Compound semiconductor photoresist stripping liquid as well as preparation method, application and cleaning method thereof

Abstract

The invention discloses a compound semiconductor photoresist stripper, and a preparation method, application and cleaning method thereof. The compound semiconductor photoresist stripper comprises the following components by weight: 30-60 parts of an alcohol ether solvent; 30-60 parts of an aprotic polar organic solvent; 1 to 15 parts of a sulfydryl corrosion inhibitor; and 1-15 parts of alcohol amine. The invention not only discloses specific components and a preparation method of the compound semiconductor photoresist stripping liquid, but also discloses application of the compound semiconductor photoresist stripping liquid in effective removal of photoresist, and the compound semiconductor photoresist stripping liquid has a good protection effect on a substrate in the application. And corrosion can be effectively prevented. In addition, the two solvents are synergistically used, so that the photoresist can be more effectively removed.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of semiconductor, and particularly relates to a compound semiconductor photoresist stripping solution, a preparation method, application and cleaning method thereof. BACKGROUND

[0002] In the process of manufacturing semiconductor components, a mask of photoresist is formed on the surface of some materials, and after exposure, pattern transfer is performed. After the desired pattern is obtained, the residual photoresist needs to be removed before the next process. In the process of removing the photoresist, the unwanted photoresist needs to be completely removed, and at the same time, any substrate cannot be corroded.

[0003] At present, the photoresist cleaning solution mainly consists of polar organic solvents, strong alkali and / or water, etc. The photoresist on the semiconductor wafer is removed by immersing the semiconductor wafer in the cleaning solution or by washing the semiconductor wafer with the cleaning solution. With the rapid development of semiconductors, the cleaning requirements for photoresist residues have also been improved accordingly. Therefore, it is necessary to find a more effective photoresist cleaning solution as the priority for improvement. Generally speaking, the cleaning ability of the alkaline photoresist cleaning solution is improved mainly by increasing the alkalinity of the cleaning solution, selecting a more effective solvent system, increasing the operating temperature and prolonging the operating time.

[0004] However, increasing the alkalinity of the cleaning solution and the operating temperature and prolonging the cleaning time often increase the corrosion of the compound semiconductor. In recent years, in order to further reduce costs and improve yield, some manufacturers have begun to require that the photoresist cleaning solution also further inhibit the corrosion of the compound semiconductor. For example, patent CN202410880916.4 discloses a new cleaning solution containing: a) organic amine; b) wetting agent; c) organic solvent; d) corrosion inhibitor. The method is easy to have photoresist residues and has great corrosion to the compound semiconductor, which will affect the subsequent electrical properties. In order to adapt to the new situation, it is necessary to develop a kind of photoresist cleaning solution which has strong photoresist removing ability and also has little corrosion to the compound semiconductor. SUMMARY

[0005] The main purpose of the present application is to provide a compound semiconductor photoresist stripping solution, a preparation method, application and cleaning method thereof. The technical problem to be solved by the present application is to provide a photoresist cleaning agent which has strong photoresist cleaning ability and low corrosion to the semiconductor wafer pattern and substrate, aiming at the defects of the existing photoresist cleaning solution, such as insufficient cleaning ability or strong corrosion to the semiconductor pattern and substrate.

[0006] In order to solve the above technical problems, the present application provides the following technical solutions: A compound semiconductor photoresist stripping solution, which comprises the following components in a weight ratio: alcohol ether solvent 30-60 parts; aprotic polar organic solvent 30-60 parts; mercapto corrosion inhibitor 1-15 parts; alcohol amine 1-15 parts.

[0007] As a preferred solution of the compound semiconductor photoresist stripping solution, the alcohol ether solvent is any one or more of diethylene glycol monobutyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, triethylene glycol butyl ether, propylene glycol phenyl ether.

[0008] Further, the alcohol ether solvent is preferably 40-50 parts.

[0009] As a preferred solution of the compound semiconductor photoresist stripping solution, the aprotic polar organic solvent is at least one of dimethyl sulfoxide, ethyl methyl sulfoxide, dimethyl sulfone, diethyl sulfone, tetramethylene sulfone, N,N-dimethyl formamide, N-methyl formamide, N,N-dimethyl acetamide, N-methyl acetamide, β-propiolactone, γ-butyrolactone, γ-valerolactone, 8-hexanolactone, γ-octanolactone, ethylene carbonate, propylene carbonate, butylene carbonate.

