Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/42—Separation; Purification; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/63—Esters of sulfonic acids
  • C07C309/72—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/76—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/0223—Iminoquinonediazides; Para-quinonediazides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives

Definitions

• the present invention relates to a quinonediazide-based photosensitizer solution having excellent temporal stability and a positive resist composition in which precipitation of the quinonediazide-based photosensitizer is suppressed.
• Positive resist compositions in which an alkali-soluble resin such as a novolak resin is dissolved in an organic solvent and a crosslinking agent such as an epoxy resin, a quinonediazide-based photosensitizer, and the like are widely used in the semiconductor field and the electronic parts field .
• a positive resist composition is subjected to a foreign matter removal process in which foreign matters are separated into furnaces by a filter at the time of production.
• Patent Document 1 proposes thermally modify the quinonediazide photosensitizer.
• the quinonediazide-based photosensitizer when the quinonediazide-based photosensitizer is heat-denatured, although the problem of precipitation is reduced, it may be thermally decomposed during heat denaturation, and the photosensitivity as the photosensitizer may be reduced.
• the quinonediazide-based photosensitizer is handled as a powdered solid, and there is a problem that it is difficult to dissolve in the composition when preparing a positive resist composition.
• the present invention is intended to solve the above-described conventional problems, and can suppress or prevent the precipitation of a quinonediazide-based photosensitizer from a positive resist composition without performing heat denaturation treatment. It is an object of the present invention to facilitate the dissolution of a quinonediazide-based photosensitizer in a positive resist composition when preparing a resist composition.
• the present inventor can suppress or prevent the precipitation of the quinone diazide photosensitizer by allowing the quinone diazide photosensitizer to coexist with the quinone diazide photosensitizer. It has been found that even in a solution in which a compound is dissolved, precipitation of a quinonediazide photosensitizer can be suppressed or prevented, and such a solution can be easily mixed with a positive resist composition, and the present invention has been completed.
• the present invention relates to a quinonediazide photosensitizer solution in which a quinonediazide photosensitizer is dissolved in an organic solvent, which contains a thiol compound as a quinonediazide photosensitizer precipitation inhibitor, Provide a solution.
• the present invention also provides a positive resist composition containing an alkali-soluble resin, a crosslinking agent, a quinonediazide photosensitizer, and an organic solvent, and further comprising a thiol compound as a precipitation inhibitor for the quinonediazide photosensitizer.
• a positive resist composition is provided.
• the present invention is a method for suppressing or preventing the precipitation of a quinone diazide photosensitizer from a positive resist composition containing an alkali-soluble resin, a crosslinking agent, a quinone diazide photosensitizer, and an organic solvent
• a method for suppressing or preventing quinonediazide-based photosensitizer deposition which comprises adding a thiol compound as a quinonediazide-based photosensitizer precipitation inhibitor to a positive resist composition.
• quinonediazide photosensitizer solution or positive resist composition of the present invention a quinonediazide photosensitizer and a thiol compound coexist. For this reason, precipitation of a quinonediazide type photosensitizer can be suppressed or prevented in a quinonediazide type photosensitizer solution or a positive resist composition.
• the quinonediazide photosensitizer solution of the present invention is obtained by dissolving a quinonediazide photosensitizer in an organic solvent and further containing a thiol compound as a precipitation inhibitor. Thereby, precipitation of a quinonediazide type photosensitizer can be suppressed or prevented.
• a thiol compound is used as an anti-precipitation agent for a quinonediazide photosensitizer.
• the thiol compound is an aromatic or aliphatic compound having one or more, preferably two or more thiol groups in the molecule.
• bismuthiol (chemical structural formula (A): MTD, Tokyo Chemical Industry Co., Ltd.) ), 2-methylthio-5-mercaptothiadiazole (chemical structural formula (B): M1384, Tokyo Chemical Industry Co., Ltd.), pentaerythritol-tetrakis-mercaptopropionate (chemical structural formula (C): PEMPII, Sakai Chemical Co., Ltd.) )), Pentaerythritol-tetrakis-mercaptobutyrate (chemical structural formula (D): MTPE1, Showa Denko KK), 2-dibutylamino-4,6-dithio-s-triazine (chemical structural formula (E): Zisnet-DB, Sankyo Kasei Co., Ltd.). Two or more of these may be used in combination. Among these, bismuth thiol having the highest precipitation suppression or prevention effect can be preferably used.
• the content of the thiol compound as a quinonediazide photosensitizer precipitation inhibitor is too small, the effect of suppressing or preventing the precipitation of the quinonediazide photosensitizer is insufficient.
• quinonediazide photosensitizers conventionally used as photosensitizers for positive resist compositions can be used.
