydroxide.

The corrosion inhibitor is not particularly limited, but for example, benzotriazole, aminotetrazole, 5-amino-1-phenyltetrazole, 5-amino-1-(1-naphthyl) Tetrazole, 1-methyl-5-aminotetrazole, 1,5-diaminotetrazole, imidazole, indole, purine, pyrazole, pyridine, pyrimidine, pyrrole, pyrrolidine, pyrroline, etc. Nitrogen-containing heterocyclic compounds, maltol, creatinine, etc. These may be used alone or in combination of two or more kinds. From the viewpoint of corrosion resistance to a plurality of metals, it is preferable to contain maltol and creatinine. From the viewpoint of corrosion resistance to Cu, it is preferable to contain benzotriazole, indole, and pyrroline. The content of the corrosion inhibitor is preferably 0.01 to 5% by weight.

As organic solvents other than (C) component, ethylene carbonate, propylene carbonate, N-methylpyrrolidone, etc. are mentioned. The content of these organic solvents is preferably 1-10% by weight.

Examples of the surfactant include: cationic surfactants such as dioctadecyldimethylammonium chloride; anionic surfactants such as alkylbenzene sulfonates; cocamidopropyl betaine ) And other amphoteric surfactants; non-ionic surfactants such as polyoxyethylene alkyl ethers, etc. The content of the surfactant is preferably 0.01 to 1% by weight.

As the defoaming agent, silicone oil, fatty acid ester, etc. may be mentioned. The content of the defoamer is preferably 0.01 to 1% by weight.

The photoresist stripping liquid of the present invention can be prepared by mixing the above-mentioned components by a usual method. After preparation, it can be stored at a temperature of -5 to 40°C without turbidity, solidification, and precipitation.

The photoresist stripping solution of the present invention can be used to strip unnecessary photoresist after the etching process of metal wiring and the like in the manufacturing steps of semiconductor substrates or flat panel display (FPD) substrates. The photoresist stripping liquid of the present invention can be used at room temperature, and can also be used, for example, by heating to 30°C to 80°C. The time required for peeling depends on the degree of deterioration of the photoresist, etc. Generally, it is about 30 seconds to 10 minutes, for example. After treatment, water washing, air drying, etc. can be carried out as needed.

To use the photoresist stripping solution of the present invention to peel off the photoresist of a metal wiring substrate with a copper layer or a copper alloy layer, as long as the photoresist is used to form a metal wiring with a copper layer or a copper alloy layer on the substrate, the present invention is used The photoresist stripping liquid removes unnecessary photoresist to prevent corrosion of the copper layer or copper alloy layer. More specifically, the substrate is immersed in the photoresist stripping solution of the present invention at room temperature to 80°C for 1 to 30 minutes. At this time, if necessary, the photoresist peeling liquid may be stirred or the substrate may be vibrated. Alternatively, the photoresist stripping liquid of the present invention can also be blown to the substrate by spraying or spraying. At this time, by washing with a brush together, the photoresist peelability can also be improved.

After the photoresist is dissolved or peeled off, it is preferable to use pure water to wash and remove the photoresist stripping solution containing the dissolved photoresist, so as to remove the photoresist from the substrate. Thereafter, the liquid on the substrate is blown away with an air knife or the like to dry the substrate. Thereby, it is possible to prevent the copper layer or the copper alloy layer from being excessively corroded to cause the line width of the copper wiring or the copper alloy wiring to become thin, so that a good metal wiring can be formed without damaging the cross-sectional shape of the wiring formed by etching. Examples of multilayer forms of metal wiring include: 1-layer wiring with copper or copper alloy in order from the upper layer; 2-layer copper or copper alloy with copper or copper alloy in order from the upper layer/two layers of copper or copper alloy with different composition from the upper layer Wiring; from the top layer is a 2-layer wiring of copper or copper alloy/molybdenum, titanium and other covering metals; from the upper layer, it is a two-layer wiring of covering metals such as molybdenum and titanium/copper or copper alloy/molybdenum, titanium and other covering metals 3 Layer wiring, etc.

The photoresist stripping solution of the present invention can be used for the stripping of either positive type or negative type photoresist. Because of its high photoresist stripping property, it is suitable for stripping negative type dry film photoresist. [Example]

Hereinafter, examples are given to illustrate the present invention, but the present invention is not limited to these examples.

The Hansen solubility parameters of the organic solvents used in the examples are shown in Table 1. [Table 1] Organic solvent (C) Hansen solubility parameter dD dP dH C1 Dimethyl sulfoxide 18.4 16.4 10.2 Ring Dingzhu 18.4 16.6 7.4 Dimethyl sulfide 19.0 19.4 12.3 C2 Glycerol 17.4 12.1 29.3 1-butoxy-2-propanol 15.3 4.5 9.2 Triethylene glycol 16.0 12.5 18.6 3-methoxy-3-methylbutanol 15.7 6.0 9.9 Propylene Glycol 16.8 9.4 23.3 C3 Ethylene glycol dibutyl ether 15.7 4.5 4.2 Diethylene glycol dimethyl ether 15.7 6.1 6.5 Triethylene glycol dimethyl ether 16.1 5.8 6.8 Dipropylene glycol dimethyl ether 15.8 4.9 4.7

(Examples 1 to 12, Comparative Examples 1 to 5) The components (A) to (D) were mixed in the weight ratio shown in Table 2 below to obtain a photoresist peeling liquid. The liquid state and photoresist peelability of the obtained photoresist peeling liquid were evaluated by the following method. The results are shown in Table 2.