[0010] Further, the aprotic polar organic solvent is preferably at least one of dimethyl sulfoxide, ethyl methyl sulfoxide, dimethyl sulfone, diethyl sulfone, tetramethylene sulfone.

[0011] Further, the aprotic polar organic solvent is preferably at least one of dimethyl sulfoxide, tetramethylene sulfone.

[0012] Further, the aprotic polar organic solvent is preferably 30-40 parts.

[0013] The alcohol ether solvent and the aprotic polar organic solvent both have excellent sol-gel ability and can swell the photoresist through nucleophilic reaction, penetration, and expansion of the photoresist, which is conducive to the further penetration of other components.

[0014] As a preferred solution of the compound semiconductor photoresist stripping solution, the mercapto corrosion inhibitor is one or more of dimercapto propanol, mercaptobenzothiazole, 3-mercapto ethyl butyrate, 3-mercapto methyl propionate, 3-mercapto hexanol butyrate.

[0015] Further, the mercapto corrosion inhibitor is preferably 5-8 parts.

[0016] The mercapto group in the mercapto corrosion inhibitor can be adsorbed on the surface of the compound semiconductor to form a protective film, thereby preventing the compound semiconductor from contacting the corrosion medium and playing a corrosion inhibition role.

[0017] As a preferred solution of the compound semiconductor photoresist stripping solution, the alcohol amine is selected from one or more of monoethanolamine, N-methylethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethyldiethanolamine, N,N-diethylethanolamine, N-(2-aminoethyl) ethanolamine, and diglycolamine.

[0018] Further, the alcohol amine is preferably 10-15 parts.

[0019] The alcohol amine can undergo nucleophilic addition reaction with polar groups such as carbonyl and carboxyl in the photoresist, break the chemical bonds formed by these functional groups, cause certain main chain breakage of the photoresist, and cut off the covalent bonds between the macromolecular segments.

[0020] Another object of the present application is to disclose a preparation method of a compound semiconductor photoresist stripping solution, comprising the following steps: Step 1: adding the alcohol ether solvent and the aprotic polar organic solvent into a container, stirring for 0.5-1 hour until completely dissolved, and the solution is clear and transparent; Step 2: adding the alcohol amine into the solution of step 1, stirring for 1-2 hours until completely dissolved, and the solution is clear and transparent; Step 3: adding the mercapto corrosion inhibitor into the solution of step 2 while stirring, stirring for 0.5-2 hours until completely dissolved, and the solution is clear and transparent, thereby preparing the compound semiconductor photoresist stripping solution.

[0021] Further, the stirring temperature is controlled below 40℃.

[0022] Further, the prepared compound semiconductor photoresist stripping solution is filtered by 0.2μm and 0.1μm filter cores.

[0023] Another object of the present application also discloses an application of the compound semiconductor photoresist stripping solution in the field of removing photoresist.

[0024] Another object of the present application also discloses a cleaning method of the compound semiconductor photoresist stripping solution, comprising the following steps: placing the semiconductor wafer in the compound semiconductor photoresist stripping solution at 40-90℃, soaking, ultrasonicating or oscillating for 5-30min, taking out, rinsing with ultrapure water, and then blowing dry with nitrogen; Alternatively, the compound semiconductor photoresist stripping solution at 40-90℃ is sprayed onto the rotating semiconductor wafer by using a single-chip machine table, rinsing for 5-10min, taking out, rinsing with ultrapure water, and then blowing dry with nitrogen.

[0025] The present application has the following beneficial effects: 1) Alcohol ether solvents and aprotic polar organic solvents are nucleophilic and have excellent sol-gel capabilities. Through nucleophilic reactions, penetration, and expansion of the photoresist, the photoresist structure expands, which is conducive to the further penetration of other tissues.

[0026] 2) The thiol groups in thiol-based corrosion inhibitors can be adsorbed onto the surface of compound semiconductors to form a protective film, isolating the compound semiconductor from contact with the corrosive medium, thereby playing a role in corrosion inhibition.

[0027] 3) Alkylamines can undergo nucleophilic addition reactions with polar groups such as carbonyl and carboxyl groups in photoresist, breaking the chemical bonds formed by these functional groups, causing certain main chain breakage in the photoresist, cutting the covalent bonds between macromolecular chain segments, and dissolving the photoresist after dry etching.

