JP2001117241A - Rinsing solution for lithography - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rinsing solution having good solvent power and removing ability not only to a resist or an antireflection film formed from a solution in an organic solvent but also to an antireflection film formed from an aqueous solution, reducing the danger of a fire and easy to handle. SOLUTION: The rinsing solution for lithography comprises a homogeneous solution containing one or more solvents selected from the group comprising 1,3-propanediol alkyl ethers, 1,3-propanediol alkyl ether acetates, 1,3-propanediol dialkyl ethers and 1,3-propanediol diacetate and water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rinse liquid for lithography, and more particularly to a cured or uncured unnecessary resist from a substrate or a resist coating device in an integrated circuit device, a color filter, a liquid crystal display device, etc. The present invention relates to a lithography rinse solution useful for dissolving or peeling off a film or the like.

[0002]

2. Description of the Related Art Lithography has conventionally been used for manufacturing integrated circuit elements, color filters, liquid crystal display elements and the like. In the manufacture of integrated circuit elements and the like using lithography technology, for example, after forming an antireflection film on a substrate as necessary, a positive or negative resist is applied, and after removing the solvent by baking, the resist film is formed on the resist film. An anti-reflection film is formed if necessary, exposed to various radiations such as ultraviolet rays, far ultraviolet rays, electron beams, and X-rays, and developed to form a resist pattern.

[0003] The application of the above resist and the like is performed by spin coating, roll coating, reverse roll coating, casting coating,
Various known methods such as doctor coating and dip coating are employed. For example, in the production of integrated circuit elements, spin coating is mainly used as a resist coating method. In the spin coating method, a resist solution is dropped on a substrate, and the dropped resist solution is cast in the direction of the outer periphery of the substrate by rotation of the substrate, and excess resist solution is scattered and removed from the outer periphery of the substrate to obtain a desired film thickness. Is formed. However, at this time, there is a defect that a part of the resist solution goes around to the back surface of the substrate, or the resist solution remains thicker than the other portions on the outer peripheral edge of the substrate, that is, a so-called bead is formed. It is necessary to remove unnecessary resist from the part or the back surface, or to remove beads. This is not limited to the manufacture of integrated circuit devices,
The same applies to the manufacture of color filters, liquid crystal display elements, and the like. In addition, in a coating method other than the spin coating method, the resist may adhere to unnecessary portions as in the case of the spin coating method. In the case of an integrated circuit device having an antireflection film between the substrate and the resist film, it is necessary to remove the antireflection film after the pattern is formed. On the other hand, since the resist solution adheres to the coating apparatus, it is necessary to wash the coating apparatus for further use.

A rinsing solution comprising an organic solvent is considered to be preferable for removing such a resist or an anti-reflection film, preventing peeling or bead formation, and further cleaning the coating apparatus. A rinsing liquid consisting of only a solvent is used (for example, Japanese Patent Publication No. 4-49938). In fact, such a rinsing liquid is required to be further excellent in solubility and releasability with respect to a resist or an antireflection film.

Japanese Patent Application Laid-Open No. Hei 6-324499 discloses a patent which uses β-type propylene glycol monoalkyl ether acetate to improve the solubility of a resin and the solubility of an initiator. However, propylene glycol-based 1,2
-It is considered that the cause is the presence of a substituent at the site, and the improvement was still insufficient.

On the other hand, JP-A-5-188598, JP-A-6-69120, JP-A-6-148896 and the like propose that an antireflection film is formed from an aqueous solution, and a recent antireflection film is formed. At this time, an aqueous solution is often used. It is also desired to provide a rinsing solution that has a favorable rinsing effect, such as shortening the dissolution time of the antireflection film formed from such an aqueous solution, and also satisfies fire and handling safety. Although rare, it has been difficult to satisfy these demands simultaneously with a conventional rinsing liquid.

