JP2013504782A - Resist removing composition for forming copper-based wiring - Google Patents

Abstract

A resist removing composition for forming a copper-based wiring is provided.
The resist removing composition of the present invention is characterized by using a compound containing a sulfone and / or sulfine and / or an ester group as a release agent. The resist removing composition is a conductive metal film such as copper or copper alloy wiring located under the resist, and an insulating film such as a silicon oxide film or a silicon nitride film, without using isopropanol as an intermediate cleaning liquid. It is possible to effectively prevent corrosion, and to remove the denatured and / or hardened resist cleanly within a short time even at a low temperature.
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Description

  The present invention relates to a resist removing composition for forming a copper-based wiring used during a manufacturing process of a semiconductor element or a flat panel display element. More specifically, the present invention relates to a copper film used as a wiring when removing a resist. The present invention relates to a resist removal composition that can prevent corrosion of the resist.

  The manufacturing process of an integrated circuit of a semiconductor element or a fine circuit of a flat panel display element includes a conductive metal film such as aluminum or aluminum alloy, copper or copper alloy formed on a substrate, or an insulating film such as a silicon oxide film or a silicon nitride film. A photoresist is uniformly applied thereon, selectively exposed, and developed to form a photoresist pattern. Then, the conductive metal film or the insulating film is wet using the patterned photoresist film as a mask. After the fine circuit pattern is transferred to the lower layer of the photoresist by etching or dry etching, the wasteful photoresist is removed with a stripping solution (stripper) composition.

  The stripping composition for removing a photoresist used in the manufacturing process of the semiconductor device or the flat panel display device must be able to strip the photoresist within a short time at a low temperature. After cleaning (rinsing), The photoresist residue should not be left on the substrate and the metal film or insulating film of the lower layer of the photoresist should not be damaged.

  On the other hand, recently, copper-based metal films such as copper films and copper-molybdenum films have attracted attention as metal films for forming metal wiring in the field of semiconductor elements or flat panel display elements. This is because solving the RC signal delay problem in TFT-LCD (thin film transistor-liquid crystal display) is the key to increasing the panel size and realizing high resolution, but resistance is an important factor inducing RC signal delay That's why.

  However, photoresist stripping compositions using amine compounds and glycol ether compounds that have been developed to date as a release agent are severely corrosive to copper-based metal films, causing environmental pollution problems due to strong toxicity, and as a post-process. There are drawbacks such as the occurrence of defects with high probability during gate insulating film deposition, and there is a need for improvement of such problems.

  The present invention effectively corrodes conductive metal films, such as copper or copper alloy wiring, and insulating films, such as silicon oxide films and silicon nitride films, which are resist lower layers, without performing intermediate cleaning with isopropanol or the like. An object of the present invention is to provide a resist removing composition for forming a copper-based wiring that can be prevented easily.

  In addition, the present invention can be applied to all of the dip method, the single wafer type and the spray type peeling process, and the resist film altered and / or hardened by a severe lithography process and a wet etching process can be removed cleanly at a low temperature within a short time. An object of the present invention is to provide a resist removing composition for forming a copper-based wiring.

  The present invention relates to (A) 1 to 45% by weight of at least one compound selected from the compounds represented by the following chemical formulas (1) to (3) with respect to the total weight of the composition, and (B Resist removal for forming copper-based wiring, comprising 0.01 to 5% by weight of an additive containing an azole-based compound, and the balance comprising (C) a solvent containing a compound represented by the following chemical formula (4) Providing a composition for:

In the chemical formulas (1) to (4),
R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group having 1 to 6 carbon atoms, and R ₁ and R ₂ , and R ₃ and R ₄ are bonded to each other to form 4 to 6 carbon atoms. Can form a ring;
R ₅ and R ₆ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 1 to 8 carbon atoms, -R _10- (OR ₁₁ ) m- OR ₁₂ or —R ₁₃ — (O) n — (C═O) — (O) o —R ₁₄ , where m is a natural number from 1 to 4, n is 0 or 1, and o Is 0 or 1, R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each independently an alkyl group having 1 to 5 carbon atoms, R ₁₂ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ₅ and R ₆ can be bonded to each other to form a ring having 4 to 6 carbon atoms;
R ₇ is hydrogen or an alkyl group having 1 to 5 carbon atoms; R ₈ and R ₉ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms; ₇ and R ₈ can be bonded to each other to form a ring having 4 to 6 carbon atoms;
The alkyl group may be a linear or branched alkyl group.

