Long-acting photoresist stripping liquid and application thereof

Abstract

The invention provides a long-acting photoresist stripping liquid and application thereof. The long-acting photoresist stripping liquid comprises the following raw materials in percentage by mass: 30-60% of an ether solvent, 10-30% of an amine solvent, 10-30% of a ketone solvent, 1-5% of an amide solvent and an alcohol amine solvent as effective components, and a trace corrosion inhibitor. Through the synergistic effect of the components, the long-acting photoresist stripping liquid disclosed by the invention has a good removal effect on photoresist residues on a wafer, is effective for a long time, basically does not corrode metal aluminum, copper and the like on a substrate, and has a good application prospect in the fields of semiconductors and LEDs (Light Emitting Diodes).

Description

Technical Field

[0001] The invention belongs to the technical field of semiconductor consumables, and in particular relates to a long-acting photoresist stripping solution and application thereof. Background Art

[0002] In semiconductor manufacturing, after photoresist is coated on the surface of the wafer, the pattern is transferred by exposure using a mask or metal plating. After the pattern is etched or photolithographically onto the underlying substrate, the photoresist needs to be stripped. During the stripping process, the photoresist needs to be completely removed without leaving any residual glue, and at the same time, no damage should be caused to the substrate pattern. Long-lasting photoresist stripping solution is a chemical reagent used to dissolve the soluble part of the photoresist after exposure. Its stripping mechanism is mainly based on the fact that the solubility of the base material resin in the photoresist component after exposure will change significantly under the action of hydrogen ions. At present, the most commonly used long-lasting photoresist stripping solution is DMSO solution and its formulated products. Compared with alkaline solutions such as NMP, its corrosion to metals is weaker and the corrosion effect caused is smaller.

[0003] Because the photoresist stripping is completed on the substrate, the long-lasting photoresist stripping solution will contact the substrate. However, the long-lasting photoresist stripping solution provided by the prior art has a high degree of damage to metal substrates, and there is a risk of corroding indium phosphide, gallium nitride substrates and the metal circuits attached thereto, resulting in low product yield. Summary of the invention

[0004] The main purpose of the present invention is to provide a long-lasting photoresist stripping solution and its application, wherein the long-lasting photoresist stripping solution of the present invention completely removes the photoresist without leaving any residual glue, and at the same time does not cause damage to the substrate pattern, and the effect lasts for a long time. The photoresist suitable for this long-lasting photoresist stripping solution can be positive or negative, and has universality.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] A long-acting photoresist stripping solution comprises: ether solvents, amine solvents, ketone solvents, amide solvents, alcoholamine solvents, and trace corrosion inhibitors.

[0007] As a preferred embodiment of a long-lasting photoresist stripping solution, the pH of the long-lasting photoresist stripping solution is 7-8.

[0008] As a preferred embodiment of a long-lasting photoresist stripping solution, the ether solvent is methyl ether, ethyl ether, phenyl ether, anisole, phenethyl ether or p-phenylenedimethyl ether.

[0009] As a preferred solution of a long-lasting photoresist stripping solution, the long-lasting photoresist stripping solution further comprises: one or more of an organic base and an organic acid.

[0010] As a preferred embodiment of a long-lasting photoresist stripping solution, the ether solvent is selected from at least one of the compounds shown in Formula 1:

[0011]

[0012] In formula 1, R1 and R2 are the same or different and are independently selected from C1-3 alkyl, alcohol, and phenyl groups; the ether solvent is selected from one or more of diethyl ether, diethylene glycol methyl ether, triethylene glycol methyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol phenyl ether, and diethylene glycol ethyl ether; and the weight percentage of the ether solvent is 30wt% to 60wt%.

[0013] As a preferred embodiment of a long-lasting photoresist stripping solution, the amine solvent is selected from at least one of the compounds shown in Formula 2:

[0014]

[0015] In formula 2, R1, R2, and R3 are the same or different and are independently selected from H or C1-C3 alkyl or amino groups. The amine solvent is selected from one or more of trimethylamine, diethylamine, triethylamine, hydrazine hydrate, and urea. The weight percentage of the amine solvent is 10wt% to 30wt%.