[0007]

SUMMARY OF THE INVENTION The present invention is applied not only to a resist or an antireflection film formed from an organic solvent solution which does not have the above-mentioned disadvantages but also to an antireflection film formed from an aqueous solution. An object of the present invention is to provide a rinsing liquid which has good solubility and peelability, has an improved risk of fire, and is easy to handle under the Fire Service Law.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that water is added to and contained in a water-soluble organic solvent conventionally used as a solvent for a resist or an antireflection film or a rinsing liquid. Compared to the case where only soluble organic solvent is used, the solubility or peelability of resist and anti-reflective coating etc. is improved, and the flash point of the mixed solvent is increased due to the inclusion of water, and the danger of fire is reduced. The present invention has been made based on the finding that the above-mentioned handling safety is also improved.

That is, a first aspect of the present invention is to provide a 1,3-propanediol alkyl ether, a 1,3-propanediol alkyl ether acetate, a 1,3-propanediol dialkyl ether, and a 1,3-propanediol diacetate. An object of the present invention is to provide a lithography rinse solution comprising a homogeneous solution containing at least one selected solvent and water. The second aspect of the present invention is
An object of the present invention is to provide a first lithography rinse liquid of the present invention, wherein the solvent is 1,3-propanediol alkyl ether and / or 1,3-propanediol alkyl ether acetate. A third aspect of the present invention is the lithographic rinse of the first or second aspect, wherein the 1,3-propanediol alkyl ether is at least one selected from methyl ether, ethyl ether, propyl ether, and butyl ether. A liquid is provided. A fourth aspect of the present invention is that the 1,3-propanediol alkyl ether acetate is at least one selected from methyl ether acetate, ethyl ether acetate, propyl ether acetate and butyl ether acetate. 3. A rinse liquid for lithography according to any one of 3. A fifth aspect of the present invention is to provide a rinse liquid for lithography according to any one of the first to fourth aspects of the present invention, which comprises using another water-soluble organic solvent in combination. A sixth aspect of the present invention provides the rinse liquid for lithography according to any one of the first to fifth aspects, wherein the content of water is in the range of 0.5 to 200 parts by mass relative to 100 parts by mass of the total organic solvent. It is. A seventh aspect of the present invention is to provide a lithography rinse liquid according to any one of the first to sixth aspects of the present invention for rinsing a resist film or an antireflection film.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The solvent used in the present invention is 1,3-
It is selected from propanediol alkyl ether, 1,3-propanediol alkyl ether acetate, 1,3-propanediol dialkyl ether, and 1,3-propanediol diacetate. Among them, alkyl ethers and / or alkyl ether acetates of 1,3-propanediol are particularly preferred. Each of these may be used alone, or two or more of them may be used in a mixture at an arbitrary ratio.

The 1,3-propanediol alkyl ether includes 1,3-propanediol methyl ether, 1,3-propanediol ethyl ether, 1,3
-Propanediol-1-propyl ether, 1,3-
Propanediol-2-propyl ether, 1,3-propanediol-n-butyl ether, 1,3-propanediol-iso-butyl ether, 1,3-propanediol-t-butyl ether;
As propanediol alkyl ether acetate, 1,3-propanediol methyl ether acetate, 1,3-propanediol ethyl ether acetate, 1,3-propanediol-1-propyl ether acetate, 1,3-propanediol-2- Propyl ether acetate, 1,3-propanediol-n-
Butyl ether acetate, 1,3-propanediol-iso-butyl ether acetate, 1,3-propanediol-t-butyl ether acetate, and the like.

Examples of the 1,3-propanediol dialkyl ether include dialkyl ethers corresponding to the above-mentioned 1,3-propanediol alkyl ether, and those comprising a combination of different alkyl groups as the alkyl group of the dialkyl ether. Are also exemplified.

As a mixture of two or more of these solvents, for example, 1,3-propanediol methyl ether and 1,3-propanediol methyl ether acetate,
1,3-propanediol methyl ether and propylene glycol monomethyl ether acetate, 1,3-propanediol ethyl ether and 1,3-propanediol methyl ether acetate, 1,3-propanediol ethyl ether and propylene glycol monomethyl ether acetate, propylene Glycol methyl ether and 1,3-propanediol methyl ether acetate, propylene glycol ethyl ether and 1,3-
Preferred are, for example, propanediol methyl ether acetate.