  The present invention also provides a method for manufacturing a semiconductor device or a flat panel display device, which includes a lithography process for forming a copper-based wiring, wherein the used resist is removed using the resist removing composition of the present invention. Provide a method.

  The resist removing composition of the present invention is a conductive metal film such as copper or copper alloy wiring formed under the resist without using isopropanol as an intermediate cleaning solution, and a silicon oxide film or a silicon nitride film. In addition to effectively preventing corrosion of insulating films, it can be applied to all dip, single wafer and spray stripping processes, and resists that have been altered and / or hardened by harsh lithography and etching processes can be shortened even at low temperatures. Since it can be removed cleanly in time, it can be used very effectively in the manufacturing process of a semiconductor device or a flat panel display device.

  The present invention relates to (A) 1 to 45% by weight of at least one compound selected from the compounds represented by the following chemical formulas (1) to (3) with respect to the total weight of the composition, and (B Resist removal for forming copper-based wiring, comprising 0.01 to 5% by weight of an additive containing an azole-based compound, and the balance comprising (C) a solvent containing a compound represented by the following chemical formula (4) Regarding the composition for:

In the chemical formulas (1) to (4),
R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group having 1 to 6 carbon atoms, and R ₁ and R ₂ , and R ₃ and R ₄ are bonded to each other to form 4 to 6 carbon atoms. Can form a ring;
R ₅ and R ₆ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 1 to 8 carbon atoms, -R _10- (OR ₁₁ ) m- OR ₁₂ or —R ₁₃ — (O) n — (C═O) — (O) o —R ₁₄ , where m is a natural number from 1 to 4, n is 0 or 1, and o Is 0 or 1, R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each independently an alkyl group having 1 to 5 carbon atoms, R ₁₂ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ₅ and R ₆ can be bonded to each other to form a ring having 4 to 6 carbon atoms;
R ₇ is hydrogen or an alkyl group having 1 to 5 carbon atoms; R ₈ and R ₉ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms; ₇ and R ₈ can be bonded to each other to form a ring having 4 to 6 carbon atoms;
The alkyl group may be a linear or branched alkyl group.

  The copper-based wiring in the present invention means a wiring formed of a copper film or a copper alloy film or a wiring including a copper film or a copper alloy film in a semiconductor element or a flat panel display element.

  At least one compound selected from the compounds represented by (A) chemical formula (1) to chemical formula (3) contained in the resist removal composition of the present invention is 1 to 4 based on the total weight of the composition. It is contained at 45% by weight, preferably 30-40% by weight. When the above-described range is satisfied, the peeling force for the modified photoresist is excellent, and corrosion of a conductive metal film such as a copper film as the photoresist lower layer is prevented.

  Representative examples of the compound represented by the chemical formula (1) or the chemical formula (2) include dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, sulfolane, and the chemical formula (3). Representative examples of the compounds represented include dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, γ-butyrolactone, n-butyl acetate, ethyl butanoate, and ethyl lactate.

  The additive containing the (B) azole compound contained in the resist removal composition of the present invention serves to minimize corrosion of the conductive metal film and the insulating film under the resist. Representative examples of the azole compounds include tritriazole, 1,2,3-benzotriazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2 , 4-triazole, 4-amino-4H-1,2,4-triazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 2-methylbenzotriazole, benzotriazole-5-carboxylic acid, nitrobenzotriazole, 2 -(2H-benzotriazol-2-yl) -4,6-di-t-butylphenol and adenine can be mentioned, and these can be used alone or in combination of two or more.

  In particular, a compound containing a triazole ring is preferable. This is because the unshared electron pair of the nitrogen atom present in the triazole ring is electronically bonded to copper and suppresses corrosion of the metal.

  Generally, in the case of immediately washing with water without using isopropanol as an intermediate cleaning solution, the amine component in the resist removal composition is mixed with water to generate highly corrosive alkali hydroxy ions. Promotes corrosion of conductive metal films such as copper alloys. However, the additive containing the (B) azole-based compound forms a metal film and a complex compound in an alkaline state and adsorbs on the surface to form a protective film, thereby forming a metal by hydroxy ions without using isopropanol. Corrosion of can be prevented.

  The additive containing the (B) azole compound is contained in an amount of 0.01 to 5% by weight, preferably 0.1 to 3% by weight, based on the total weight of the composition. When the above-mentioned range is satisfied, damage to the conductive metal film and the insulating film as the lower layer is minimized at the time of removing the resist, and the characteristics are excellent economically.

  In the resist removal composition of the present invention, (C) the solvent containing a compound represented by the following chemical formula (4) contains a compound represented by the following chemical formula (4) containing an amide functional group. .

