Photoresist stripping liquid composition and application

Abstract

The invention discloses a photoresist stripping liquid composition and application thereof, and the photoresist stripping liquid composition comprises the following components by mass: 10-40wt% of an alcohol ether solvent, 10-40wt% of a solvent, 10-40wt% of a solvent, 10-40wt% of a solvent, and 10-40wt% of a solvent. 20 wt% to 50 wt% of a polyol solvent; 0.5 wt% to 10 wt% of an alkanolamine compound; 0.02 wt%-2 wt% of a metal corrosion inhibitor; 0.01 wt% to 1 wt% of a surfactant; 0.01 wt%-1 wt% of an auxiliary additive; and the balance of water. According to the invention, the octanol / water partition coefficient of the mixed solvent of the alcohol ether solvent and the polyhydric alcohol is limited, so that the dissolving capacity of the stripping liquid to photoresist is improved, the service life of the stripping liquid is prolonged, and the stripping liquid is easy to wash and remove and less in residual quantity; in addition, the organic acid metal corrosion inhibitor and the metal inhibitor in the photoresist stripping liquid composition are matched with each other, so that the photoresist stripping liquid composition can be compatible with copper and aluminum processes, and corrosion of the photoresist stripping liquid composition to a metal layer is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of photoresist cleaning, and more particularly to a photoresist stripping liquid composition and its application. Background Art

[0002] In current TFT (Thin Film Transistor) thin film transistor and IC (integrated circuit) integrated circuit manufacturing processes, a layer of photoresist is usually spin-coated on a glass substrate or a silicon wafer, and then exposed and developed using a required mask. Finally, according to the characteristics of the photoresist (positive photoresist or negative photoresist), the corresponding photoresist stripping liquid is used to remove the exposed or unexposed photoresist, and a pattern is formed in the required part.

[0003] With the progress of technology, the requirement for the life of the stripping liquid is getting higher and higher, that is, under the condition that the stripping liquid can maintain effective stripping ability, it is required to dissolve more and more photoresist, and still be able to effectively clean the photoresist during water washing under the condition of high sol amount. The existing stripping liquids still cannot meet these requirements. When the life of the stripping liquid is not high enough, it needs to be replaced frequently, which reduces the production efficiency. When the photoresist cannot be completely removed after stripping, the residues are likely to cause metal corrosion during subsequent high-temperature film formation, or cause abnormal electrical properties of the semiconductor layer in the TFT structure, ultimately resulting in poor performance of the TFT switch or a decrease in the yield of the product.

[0004] In view of this, a long-life photoresist stripping liquid is particularly necessary. Summary of the Invention

[0005] The purpose of the present invention is to provide a photoresist stripping liquid composition and its application, which overcome the problems of the low life of the existing photoresist stripping liquid, the need for frequent replacement, and the reduction of production efficiency.

[0006] The present invention is implemented as follows:

[0007] In a first aspect, the present invention provides a photoresist stripping liquid composition, which includes the following components by mass fraction:

[0008] Alcohol ether solvent: 10 wt% - 40 wt%;

[0009] Polyhydric alcohol solvent: 20 wt% - 50 wt%;

[0010] Alkanolamine compound: 0.5 wt% - 10 wt%;

[0011] Metal corrosion inhibitor: 0.02 wt% - 2 wt%;

[0012] Surfactant: 0.01 wt% - 1 wt%;

[0013] Auxiliary additive: 0.01 wt% - 1 wt%;

[0014] The balance is water;

[0015] Wherein, the alcohol ether solvent and the polyol solvent in the photoresist stripping liquid composition form a mixed solvent, and the octanol / water partition coefficient LogP of the mixed solvent x is -0.3 to 0.2, wherein,

[0016] LogP x = LogP a ×A + LogP b ×B;

[0017] LogP a : The octanol / water partition coefficient of the alcohol ether solvent under the condition of 25°C;

[0018] LogP b : The octanol / water partition coefficient of the polyol solvent under the condition of 25°C;

[0019] A: The mass fraction of the alcohol ether solvent in the mixed solvent;

[0020] B: The mass fraction of the polyol solvent in the mixed solvent.

[0021] In the photoresist stripping liquid composition of the present application, the alcohol ether solvent and the polyol solvent are selected as the mixed solvent, which is beneficial to improving the dissolution ability of the stripping liquid for the photoresist and prolonging the life of the stripping liquid. At the same time, the stripping liquid itself is also easy to be washed off with water and has less residue; in addition, the organic acid metal corrosion inhibitor and the metal inhibitor in the photoresist stripping liquid composition cooperate with each other, enabling it to be compatible with the copper-aluminum process and being beneficial to reducing the corrosion of the metal layer.