• diazonaphthoquinone DNQ
• 1,2- Ester compounds of naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid and low-molecular aromatic hydroxy compounds such as 2,3,4-trihydroxybenzophenone
• Examples include 1,3,5-trihydroxybenzene, 2,3,4,4′-tetrahydroxybenzophenone, 2- and 4-methylphenol, esters with 4,4′-hydroxypropane, and the like.
• Particularly preferred quinonediazide photosensitizers include naphthoquinonediazide derivatives.
• specific examples of the naphthoquinone diazide derivative include naphthoquinone diazide derivatives represented by the following chemical structural formulas (F), (G), and (H). Two or more of these can be used in combination.
• the naphthoquinone diazide derivative of the chemical structural formula (G) can be preferably used from the viewpoint of high sensitivity.
• the content of the quinonediazide photosensitizer in the quinonediazide photosensitizer solution of the present invention varies depending on the type of organic solvent used, but if it is too small, it will be difficult to form a pattern as a photoresist. Therefore, the amount is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the resist solid content.
• organic solvent used in the quinonediazide-based photosensitizer solution of the present invention various aromatic hydrocarbons, aliphatic or alicyclic esters, polyethers, and the like can be appropriately used. From this viewpoint, it is preferable to use ⁇ -butyrolactone or triglyme. In addition, you may use an organic solvent in mixture of 2 or more types.
• a quinonediazide-based photosensitizer and a thiol compound as an anti-precipitation agent are charged into an organic solvent, and preferably the mixture is heated at a temperature not higher than the thermal decomposition temperature of the quinonediazide-based photosensitizer for 1 hour.
• it can prepare by stirring using stirring apparatuses, such as a ball mill, and dissolving them in an organic solvent.
• the obtained quinonediazide photosensitizer solution may be further subjected to a filtration treatment in order to remove insoluble matters.
• the quinonediazide photosensitizer solution thus obtained can be preferably used as a photosensitizer for a positive resist composition.
• This positive resist composition is a positive resist composition containing an alkali-soluble resin, a crosslinking agent, a quinonediazide-based photosensitizer, and an organic solvent, and further includes a thiol as a precipitation inhibitor for the quinonediazide-based photosensitizer. It contains a compound. Therefore, the positive resist composition of the present invention suppresses or prevents the quinonediazide photosensitizer from precipitating during storage.
• the positive resist composition of the present invention is basically composed of a conventional positive resist composition (component types, ratios thereof, etc.) except that it contains a thiol compound as a quinonediazide-based photosensitizer precipitation inhibitor.
• a crosslinking agent that does not substantially react with the thiol compound. Therefore, although it is not impossible, it is preferable to avoid the use of an epoxy-based crosslinking agent that may react with the thiol compound.
• the kind of quinonediazide-based photosensitizer and the thiol compound that is a precipitation inhibitor thereof are as described in the quinonediazide-based photosensitizer solution of the present invention.
• the amount of the thiol compound in the positive resist composition is determined according to the amount of the quinone diazide photosensitizer as in the case of the quinone diazide photosensitizer solution, and the amount of the quinone diazide photosensitizer will be described later. It is determined by the blending amount of the alkali-soluble resin.
• the amount of the quinonediazide-based photosensitizer in the positive resist composition is too small, pattern formation may be difficult, and if it is too large, the physical properties of the film may be lowered.
• it is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass.
• alkali-soluble resin constituting the positive resist composition of the present invention examples include phenol novolac resins, cresol novolac resins, alkali-soluble polyimide resins, polybenzoxazole precursors, and the like.
• the crosslinking agent can be selected from diamines, polyisocyanates, benzoxazines, resoles and the like according to the type of alkali-soluble resin. If the blending amount of the crosslinking agent is too small, the film physical properties may be lowered, and if it is too much, the photosensitivity may be lowered. Therefore, the amount is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. 30 parts by mass, more preferably 1 to 10 parts by mass.
• Examples of the organic solvent constituting the positive resist composition of the present invention include toluene, ⁇ -butyrolactone, triglyme, diglyme, methyl benzoate, ethyl benzoate, N-methylpyrrolidone, N, N-dimethylacetamide, N, N— Examples include dimethylformamide. Of these, ⁇ -butyrolactone and triglyme having good printability can be preferably used.
• the amount of the organic solvent used is usually preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass with respect to 100 parts by mass of the resist solid content.
• the positive resist composition of the present invention can be prepared by uniformly mixing an alkali-soluble resin, a crosslinking agent, a quinonediazide-based photosensitizer, an organic solvent, and a thiol compound by a conventional method.