[0016] As a preferred embodiment of a long-lasting photoresist stripping solution, the ketone solvent is selected from at least one of the compounds shown in Formula 3:

[0017]

[0018] In formula 3, R1 and R2 are the same or different and are independently selected from hydrogen and C1-C3 alkyl, and the ketone solvent is selected from one or more of butanone, cyclopentanone and cyclohexanone. The weight percentage of the ketone solvent is 10wt% to 30wt%.

[0019] As a preferred embodiment of a long-lasting photoresist stripping solution, the amide solvent is selected from at least one of the compounds shown in Formula 4:

[0020]

[0021] The amide solvent is selected from one or more of polyacrylamide, oleamide, coconut oil diethanolamide, stearamide, glutamine, and N,N-methylenebisacrylamide, and the weight percentage of the amide solvent is 1wt%-5wt%.

[0022] As a preferred embodiment of a long-lasting photoresist stripping solution, the alcohol amine solvent is selected from at least one of the compounds shown in Formula 5:

[0023]

[0024] The alcoholamine solvent is selected from one or more of diethanolamine, triethanolamine, diisopropanolamine and triisopropanolamine, and the weight percentage of the alcoholamine solvent is 1wt%-5wt%.

[0025] As a preferred embodiment of a long-lasting photoresist stripping solution, the corrosion inhibitor is selected from at least one of fructose, glucose, galactose, sorbitol, xylitol, lactic acid, malic acid, and citric acid, and the weight percentage of the corrosion inhibitor is 0.01wt%-2wt%.

[0026] In a second aspect, the present invention further provides a use of a long-lasting photoresist stripping solution as described in any one of the above items in improving the dissolution ability of photoresist, for example, it can be used to remove photoresist formed on the surface during the chip preparation process.

[0027] The beneficial effects of the present invention are:

[0028] The present invention proposes a long-lasting photoresist stripping solution and its application, wherein the long-lasting photoresist stripping solution of the present invention completely removes the photoresist without leaving any residual glue, and at the same time does not cause damage to the substrate pattern, and the effect lasts for a long time. The photoresist suitable for this long-lasting photoresist stripping solution can be positive or negative, and has universal applicability. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required for use in the description of the embodiments are briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative work, and all of them belong to the protection scope of the present invention, among which:

[0030] Figure 1 This is a microscope picture of the control group of the long-acting photoresist stripping solution provided by the present invention after cleaning;

[0031] Figure 2 This is a microscope picture of Example 8 of the long-acting photoresist stripping solution provided by the present invention after cleaning.

[0032] Figure 3 This is a microscope picture of Example 14 of the long-lasting photoresist stripping solution provided by the present invention after cleaning.

[0033] Figure 4 This is a microscope picture of Example 15 of the long-lasting photoresist stripping solution provided by the present invention after cleaning. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] In order to make the purpose, technical scheme and advantages of the embodiments of the present invention clearer, the technical scheme in the embodiments of the present invention is described clearly and completely below. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0036] In semiconductor manufacturing, after photoresist is coated on the surface of the wafer, the pattern is transferred by exposure using a mask or metal plating. After the pattern is etched or photolithographically onto the underlying substrate, the photoresist needs to be stripped. During the stripping process, the photoresist needs to be completely removed without leaving any residual glue, and at the same time, no damage should be caused to the substrate pattern. Long-lasting photoresist stripping solution is a chemical reagent used to dissolve the soluble part of the photoresist after exposure. Its stripping mechanism is mainly based on the fact that the solubility of the base material resin in the photoresist component after exposure will change significantly under the action of hydrogen ions. At present, the most commonly used long-lasting photoresist stripping solution is DMSO solution and its formulated products. Compared with alkaline solutions such as NMP, its corrosion to metals is weaker and the corrosion effect caused is smaller.

[0037] Because the photoresist stripping is completed on the substrate, the long-lasting photoresist stripping solution will contact the substrate. However, the long-lasting photoresist stripping solution provided by the prior art has a high degree of damage to metal substrates, and there is a risk of corroding indium phosphide, gallium nitride substrates and the metal circuits attached thereto, resulting in low product yield.

