JP2005070230A - Resist stripping composition and resist stripping method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoresist stripping composition having excellent stripping/eliminating property, excellent corrosion preventing property for a metal wiring material and favorably suppressing corrosion of the metal wiring material even in a water washing process after the stripping process, and to provide a method for stripping a photoresist by using the composition. <P>SOLUTION: The resist stripping composition is a non-aqueous resist stripping composition containing 2,3-dihydroxynaphthalene (A), an organic amine compound (B) and a polar organic solvent (C). The method for stripping a resist is carried out by using the composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photoresist stripping composition used in the manufacture of semiconductor integrated circuits, semiconductor device circuits of liquid crystal panels, and the like, and a photoresist stripping method using the same. More specifically, the present invention relates to a photoresist stripping composition that can effectively remove a photoresist residue that is no longer required when wiring is formed on a semiconductor substrate or a liquid crystal glass substrate.

The photoresist stripping composition is used when stripping a photoresist used in the manufacture of a semiconductor integrated circuit, a semiconductor element circuit of a liquid crystal panel, and the like from a substrate. Manufacture of the semiconductor element circuit of a liquid crystal panel or an accompanying electrode part is performed as follows, for example. First, a photoresist is uniformly coated on a metal film formed by CVD, sputtering, or the like on a substrate such as silicon or glass, or an insulating film such as a SiO ₂ film, and this is exposed and developed to form a resist pattern. Next, the metal film and the insulating film are selectively etched using the patterned photoresist as a mask; then, the unnecessary photoresist layer is peeled off and removed using the stripping composition. In the case of laminating a plurality of circuit patterns, the circuit or the electrode part is formed by repeating these operations as necessary. As the above metal film, aluminum, aluminum alloy such as aluminum-copper, etc .; titanium, titanium nitride, etc .; silicon such as a-Si, p-Si, etc. are used, and these are formed on the substrate in a single layer or multiple layers. Then, a metal wiring is formed through an etching process.

  Conventionally, for photoresist stripping, a compound such as an organic amine, inorganic alkali, organic acid, inorganic acid or the like is used alone or in combination of two or more, dissolved in an organic solvent or water, and if necessary, blended with additives The composition for use is used. For example, a non-aqueous stripping solution composed of a mixture of monoethanolamine (MEA) and an organic solvent is widely used, but has a drawback that the aluminum wiring is corroded in the water washing step after the stripping treatment. .

  On the other hand, as the resist stripping composition with improved aluminum corrosion resistance, for example, at least one nitrogen-containing organic hydroxy compound selected from the group consisting of N-hydroxyalkyl-substituted amines and nitrogen-containing heterocyclic hydroxy compounds, and Resist in which a specific anticorrosive agent selected from maltol, kojic acid or the like is added to a resist remover containing pyrocatechol (see, for example, Patent Document 1), an organic amine, and water. A release agent composition (see, for example, Patent Document 2), a photoresist remover containing a 2,3-dihydroxynaphthalene compound in a release agent containing organic amine and water (for example, see Patent Document 3), and the like are known. It has been.

  However, with the recent miniaturization of wiring materials, the required level of metal corrosion amount for aluminum and other wiring materials has become increasingly strict, and even the resist stripping composition described in Patent Document 2 is aluminum. The anticorrosion property for the wiring material is not always sufficient depending on the application, and it is not possible to satisfactorily prevent aluminum corrosion particularly in the water washing step after the peeling treatment.

  Therefore, it is possible to effectively remove and remove photoresists that have been altered by heat or etching, or to remove corrosion residues, and to prevent corrosion even for miniaturized metal wiring materials. A stripping composition is desired.

