WO2002073319A1

WO2002073319A1 - Resist releasing composition

Info

Publication number: WO2002073319A1
Application number: PCT/JP2002/002262
Authority: WO
Inventors: Mizuki Takei; Emi Uchida; Takeshi Kotani
Original assignee: Nagase Chemtex Corporation
Priority date: 2001-03-13
Filing date: 2002-03-11
Publication date: 2002-09-19
Also published as: KR20040030532A; CN1280679C; TWI275903B; JP3928130B2; CN1496497A; JPWO2002073319A1; KR100831886B1

Abstract

A resist releasing composition comprising a nitro group containing organic compound (A) and a resist releasing agent (B). The resist releasing composition can be used for removing with high efficiency a resist residue formed during wiring in a production process for an electronic circuit or the like for a semiconductor or a liquid crystal, while suppressing the corrosion of a silicon substrate and preventing effectively the corrosion of a-Si and p-Si which are constituent metals of a thin film transistor.

Description

Description Resist stripping composition Technical field

The present invention relates to a photoresist stripping composition used for manufacturing semiconductor integrated circuits, semiconductor element circuits for liquid crystal panels, and the like. More specifically, the photoresist is effectively peeled off from the substrate and the corrosion of the silicon substrate is suppressed, or amorphous silicon (hereinafter a-Si) and polysilicon (hereinafter a-Si) which are constituent metals of thin film transistors are used. , P—S i) which suppress the dissolution of the photoresist. Background art

When a photoresist used for manufacturing a semiconductor integrated circuit, a semiconductor element circuit of a liquid crystal panel, or the like is peeled off from a substrate, a peeling composition is used. For example, manufacture of a semiconductor element circuit or an associated electrode unit is performed as follows. First, a silicon, a photoresist is uniformly coated on an insulating film such as a C VD Ya metal film formed by sputtering or S i 0 ₂ film on a substrate such as glass, exposed to light, and developed resist pattern Form. The metal film and the insulating film are etched using the patterned photoresist as a mask. Thereafter, the unnecessary photoresist film is stripped and removed using a stripping composition. By repeating these operations, the circuit or the electrode portion is formed. Here, the above-mentioned metal film includes, for example, aluminum alloy (A 1); aluminum alloy such as aluminum-em-silicon-copper (A 1—Si i Cu); titanium (T i); titanium nitride Titanium alloys such as (T i N); or silicon such as a-Si and D-Si are used. These metal films or insulating films are single-layer or It is formed on a substrate in a plurality of layers.

Conventionally, photoresist has been stripped by dissolving a compound such as an organic alkali, an inorganic alkali, an organic acid, or an inorganic acid alone or in combination of two or more in an organic solvent or water, and compounding additives as necessary. Compositions are used. For example, in a manufacturing process of a semiconductor device circuit or the like, at least one of an alkylamine and an alkylammonium hydroxide, and an organic solvent or water are mainly used to remove resist residues generated during wiring formation. Resist stripping compositions are well known.

Of these, the non-aqueous stripper consisting of a mixture of monoethanolamine (MEA) and an organic solvent, which is often used at present, does not corrode a-Si and!) Si. However, such a non-aqueous stripping solution is inferior in stripping and removing the resist as compared with a water-containing stripping solution. Furthermore, the removal and removal of the altered resist film (resist film that has been altered by treatment with a chemical solution such as heat or acid or exposure to plasma) is inferior to that of the aqueous stripper. Furthermore, non-aqueous strippers must be used at higher temperature conditions than hydrous strippers. On the other hand, a water-based stripping solution consisting of a mixture of monoethanolamine and water contains a—Si and! 1) S i (These are unfavorable because they corrode metal constituting a thin film transistor (TFT) element of a liquid crystal display (LCD)). Further, the stripping solution corrodes the silicon substrate, which is not preferable because it may cause dust or particles on the substrate in the manufacture of a semiconductor integrated circuit and may lower the yield.

Japanese Patent Application Laid-Open No. 5-269066 discloses an aqueous solution containing at least one compound selected from the group consisting of aromatic phenolic compounds and aromatic carboxylic acid compounds and an organic amine. The following photoresist stripping solution is described. This stripping solution also rots the silicon substrate, a-Si and p-Si. I can't control food.

Further, Japanese Patent Application Laid-Open No. 8-200501 discloses a photoresist stripping composition containing an alkanolamine, an alkoxyamine, an alkoxyalkanolamine, or an acid amide, wherein a saccharide is used as a metal anticorrosive. Or using sugar alcohol. Also, this stripper also has a silicon substrate, a-Si, and! ) One Si corrosion cannot be suppressed.