[0028] In summary, this invention is used for photoresist stripping in the semiconductor chip industry, ensuring photoresist stripping capability while providing excellent protection for compound semiconductors. Attached Figure Description

[0029] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be 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 effort, and all of them fall within the protection scope of the present invention. Appendix Figure 1 These are magnified microscope images of chips after cleaning with the compound semiconductor photoresist stripping solution prepared in Example 1; Appendix Figure 2 These are magnified microscope images of chips after cleaning with the compound semiconductor photoresist stripping solution prepared in Comparative Example 1; Appendix Figure 3 This is a magnified microscope image of a chip after it has been cleaned using the compound semiconductor photoresist stripping solution prepared in Comparative Example 2. Detailed Implementation

[0030] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0031] Unless otherwise stated, all units used in this specification are international standard units, and all numerical values ​​and ranges appearing in this invention should be understood to include systematic errors that are unavoidable in industrial production.

[0032] In the present specification, a numerical range indicated by "numerical value A - numerical value B" means a range including the end point values A, B.

[0033] In the present specification, a numerical range indicated by "above" or "below" means a range including the numerical value.

[0034] In the present specification, the meaning indicated by "may" includes both the meaning of performing a certain process and the meaning of not performing the certain process.

[0035] In the present specification, "optionally" or "optional" means that the use or non-use of certain substances, components, execution of steps, application of conditions, and the like factors.

[0036] In the present specification, when "room temperature" is used, the temperature can be 15 to 25°C.

[0037] In the present specification, when the manufacturer of a reagent or an apparatus is not mentioned, it means a general product that can be purchased.

[0038] As shown in Figure 1 , Figure 2 and Figure 3 , the present application discloses a compound semiconductor photoresist stripping solution, which comprises the following components in the following proportions by weight: alcohol ether solvent 30-60 parts; aprotic polar organic solvent 30-60 parts; mercapto-based corrosion inhibitor 1-15 parts; alcohol amine 1-15 parts.

[0039] As a preferred solution of the compound semiconductor photoresist stripping solution, the alcohol ether solvent is any one or more of diethylene glycol monobutyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, triethylene glycol butyl ether, and propylene glycol phenyl ether.

[0040] Further, the alcohol ether solvent is preferably 40-50 parts.

[0041] As a preferred solution of the compound semiconductor photoresist stripping solution, the aprotic polar organic solvent is at least one selected from the group consisting of dimethyl sulfoxide, ethyl methyl sulfoxide, dimethyl sulfone, diethyl sulfone, cyclobutyl sulfone, N, N-dimethylformamide, N-methylformamide, N, N-dimethylacetamide, N-methylacetamide, β-propiolactone, γ-butyrolactone, γ-valerolactone, 8-hexanolactone, γ-octanolactone, ethylene carbonate, propylene carbonate, and butylene carbonate.

[0042] Further, the aprotic polar organic solvent is preferably at least one of dimethyl sulfoxide, ethyl methyl sulfoxide, dimethyl sulfone, diethyl sulfone, and sulfolane.

[0043] Further, the aprotic polar organic solvent is preferably at least one of dimethyl sulfoxide and sulfolane.

[0044] Further, the aprotic polar organic solvent is preferably 30-40 parts.

[0045] The alcohol ether solvent and the aprotic polar organic solvent are both nucleophilic and have excellent sol solubility, and by nucleophilic reaction, penetration, and expansion of the photoresist, the photoresist reticular structure is expanded, which is conducive to the further penetration of other components.

[0046] As a preferred solution of the compound semiconductor photoresist stripping solution, the mercapto-based corrosion inhibitor is selected from one or more of dimercapto propanol, mercaptobenzothiazole, 3-mercapto ethyl butyrate, 3-mercapto methyl propionate, and 3-mercapto hexanol butyrate.

[0047] Further, the mercapto-based corrosion inhibitor is preferably 5-8 parts.

[0048] The mercapto group in the mercapto-based corrosion inhibitor can be adsorbed on the surface of the compound semiconductor to form a protective film, thereby preventing the compound semiconductor from contacting the corrosion medium, thereby playing a corrosion inhibition role.

[0049] As a preferred solution of the compound semiconductor photoresist stripping solution, the alcohol amine is selected from one or more of monoethanolamine, N-methyl ethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethyl diethanolamine, N, N-diethyl ethanolamine, N-(2-aminoethyl) ethanolamine, and diethylene glycol amine.