Conventionally, any organic solvent which is conventionally used as a solvent or a rinsing liquid for a resist or an antireflection film and is soluble in water can be used in combination, and may be used alone or as a mixture of two or more. Examples of the water-soluble organic solvent used in the present invention include propylene glycol alkyl ether, propylene glycol alkyl ether acetate, ethyl lactate (EL),
Examples include methyl ethyl ketone, methyl isobutyl ketone, acetone and the like.

The propylene glycol alkyl ether includes, for example, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and the like, and the propylene glycol alkyl ether acetate includes propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and the like. Propylene glycol propyl ether acetate;

In the present invention, the above-mentioned organic solvent is used together with water. However, the preferable content of water in the rinsing solution differs depending on the solvent used and cannot be determined uniquely. However, it is generally preferred to use 0.5 to 200 parts by mass with respect to 100 parts by mass of the total organic solvent, and more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the total organic solvent. The rinse solution of the present invention is a homogeneous solution containing water as described above. A homogeneous solution is preferably a solution in which each solvent and water are completely dissolved under use conditions, and in addition, when a component is dispersed in another component unless a separation layer is formed. Also refers to.

The rinsing liquid of the present invention can be applied to any of known positive resists, negative resists and antireflection films. To exemplify typical resists to which the rinse solution of the present invention can be applied, a positive type, for example, a quinonediazide-based photosensitive agent and an alkali-soluble resin, a chemically amplified resist, and the like, a negative type, for example, Those containing a polymer compound having a photosensitive group such as polyvinyl cinnamate, those containing an aromatic azide compound or those containing an azide compound such as a cyclized rubber and a bisazide compound, those containing a diazo resin, Examples thereof include a photopolymerizable composition containing an addition-polymerizable unsaturated compound, and a chemically amplified negative resist.

The resist material comprising the quinonediazide-based photosensitizer and the alkali-soluble resin is preferred for use in the rinsing solution of the present invention, and the quinonediazide-based resist material comprising the quinonediazide-based photosensitizer and the alkali-soluble resin is used. Examples of quinonediazide-based photosensitizers include:
2-benzoquinonediazide-4-sulfonic acid, 1,2-
Naphthoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-5-sulfonic acid, esters or amides of these sulfonic acids, and alkali-soluble resins such as polyvinylphenol, polyvinylalcohol, acrylic acid or methacrylic acid And phenol, o-cresol, m-cresol, p
-Novolak resins produced from one or more phenols such as cresol and xylenol and aldehydes such as formaldehyde and paraformaldehyde.

A chemically amplified resist is also a preferable resist to which the rinsing solution of the present invention is applied. Chemically-amplified resists generate an acid by irradiation and change the solubility of the irradiated part in a developing solution by a chemical change caused by the catalytic action of the acid to form a pattern. An acid-generating compound to be generated, and an acid-sensitive group-containing resin that is decomposed in the presence of an acid to produce an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, an alkali-soluble resin and a crosslinking agent, and acid generation. Agents.

