阅读说明：本技术 一种适用半导体集成电路的光刻胶剥离液及制备方法 (Photoresist stripping liquid suitable for semiconductor integrated circuit and preparation method thereof ) 是由 刘江华 冯继恒 尹淞 鲁晨泓 张建 于 2020-12-17 设计创作，主要内容包括：本发明公开了一种适用半导体集成电路的光刻胶剥离液及制备方法,包括非腐蚀性有机胺和极性非离子溶剂；以质量百分比计,非腐蚀性有机胺1-70％,极性非离子溶剂30-99％。本发明不含有腐蚀性的强碱,清洗后无光刻胶残留,可直接水洗,不会产生金属层腐蚀。(The invention discloses a photoresist stripping liquid suitable for a semiconductor integrated circuit and a preparation method thereof, comprising non-corrosive organic amine and a polar non-ionic solvent; 1-70% of non-corrosive organic amine and 30-99% of polar non-ionic solvent by mass percentage. The invention does not contain corrosive strong base, has no photoresist residue after cleaning, can be directly washed by water, and does not generate corrosion of a metal layer.)

1. A photoresist stripper suitable for semiconductor integrated circuits is characterized in that: comprises a non-corrosive organic amine and a polar non-ionic solvent; 1-70% of non-corrosive organic amine and 30-99% of polar non-ionic solvent by mass percentage.

2. The resist stripping solution for semiconductor integrated circuits according to claim 1, wherein: 5-45% of non-corrosive organic amine and 60-98% of polar non-ionic solvent by mass percentage.

3. The resist stripping solution for semiconductor integrated circuits according to claim 1, wherein: the non-corrosive organic amine is selected from one or more of diethanolamine, triethanolamine, 3-propanolamine, monoisopropanol, diisopropanolamine, triisopropanolamine, diglycolamine, triglycolamine, N-methylethanolamine, N-ethylethanolamine, N-methyldiethanolamine, N 'N-dimethylethanolamine, N' N-diethylethanolamine, N-benzyl-N-methylethanolamine, cyclohexylamine, piperazine, morpholine, hydroxylamine and caprolactam.

4. The resist stripping solution for semiconductor integrated circuits according to claim 1, wherein: the polar aprotic solvent is selected from one or more of formamide, N-methylformamide, N-methylacetamide, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, acetonitrile, benzonitrile, N-methyl-pyrrolidone, N-ethyl-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, hexamethylenetetramine and propylene carbonate.

5. The resist stripping solution for semiconductor integrated circuits according to claim 1, wherein: the photoresist stripping liquid also comprises a corrosion inhibitor, and the corrosion inhibitor accounts for 0-20% by mass.

6. The resist stripping solution for semiconductor integrated circuits according to claim 5, wherein: 0-10% of corrosion inhibitor in percentage by mass; the corrosion inhibitor is selected from corrosion inhibitors having an action with oxygen or corrosion inhibitors having an adsorption or chelation action with the substrate.

7. The resist stripping solution for semiconductor integrated circuits according to claim 5, wherein: the corrosion inhibitor which reacts with oxygen is selected from hydrazine carbonate, dihydroxyethyl hydrazine, acetyl hydrazine, 2-hydrazino acetamide, hydroxylamine, 2-ethyl hydroxylamine, N-diethyl hydroxylamine and acetyl hydroxylamine; the corrosion inhibitor with adsorption or chelating function is selected from alcohols, phenols, azoles and carboxylic acids.