JP-A-11-258825 (Claims, Claim 1) JP 2002-351093 A (page 3) Patent 3373105 (Claims, Claim 1)

  In view of the above-mentioned present situation, the object of the present invention is excellent in peeling / removing property, has excellent anticorrosive properties for metal wiring materials, and also satisfactorily suppresses corrosion of metal wiring materials even in a water washing step after peeling treatment. An object of the present invention is to provide a photoresist stripping composition that can be used and a photoresist stripping method using the same.

  As a result of repeating various experiments in order to solve the above problems, the inventor can effectively remove a resist residue by combining an organic amine compound and a polar organic solvent with respect to a specific phenolic compound, and further to a wiring material. It has been found that the anticorrosion property is also excellent, and the present invention has been completed.

  That is, the present invention is a non-aqueous resist stripping composition containing 2,3-dihydroxynaphthalene (A), an organic amine compound (B), and a polar organic solvent (C) (hereinafter also referred to as the composition of the present invention). ).

  The present invention also includes a step of treating a photoresist on a semiconductor substrate or a liquid crystal glass substrate with the resist stripping composition, a step of rinsing the semiconductor substrate or liquid crystal glass substrate treated in the above step, and It is also a method for removing a resist from a semiconductor substrate or a glass substrate for liquid crystal having a step of drying the semiconductor substrate or the glass substrate for liquid crystal.

The composition of the present invention has excellent peelability and removability, has excellent anticorrosive properties for metal wiring materials, and can satisfactorily suppress corrosion of metal wiring materials even in a water washing step after the peeling treatment.
By using the composition of the present invention for the removal of the resist residue generated during the formation of the wiring in the manufacturing process of a semiconductor or liquid crystal element circuit or the like, the resist residue is efficiently removed without corroding the metal wiring material. Further, even when direct water washing is performed after the peeling treatment, since corrosion of aluminum is well prevented, intermediate rinsing such as alcohol rinsing is not required, and the economy is excellent.
The resist stripping method of the present invention is suitably used for manufacturing processes such as semiconductor or liquid crystal electronic circuits.
Hereinafter, the present invention will be described in detail.

  The resist stripping composition of the present invention contains 2,3-dihydroxynaphthalene (A), an organic amine compound (B), and a polar organic solvent (C), and does not contain water.

  The content of 2,3-dihydroxynaphthalene (A) (hereinafter referred to as “compound (A)”) in the composition of the present invention is preferably 0.01% by weight or more from the viewpoint of anticorrosive properties against aluminum wiring, and is economical. To 10% by weight or less, more preferably 0.1 to 5% by weight.

  As the organic amine compound (B), primary alkanolamines such as monoethanolamine, monoisopropanolamine, and diglycolamine are preferable, and monoisopropanolamine and diglycolamine are preferable from the viewpoint of achieving both peelability and anticorrosion against aluminum. Particularly preferred. These can be used alone or in combination.

  The content of the organic amine compound (B) is preferably 1% by weight or more in the composition of the present invention from the viewpoint of resist residue removability, and suppresses aluminum corrosion in the water washing step after the peeling treatment step. From the viewpoint of achieving this, 50% by weight or less is preferable. More preferably, it is 5 to 40% by weight.

  The polar organic solvent (C) is not particularly limited. For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether (BDG), N, N-dimethylacetamide, N, N-dimethylformamide. N-methyl-2-pyrrolidone, γ-butyrolactone, dimethyl sulfoxide (DMSO), ethylene glycol, propylene glycol and the like. These solvents can be used alone or in combination of two or more.

  The content of the polar organic solvent (C) is not particularly limited. As long as the compound (A), the organic amine compound (B) and, if applicable, an additive such as an anticorrosive described in detail below can be dissolved to form a resist stripping composition, an appropriate amount is used. Can be used. Generally, in the composition of the present invention, the balance of the compound (A) and the organic amine compound (B) may be a polar organic solvent (C).

  As above-mentioned, in the composition of this invention, since the polar organic solvent (C) is used as a solvent and water is not contained, the corrosion resistance with respect to a metal wiring material can further be improved.