[0022] LogP x Within the range of -0.3 to 0.2, it is beneficial for the photoresist stripping liquid composition to have both good photoresist dissolution ability and low residue performance.

[0023] In an alternative embodiment, the photoresist stripping liquid composition satisfies at least one of the following characteristics A - G:

[0024] A. The mass fraction of the alcohol ether solvent is 20 wt% - 35 wt%;

[0025] B. The mass fraction of the polyol solvent is 30 wt% - 45 wt%;

[0026] C. The mass fraction of the alkanolamine compound is 1 wt% - 5 wt%;

[0027] D. The metal corrosion inhibitor includes organic acid-based metal corrosion inhibitors, and the mass fraction of the organic acid-based metal corrosion inhibitors is 0.01 wt% - 1 wt%.

[0028] E. The metal corrosion inhibitor includes benzothiazole-based metal inhibitors, and the mass fraction of the benzothiazole-based metal inhibitors is 0.01 wt% - 1 wt%.

[0029] F. The mass fraction of the surfactant is 0.05 wt% - 0.5 wt%.

[0030] G. The mass fraction of the auxiliary additive is 0.05 wt% - 0.5 wt%.

[0031] By optimizing the dosage of each component in the photoresist stripper composition, it is beneficial to further improve the dissolution ability of the photoresist stripper composition for photoresist, extend the life of the photoresist stripper composition, or reduce the corrosion of the metal layer by the photoresist stripper composition.

[0032] In an alternative embodiment, the alcohol ether solvent is selected from at least one of diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, dipropylene glycol monoethyl ether, and ethylene glycol monobutyl ether.

[0033] Selecting a suitable alcohol ether solvent is beneficial to further improve the dissolution ability of the photoresist stripper composition for photoresist and extend the life of the photoresist stripper composition.

[0034] In an alternative embodiment, the structural general formula of the polyol solvent is as shown in Formula I:

[0035]

[0036] Among them, when R1 is H n = 1 - 3;

[0037] When R1 is -OH, R2 is an alkyl group with 1 - 3 carbon atoms.

[0038] Selecting a suitable polyol solvent is beneficial to improve the water washing ability of the photoresist stripper composition and reduce the residue of the photoresist stripper composition.

[0039] It should be noted that the water washing ability of the photoresist stripper composition in this application refers to whether the photoresist stripper composition is easily removed by water washing.

[0040] In an alternative embodiment, the octanol / water partition coefficient LogP of the polyol solvent b is -2 to 0.

[0041] LogP bIn the range of -2 to 0, it is beneficial for the photoresist stripping liquid composition to have both good photoresist dissolution ability and low residue performance.

[0042] In an alternative embodiment, the alkanolamine compound is selected from at least one of 2-aminoethanol, 2,2-dihydroxydiethylamine, 2-(ethylamino)ethanol, 2-(methylamino)ethanol, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylaminoethanol, 2-(2-aminoethylamino)-1-ethanol, 1-amino-2-propanol, and 2-amino-1-propanol; preferably selected from at least one of 2-aminoethanol and 2,2-dihydroxydiethylamine.

[0043] The cooperation of the alkanolamine compound with components such as solvents is beneficial to stripping the photoresist from the substrate while reducing the corrosion of the substrate.

[0044] In an alternative embodiment, the organic acid metal corrosion inhibitor is selected from at least one of salicylic acid, citric acid, succinic acid, malic acid, and tartaric acid; preferably selected from at least one of citric acid and malic acid.

[0045] In an alternative embodiment, the metal inhibitor includes the compound shown in Formula II:

[0046]

[0047] wherein R is selected from at least one of methyl, ethyl, isopropyl, mercapto, and amino; preferably selected from mercapto.

[0048] In this application, when the photoresist stripping liquid composition is used, it will act on the metal wiring at the bottom of the substrate. The combined action of the organic acid metal corrosion inhibitor and the metal inhibitor is beneficial to protecting the metal wiring from being corroded by the photoresist stripping liquid composition.

[0049] In an alternative embodiment, the surfactant is selected from fatty alcohol polyoxyethylene polyoxypropylene ether; it is beneficial for the photoresist to come into full contact with the photoresist stripping liquid composition and is beneficial for the photoresist to be stripped from the substrate.

[0050] In an alternative embodiment, the molecular general formula of the fatty alcohol polyoxyethylene polyoxypropylene ether is R3O(C2H4O) m (C3H6O) o H, wherein R3 is an alkyl group with 8 - 13 carbon atoms, m and o are the polymerization degrees of polyoxyethylene and polyoxypropylene respectively, and both m and o are less than 20. Preferably, R3 is isodecyl, which is more beneficial for the photoresist to be stripped from the substrate.