[0050] Further, the alcohol amine is preferably 10-15 parts.

[0051] The alcohol amine can undergo nucleophilic addition reaction with the polar groups such as carbonyl and carboxyl in the photoresist, thereby breaking the chemical bonds formed by these functional groups, causing certain main chain rupture of the photoresist, cutting the covalent bonds between the macromolecular segments, and dissolving the photoresist after dry etching.

[0052] Another object of the present application is to disclose a preparation method of a compound semiconductor photoresist stripping solution, which comprises the following steps: Step 1: The alcohol ether solvent and the aprotic polar organic solvent are added to a container, and stirred for 0.5-1 hour until completely dissolved, and the solution is clear and transparent; Step 2: The alcohol amine is added to the solution of step 1, and stirred for 1-2 hours until completely dissolved, and the solution is clear and transparent; Step 3: the mercapto type corrosion inhibitor is added into the solution of step 2 while stirring, and stirring is performed for 0.5-2 hours until complete dissolution, and the solution is clear and transparent, thereby preparing the compound semiconductor photoresist stripping solution.

[0053] Further, the stirring temperature is controlled below 40℃.

[0054] Further, the compound semiconductor photoresist stripping solution is filtered by a filter core with a pore size of 0.2um and 0.1um after preparation.

[0055] Another object of the present application also discloses an application of the compound semiconductor photoresist stripping solution in the field of photoresist removal.

[0056] Another object of the present application also discloses a cleaning method of the compound semiconductor photoresist stripping solution, which comprises the following steps: placing a semiconductor wafer in the compound semiconductor photoresist stripping solution at 40-90℃, and soaking, ultrasonicating or oscillating for 5-30 minutes, and then taking out, rinsing with ultrapure water, and nitrogen blowing. Alternatively, the compound semiconductor photoresist stripping solution at 40-90℃ is sprayed onto a rotating semiconductor wafer by using a single-chip machine, and rinsing is performed for 5-10 minutes, and then taking out, rinsing with ultrapure water, and nitrogen blowing.

[0057] Specific embodiments are as follows: The present embodiment discloses a plurality of compound semiconductor chip photoresist stripping solutions, which comprise the components and weight ratios shown in Table 1, and the preparation method is as follows: Step 1: alcohol ether solvent and aprotic polar organic solvent are added into a container, and stirring is performed for 0.5-1 hour until complete dissolution, and the solution is clear and transparent; Step 2: alcohol amine is added into the solution of step 1 while stirring, and stirring is performed for 1-2 hours until complete dissolution, and the solution is clear and transparent; Step 3: the mercapto type corrosion inhibitor is added into the solution of step 2 while stirring, and stirring is performed for 0.5-2 hours until complete dissolution, and the solution is clear and transparent, thereby preparing the compound semiconductor photoresist stripping solution.

[0058] The stirring temperature is controlled below 40℃.

[0059] The compound semiconductor photoresist stripping solution is filtered by a filter core with a pore size of 0.2um and 0.1um after preparation.

[0060] Table 1: Components and weight ratios of compound semiconductor chip photoresist stripping solutions in examples 1-8 Table 2: Components and weight ratios of examples 1-3 The stripping method of the stripping solution in the present application is as follows: The semiconductor wafer is placed in the compound semiconductor chip photoresist stripping solution at 40-90 ℃, soaked, ultrasonically treated or shaken for 5-30 min, taken out, rinsed with ultrapure water, and dried with nitrogen.

[0061] Table 3: Wafer cleaning conditions of examples and comparative examples Corrosion: ◎ basically no corrosion; cleaning: ◎ completely removed; O slight corrosion; O small amount of residue; △ moderate corrosion; △ more residue; x severe corrosion; x large amount of residue.

[0062] As can be seen from Table 3, the cleaning solution of the present application has good cleaning effect on photoresist, has wide use temperature range, and can effectively inhibit the corrosion of the substrate at the same time.

[0063] In summary, the present application has the following advantages: 1) The alcohol ether solvent and the aprotic polar organic solvent have nucleophilicity, both have excellent sol gel capacity, and the photoresist is expanded by nucleophilic reaction, penetration and expansion, which is beneficial to the further penetration of other components.