In the chemical formula (4), R ₇ is hydrogen or an alkyl group having 1 to 5 carbon atoms, and R ₈ and R ₉ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a hydroxy group having 1 to 4 carbon atoms. An alkyl group, and R ₇ and R ₉ may be bonded to each other to form a ring having 4 to 6 carbon atoms.

  (C) The amide functional group contained in the solvent containing the compound represented by the chemical formula (4) is superior in the solvent power to the polymer resin and the photoactive compound, which are the main components of the resist, to other existing solvents. To play a role. The solvent containing the compound represented by the chemical formula (4) (C) is contained in an amount (remaining amount) so that the total weight of the composition becomes 100% by weight. When the solvent is contained in the above-described content range, excellent peeling force is realized, galvanic corrosion is prevented, and economy is excellent. Representative examples of the compound represented by the chemical formula (4) include N-methylpyrrolidone, dimethylacetamide, dimethylformamide, N-methylformamide, acetamide, N-methylacetamide, N- (2-hydroxyethyl) acetamide. , 2-pyrrolidone and the like can be mentioned, and these can be used alone or in combination of two or more.

  The resist removing composition of the present invention may further contain (D) water. The (D) water is preferably deionized water, and water of 18 MΩ / cm or more is preferably used for a semiconductor process.

  The resist-removing composition for forming a copper-based wiring of the present invention can be applied to all dipping, spraying, and single wafer peeling processes. In addition, the resist film that has been altered and / or hardened by a severe lithography process and wet etching process can be removed cleanly in a short time not only at a high temperature but also at a low temperature. Moreover, without using isopropanol as an intermediate cleaning solution, corrosion on the resist lower layer, that is, conductive metal films such as copper or copper alloy wiring, and insulating films such as silicon oxide films and silicon nitride films can be minimized at the same time. Can do.

  The present invention also provides a method for manufacturing a semiconductor device or a flat panel display device, which includes a lithography process for forming a copper-based wiring, wherein the used resist is removed using the resist removing composition of the present invention. Regarding the method.

  Hereinafter, preferred examples will be presented to help the understanding of the present invention. However, the following examples are merely illustrative of the present invention and do not limit the scope of the present invention.

Examples 1 to 13 and Comparative Examples 1 to 4: Production of Resist Removal Composition Resist removal compositions were produced according to the components and composition ratios described in Table 1 below.

[note]
DMSO: dimethyl sulfoxide DESO: diethyl sulfoxide DPGMEA: dipropylene glycol methyl ether acetate PGMEA: propylene glycol monomethyl ether acetate GBL: γ-butyrolactone DMEA: dimethylethanolamine MEA: monoethanolamine DGA: diglycolamine NMP: N-methylpyrrolidone BDG : Butyl diglycol DMAC: Dimethylacetamide NMF: N-methylformamide TTA: Tritriazole BTA: 1,2,3-benzotriazole Test example: Evaluation of etching characteristics Copper produced in Examples 1 to 13 and Comparative Examples 1 to 4 Using the resist removing composition for forming the system wiring, the peeling force and the degree of corrosion on the copper wiring were evaluated by the following method.

  A single metal film and a multiple alloy film were laminated to a thickness of 200 to 500 mm on a glass substrate by a TFT circuit manufacturing process of LCD, and a Cu layer having a thickness of 3,000 mm was formed thereon. Then, a positive photoresist was applied, dried and a pattern was formed by photolithography, and a test piece in a state where the wet etching was completed was produced.

(1) Evaluation of peeling force The temperature of the resist removing composition for forming the copper-based wiring produced in Examples 1 to 13 and Comparative Examples 1 to 4 was maintained at 40 ° C., and the prepared test piece was used here. The resist pattern was removed by immersing each for 10 minutes. Thereafter, it was washed with deionized water for 60 seconds and dried with nitrogen. After completion of the drying, each test piece was observed with an electron microscope (FE-SEM) with a magnification of 40,000 to 80,000, and the degree of peeling of the photoresist was observed. The results are shown in Table 2 below.

(2) Corrosion evaluation 1
After maintaining the temperature of the composition for resist removal for forming the copper-based wiring manufactured in Examples 1 to 13 and Comparative Examples 1 to 4 at 60 ° C., and immersing the prepared test piece for 30 minutes here Wash with deionized water for 30 seconds and dry with nitrogen. After completion of drying, the degree of corrosion of the surface, side surface and end surface of each test piece was observed with an electron microscope (FE-SEM) at a magnification of 40,000 to 80,000, and the results are shown in Table 2 below. It was.