[0051] In an alternative embodiment, the auxiliary additive includes at least one of the compounds shown in Formula III and Formula IV:

[0052]

[0053] Among them, R4 is an alkyl group with 1 to 4 carbon atoms, and R5 is or an alkyl group with 4 to 6 carbon atoms.

[0054] Preferably, the auxiliary additive is selected from at least one of glyceryl triacetate, dioctyl sebacate, and dibutyl phthalate; more preferably, it is selected from glyceryl triacetate.

[0055] The auxiliary additive can disperse the photoresist, which is beneficial to reducing the size of the photoresist removed by stripping, avoiding clogging of the equipment, and reducing the residue of the photoresist stripping solution.

[0056] The preparation method of the photoresist stripping solution in this application includes: mixing each raw material according to a ratio to obtain a mixed solution, and subjecting the mixed solution to circulating filtration to obtain the photoresist stripping solution. The preparation method is simple and beneficial to industrial production.

[0057] In a second aspect, the present invention provides a method for stripping a photoresist, which immerses a substrate with an attached photoresist in a photoresist stripping solution composition at 40°C - 60°C to remove the photoresist on the surface of the substrate.

[0058] The present invention has the following beneficial effects:

[0059] The photoresist stripping solution composition in this application selects an alcohol ether solvent and a polyol solvent as a mixed solvent, which is beneficial to improving the dissolution ability of the stripping solution for the photoresist and prolonging the life of the stripping solution. At the same time, the stripping solution is also easy to be removed by water washing and has a small residue amount; in addition, the organic acid-based metal corrosion inhibitor and the metal inhibitor in the photoresist stripping solution composition cooperate with each other, enabling it to be compatible with copper-aluminum processes and being beneficial to reducing the corrosion of the metal layer. Description of the Drawings

[0060] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the present invention, and therefore should not be regarded as limiting the scope. For those of ordinary skill in the art, other relevant drawings can also be obtained based on these drawings without creative efforts.

[0061] Figure 1 SEM image of the sample after treatment in Example 3 of Test Example 1;

[0062] Figure 2 SEM image of the sample after treatment in Comparative Example 1 of Test Example 1;

[0063] Figure 3 SEM image of the sample after treatment in Example 6 of Test Example 3;

[0064] Figure 4 SEM image of the sample after being processed in Comparative Example 2 in Test Example 3;

[0065] Figure 5 SEM image of the sample after being processed in Comparative Example 3 in Test Example 3;

[0066] Figure 6 SEM image of the sample after being processed in Comparative Example 4 in Test Example 3. Specific Embodiments

[0067] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. For those not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer are followed. For reagents or instruments without indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0068] The embodiments of the present invention provide a photoresist stripping liquid composition, which includes the following components by mass fraction:

[0069] Alcohol ether solvent: 10 wt% - 40 wt%;

[0070] Polyol solvent: 20 wt% - 50 wt%;

[0071] Alkanolamine compound: 0.5 wt% - 10 wt%;

[0072] Metal corrosion inhibitor: 0.02 wt% - 2 wt%;

[0073] Surfactant: 0.01 wt% - 1 wt%;

[0074] Auxiliary additive: 0.01 wt% - 1 wt%;

[0075] The balance is water;

[0076] Among them, the alcohol ether solvent and the polyol solvent in the photoresist stripping liquid composition form a mixed solvent, and the octanol / water partition coefficient LogP of the mixed solvent x is -0.3 to 0.2, where

[0077] LogP x = LogP a ×A + LogP b ×B;

[0078] LogP a : Octanol / water partition coefficient of the alcohol ether solvent under the condition of 25°C;

[0079] LogP b : Octanol / water partition coefficient of the polyol solvent under the condition of 25°C;

[0080] A: The mass fraction of the alcohol ether solvent in the mixed solvent;

[0081] B: The mass fraction of the polyol solvent in the mixed solvent.

[0082] The photoresist stripping liquid composition of the present application selects an alcohol ether solvent and a polyol solvent as the mixed solvent, which is beneficial to improving the dissolution ability of the stripping liquid for the photoresist, prolonging the life of the stripping liquid, and at the same time, the stripping liquid itself is easy to be washed off with water and has a small residue amount; in addition, the organic acid-based metal corrosion inhibitor and the metal inhibitor in the photoresist stripping liquid composition cooperate with each other, enabling it to be compatible with copper-aluminum processes and being beneficial to reducing the corrosion of the metal layer.