On the other hand, as the antireflection film to which the rinsing liquid of the present invention is applied, any antireflection film made of an organic material may be used. Examples of such an antireflection film include polyamic acid or polybutenoic acid to which a dye is added (US Pat. No. 4,910,122), a copolymer to which a dye is added (for example, JP-A-6-118656), a maleic anhydride polymer , A polymer composed of itaconic anhydride polymer, polyacrylate or polymethacrylate and grafted with a dye or the like (US Pat. No. 2,751,373)
U.S. Pat. No. 2,811,509, U.S. Pat.
No. 086, U.S. Pat. No. 3,854,946, U.S. Pat.
No. 609614), a reaction product of an amino aromatic chromophore and a polymer having an anhydride group (US Pat. No. 5,294,680).
), A solution comprising a water-soluble polymer and a water-soluble perfluorocarboxylic acid (JP-A-5-188598), an organic alkali solution such as tetramethylammonium hydroxide containing a water-soluble polymer (JP-A-6-69120), A composition comprising a water-soluble film-forming component and a fluorine-based surfactant (Japanese Patent Application Laid-Open No. 148896/1994); Those composed of sulfonic acid, organic amine, polyvinylpyrrolidone, and water-soluble alkylsiloxane polymer (Japanese Patent Application No. 8-1)
No. 29056), and those formed from an organic solvent or an aqueous solution. Since the rinsing liquid of the present invention contains water, it is well compatible with a film formed from an aqueous solution (has a small contact angle), and a good rinsing effect can be obtained even for an antireflection film formed from an aqueous solution.

The application of the rinsing liquid of the present invention together with the method of forming a resist pattern will be further described. First, a resist solution is applied by a conventionally known coating method such as a spin coating method.
It is applied to a pre-treated silicon substrate, glass substrate or the like as necessary. An anti-reflection film is applied as necessary before or on the resist film that has been formed before the application of the resist,
It is formed. For example, in the spin coating method, a bead of a resist or an anti-reflection film tends to be formed on the edge of the substrate. However, the flow of the bead is promoted by spraying the rinse liquid of the present invention on the rotating edge bead. A resist film or an antireflection film having a substantially uniform thickness can be formed thereon. Further, the resist or the anti-reflection film that has spread around the side surface or the back surface of the substrate can be removed by spraying a rinsing liquid. In addition, for example, in the case of a positive resist, if an antireflection film is present between the substrate and the resist film, after the pattern is formed by exposure and development, the antireflection film on the portion without the resist film is rinsed with the rinse liquid. It can also be used for wet removal.

The resist applied to the substrate is prebaked, for example, on a hot plate to remove the solvent, and is usually formed into a resist film having a thickness of about 1 to 2.5 microns.
The prebake temperature varies depending on the type of solvent or resist used, and is usually 20 to 200 ° C, preferably 50 to 1 ° C.
This is performed at a temperature of about 50 ° C. The resist film is then applied to a high-pressure mercury lamp, metal halide lamp, ultra-high-pressure mercury lamp,
KrF excimer laser, ArF excimer laser, F
Exposure is performed using a known irradiation device such as a laser, a soft X-ray irradiation device, or an electron beam lithography device through a mask if necessary. After exposure, after-baking as necessary to improve developability, resolution, pattern shape, etc.,
Development is performed to form a resist pattern. The development of the resist is usually carried out using a developing solution, utilizing the difference in solubility between the exposed area and the unexposed area in a solvent or an alkaline solution. Examples of the alkaline developer include sodium hydroxide and tetramethylammonium hydroxide (TMAH).
An aqueous solution or an aqueous solution such as this is used.

The application of the resist film or the anti-reflection film is performed by using a coating device. After the resist or the anti-reflection film is applied on the substrate, the device after the coating is used as a coating device of another kind of material. Used again, for example, from the resist to the anti-reflective film, from the resist to another type of resist or from the anti-reflective film to the resist or the like may be used as a coating device, in such a case, before using as a coating device of another type of material The applicator is cleaned, and the rinsing liquid of the present invention can be effectively used in such a case.

[0024]

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. Example 1 The following quinonediazide photosensitizer and novolak resin were mixed with 100 parts of novolak resin (mass, the same applies hereinafter).
And a propylene glycol monomethyl ether acetate (PGMEA) solvent to dissolve the solid components in an amount of 25% by mass to prepare a resist composition. Quinonediazide photosensitizer: Esterified product of 2,3,4,4'-tetrahydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonyl chloride Novolak resin: m-cresol / p-cresol = 6
/ 4 and polycondensate of formaldehyde The resist composition thus prepared is spin-coated on a 4-inch silicon substrate so that the film thickness after pre-baking becomes 2.6 μm, and is heated at 100 ° C. on a direct hot plate. Pre-baking was performed for 90 seconds to form a resist film. In the examples, the thickness of the resist was set to be thicker than a commonly used thickness in order to conduct a solubility test. The formed resist film was prepared by using a 1- (1) to 1- (8) rinsing solution comprising a mixed solvent (solvent A) and water shown in Table 1 and a solubility test based on the following solubility test. The test was performed and the results in Table 1 were obtained.