8. The photoresist stripper for semiconductor integrated circuits according to claim 7, wherein: the alcohol with corrosion inhibitor having adsorption or chelating effect is one or more selected from ethylene glycol, 1, 2-propylene glycol, glycerol, diethylene glycol, dipropylene glycol, erythritol, xylitol, sorbitol, methyl mercaptan, ethanethiol, ethanedithiol, 1-propanethiol, 1, 3-propanedithiol, benzyl mercaptan, tert-butyl mercaptan, 1-hexanethiol, 1-dodecyl mercaptan and 1-hexadecyl mercaptan; the phenols with corrosion inhibitor having adsorption or chelating effect are selected from one or more of catechol, resorcinol, hydroquinone, 4-methyl catechol, 4-tert-butyl catechol, 4-carboxyl catechol, pyrogallol, gallic acid, methyl gallate, ethyl gallate and n-propyl gallate; the azoles of the corrosion inhibitor with adsorption or chelation effects are selected from one or more of 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 5-aminotetrazole, benzimidazole, 2-mercapto-1-methylimidazole, 2-mercaptobenzoxazole, mercapto-benzothiazole, benzotriazole, methylbenzotriazole, 1-hydroxybenzotriazole and 1-phenyl-5-mercaptotetrazole.

9. A preparation method of photoresist stripping liquid suitable for a semiconductor integrated circuit is characterized by comprising the following steps: the preparation process comprises the following steps: adding non-corrosive organic amine, a polar non-ionic solvent and a corrosion inhibitor in sequence, stirring and dissolving, controlling the heat release phenomenon of the organic base in the dissolving process, controlling the temperature below 30 ℃ in the whole dissolving process, and filtering by using a filter element of 0.1um after complete dissolution.

Technical Field

The invention relates to a photoresist stripping liquid suitable for a semiconductor integrated circuit and a preparation method thereof.

Background

Photolithography is one of the most important steps in the manufacture of semiconductors and displays. The method has the main function of copying the patterns on the mask plate to a silicon wafer or other substrates to prepare for the next etching or ion implantation process. In the photoetching process, a layer of photoresist is required to be coated on a substrate, after ultraviolet exposure, the chemical property of the photoresist is changed, and after development, the exposed positive photoresist (the negative photoresist is an unexposed area and is developed and removed) is removed, so that the circuit pattern is transferred to the photoresist from a mask. And then the circuit pattern is transferred to the substrate from the photoresist through an etching process. After the above-mentioned pattern transfer is completed, the photoresist and its residues need to be cleaned for the next operation.

The main component of the current photoresist stripping solution contains organic amine with strong ionization. As follows:

for example, the products of the photoresist stripper of dupont EKC200 series, the products of sanfu, M15 series, taiwan, etc. contain corrosive or strongly ionized organic amine, and need to be rinsed with intermediate solvents such as IPA (isopropyl alcohol), NMP (N-methyl pyrrolidone), etc., which results in increased cost and process flow.

Disclosure of Invention

The invention aims to solve the technical problems that the photoresist stripping solution does not contain corrosive organic amine, has no photoresist residue after cleaning, can be directly washed by water and does not generate metal layer corrosion.

The photoresist stripping liquid applicable to the semiconductor integrated circuit is realized by the following technical scheme: comprises a non-corrosive organic amine and a polar non-ionic solvent; 1-70% of non-corrosive organic amine and 30-99% of polar non-ionic solvent by mass percentage.

As a preferable technical scheme, the non-corrosive organic amine accounts for 5-45% by mass, and the polar non-ionic solvent accounts for 60-98% by mass.

As a preferable technical scheme, the non-corrosive organic amine is one or more selected from diethanolamine, triethanolamine, 3-propanolamine, monoisopropanol, diisopropanolamine, triisopropanolamine, diglycolamine, triglycolamine, N-methylethanolamine, N-ethylethanolamine, N-methyldiethanolamine, N 'N-dimethylethanolamine, N' N-diethylethanolamine, N-benzyl-N-methylethanolamine, cyclohexylamine, piperazine, morpholine, hydroxylamine and caprolactam.

The polar aprotic solvent is preferably one or more selected from formamide, N-methylformamide, N-methylacetamide, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetramethylene sulfone, acetonitrile, benzonitrile, N-methyl-pyrrolidone, N-ethyl-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, hexamethylenetetramine, and propylene carbonate.

As a preferable technical scheme, the photoresist stripping liquid also comprises a corrosion inhibitor, and the corrosion inhibitor accounts for 0-20% by mass percent.

As a preferred technical scheme, the corrosion inhibitor is 0-10% by mass percent; the corrosion inhibitor is selected from corrosion inhibitors having an action with oxygen or corrosion inhibitors having an adsorption or chelation action with the substrate.