For the above reasons, there is a need for a stripping composition that effectively removes the resist residue and has a silicon substrate, a-Si, and p-Si anticorrosion function. Disclosure of the invention

The present invention has been made in order to solve the above-mentioned conventional problems, and has as its object the corrosion of a silicon substrate used in the manufacture of a semiconductor integrated circuit, and the formation of a-Si and p-Si which are constituent metals of a thin film transistor element. An object of the present invention is to provide a resist stripping composition capable of suppressing or preventing dissolution.

As a result of repeated experiments, the inventor has found that the resist stripping composition further contains an organic compound containing a thiol group to effectively remove the resist residue, thus corroding the silicon substrate and a- The present inventors have found that the dissolution of Si and p_Si can be favorably suppressed, and have completed the present invention.

The resist stripping composition of the present invention contains a nitro group-containing organic compound (A) and a resist stripping agent (B).

In a preferred embodiment, the nitro group-containing organic compound is at least one compound selected from the group consisting of aromatic and heterocyclic compounds.

In a preferred embodiment, the resist remover (B) contains at least one amine selected from the group consisting of alkylamines, alkanolamines and quaternary ammonium compounds, and water. In a preferred embodiment, the composition further contains a water-soluble organic solvent (C).

In a preferred embodiment, the content of the nitro group-containing organic compound (A) is 0.01 to 10% by weight, the content of amines is 1 to 94% by weight, and the content of water is 5 to 5%. 885% by weight, and the balance is a water-soluble organic solvent (C). In a preferred embodiment, the composition further contains an anticorrosive for aluminum or copper. BEST MODE FOR CARRYING OUT THE INVENTION

As described above, the composition of the present invention includes the nitro group-containing organic compound (A) (hereinafter sometimes referred to as compound A).

The following compounds may be used as the organic compound having a dihydroxy group (A): dimethoxy ethane, 2-nitroethanol, 2- (hydroxymethynole) 1-2-2-nitro-1,3-propanediol, etc. Aliphatic nitro compounds; o-etroaniline, _m -etroaniline, p-tutroaniline, o-nitrophenolone, m-2-trophenol, p-trofenenole, o-nitrone M-Nitrobenzoic acid, P-nitrobenzoic acid, 2-Nitroa-sol, 3-Nitroa-so-one, 4-Nitroanisone, o-Nitrobenzenesnolephonic acid, m-Nitrobenzenesnole Fonic acid,; -nitrobenzenesnolephonic acid, 2-methoxy-4-nitro-phosphorin, 2-amino-1-5-nitrothiazole, 2,3-dimethylnitrobenzene, 3,4-dimethinolenitrobenzene 4-Nitrobenzenecinnamic acid, 4-Hydroxymethylnitrobenzene, 4-Hydroxyshethylnitrobenzene, 4-Etrophenylacetic acid, 4-Methyl-2-nitroaniline, 4-Methyl-3-trobenzoic acid , 2,6-Jib mouth mo 4-12 troaniline, 4-ethynolenitrobenzene, 4, 1-troacetophenone, 4, 12-troacetayllide, 4- 1-trobenzamide, 3-2 trophthalanolic acid, 4 12 Troph Luric acid, 4-nitrobenzotriol, 3-nitrobenzotrifluoride, 4-nitrobenzinochloride, 6-nitro-m-creso-mono, 5-nitro-ko-mono, 2-nitro- 1,2-phenylenediamine, 4-nitro-1,1,2-phenylenediamine, 4-nitro-1,3-phenylenediamine, 1,3-diamino-1,2,4,6-trinitrobenzene, etc. Aromatic nitro compounds of the formula: 5-nitroindazolone, 2-methyl-5-troymidazolone, 1-1etanore, 5_etrobenzimidazole, 2-amino-5-nitropyridine, 4-nitromidazolone, 1-1 (4-12 Trofe-/ re)-3-methinole 1-5 Heterocyclic-toro compounds such as pyrazolone. Among them, an aromatic cyclic compound and a heterocyclic compound are preferably used.