[0083] LogP x is the octanol-water partition coefficient of the mixed solvent. The larger the value of LogP x , the greater the solubility of the organic matter in the organic phase and the smaller the solubility in water. LogP x Within the range of -0.3 to 0.2, specifically, it can be -0.3, -0.2, -0.1, 0.0, 0.1, 0.2 or any value between -0.3 and 0.2, which is beneficial for the photoresist stripping liquid composition to have both good photoresist dissolution ability and low residue performance. Specifically, in an alternative embodiment:

[0084] The mass fraction of the alcohol ether solvent in the photoresist stripping liquid composition can be 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt% or any value between 10wt% and 40wt%, preferably 20wt% - 35wt%; when the concentration of the alcohol ether solvent is in the range of 10wt% - 40wt%, it can cooperate with the polyol solvent, enabling the photoresist stripping liquid composition to have both good sol-gel performance and water washing performance.

[0085] The mass fraction of the polyol solvent in the photoresist stripping liquid composition can be 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt% or any value between 20wt% and 50wt%, preferably 30wt% - 45wt%; when the mass concentration of the polyol is in the range of 20wt% - 50wt%, the photoresist can be better dissolved, and the photoresist stripping liquid composition has good water washing performance, reducing the residue problem of the photoresist stripping liquid composition and reducing the corrosion of the metal layer by high-temperature film formation in the subsequent process. When the mass concentration of the polyol is too high, the completely stripped photoresist cannot be completely dissolved and there will be some residues on the glass substrate; when the mass concentration of the polyol is too low, although the stripped photoresist can be completely dissolved, the water washing performance decreases and it is easy to cause residues during cleaning.

[0086] In the photoresist stripping liquid composition, the mass fraction of the alkanolamine compound can be 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt% or any value between 0.5 wt% and 10 wt%. Preferably, it is 1 wt% - 5 wt%. When the mass concentration of the alkanolamine substance is in the range of 1 wt% - 5 wt%, the photoresist can be completely stripped. When the mass concentration is above 5 wt%, although the photoresist can be completely stripped from the glass substrate, since most alkanolamine substances are strongly alkaline, they will cause a certain degree of corrosion to the metal film layer. When the mass concentration is below 1 wt%, the photoresist cannot be completely stripped, resulting in residue on the substrate.

[0087] The metal corrosion inhibitor includes an organic acid-based metal corrosion inhibitor. In the photoresist stripping liquid composition, the mass fraction of the organic acid-based metal corrosion inhibitor can be 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt% or any value between 0.01 wt% and 1 wt%. Preferably, it is 0.05 wt% - 0.5 wt%.

[0088] The metal corrosion inhibitor includes a benzothiazole-based metal inhibitor. In the photoresist stripping liquid composition, the mass fraction of the benzothiazole-based metal inhibitor can be 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt% or any value between 0.01 wt% and 1 wt%. Preferably, it is 0.05 wt% - 0.5 wt%.

[0089] When the photoresist stripping liquid composition in this application is in use, it will act on the metal wiring at the bottom of the substrate. The combined action of the organic acid metal corrosion inhibitor and the metal inhibitor is beneficial to protecting the metal wiring from being corroded by the photoresist stripping liquid composition. Specifically, the organic acid metal corrosion inhibitor can specifically protect metal aluminum, and the benzothiazole metal inhibitor composition can specifically protect metal copper. Based on the total weight of the compound, both metal corrosion inhibitors are used in an amount of 0.01 wt% - 1 wt%, and preferably in an amount of 0.05 wt% - 0.5 wt%. When the addition amount of the organic acid metal corrosion inhibitor or the benzothiazole metal inhibitor is lower than 0.05 wt%, over time, the organic acid metal corrosion inhibitor or the benzothiazole metal inhibitor in the photoresist stripping liquid composition cannot be fully adsorbed on the bottom metal wiring or form a corrosion-resistant complex with the metal wiring, resulting in the corrosion of the substrate metal wiring by the photoresist stripping liquid composition; when the additive is higher than 0.5 wt%, the organic acid metal corrosion inhibitor or the benzothiazole metal inhibitor will affect the stripping performance of the photoresist stripping liquid and cause the physical and chemical properties to exceed the standard, resulting in the precipitation of the additive during long-term storage of the liquid medicine at low temperature.

[0090] The mass fraction of the surfactant in the photoresist stripping liquid composition can be 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt% or any value between 0.01 wt% - 1 wt%, preferably 0.05 wt% - 0.5 wt%; the dosage of the surfactant within the above range is beneficial to the full contact between the photoresist and the photoresist stripping liquid composition, and is beneficial to the stripping of the photoresist from the substrate.

[0091] The mass fraction of the auxiliary additive in the photoresist stripping liquid composition can be 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt% or any value between 0.01 wt% - 1 wt%, preferably 0.05 wt% - 0.5 wt%. The dosage of the auxiliary additive within the above range can disperse the photoresist, which is beneficial to reducing the size of the stripped photoresist, avoiding clogging of the equipment, and reducing the residue of the photoresist stripping liquid.