  In addition to the above components, the composition of the present invention includes an aromatic hydroxyl compound other than 2,3-dihydroxynaphthalene, acetylene alcohol, a carboxyl group-containing organic compound, and a carboxyl group-containing organic, as long as the effects of the present invention are not impaired. At least one compound (D) selected from the group consisting of compound anhydrides, triazole compounds, sugars and phosphoric acid can be blended as an anticorrosive. These can be used alone or in combination of two or more. The content of the anticorrosive is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight in the composition of the present invention.

Examples of the aromatic hydroxyl compound include resorcinol.
Examples of acetylene alcohol include 2-butyne-1,4-diol.
As the carboxyl group-containing organic compound, for example, benzoic acid, phthalic acid, malic acid and the like are preferably used.
Examples of the triazole compound include 1-hydroxybenzotriazole, 1,2,3-benzotriazole, 1,2,4-triazole, and the like.
Examples of the saccharide include sorbitol and xylitol.

An example in the case of producing a semiconductor element using a semiconductor substrate or a glass substrate for liquid crystal will be given, and a resist peeling method for the semiconductor substrate or liquid crystal glass substrate using the composition of the present invention will be described. First, a metal film such as an Al alloy or an insulating film such as SiO ₂ is formed on the substrate by CVD, sputtering, or the like. Next, a photoresist is formed thereon, a photomask is placed and exposed, and processing such as development is performed to form a pattern. The metal thin film is etched using the patterned photoresist as an etching mask. Then, the resist residue which became unnecessary is peeled and removed using the composition of this invention. Specifically, for example, a step of immersing a photoresist on a semiconductor substrate after etching or a glass substrate for liquid crystal in the composition of the present invention, or treating the photoresist by spraying the composition of the present invention, A rinsing process using a pure water shower and a drying process using nitrogen or the like are performed. The immersion temperature is preferably 24 to 100 ° C., and the immersion time is preferably 30 seconds to 30 minutes, more preferably 1 minute to 20 minutes. In this way, a semiconductor element or the like having a wiring or the like formed on the surface is manufactured.

  When the composition of the present invention is used, the photoresist residue is easily peeled and removed from the substrate surface, and the formed metal film such as an Al alloy does not corrode. When such a composition is used, a highly accurate patterned substrate is formed.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these.

Examples 1-7, Comparative Examples 1-9
Photoresist (Novolac resin / diazonaphthoquinone-based resist, manufactured by Nagase ChemteX Corp.) formed on Al-deposited glass with a film thickness of 1 μm was baked at 100 ° C. for 2 minutes and exposed with an ultrahigh pressure mercury lamp. Thereafter, the film was developed with an aqueous 2.38% TMAH (tetramethylammonium hydroxide) solution. Thereafter, etching was performed using an etching solution of phosphoric acid / acetic acid / nitric acid, washed with water, dried, and further baked at 160 ° C. for 2 minutes, to be an object to be peeled.

This stripping object was immersed in a photoresist stripper composition having the composition (% by weight) shown in Tables 1 and 2 at 80 ° C. for 5 minutes, and then gently immersed in a petri dish filled with pure water at room temperature for 2 minutes. After standing still, pure water shower rinsing was performed for 15 seconds, and then pure water was blown off with an air gun using N ₂ gas, followed by natural drying. The object to be peeled after the peeling treatment was observed with a scanning electron microscope (SEM), and the peeling / removability of the photoresist and the degree of Al corrosion were observed. The results are shown in Tables 1 and 2. Evaluation was performed according to the following criteria.
Peelability ○: No resist residue Δ: Slightly resist residue ×: Al anticorrosion property with many resist residues observed ○: No Al wiring corrosion Δ: Al wiring is slightly thinned
X: Al wiring corrosion is severe.