[0064] 2) The mercapto group in the mercapto corrosion inhibitor can be adsorbed on the surface of the compound semiconductor to form a protective film, so as to isolate the compound semiconductor from the contact with the corrosion medium, thereby playing a corrosion inhibition effect.

[0065] 3) The alcohol amine can occur nucleophilic addition reaction with the polar groups such as carbonyl and carboxyl in the photoresist, break the chemical bonds formed by these functional groups, cause certain main chain rupture of the photoresist, cut off the covalent bonds between the macromolecular segments, and dissolve the photoresist after dry etching.

[0066] The embodiments of the present application are described in detail in combination with the drawings, but the present application is not limited to the described embodiments. For those skilled in the art, various changes, modifications, replacements and variations of the embodiments can be made without departing from the principles and spirits of the present application, and still fall within the protection scope of the present application.

Claims

1. A compound semiconductor photoresist stripping solution, characterized in that, The components include the following weight proportions: 30-60 parts of alcohol ether solvents; 30-60 parts of aprotic polar organic solvent; 1-15 parts of mercapto-based corrosion inhibitor; 1-15 parts of alcohol amine.

2. The compound semiconductor photoresist stripping solution as described in claim 1, characterized in that, The alcohol ether solvent is any one or more of diethylene glycol monobutyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether, diethylene glycol ethyl ether, triethylene glycol butyl ether, and propylene glycol phenyl ether.

3. The compound semiconductor photoresist stripping solution as described in claim 1, characterized in that, The aprotic polar organic solvent is selected from at least one of dimethyl sulfoxide, ethyl methyl sulfoxide, dimethyl sulfone, diethyl sulfone, sulfolane, N,N-dimethylformamide, N-methylformamide, N,N-dimethylacetamide, N-methylacetamide, β-propiolactone, γ-butyrolactone, γ-valerolactone, 8-caprolactone, γ-octyllactone, ethylene carbonate, propylene carbonate, and butyl carbonate.

4. The compound semiconductor photoresist stripping solution as described in claim 1, characterized in that, The thiol-based corrosion inhibitor is selected from one or more of dimercaprol, mercaptobenzothiazole, ethyl 3-mercaptobutyrate, methyl 3-mercaptopropionate, and 3-mercaptohexylbutyrate.

5. The compound semiconductor photoresist stripping solution as described in claim 1, characterized in that, The alkanolamine is selected from one or more of monoethanolamine, N-methylethanolamine, diethanolamine, triethanolamine, isopropanolamine, ethyldiethanolamine, N,N-diethylethanolamine, N-(2-aminoethyl)ethanolamine, and diethylene glycolamine.

6. A method for preparing the compound semiconductor photoresist stripping solution according to any one of claims 1-5, characterized in that, Includes the following steps: Step 1: Add the alcohol ether solvent and the aprotic polar organic solvent to a container and stir for 0.5-1 hour until completely dissolved and the solution is clear and transparent; Step 2: Add the alkanolamine to the solution from Step 1 and stir for 1-2 hours until it is completely dissolved and the solution is clear and transparent; Step 3: Add the thiol-based corrosion inhibitor to the solution from Step 2 while stirring, and stir for 0.5-2 hours until completely dissolved and the solution is clear and transparent to prepare the compound semiconductor photoresist stripping solution.

7. The method for preparing the compound semiconductor photoresist stripping solution as described in claim 6, characterized in that, The stirring temperature is controlled below 40°C.

8. The method for preparing the compound semiconductor photoresist stripping solution as described in claim 6, characterized in that, The compound semiconductor photoresist stripping solution was prepared and then filtered using 0.2 μm and 0.1 μm filter elements.

9. The application of the compound semiconductor photoresist stripping solution as described in any one of claims 1-5 in the field of photoresist removal.

10. A cleaning method for the compound semiconductor photoresist stripping solution as described in any one of claims 1-5, characterized in that, The process includes the following steps: placing the semiconductor wafer in the compound semiconductor photoresist stripping solution at 40-90°C, immersing, sonicating or agitating for 5-30 minutes, removing it, rinsing it with ultrapure water, and then drying it with nitrogen. Alternatively, a single-chip microcomputer can be used to spray the compound semiconductor photoresist stripping solution at 40-90°C onto the rotating semiconductor wafer, rinse for 5-10 minutes, remove and rinse with ultrapure water, and then dry with nitrogen.

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