[0092] By optimizing the dosage of each component in the photoresist stripping liquid composition, it is beneficial to further improve the dissolution ability of the photoresist stripping liquid composition for the photoresist, extend the lifespan of the photoresist stripping liquid composition, or reduce the corrosion of the metal layer by the photoresist stripping liquid composition.

[0093] In an alternative embodiment, the alcohol ether solvent is selected from at least one of diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, dipropylene glycol monoethyl ether, and ethylene glycol monobutyl ether.

[0094] Selecting a suitable alcohol ether solvent is beneficial to further improving the dissolution ability of the photoresist stripping liquid composition for the photoresist and extending the lifespan of the photoresist stripping liquid composition.

[0095] In an alternative embodiment, the general structural formula of the polyol solvent is as shown in Formula I:

[0096]

[0097] Wherein, when R1 is H n = 1 - 3;

[0098] When R1 is -OH, R2 is an alkyl group with 1 - 3 carbon atoms;

[0099] Selecting a suitable polyol solvent is beneficial to improving the water washing ability of the photoresist stripping liquid composition and reducing the residue of the photoresist stripping liquid composition. Preferably, the polyol solvent is selected from at least one of 1,2 - propylene glycol (LogP b = -0.6405) and diethylene glycol (LogP b = -1.0124).

[0100] In an alternative embodiment, the octanol / water partition coefficient LogP of the polyol solvent b is -2 to 0.

[0101] LogP b Within the range of -2 to 0, it is beneficial for the photoresist stripping liquid composition to have both good photoresist dissolution ability and low residue performance. LogP b < -2 will make the stripping liquid too hydrophilic and not conducive to solubilization.

[0102] In an alternative embodiment, the alcohol ether solvent and the polyol solvent in the photoresist stripping liquid composition form a mixed solvent, and the octanol / water partition coefficient LogP of the mixed solvent x is -0.3 to 0.2, wherein,

[0103] LogP x = LogP a ×A + LogP b ×B;

[0104] LogP a : The octanol / water partition coefficient of the alcohol ether solvent;

[0105] LogP b : The octanol / water partition coefficient of the polyol solvent;

[0106] A mass fraction of the alcohol ether solvent in the mixed solvent;

[0107] B: A mass fraction of the polyol solvent in the mixed solvent.

[0108] LogP x In the range of -0.3 to 0.2, it is beneficial for the photoresist stripper composition to have both good photoresist dissolution ability and water washing performance.

[0109] In an alternative embodiment, the alkanolamine compound is selected from at least one of 2-aminoethanol, 2,2-dihydroxydiethylamine, 2-(ethylamino)ethanol, 2-(methylamino)ethanol, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylaminoethanol, 2-(2-aminoethylamino)-1-ethanol, 1-amino-2-propanol, and 2-amino-1-propanol; preferably selected from at least one of 2-aminoethanol and 2,2-dihydroxydiethylamine.

[0110] The cooperation of the alkanolamine compound with components such as the solvent is beneficial to stripping the photoresist from the substrate while reducing the corrosion of the substrate.

[0111] In an alternative embodiment, the organic acid metal corrosion inhibitor is selected from at least one of salicylic acid, citric acid, succinic acid, malic acid, and tartaric acid; preferably selected from at least one of citric acid and malic acid.

[0112] In an alternative embodiment, the metal inhibitor includes the compound shown in Formula II:

[0113]

[0114] Wherein R is selected from at least one of methyl, ethyl, isopropyl, mercapto, and amino; preferably selected from mercapto.

[0115] In the present application, when the photoresist stripper composition is used, it will act on the metal wiring at the bottom of the substrate. The combined action of the organic acid metal corrosion inhibitor and the metal inhibitor is beneficial to protecting the metal wiring from being corroded by the photoresist stripper composition.

[0116] In an alternative embodiment, the surfactant is selected from fatty alcohol polyoxyethylene polyoxypropylene ether; it is beneficial for the photoresist to be in full contact with the photoresist stripper composition and beneficial for the photoresist to be stripped from the substrate.

[0117] In an alternative embodiment, the molecular general formula of the fatty alcohol polyoxyethylene polyoxypropylene ether is R3O(C2H4O) m (C3H6O) oH, wherein R3 is an alkyl group having 8 to 13 carbon atoms, m and o are the degrees of polymerization of polyoxyethylene and polyoxypropylene respectively, and both m and o are less than 20. Preferably, R3 is isodecyl, which is more conducive to the stripping of the photoresist from the substrate.

[0118] In an alternative embodiment, the auxiliary additive includes at least one of the compounds represented by Formula III and Formula IV:

[0119]

[0120] wherein, R4 is an alkyl group having 1 to 4 carbon atoms, and R5 is or an alkyl group having 4 to 6 carbon atoms.