[0038] In the present invention, an embodiment of the present invention provides a long-lasting photoresist stripping solution, which includes: ether solvents, amine solvents, ketone solvents, amide solvents, alcohol amine solvents, and trace corrosion inhibitors.

[0039] In the present invention, in the production process of electronic products, it is usually necessary to etch various precise functional structures on the substrate surface. The functional structures are located in different areas on the substrate surface. In order to avoid affecting the functional structures in other areas on the substrate, it is generally necessary to coat the substrate surface with photoresist to form protection before etching. After the etching is completed, the photoresist is removed and the electronic product is formed after subsequent processing. The photoresist stripping solution provided by the present invention is mainly used to strip the photoresist coated on the substrate surface during the production process of electronic products.

[0040] As a preferred embodiment of the long-acting photoresist stripping solution, the pH value of the long-acting photoresist stripping solution is 7-8.

[0041] As a preferred embodiment of the long-acting photoresist stripping solution, the ether solvent is methyl ether, ethyl ether, phenyl ether, anisole, phenethyl ether or p-phenylenedimethyl ether.

[0042] As a preferred solution of the long-lasting photoresist stripping solution, the long-lasting photoresist stripping solution further comprises: one or more of an organic base and an organic acid.

[0043] As a preferred embodiment of the long-lasting photoresist stripping solution, the ether solvent is selected from at least one of the compounds shown in Formula 1:

[0044]

[0045] In formula 1, R1 and R2 are the same or different and are independently selected from C1-3 alkyl, alcohol, and phenyl groups; the ether solvent is selected from one or more of diethyl ether, diethylene glycol methyl ether, triethylene glycol methyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol phenyl ether, and diethylene glycol ethyl ether; and the weight percentage of the ether solvent is 30wt% to 60wt%.

[0046] As a preferred embodiment of the long-lasting photoresist stripping solution, the amine solvent is selected from at least one of the compounds shown in Formula 2:

[0047]

[0048] In formula 2, R1, R2, and R3 are the same or different and are independently selected from H or C1-C3 alkyl or amino groups. The amine solvent is selected from one or more of trimethylamine, diethylamine, triethylamine, hydrazine hydrate, and urea. The weight percentage of the amine solvent is 10wt% to 30wt%.

[0049] As a preferred embodiment of the long-lasting photoresist stripping solution, the ketone solvent is selected from at least one of the compounds shown in Formula 3:

[0050]

[0051] In formula 3, R1 and R2 are the same or different and are independently selected from hydrogen and C1-C3 alkyl, and the ketone solvent is selected from one or more of butanone, cyclopentanone and cyclohexanone. The weight percentage of the ketone solvent is 10wt% to 30wt%.

[0052] As a preferred embodiment of the long-lasting photoresist stripping solution, the amide solvent is selected from at least one of the compounds shown in Formula 4:

[0053]

[0054] The amide solvent is selected from one or more of polyacrylamide, oleamide, coconut oil diethanolamide, stearamide, glutamine, and N,N-methylenebisacrylamide, and the weight percentage of the amide solvent is 1wt%-5wt%.

[0055] As a preferred embodiment of the long-lasting photoresist stripping solution, the alcohol amine solvent is selected from at least one of the compounds shown in Formula 5:

[0056]

[0057] The alcoholamine solvent is selected from one or more of diethanolamine, triethanolamine, diisopropanolamine and triisopropanolamine, and the weight percentage of the alcoholamine solvent is 1wt%-5wt%.

[0058] As a preferred embodiment of the long-lasting photoresist stripping solution, the corrosion inhibitor is selected from at least one of fructose, glucose, galactose, sorbitol, xylitol, lactic acid, malic acid and citric acid, and the weight percentage of the corrosion inhibitor is 0.01wt%-2wt%.

[0059] In a second aspect, the present invention further provides a use of a long-lasting photoresist stripping solution as described in any one of the above items in improving the dissolution ability of photoresist.

[0060] Blank group

[0061] Mass percentage: N-methylpyrrolidone 100.00wt%.

[0062] Example 1

[0063] A method for preparing a long-acting photoresist stripping solution comprises the following steps: by mass percentage: 100.00 wt % of an ether solvent.

[0064] Example 2

[0065] A method for preparing a long-acting photoresist stripping solution comprises the following steps: by mass percentage: 100.00 wt % of an amine solvent.