Abbreviations in the table are as follows.
MIPA: monoisopropanolamine, DGA: diglycolamine, BDG: butyl diglycol (diethylene glycol monobutyl ether), DMSO: dimethyl sulfoxide, DMAC: N, N-dimethylacetamide, NMP: N-methyl-2-pyrrolidone, MEA: mono Ethanolamine, NMEA: N-methylethanolamine, DEAE: N, N-diethylaminoethanol, 2,3-DHN: 2,3-dihydroxynaphthalene.

Examples 8-10, Comparative Examples 10-12
A petri dish filled with pure water after immersing a stripping object similar to that used in Examples 1 to 7 in a photoresist stripper composition having the composition (% by weight) shown in Table 3 at 80 ° C. for 5 minutes. Then, after standing still for 2 minutes at room temperature, pure water shower rinsing was further performed for 15 seconds, and then pure water was blown off with an air gun using N ₂ gas, followed by natural drying. The peel target after the peel treatment was evaluated in the same manner as in Examples 1-7. The results are shown in Table 3.

  From the results in Table 1, in the photoresist stripping composition, by including the compound (A) in the mixed solution with the organic amine compound and the polar organic solvent, the stripping can be performed without interposing an intermediate rinse such as alcohol after the stripping treatment. It can be seen that corrosion of the aluminum wiring is suppressed without degrading the properties.

  Since Comparative Examples 1 and 2 did not contain a polar organic solvent, sufficient peelability was not obtained, and since no compound (A) was contained, aluminum was also corroded. Comparative Example 3 is an example using only a polar organic solvent, but although the aluminum anticorrosive property was excellent, the resist residue could hardly be peeled off. In Comparative Examples 4 to 6, since the compound (A) was not included, aluminum was corroded. Furthermore, since Comparative Example 6 contained water, the aluminum corrosivity was increased. Comparative Examples 7 to 9 are examples in which maltol was added as an anticorrosive to a non-aqueous resist stripping composition composed of an organic amine compound and an organic solvent, but it was not possible to achieve both peelability and aluminum corrosion resistance. .

  Examples 8 to 10 are examples in which at least one compound selected from the group consisting of benzoic acid, phthalic acid and phosphoric acid was further added to the composition of Example 7 as an anticorrosive agent (additional) The amount was adjusted with a polar organic solvent so that the whole would be 100% by weight.) A further improvement in aluminum corrosion resistance was observed due to a synergistic effect as compared with using 2,3-dihydroxynaphthalene alone.

  Comparative Examples 10 to 12 are examples in which benzoic acid, phthalic acid, and phosphoric acid were used alone, but sufficient aluminum corrosion resistance was not obtained.

Claims (5)

A non-aqueous resist stripping composition containing (A) 2,3-dihydroxynaphthalene, (B) an organic amine compound, and (C) a polar organic solvent. The resist stripping composition according to claim 1, wherein the organic amine compound (B) is at least one selected from the group consisting of monoisopropanolamine and diglycolamine. Further, it contains at least one compound (D) selected from the group consisting of aromatic hydroxyl compounds, acetylene alcohols, carboxyl group-containing organic compounds, carboxyl group-containing organic compounds, triazole compounds, saccharides, and phosphoric acid. The resist stripping composition according to claim 1 or 2. Compound (D) is resorcinol, 2-butyne-1,4-diol, benzoic acid, phthalic acid, malic acid, 1-hydroxybenzotriazole, 1,2,3-benzotriazole, 1,2,4-triazole, The resist stripping composition according to claim 3, which is at least one compound selected from the group consisting of sorbitol, xylitol, and phosphoric acid. A step of treating a photoresist on a semiconductor substrate or a glass substrate for liquid crystal with the resist stripping composition according to any one of claims 1 to 4, rinsing the semiconductor substrate or glass substrate for liquid crystal treated in the step. A method for removing a resist from a semiconductor substrate or a liquid crystal glass substrate, comprising: a step of drying the semiconductor substrate or the glass substrate for liquid crystal.