The content of the compound (A) in the resist-stripping composition is preferably from 0.01 to 10% by weight, and more preferably from 0.1 to 5% by weight. When the content of the compound (A) is less than 0.01% by weight, the anticorrosion effect on the silicon substrate, a-Si, and p-Si tends not to be obtained. On the other hand, if it exceeds 10% by weight, corrosion on aluminum tends to be severe. As the resist stripping agent (B) contained in the present invention, a solution generally used in the field of the resist stripping agent, for example, a compound such as an acid or a base, or a mixture thereof is used together with water. Preferably, a resist stripping agent containing, as a base, an amine which is at least one of alkylamine, alkanolamine and quaternary ammonium compounds, and water is used. The above-mentioned amines include the following compounds: alkylamines such as triethylenetetramine, N, N, N ,, N'-tetramethylethylenediamine; monoethanolamine (MEA), diglycolamine Primary alkanolamines such as (DGA); secondary alkanolamines such as N-methylethanolamine, N-ethylethylanolamine, N-butylethanolamine, N, N-diethanolamine; N, N-dimethylethanolamine Min, N, N— Tertiary alkanolamines such as getylethanolamine, N, N-dibutylethanolamine, N-methylol N, N-diethanolamine, N, N-bis (2-hydroxyxethyl) hexylamine; Quaternary ammonium compounds such as tetramethylammonium hydroxide and trimethyl (2-hydroxyshethyl) ammonium hydroxide.

Of these, primary alcohols such as monoethanolamine and diglycolamine are preferably used.

The amine contained in the resist stripping agent (B) is 1 to 94 weight in the composition. / ₀ is preferably included. More preferably, it is 5 to 80% by weight. When the content of amines in the resist stripping agent is less than 1% by weight, the resist residue tends to be hardly removed sufficiently. On the other hand, if it exceeds 94% by weight, the resist residue tends not to be removed because the content of other components is reduced. Water is preferably contained in the composition at a ratio of 5 to 85% by weight, more preferably 5 to 60% by weight, and even more preferably 5 to 40% by weight. When the water content is less than 5% by weight, the resist residue tends to be hardly removed. On the other hand, 8

If the content exceeds 5% by weight, the content of other components is reduced, so that the effect of sufficiently removing the resist residue and the anticorrosive effect on the silicon substrate, a-Si, and p_Si tend to be hardly obtained. is there.

As the water-soluble organic solvent (C) which may be contained in the composition of the present invention, the following compounds may be used: diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether ether, and diethylene glycol monomethyl alcohol. Monoter, diethylene glycol monobutyl ether (BDG), N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolatatone, dimethylsulfoxide (DMSO), Ethylene glycol / propylene glycol glycol etc.

As the anticorrosive for metals such as aluminum and copper which may be contained in the composition of the present invention, the following compounds may be used: catechol, 4-t-butyl Lucatechol, 1, 2, 3-benzotriazole, 2-mercaptobenzoimidazole, 2,3-dihydroxynaphthalene, D-sorbitol, benzoic acid, etc.

The content of the water-soluble organic solvent (C) is not particularly limited. The balance of the compound (A), the resist stripping agent (B), and the optional compound such as an anticorrosive may be a water-soluble organic solvent (C).

At least one compound can be used for each of the compound (A), the resist stripping agent (B), and the water-soluble organic solvent (C).

The resist stripping composition of the present invention containing the compound (A), the resist stripping agent (B) and, if necessary, the water-soluble organic solvent (C) is used for stripping the resist from the substrate. Used.

Next, a method for using the composition of the present invention will be described with reference to an example in which a semiconductor element is manufactured using a semiconductor substrate or a glass substrate for liquid crystal. For example, a metal film such as a-Si, p-Si, or an insulating film such as SiO ₂ is formed on a substrate by CVD, sputtering, or the like. Next, a photoresist is formed thereon, a photomask is placed thereon, exposed, and a process such as development is performed to form a pattern. The metal thin film is etched using the patterned photoresist as an etching mask. Thereafter, the resist is ashed by asshing. The resist residue remaining after incineration is stripped and removed using the composition of the present invention. Specifically, by immersing the ashed substrate in the composition of the present invention, the photoresist residue is dissolved or peeled and removed. The immersion temperature is usually 24 to 75 ° C, and the immersion time is 30 seconds to 30 minutes. In this way, a semiconductor element 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 off from the substrate surface, and the silicon film itself is corroded or the formed metal film such as a-Si, p-Si is peeled off. There is no. When such a composition is used, a highly accurate patterned substrate is formed. Example

Hereinafter, examples and comparative examples are shown, and the features of the present invention will be described more clearly. It goes without saying that the present invention is not limited by this embodiment.