[0066] Example 3

[0067] A method for preparing a long-acting photoresist stripping solution comprises the following steps: by mass percentage: 100.00 wt % of ketone solvent.

[0068] Example 4

[0069] A method for preparing a long-acting photoresist stripping solution comprises the following steps: by mass percentage: 100.00 wt % of an alcohol amine solvent.

[0070] Example 5

[0071] A method for preparing a long-acting photoresist stripping solution comprises the following steps: by mass percentage: 50 wt % of ether solvent and 50 wt % of amine solvent.

[0072] Example 6

[0073] A method for preparing a long-acting photoresist stripping solution comprises the following steps: by mass percentage: 50 wt % of an ether solvent and 50 wt % of a ketone solvent.

[0074] Example 7

[0075] A method for preparing a long-acting photoresist stripping solution comprises the following steps: by mass percentage: 50 wt % of ether solvent and 50 wt % of alcoholamine solvent.

[0076] Example 8

[0077] A method for preparing a long-acting photoresist stripping solution comprises the following steps: by mass percentage: 25 wt% of ether solvent; 25 wt% of amine solvent; 25 wt% of ketone solvent; and 25 wt% of alcoholamine solvent.

[0078] Example 9

[0079] A method for preparing a long-acting photoresist stripping solution comprises the following steps: by mass percentage: 70 wt% of ether solvent; 10 wt% of amine solvent; 10 wt% of ketone solvent; and 10 wt% of alcoholamine solvent.

[0080] Example 10

[0081] A method for preparing a long-acting photoresist stripping solution comprises the following steps: by mass percentage: 50 wt% of ether solvent; 30 wt% of amine solvent; 10 wt% of ketone solvent; and 10 wt% of alcoholamine solvent.

[0082] Embodiment 11

[0083] A method for preparing a long-acting photoresist stripping solution comprises the following steps: by mass percentage: 50 wt% of ether solvent; 10 wt% of amine solvent; 30 wt% of ketone solvent; and 10 wt% of alcoholamine solvent.

[0084] Example 12

[0085] A method for preparing a long-acting photoresist stripping solution comprises the following steps: by mass percentage: 50 wt% of ether solvent; 10 wt% of amine solvent; 10 wt% of ketone solvent; and 30 wt% of alcoholamine solvent.

[0086] Embodiment 13

[0087] A method for preparing a long-acting photoresist stripping solution comprises the following steps: by mass percentage: 50 wt% of ether solvent; 20 wt% of amine solvent; 20 wt% of ketone solvent; and 10 wt% of alcoholamine solvent.

[0088] Embodiment 14

[0089] A method for preparing a long-acting photoresist stripping solution comprises the following steps: by mass percentage: 50 wt% of ether solvent; 20 wt% of amine solvent; 20 wt% of ketone solvent; 5 wt% of alcoholamine solvent; and 5 wt% of amide solvent.

[0090] Embodiment 15

[0091] A method for preparing a long-lasting photoresist stripping solution comprises the following steps: by mass percentage: 50wt% of ether solvent; 20wt% of amine solvent; 20wt% of ketone solvent; 5wt% of alcoholamine solvent; 5wt% of amide solvent, and 0.01wt% of corrosion inhibitor.

[0092] Test samples: The long-lasting photoresist stripping solution obtained in Examples 1-15 was used as the test sample, and a long-lasting photoresist stripping solution with a commonly used ratio was used as the blank group.

[0093] Test method: Fill the blank group with a degumming tank (20 liters) in Examples 1-15, keep the temperature at 75°C, set the degumming time to 120 seconds, wash with isopropyl alcohol for 120 seconds, then wash with water for 120 seconds, and then enter the baking step. After the surface is completely dry, use a microscope to observe the smoothness and integrity of the wafer surface pattern. Wash 1000 wafers with each tank of degumming solution. If it can still be cleaned after 1000 wafers, add additional tests.