• the quinonediazide photosensitizer and the thiol compound may be dissolved in a part of an organic solvent in advance to obtain a quinonediazide photosensitizer solution, and the solution and other components may be mixed.
• the quinonediazide-based photosensitizer solution and the positive resist composition of the present invention have been described above.
• the present invention also has an aspect as a method for suppressing or preventing quinonediazide-based photosensitizer precipitation described below. This method is also encompassed by the present invention.
• one aspect of the present invention is a method for suppressing or preventing precipitation of a quinone diazide photosensitizer from a positive resist composition containing an alkali-soluble resin, a crosslinking agent, a quinone diazide photosensitizer, and an organic solvent.
• a quinonediazide-based photosensitizer deposition inhibiting or preventing method comprising blending a thiol compound as a quinonediazide-based photosensitizer precipitation inhibitor into a positive resist composition.
• a quinonediazide photosensitizer solution obtained by dissolving a quinonediazide photosensitizer and a thiol compound as an anti-precipitation agent in an organic solvent is used. Can do.
• Comparative Example 1 an example in which no thiol compound was blended, as Comparative Example 2, in which a compound of the chemical structural formula (I) (CDA-10, ADEKA Co., Ltd.) was blended instead of a thiol compound, An example in which a compound of the structural formula (J) (BF-BXZ, Konishi Chemical Co., Ltd.) is blended in place of the compound is shown.
• the obtained solution was continuously stirred at room temperature, and the number of days on which the photosensitive agent was deposited on the inner wall of the container was examined visually.
• the obtained results are shown in Table 1. When no precipitation is observed for 7 days or more, it can be evaluated that there is no precipitation.
• Example 2 Compared to the case of Comparative Example 1 in which the thiol compound was not blended, in the case of Example 2 in which the monothiol compound was blended, the number of days in which precipitation occurred was 2 to 4 days, and the precipitation suppression effect was sufficiently confirmed. . In Examples 1 and 3 to 5 containing a dithiol compound, no quinonediazide-based photosensitizer was observed even after 7 days.
• Example 6 the precipitation inhibitory effect by the addition amount of bismuthiol was investigated. That is, as shown in Table 2, 10 g of a naphthoquinonediazide photosensitizer (4NT-300, Toyo Gosei Co., Ltd.) having a chemical structural formula (G), 10 g of ⁇ -butyrolactone, and a thiol having a chemical structural formula (A)
• the compound (bismuthiol) 0.25 g, 0.5 g, or 1 g was stirred with a ball mill at room temperature for half a day and dissolved uniformly.
• the obtained solution was continuously stirred at room temperature, and the number of days that the photosensitizer was deposited on the inner wall of the container was examined visually.
• Table 2 The obtained results are shown in Table 2.
• Example 7 it was tested whether a photosensitizer other than 4NT-300 also exhibited the effect of suppressing the precipitation of bismuththiol from the viewpoint of water content. That is, as shown in Table 3, 10 g of a naphthoquinone diazide photosensitizer of chemical structural formula (G) or (H), 10 g of ⁇ -butyrolactone, and 1 g of thiol compound (bismuthiol) of chemical structural formula (A) are added at room temperature. Then, the mixture was stirred for half a day with a ball mill and dissolved uniformly. The obtained solution was continuously stirred at room temperature, and the number of days that the photosensitizer was deposited on the inner wall of the container was examined visually. The obtained results are shown in Table 3.
• G * 1 Photosensitizer of chemical structural formula (G) (4NT-300, Toyo Gosei Co., Ltd.)
• G * 2 Photosensitizer with chemical structural formula (G) (DTEP-300, Daitokemix Co., Ltd.)
• G * 3 Photosensitizer with chemical structural formula (G) (DTEP-250, Daitokemix Co., Ltd.)
• H * 1 Photosensitizer of chemical structural formula (H) (4C-PA-280, Daito Chemix Co., Ltd.)
• G * 1 , G * 2, and G * 3 have the same chemical structural formula, but different manufacturers. 4NT-300 and DTEP-300 are considered equivalent. Further, G * 2 has a higher naphthoquinonediazosulfonyl group substitution (tetra-substituted product) ratio than G * 3 .
• the quinonediazide photosensitizer solution or positive resist composition of the present invention a quinonediazide photosensitizer and a thiol compound coexist. For this reason, precipitation of a quinonediazide type photosensitizer can be suppressed or prevented in a quinonediazide type photosensitizer solution or a positive resist composition. Therefore, the quinonediazide-based photosensitizer solution or positive resist composition of the present invention has excellent storage stability and is particularly useful for the production of electronic components.

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2009
  • 2009-11-10 JP JP2009256813A patent/JP5593678B2/ja active Active
• 2010
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