(Example 1)

The silicon substrate was immersed in a 0.5% HF aqueous solution (24 ° C.) for 5 minutes, and the substrate was pretreated by removing the natural oxide film on the silicon substrate surface. Next, the silicon substrate having been subjected to this pretreatment was peeled off using a composition comprising a compound (A), a resist release agent composition (B), and a water-soluble organic solvent (C) as shown in Table 1. It was immersed at 70 ° C for 1 hour. This was washed with pure water and dried naturally with N ₂ gas. The surface condition of Si was observed with a scanning microscope (SEM), and the corrosion resistance of silicon was compared.

〇: No corrosion

Δ: Pitting corrosion is observed on the entire surface

X: uniform corrosion is observed on the entire surface

The results are shown in Table 1.

In order to confirm the anticorrosion effect on silicon in more detail, the weight change of the silicon substrate when the above operation was performed was measured. The change in film thickness was determined by dividing the change in weight of the silicon substrate by the specific gravity of silicon and the substrate area. Further, the amount of change in film thickness per hour, that is, the amount of etching of silicon per unit time (etching rate; unit: angstrom) was determined from the change in film thickness and the immersion time.

. Alternatively, after a 1 mu membrane film with resist thickness of m to C r on the substrate 1 0 0 ° C with and beta 2 minutes exposure, 2 3 8 weight ^_0/0 tetramethyl § Nmo -現像 Developed with aqueous solution of mumoxide (TMAH). Furthermore, after beta treatment at 140 ° C for 2 minutes, a second etching solution of ammonium nitrate-based Cr is used. For 1 minute at room temperature. Then, it was immersed in a peeling yarn composition having the composition shown in Table 1 at 50 ° C. for 1 minute. This was washed with pure water, and the pure water was blown off with an air gun to air dry. The degree of resist removal was observed with an optical microscope and evaluated according to the following criteria.

〇: No residue

△: Some residue remains

X: Most residue remains

The results are shown in Table 1 as resist strippability.

(Examples 2 to 9)

Example 1 is the same as Example 1 except that the compound (A), the resist stripping agent (B), and the water-soluble organic solvent (C) were changed to the amounts of the compounds shown in Table 1.

(Comparative example:! ~ 18)

Example 1 is the same as Example 1 except that the compound (A), the resist stripping agent (B), and the water-soluble organic solvent (C) were changed to the compounds and amounts shown in Table 1.

MEA: monoethanolamine BDG: diethylene glycol monobutyl ether TETA: triethylenetetramine DMSO: dimethyl sulfoxide

Example:! No. 9 to No. 9 are compositions containing a nitro group-containing organic compound (A), alkanolamine water as a resist stripping agent (B), and optionally a water-soluble organic solvent (C). It is. As is clear from Table 1, it is understood that the composition having such components has a high performance of removing the resist and has a high silicon corrosion protection.

The above Examples 1 to 4 are compositions in which an aromatic cyclic double-mouthed compound was added to the composition of Comparative Example 1 or Comparative Example 2 (the solvent amount was adjusted; the same applies hereinafter). The etching rate of silicon in the case of using the composition of Comparative Example 1 was 281 Å / min, whereas the etching rate of silicon in Examples 1 and 2 was almost zero. Similarly, when the composition of Comparative Example 2 was used, the silicon etching rate was 419 Å / min, while in Examples 3 and 4, the silicon etching rate was almost zero. . From these facts, it is understood that the aromatic nitro compound favorably stops silicon etching in the P direction. Similarly, the compositions of Examples 5 and 6 in which the aromatic compound-toro compound was added to the yarn composition of Comparative Example 4; The composition of Example 7; the composition of Example 8 in which part of the amines of the composition of Comparative Example 6 was replaced with an aromatic cyclic compound; and the part of the amines of the composition of Comparative Example 7 Also in the case of using the composition of Example 9 in which the compound was replaced with a heterocyclic compound, the etching rate of silicon was almost zero in each case.

Comparative Examples 1 and 2 are yarn compositions obtained by removing the organic compound (A) containing an etro group from the compositions shown in Examples 1 to 4. When such a composition was used, the resist was sufficiently removed, but the silicon was severely corroded.

Comparative Example 3 is a composition comprising only monoethanolamine. When this composition was used, no corrosion of silicon was observed, but the removal of the resist residue was insufficient. Comparative Examples 4 to 6 are compositions obtained by adding water to monoethanolamine. When these compositions were used, the resist was sufficiently removed, but the silicon was severely corroded.

Comparative Example 7 is a composition in which an alkylamine was used as an amine and water was added thereto. When this yarn composition was used, the resist was severely corroded by the sufficiently removed 1S silicon.