(Solubility Test) A rinse solution (0.03 ml) was dropped on the resist film, and the time (sec) from dropping until the underlying silicon was seen was measured. ) Was taken as the dissolution rate.

(Comparative Example 1) The procedure of Example 1 was repeated, except that a rinsing solution consisting of only the solvent A containing no water was used, and the results shown in Table 1 were obtained.

[0027]

[Table 1]

As is clear from Table 1, 1,3-PDM
Adding water to a mixed solvent consisting of E and 1,3-PDMEA,
It can be seen that the dissolution rate is drastically increased by the inclusion.

(Example 2) 1 part of polyvinylpyrrolidone,
4 parts of perfluorooctanesulfonic acid, 0.35 part of 2-aminoethanol, water-soluble alkylsiloxane polymer (Polyfur-KL-245, manufactured by Kyoeisha Yushi Co., Ltd.) 0.00
A composition for forming an antireflection film consisting of 4 parts and 94.646 parts of pure water is applied on a 4-inch silicon substrate by spin coating, baked at 90 ° C. for 90 seconds, and 650 ° C.
Was formed. Example 1 on this antireflection film
Was dropped. The contact angle of the rinsing liquid to the antireflection film immediately after the dropping was small, the rinsing liquid was well adapted to the antireflection film, and a smoother dissolution than the rinsing liquid containing no water could be achieved.

[0030]

As described above, in the present invention, water is added to and contained in a specific organic solvent, so that a resist film and an antireflection film can be obtained as compared with the case where only a conventional water-soluble organic solvent is used as a rinsing liquid. In addition to improving the solubility of the rinsing liquid, the rinsing liquid is well adapted to a film formed from an aqueous solution, and has the effect of achieving smooth dissolution. In addition, since the rinsing liquid contains water, the flash point of the rinsing liquid is increased, the regulations of the Fire Service Law are relaxed, and there is also an effect that handling at a manufacturing site or a factory is simplified.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H05K 3/26 H01L 21/30 569E F-term (Reference) 2H096 AA00 AA25 AA27 AA28 CA20 GA18 4H003 BA12 DA15 DB03 ED02 ED29 ED32 FA03 FA04 5E343 AA02 EE02 ER11 GG11 5F046 LA12

Claims (7)

[Claims] 1. One or more kinds selected from the group consisting of 1,3-propanediol alkyl ether, 1,3-propanediol alkyl ether acetate, 1,3-propanediol dialkyl ether, and 1,3-propanediol diacetate. A rinse liquid for lithography, comprising a homogeneous solution containing a solvent and water. 2. The lithography rinse according to claim 1, wherein the solvent is 1,3-propanediol alkyl ether and / or 1,3-propanediol alkyl ether acetate. 3. The lithography rinse according to claim 1, wherein the 1,3-propanediol alkyl ether is at least one selected from methyl ether, ethyl ether, propyl ether and butyl ether. 4. The method according to claim 1, wherein the 1,3-propanediol alkyl ether acetate is at least one selected from methyl ether acetate, ethyl ether acetate, propyl ether acetate, and butyl ether acetate. The rinsing liquid for lithography according to 1. 5. The lithography rinse liquid according to claim 1, wherein another water-soluble organic solvent is used in combination. 6. The lithography rinse solution according to claim 1, wherein the content of water is in the range of 0.5 to 200 parts by mass based on 100 parts by mass of the total organic solvent. 7. The lithography rinse according to claim 1, which is used for rinsing a resist film or an antireflection film.