[0121] Preferably, the auxiliary additive is selected from at least one of glycerol triacetate, dioctyl sebacate, and dibutyl phthalate; more preferably, it is selected from glycerol triacetate.

[0122] The auxiliary additive can disperse the photoresist, which is beneficial to reducing the size of the stripped photoresist, avoiding clogging of the equipment, and reducing the residue of the photoresist stripping solution.

[0123] The preparation method of the photoresist stripping solution in the present application includes: mixing each raw material according to the ratio to obtain a mixed solution, and circulating and filtering the mixed solution to obtain the photoresist stripping solution. The preparation method is simple and is conducive to industrial production.

[0124] The embodiment of the present invention also provides a method for stripping a photoresist, which is to immerse the substrate with the attached photoresist in the photoresist stripping solution composition at 40°C - 60°C to remove the photoresist on the surface of the substrate.

[0125] Specifically, the temperature of the photoresist stripping solution composition can be 40°C, 45°C, 50°C, 55°C, 60°C, or any value between 40°C - 60°C. The photoresist stripping does not require too high a temperature, which is beneficial to cost savings and at the same time reduces damage to the substrate.

[0126] The features and properties of the present invention will be further described in detail below in conjunction with examples.

[0127] Example 1

[0128] This embodiment provides a photoresist stripper, which, by mass percentage, includes: 25% of an alcohol ether solvent, 40% of a polyol solvent, 3% of an alkanolamine substance, 0.1% of an organic acid metal corrosion inhibitor, 0.1% of a benzothiazole metal inhibitor, 0.2% of a surfactant, and 0.05% of an auxiliary additive. Among them, the alcohol ether solvent is diethylene glycol butyl ether, the polyol solvent is diethylene glycol, the alkanolamine is 2,2-dihydroxydiethylamine, the organic acid metal corrosion inhibitor is citric acid, the benzothiazole metal inhibitor is 2-mercaptobenzothiazole, the surfactant is isodecyl polyoxyethylene ether, and the auxiliary additive is glyceryl triacetate.

[0129] The differences between Examples 2-4 and Comparative Examples 1-3 and Example 1 are only that: the ratios of diethylene glycol butyl ether and diethylene glycol and the dosages of the metal corrosion inhibitor are different, as shown in Table 1 specifically.

[0130] Example 5

[0131] This embodiment also provides a photoresist stripper, the difference from Example 1 being only that the polyol solvent is 1,2-propanediol and the ratio of diethylene glycol butyl ether and 1,2-propanediol is different.

[0132] The differences between Examples 6-8 and Comparative Examples 4-5 and Example 5 are only that: the ratios of diethylene glycol butyl ether and 1,2-propanediol and the dosages of the metal corrosion inhibitor and the metal inhibitor are different, as shown in Table 1 specifically.

[0133] The preparation method of the photoresist stripper in each embodiment and comparative example of this application includes: weighing each raw material according to the ratio and mixing them evenly, and then filtering with a 0.2-micron filter element to obtain the photoresist stripper.

[0134] The compositions of the photoresist stripper in each embodiment and comparative example of this application are shown in Table 1.

[0135] Table 1 Photoresist stripper compositions provided by Examples 1-8 and Comparative Examples 1-5

[0136]

[0137]

[0138] Comparative Example 6

[0139] This embodiment provides a photoresist stripper, the difference from Example 3 being only that diethylene glycol butyl ether is replaced by diethylene glycol methyl ether.

[0140] Example 9

[0141] This embodiment provides a photoresist stripper, the difference from Example 3 being only that 2,2-dihydroxydiethylamine is replaced by 2-aminoethanol.

[0142] Example 10

[0143] This example provides a photoresist stripper, which is only different from Example 3 in that citric acid is replaced by malic acid.

[0144] Example 11

[0145] This example provides a photoresist stripper, which is only different from Example 3 in that 2-mercaptobenzothiazole is replaced by 2-aminobenzothiazole.

[0146] Example 12

[0147] This example provides a photoresist stripper, which is only different from Example 3 in that isodecyl polyoxyethylene ether is replaced by octyl polyoxyethylene ether.

[0148] Example 13

[0149] This example provides a photoresist stripper, which is only different from Example 3 in that glyceryl triacetate is replaced by dioctyl sebacate.

[0150] Test Example 1

[0151] Pre-dissolve the photoresist in the photoresist strippers in some examples and comparative examples to obtain a photoresist stripper with a photoresist concentration of 2 wt%. Simulate long-term use until the photoresist concentration in the stripper reaches 2 wt%. Immerse the sample wafer in this stripper at 50 °C for 2 min, then take it out, wash, dry it, and place it in an oven at 120 °C for 24 h. Use a scanning electron microscope (SEM) to evaluate the corrosion of the metal cross-section of the metal film sample wafer taken out of the oven. If there is stripper or photoresist residue, holes will appear on the metal cross-section. The residue situation can be judged according to the corrosion situation, and the evaluation results are shown in Table 2.