[0094] Test results: The test results of Examples 1-15 and the blank group are shown in Table 1. As can be seen from Table 1, both the blank group and Examples 1-15 can achieve photoresist stripping, but the amount of film passing and the degree of cleanliness are different. This shows that the blank group cannot completely clean the residual glue. The cleaning effect of the blank group is as follows Figure 1 As shown; the ether solvents and ketone solvents in the examples have the function of fully removing the residual glue, and the amine solvents and alcohol amine solvents can increase the degumming speed. The degumming effect of Example 8 is as shown Figure 2 As shown; amide solvents have a good diffusion and solubilization effect, and have a good effect on increasing the amount of film, and the proportion is adjusted according to the efficacy of each component, which can make the pattern surface clean more smooth. The degumming effect of Example 14 is as follows Figure 3 As shown; trace addition of corrosion inhibitor can prevent the corrosion of copper wire on wafer, the degumming effect of Example 15 is as follows Figure 4 shown.

[0095] Table 1 Test results of Examples 1-15 and control samples

[0096]

[0097] The present invention is described in detail above with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions and variations of these embodiments are made without departing from the principles and spirit of the present invention, and still fall within the scope of protection of the present invention.

Claims

1. A long-lasting photoresist stripping solution, characterized in that: include: Ether solvents, amine solvents, ketone solvents, amide solvents, alcoholamine solvents, and trace corrosion inhibitors.

2. A long-lasting photoresist stripping solution according to claim 1, characterized in that: The pH of the long-acting photoresist stripping solution is 7-8.

3. A long-lasting photoresist stripping solution according to claim 1, characterized in that: The ether solvent is methyl ether, ethyl ether, phenyl ether, anisole, phenethyl ether or p-phenylenedimethyl ether.

4. A long-lasting photoresist stripping solution according to claim 1, characterized in that: The long-lasting photoresist stripping solution also includes: one or more of an organic base and an organic acid.

5. A long-lasting photoresist stripping solution according to claim 1, characterized in that: The ether solvent is selected from at least one of the compounds shown in Formula 1: In formula 1, R1 and R2 are the same or different and are independently selected from C1-3 alkyl, alcohol, and phenyl groups; the ether solvent is selected from one or more of diethyl ether, diethylene glycol methyl ether, triethylene glycol methyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol phenyl ether, and diethylene glycol ethyl ether; and the weight percentage of the ether solvent is 30wt% to 60wt%.

6. A long-lasting photoresist stripping solution according to claim 1, characterized in that: The amine solvent is selected from at least one of the compounds shown in Formula 2: In formula 2, R1, R2, and R3 are the same or different and are independently selected from H or C1-C3 alkyl or amino groups. The amine solvent is selected from one or more of trimethylamine, diethylamine, triethylamine, hydrazine hydrate, and urea. The weight percentage of the amine solvent is 10wt% to 30wt%.

7. A long-lasting photoresist stripping solution according to claim 1, characterized in that: The ketone solvent is selected from at least one of the compounds shown in Formula 3: In formula 3, R1 and R2 are the same or different and are independently selected from hydrogen and C1-C3 alkyl, and the ketone solvent is selected from one or more of butanone, cyclopentanone and cyclohexanone. The weight percentage of the ketone solvent is 10wt% to 30wt%.

8. A long-lasting photoresist stripping solution according to claim 1, characterized in that: The amide solvent is selected from at least one of the compounds shown in Formula 4: The amide solvent is selected from one or more of polyacrylamide, oleamide, coconut oil diethanolamide, stearamide, glutamine, and N,N-methylenebisacrylamide, and the weight percentage of the amide solvent is 1wt%-5wt%.

9. A long-lasting photoresist stripping solution according to claim 1, characterized in that: The alcohol amine solvent is selected from at least one of the compounds shown in Formula 5: The alcoholamine solvent is selected from one or more of diethanolamine, triethanolamine, diisopropanolamine and triisopropanolamine, and the weight percentage of the alcoholamine solvent is 1wt%-5wt%.

10. The long-lasting photoresist stripping solution according to claim 1, characterized in that: The corrosion inhibitor is selected from at least one of fructose, glucose, galactose, sorbitol, xylitol, lactic acid, malic acid and citric acid, and the weight percentage of the corrosion inhibitor is 0.01wt%-2wt%.

11. Use of the long-lasting photoresist stripping solution according to any one of claims 1 to 10 in improving the dissolving ability of photoresist.

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