(3) Corrosion evaluation 2
The temperature of the resist-removing composition for forming the copper-based wiring produced in Examples 1 to 13 and Comparative Examples 1 to 4 was maintained at 60 ° C., and the prepared test pieces were immersed therein for 10 minutes. . Thereafter, it was washed with deionized water for 30 seconds and dried with nitrogen. After performing this peeling process three times in succession, the degree of corrosion of the surface, side surface and end surface of the test piece was observed with an electron microscope (FE-SEM) at a magnification of 40,000 to 80,000, and the results are shown in the following table. It was shown in 2.

* Peeling evaluation standard ◎: Excellent peeling performance ○: Good peeling performance △: Unsatisfactory peeling performance: Poor peeling performance * Corrosion evaluation standard No: There is some corrosion on the surface and side surfaces of the Cu layer, lower metal film and alloy film. Δ: Partial corrosion on the surface and side surfaces of the Cu layer, lower metal film and alloy film. There is severe corrosion on the surface and side of metal and alloy films

  As is apparent from Table 2, the resist removal compositions of Examples 1 to 13 using an organic compound having sulfone or sulfine or an ester group as a release agent use amine or glycol ether. In comparison with Comparative Examples 1 to 4, the peel strength was equivalent or better, and the corrosion resistance of the metal film containing copper was extremely excellent.

  Therefore, it has been found that the resist removing composition of the present invention exhibits a very excellent resist removing effect even without containing an amine compound.

Claims (8)

(A) 1 to 45% by weight of at least one compound selected from the compounds represented by the following chemical formulas (1) to (3), and (B) an azole compound, based on the total weight of the composition A composition for removing a resist for the formation of a copper-based wiring, comprising 0.01 to 5% by weight of an additive containing, and the balance comprising (C) a solvent containing a compound represented by the following chemical formula (4):

In the chemical formulas (1) to (4),
R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group having 1 to 6 carbon atoms, and R ₁ and R ₂ , and R ₃ and R ₄ are bonded to each other to form 4 to 6 carbon atoms. Can form a ring;
R ₅ and R ₆ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 1 to 8 carbon atoms, -R _10- (OR ₁₁ ) m- OR ₁₂ or —R ₁₃ — (O) n — (C═O) — (O) o —R ₁₄ , where m is a natural number from 1 to 4, n is 0 or 1, and o Is 0 or 1, R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ are each independently an alkyl group having 1 to 5 carbon atoms, R ₁₂ is hydrogen or an alkyl group having 1 to 5 carbon atoms, R ₅ and R ₆ can be bonded to each other to form a ring having 4 to 6 carbon atoms;
R ₇ is hydrogen or an alkyl group having 1 to 5 carbon atoms; R ₈ and R ₉ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 1 to 4 carbon atoms; ₇ and R ₈ can be bonded to each other to form a ring having 4 to 6 carbon atoms;
The alkyl group may be a linear or branched alkyl group.   The compounds represented by the chemical formulas (1) to (3) are dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, sulfolane, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, γ-butyrolactone. The composition for removing a resist for forming a copper-based wiring according to claim 1, wherein the composition is selected from the group consisting of n-butyl acetate, ethyl butanoate and ethyl lactate.   The azole compounds include tritriazole, 1,2,3-benzotriazole, 1,2,3-triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 4-amino- 4H-1,2,4-triazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 2-methylbenzotriazole, benzotriazole-5-carboxylic acid, nitrobenzotriazole, 2- (2H-benzotriazole-2- Yl) -4,6-di-t-butylphenol and adenine are selected from the group consisting of one or two or more types, for forming a copper-based wiring according to claim 1 Resist removing composition.   The compound represented by the chemical formula (4) is composed of N-methylpyrrolidone, dimethylacetamide, dimethylformamide, N-methylformamide, acetamide, N-methylacetamide, N- (2-hydroxyethyl) acetamide and 2-pyrrolidone. The composition for removing a resist for forming a copper-based wiring according to claim 1, wherein the composition is one or more selected from the group.   The resist removal composition for forming a copper wiring according to claim 1, wherein the resist removal composition for forming the copper wiring further includes water.   2. The resist removing composition for forming a copper wiring according to claim 1, wherein the resist removing composition does not contain an amine compound.   A method for manufacturing a semiconductor device, comprising a lithography step for forming a copper-based wiring, wherein the used resist is removed using the resist removing composition according to claim 1.   A method for producing a flat panel display device, comprising a lithography step for forming a copper-based wiring, wherein a used resist is removed using the resist removing composition according to claim 1.