[0152] Table 2

[0153] Experiment <![CDATA[LogP of the mixed solvent x > Hole condition Residual condition Example 1 -0.283 □ Medium amount of residue Example 2 -0.170 ○ Small amount of residue Example 3 -0.030 ◎ No residue Example 4 0.082 ○ Small amount of residue Example 5 -0.194 ○ Small amount of residue Example 6 -0.082 ◎ No residue Example 7 0.030 ○ Small amount of residue Example 8 0.142 □ Medium amount of residue Comparative example 6 -0.660 △ Large amount of residue Example 12 -0.030 ○ Small amount of residue Example 13 -0.030 ○ Small amount of residue Comparative example 1 0.812 △ Large amount of residue

[0154] Note: Calculate LogP in the table x Required LogP a and LogP b The data is obtained from the Chemical Industry Network of Gade.

[0155] △: Severe corrosion (holes with a diameter greater than 300 nm exist);

[0156] □: Severe corrosion (holes with a diameter greater than 100 nm and less than 300 nm exist);

[0157] ○: Light corrosion (holes with a diameter greater than 10 nm and less than 100 nm exist);

[0158] ◎: No corrosion (no holes larger than 10 nm).

[0159] As can be seen from Table 2, for the photoresist stripping liquid compositions of the examples and comparative examples, excellent water washing performance at high life can be obtained only when the combined ratio of the alcohol ether solvent and the polyol solvent is appropriate. For example, in Examples 3 and 6, there is basically no residual liquid medicine on the substrate surfaces of both, and there is basically no corrosion to the metal film layer after simulated high temperature. Among them, the SEM image of the sample after treatment in Example 3 is as Figure 1 shown. According to Figure 1 , there is no corrosion and no liquid medicine residue on the copper film layer. The LogP of the mixed solvent in Comparative Example 1 x exceeds the scope of the claims, and there will be a situation of insufficient photoresist stripping or a large amount of liquid medicine residue. The SEM image of the sample after treatment in Comparative Example 1 is as Figure 2 shown. According to Figure 2 , it can be seen that the residual liquid medicine or photoresist will cause voids inside after high temperature heating.

[0160] Test Example 2

[0161] The difference from Test Example 1 is only that the photoresist is not pre-dissolved in the photoresist stripping liquid, and the evaluation results of Example 3 and Comparative Example 1 are shown in Table 3.

[0162] Table 3

[0163] Experiment <![CDATA[LogP of the mixed solvent x > Hole condition Residual condition Example 3 -0.030 ◎ No residue Comparative example 1 0.812 ◎ No residue

[0164] By comparing Table 2 and Table 3, it can be seen that although Comparative Example 1 performs well in Test Example 2, when the stripping liquid after simulated long-term use is used, the corrosion grade and the amount of liquid medicine residue increase significantly, while after the stripping liquid after simulated long-term use in Example 3, it can still remain non-corrosive and residue-free.

[0165] Test Example 3

[0166] In Examples 3, 6, 9 - 11 and Comparative Examples 1 - 5, the photoresist is pre-dissolved in the stripping liquid to obtain a photoresist stripping liquid with a photoresist concentration of 2 wt%. The metal film layer samples are respectively immersed in the stripping liquids for dissolving photoresist of the examples and comparative examples at 50 °C for 2 min, then taken out, washed, and dried to remove the residual stripping liquid and cleaning agent on the surface. Using a scanning electron microscope (SEM), the corrosion conditions of the two metals, copper and aluminum, in the samples are evaluated, and the results are shown in Table 4.

[0167] Table 4

[0168]

[0169]

[0170] □: Severe corrosion (the aluminum film layer is engraved as a whole, the copper film layer is completely damaged or has an undercut greater than 400 nanometers);

[0171] ○: Mild corrosion (partial side engraving of the aluminum film layer, partial defect of the copper film layer outline or 10-400 nanometer undercut);

[0172] ◎: No corrosion (the aluminum film has no side engraving, and the copper film has a complete outline without undercut).