[Table 2] Example Comparative example 1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 Quaternary ammonium hydroxide (A) Tetramethylammonium Hydroxide 2.225 1.250 2.225 2.750 2.225 2.750 2.500 3.000 3.000 2.225 2.225 2.225 1.250 1.250 Trimethyl ethyl ammonium hydroxide 3.210 Tetrabutylammonium Hydroxide 3.810 Benzyl trimethyl ammonium hydroxide 1.250 Water (B) DIW 4.675 2.750 4.675 5.250 4.675 5.250 5.790 5.710 2.750 6.000 10.000 10.000 4.675 4.675 4.675 2.750 2.750 Organic solvent (C) C1 Dimethyl sulfoxide 63.1 58.0 45.1 20.1 76.0 75.0 75.2 58.0 70.5 51.0 74.0 60.1 60.1 83.0 88.0 Ring Dingzhu 10.0 49.0 Dimethyl sulfide 5.0 C2 Glycerol 2.0 1-butoxy-2-propanol 10.0 63.1 Triethylene glycol 10.0 3-methoxy-3-methylbutanol 10.0 5.0 10.0 30.0 5.0 5.0 4.8 5.0 10.0 30.0 10.0 5.0 Propylene Glycol 4.0 8.0 C3 Ethylene glycol dibutyl ether 5.0 Diethylene glycol dimethyl ether 20.0 40.0 8.0 8.0 7.6 Triethylene glycol dimethyl ether 30.0 30.0 10.0 10.0 5.0 Dipropylene glycol dimethyl ether 30.0 30.0 30.0 Alkylene amine or alkanolamine (D) Monoethanolamine 3.0 3.0 3.0 3.0 3.0 3.0 3.0 2.9 3.0 22.0 3.0 3.0 3.0 3.0 3.0 Triethylenetetramine 1.0 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 103.0 100.0 100.0 Liquid state -5℃ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ×× ◎ X X 0℃ ○ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ×× ◎ X X 24℃ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Photoresist peeling after processing at 70℃ for 30 minutes ◎ ◎ ○ △ ○ ◎ ○ ○ ○ ○ ○ ○ X X ×× X △

(Evaluation method) 1. Liquid state The liquid state of the photoresist peeling liquid at -5°C, 0°C, and 24°C was visually observed, and evaluated based on the following criteria. ◎: No turbidity. ○: Slightly turbid. △: There is turbidity. ×: There is solidification. ××: There is precipitation.

2. Photoresist peeling A Ti film and a copper seed layer are respectively formed on the Si substrate by sputtering, and the photoresist is adjusted to a thickness of 240 μm (negative dry film photoresist: Sunfort "TS-B400" manufactured by Asahi Kasei Co., Ltd.) ) Perform roll lamination, pattern the photoresist by UV exposure and development, and then form a copper plating layer (film thickness of 200 μm) by electroplating. The substrate was immersed in a photoresist stripping solution adjusted to 70°C, and processed for 30 minutes. After the immersion treatment, the substrate is washed with water and air-dried. Use an electron microscope to confirm the peeling of the dry film photoresist, and evaluate it based on the following criteria. ◎: The dry film photoresist does not exist on the substrate, but is completely dissolved in the peeling liquid. ○: The dry film photoresist does not exist on the substrate, but a little residue remains in the stripping liquid. △: Residue remains thinly on the substrate. Residues also remain in the stripping liquid. ×: The residue remains thickly on the substrate. Residues also remain in the stripping liquid. ××: The dry film photoresist hardly dissolves and hardly changes from before the peeling treatment.

Comparative Example 1 does not contain an organic solvent (C3), so the photoresist peelability is poor. Comparative Example 2 does not contain an organic solvent (C2), so the freezing point is relatively high, and quaternary ammonium hydroxide precipitates at low temperature, so that the liquid state and the photoresist peelability are both poor. Comparative Example 3 does not contain an organic solvent (C1), so the photoresist peelability is poor. Comparative Examples 4 to 5 do not contain an organic solvent (C3), so the photoresist peelability is poor, and the freezing point is relatively high, and it solidifies at a low temperature. Examples 1 to 12 are stable in liquid state even at low temperatures, and the photoresist peelability is also good.

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Claims (9)

A photoresist stripping liquid comprising quaternary ammonium hydroxide (A), water (B) and organic solvent (C), and The organic solvent (C) is a mixture of the following organic solvents (C1), (C2) and (C3): For organic solvents (C1), the polarity term (dP) of the Hansen solubility parameter is 15.0 or more and less than 21.0, and the hydrogen bond term (dH) is 6.0 or more and less than 14.0; For organic solvents (C2), the polarity term (dP) of the Hansen solubility parameter is 3.0 or more and less than 14.0, and the hydrogen bond term (dH) is 8.0 or more and less than 31.0; For organic solvents (C3), the polarity term (dP) of the Hansen solubility parameter is 3.0 or more and less than 8.0, and the hydrogen bond term (dH) is 2.5 or more and less than 8.0. Such as the photoresist stripping liquid of claim 1, wherein the content of the organic solvent (C1) is 15 to 80% by weight. Such as the photoresist stripping liquid of claim 1 or 2, wherein the content of the organic solvent (C2) is 1-50% by weight. The photoresist stripping liquid according to any one of claims 1 to 3, wherein the content of the organic solvent (C3) is 3-50% by weight. The photoresist stripping liquid according to any one of claims 1 to 4, wherein the total content of the organic solvents (C1) to (C3) is 60 to 95% by weight. The photoresist stripping liquid according to any one of claims 1 to 5, which further contains an alkyleneamine or an alkanolamine (D). Such as the photoresist stripping liquid of claim 6, wherein the component (D) is an alkanolamine. The photoresist stripping liquid according to any one of claims 1 to 7, wherein the organic solvent (C1) is dimethyl sulfoxide. The photoresist stripping liquid according to any one of claims 1 to 8, which is used for stripping dry film photoresist.