As a preferred technical scheme, the corrosion inhibitor which reacts with oxygen is selected from hydrazine carbonate, dihydroxyethyl hydrazine, acetyl hydrazine, 2-hydrazino acetamide, hydroxylamine, 2-ethyl hydroxylamine, N-diethyl hydroxylamine and acetyl hydroxylamine; the corrosion inhibitor with adsorption or chelating function is selected from alcohols, phenols, azoles and carboxylic acids.

As a preferable technical scheme, the alcohol with the corrosion inhibitor having adsorption or chelation function is one or more selected from ethylene glycol, 1, 2-propylene glycol, glycerol, diethylene glycol, dipropylene glycol, erythritol, xylitol, sorbitol, methyl mercaptan, ethanethiol, ethanedithiol, 1-propanethiol, 1, 3-propanethiol, benzyl mercaptan, tert-butyl mercaptan, 1-hexanethiol, 1-dodecyl mercaptan and 1-hexadecyl mercaptan; the phenols with corrosion inhibitor having adsorption or chelating effect are selected from one or more of catechol, resorcinol, hydroquinone, 4-methyl catechol, 4-tert-butyl catechol, 4-carboxyl catechol, pyrogallol, gallic acid, methyl gallate, ethyl gallate and n-propyl gallate; the azoles of the corrosion inhibitor with adsorption or chelation effects are selected from one or more of 1,2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 5-aminotetrazole, benzimidazole, 2-mercapto-1-methylimidazole, 2-mercaptobenzoxazole, mercapto-benzothiazole, benzotriazole, methylbenzotriazole, 1-hydroxybenzotriazole and 1-phenyl-5-mercaptotetrazole.

A preparation method of photoresist stripping liquid suitable for a semiconductor integrated circuit comprises the following preparation processes: adding non-corrosive organic amine, a polar non-ionic solvent and a corrosion inhibitor in sequence, stirring and dissolving, controlling the heat release phenomenon of the organic base in the dissolving process, controlling the temperature below 30 ℃ in the whole dissolving process, and filtering by using a filter element of 0.1um after complete dissolution.

The invention has the beneficial effects that: the invention does not contain corrosive strong base, has no photoresist residue after cleaning, can be directly washed by water, and does not generate corrosion of a metal layer.

Detailed Description

TABLE 1 compositions and contents of positive photoresist stripping solutions of the examples

TABLE 1

Effects of the embodiment

In order to further examine the photoresist removing effect of the photoresist stripping solution, the invention adopts the following technical means: firstly, cleaning a copper substrate by using a special cleaning agent, washing by using ultrapure water, and drying; then, spin-coating a layer of photoresist film with the thickness of 2um on the substrate at 800-1000 rpm by a spin coater, and then curing at 150 ℃ by an oven to obtain a test piece for testing the stripping performance of the photoresist stripping liquid composition on the photoresist; the cleaning process comprises the following steps: cutting the silicon wafer coated with the photoresist into small 10 x 10cm blocks, cleaning by using the soaking or spraying process according to the embodiment, and cleaning by using deionized water and drying by using nitrogen respectively; the stripping effect and the substrate corrosion performance of the photoresist stripping solution are shown in table 2:

TABLE 2

As can be seen from the examples in the above table, the photoresist stripper of the present invention can effectively resist on the copper substrate surface without corroding the copper substrate; the method has the characteristics of large implementation range, large operation window and the like; most predominantly copper substrates; and because the tetramethyl ammonium hydroxide with strong alkalinity is adopted, copper can be corroded no matter in the processes of photoresist removal and direct washing after photoresist removal.

In summary, the present invention provides a photoresist stripper for removing photoresist on a sensitive metal film in semiconductor manufacturing, which contains no corrosive organic alkali, has no photoresist residue after cleaning, can be directly washed with water, and does not cause corrosion of the metal layer.

It should be understood that wt% in the present invention refers to mass percentage.

The photoresist stripping solution of the invention is not particularly limited in the use process, and can adopt an immersion type or a spraying type.

The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.