Comparative Example 8 is a composition containing only a water-soluble organic solvent. When this composition was used, it did not corrode silicon, but hardly removed any resist residue. Comparative Example 9 is a composition in which water was added to a water-soluble organic solvent. With this composition, the silicon did not corrode, but the resist was not removed. Comparative Example 10 is a composition comprising a mixture of monoethanolamine and diethylene glycol monobutyl ether. When this composition was used, the silicon did not corrode, but the resist residue was not sufficiently removed. Comparative Examples 11 to 18 are compositions in which a generally known metal anticorrosive was added to a resist stripper (B). When these compositions were used, resist residues were sufficiently removed, but silicon corrosion could not be suppressed.

(Examples 10 to 13)

On the silicon nitride film of the substrate having the silicon nitride film, a film was formed by sputtering in the order of A 1 and Ti, and then a photoresist was formed on the surface with a thickness of 1 Atm. The film was exposed to light at 100 ° C. for 2 minutes, placed on a photomask and exposed, and then developed using a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH). After further beta 2 min at 1 4 0 ° C, the A 1 / T i film de dry etching by C 1 ₂ and BC 1 ₃ gas to obtain a substrate having an A 1 film with a predetermined pattern. Subsequently, the photoresist was lightly ashesed with oxygen.

This substrate was placed in a stripping composition (stripping solution) having the composition shown in Table 2 at 40 ° C. After immersion for 10 minutes, the substrate was washed with pure water, and the pure water was blown off with an air gun using N ₂ gas, followed by natural drying. Then, the extent of photoresist removal and A1 corrosion protection were observed by scanning electron microscope (SEM). They were evaluated according to the following criteria.

Resist strippability

〇: No residue

Δ: Some residue remains

X: Most residue remains

A 1 Corrosion protection

◎: A 1 No corrosion

〇: A1 corrosion is slightly observed but A1 line width is not reduced. X: A1 line width is reduced.

(Comparative Example 19)

Example 10 was the same as Example 10 except that the composition of the stripping solution was changed as shown in Table 2.

The results are shown in Table 2.

to

MEA: Monoethanolamine

BDG: Diethylene glycol monobuter-ter

(Production example)

Using the resist stripping composition of Example 1, a semiconductor device was manufactured as follows. First, an a-Si metal film is formed on a semiconductor substrate by sputtering, and anneal! ) One Si. A photoresist was formed on the p-Si film, a mask was mounted, and exposure was performed. This was developed to form a pattern. The metal thin film was etched using the patterned photoresist as an etching mask. Thereafter, oxygen plasma asshing was performed to ash the resist. This substrate was immersed in the resist-stripping composition of Example 1 at 70 ° C. for 20 minutes. As a result, the remaining resist residue was removed. Thus, a semiconductor device having a desired pattern formed on the surface was obtained. Industrial applicability

According to the present invention, there is provided a resist stripping composition containing a nitro group-containing organic compound (A), a resist stripping agent (B) and, if necessary, a water-soluble organic solvent (C). You.

By using the resist stripping composition of the present invention to remove resist residues generated during wiring formation in the process of manufacturing semiconductor or liquid crystal element circuits, resist residues are removed with high performance. In addition, corrosion of a-Si and p-Si, which are constituent metals of a silicon substrate used for manufacturing a semiconductor integrated circuit or a thin film transistor, can be prevented or largely suppressed.

The resist stripping composition of the present invention is suitably used in a process of manufacturing an electronic circuit or the like for a semiconductor or a liquid crystal.

Claims

The scope of the claims

1. A resist stripping composition comprising a nitro group-containing organic compound (A) and a resist stripping agent (B).

2. The resist stripping composition according to claim 1, wherein the compound is a compound having at least one compound selected from the group consisting of a 1S aromatic nitro compound and a heterocyclic-toro compound.

3. The resist stripping agent according to claim 1 or 2, wherein the resist stripping agent (B) comprises at least one amine selected from the group consisting of alkylamines, alkanolamines and quaternary ammonium compounds, and water. Composition.

4. The resist stripping composition according to claim 1, further comprising a water-soluble organic solvent (C).

5. The content of the toro group-containing organic compound (A) is 0.01 to 10% by weight, the content of amines is 1 to 94% by weight, and the content of water is 5 to 8%. The resist stripping composition according to claim 4, wherein the composition is 5% by weight, and the balance is a water-soluble organic solvent (C).

6. The resist stripping composition according to any one of claims 1 to 5, further comprising an anticorrosive for aluminum or copper.