[0173] As shown in Table 4, only when the combination ratio of alcohol ether solvent and polyol solvent and the metal corrosion inhibitor are properly selected can the corrosion of aluminum film layer and copper film layer be reduced. As in Examples 3 and 6, the aluminum film layer and copper film layer of the two are basically free of corrosion. The SEM image of the sample after treatment in Example 6 is as follows: Figure 3 As shown. Examples 9-11 replaced the additives, and the corrosion was not as good as Examples 3 and 6. Comparative Examples 2-5 lacked some metal corrosion inhibitors, and there was severe corrosion of the aluminum film or copper film. Figures 4 - 6 They are the SEM images of the samples after treatment in Comparative Examples 2, 3 and 4, Figure 4 The top of the copper film is corroded. Figure 5 The aluminum film is corroded. Figure 6 Corrosion occurs at the bottom of the copper film layer.

[0174] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A photoresist stripping liquid composition, characterized in that, By mass fraction, it includes the following components: Alcohol ether solvent: 10wt%-40wt%; Polyol solvent: 20wt%-50wt%; Alkanolamine compound: 0.5wt%-10wt%; Metal corrosion inhibitor: 0.02wt%-2wt%; Surfactant: 0.01wt%-1wt%; Auxiliary additive: 0.01wt%-1wt%; The balance is water; Among them, the alcohol ether solvent and the polyol solvent in the photoresist stripping liquid composition form a mixed solvent, and the octanol / water partition coefficient LogP of the mixed solvent x is -0.3 to 0.2, where LogP x = LogP a × A + LogP b × B; LogP a : Octanol / water partition coefficient of alcohol ether solvents; LogP b : Octanol / water partition coefficient of the polyol solvent; A: The mass fraction of the alcohol ether solvent in the mixed solvent; B: The mass fraction of the polyol solvent in the mixed solvent.

2. The photoresist stripping liquid composition according to claim 1, wherein The photoresist stripping liquid composition satisfies at least one of the following A-G characteristics: A. The mass fraction of the alcohol ether solvent is 20wt%-35wt%; B. The mass fraction of the polyol solvent is 30wt%-45wt%; C. The mass fraction of the alkanolamine compound is 1wt%-5wt%; D. The metal corrosion inhibitor includes an organic acid-based metal corrosion inhibitor, and the mass fraction of the organic acid-based metal corrosion inhibitor is 0.01wt%-1wt%; E. The metal corrosion inhibitor includes a benzothiazole-based metal inhibitor, and the mass fraction of the benzothiazole-based metal inhibitor is 0.01wt%-1wt%; F. The mass fraction of the surfactant is 0.05wt%-0.5wt%; G. The mass fraction of the auxiliary additive is 0.05wt%-0.5wt%.

3. The photoresist stripping liquid composition according to claim 1, wherein The alcohol ether solvent is selected from at least one of diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, dipropylene glycol monoethyl ether, and ethylene glycol monobutyl ether.

4. The photoresist stripping liquid composition according to claim 1, characterized in that, The structural general formula of the polyol solvent is shown in Formula I: Wherein, when R1 is H n = 1 to 3; When R1 is -OH, R2 is an alkyl group with 1-3 carbon atoms.

5. The photoresist stripping liquid composition according to claim 1, characterized in that, The octanol / water partition coefficient LogP of the polyol solvent b is -2 to 0.

6. The photoresist stripping liquid composition according to claim 1, wherein The alkanolamine compound is selected from at least one of 2-aminoethanol, 2,2-dihydroxydiethylamine, 2-(ethylamino)ethanol, 2-(methylamino)ethanol, N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylaminoethanol, 2-(2-aminoethylamino)-1-ethanol, 1-amino-2-propanol, and 2-amino-1-propanol.

7. The photoresist stripping liquid composition according to claim 2, characterized in that, The organic acid-based metal corrosion inhibitor is selected from at least one of salicylic acid, citric acid, succinic acid, malic acid, and tartaric acid; And / or, the metal inhibitor includes a compound shown in Formula II: Wherein R is selected from at least one of methyl, ethyl, isopropyl, mercapto, and amino.

8. The photoresist stripping liquid composition according to claim 1, characterized in that, The surfactant is selected from fatty alcohol polyoxyethylene polyoxypropylene ether; And / or, the auxiliary additive includes at least one of the compounds shown in Formula III and Formula IV: wherein, R4 is an alkyl group having 1 to 4 carbon atoms, and R5 is or an alkyl group having 4 to 6 carbon atoms.

9. The photoresist stripping liquid composition according to claim 8, characterized in that, The molecular general formula of the fatty alcohol polyoxyethylene polyoxypropylene ether is R3O(C2H4O) m (C3H6O) o H, where R3 is an alkyl group with 8 - 13 carbon atoms, m and o are the degrees of polymerization of polyoxyethylene and polyoxypropylene respectively, and both m and o are less than 20.

10. A method for stripping a photoresist, characterized in that, Immerse the substrate with the attached photoresist in the photoresist stripping liquid composition at 40°C - 60°C to remove the photoresist on the surface of the substrate.

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