WO2000060416A1 - Composition de resine sensible au rayonnement - Google Patents
Composition de resine sensible au rayonnement Download PDFInfo
- Publication number
- WO2000060416A1 WO2000060416A1 PCT/JP2000/001259 JP0001259W WO0060416A1 WO 2000060416 A1 WO2000060416 A1 WO 2000060416A1 JP 0001259 W JP0001259 W JP 0001259W WO 0060416 A1 WO0060416 A1 WO 0060416A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- radiation
- novolak
- resin composition
- molecular weight
- Prior art date
Links
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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
- G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
-
- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- 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
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
-
- 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
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
-
- 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
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
Definitions
- the present invention relates to a novel radiation-sensitive resin composition, and more particularly, to a semiconductor production, a production of a panel display surface of an LCD (Liquid Crystal Display), a production of a circuit board such as a thermal head, and the like. And a radiation-sensitive resin composition containing a soluble novolak resin.
- photolithography has traditionally been used to form or process fine elements.
- Lithography One technique is used.
- a positive or negative radiation-sensitive resin composition is used to form a resist pattern.
- the most widely used positive-type radiation-sensitive resin composition is a composition containing an alkyne soluble resin and a quinonediazide compound as a photosensitive agent.
- This composition is, for example, a system using a novolak resin and a quinonediazide compound as disclosed in Japanese Patent Publication No. 54-23570 (U.S. Pat. No.
- JP-B-56-38050 U.S. Pat. No. 4,115,128, JP-A-55-73045, JP-A-61-
- Many publications such as Japanese Patent No. 205593, Japanese Patent Application Laid-Open No. Sho 62-51959, describe various compositions: These compositions containing a novolak resin and a quinone diazide compound are: Until now, novolak resin and photosensitive agent R & D has been carried out from both sides. From the viewpoint of novolak resins, not only new resins have been developed, but also photosensitive resins having excellent properties have been obtained by improving the physical properties of conventionally known resins. For example, Japanese Patent Application Laid-Open Nos. Sho 60-140235 and JP-A-Heisei 1105243 disclose excellent characteristics by providing a novolak resin with a specific molecular weight distribution. There is disclosed a technique for providing a radiation-sensitive resin composition having the following.
- JP-A-57-86831, JP-A-60-23036 and JP-A-3-230164 disclose low molecular weight by solvent separation.
- the resin component is separated, in this method, not only the monomer and dimer components but also the medium molecular weight components in the resin are separated at the same time, which causes a reduction in sensitivity.
- a method to prevent this a method in which an alkali-soluble resin whose weight average molecular weight has been reduced in advance can be considered as a solvent, but with such an alcohol-soluble resin, although sufficient sensitivity can be obtained, the remaining The film ratio and heat resistance were poor, making it very difficult to obtain a radiation-sensitive resin composition having the above properties in a well-balanced manner.
- a thin-film distillation method is already known as a compound separation method.
- This thin-film distillation method is a method in which a thin film of an object to be distilled is formed on a heat transfer dish or the like by a mechanical centrifugal force, an inertial force, a dispersing device, or the like, and distillation is performed. is there.
- thin-film distillation methods include a method for producing a polyhydroxy compound, which is a raw material of an epoxy resin (Japanese Patent Laid-Open No. 10-87538), and a method for purifying xylenol (Czechoslovakia Inventor's Certificate 23977). No.
- Japanese Patent Application Laid-Open No. 7-36218 Japanese Patent Application Laid-Open No. 7-36218
- Japanese Patent Application Laid-Open No. 3-230164 mentioned above also mentions that a low molecular weight component of a novolak resin can be removed by a thin film distillation method, but it is considered that this is equivalent to a solvent separation treatment method. It is merely an example, and there is no specific description of the processing conditions, etc., and it shows only the possibility and does not indicate that the thin film distillation method is more than the solvent fractionation method.
- the present invention does not have the above-mentioned drawbacks, and is excellent in all of the characteristics required for photo-resist, such as sensitivity, resolution, pattern shape, heat resistance, etc., and furthermore, has a good balance of these characteristics. It is intended to provide a conductive resin composition. Disclosure of the invention
- the present inventors have conducted intensive studies and studies, and as a result, have found that alkaline soluble resins
- a novolak resin is used as an alkali-soluble resin, and the novolak resin is treated by a thin-film distillation method to obtain monomers in the resin.
- the present invention has been accomplished by finding that the above object can be achieved by partially and selectively removing the monomer and the dimer so that the amount of the dimer falls within a predetermined range.
- the present invention provides a radiation-sensitive resin composition containing a photosensitive agent containing an alkali-soluble resin and a quinonediazide group, wherein the resin is a novolak resin treated by a thin-film distillation method.
- the present invention relates to a radiation-sensitive resin composition.
- FIG. 1 is an explanatory diagram illustrating a high molecular area A, a medium molecular area B, a monomer, and a dimer area C of a novolak resin according to a GPC chart.
- FIG. 2 is a GPC chart and a peak table of the raw material novolak resin A-1.
- FIG. 3 shows a GPC chart and a peak table of Novolac resin A-2 obtained by subjecting the raw material novolak resin A-1 to thin-film distillation.
- FIG. 4 shows a GPC chart and a peak table of novolak resin A-3 obtained by treating raw material novolak resin A-1 by a solution fractionation method.
- the novolak resin used in the present invention is a novolak type phenol resin obtained by polycondensation of various phenols alone or a mixture of plural kinds thereof with aldehydes such as formalin. Monomer and dimer content reduced by thin film distillation It is removed so that it falls within a predetermined range.
- the novolak resin treated by the thin film distillation method is a polymer region of a pattern obtained by gel permeation chromatography (GPC) using a detector at 280 nm.
- the area ratio is C 2 / (A 2 + B 2 + C 2) ⁇ 0. 0 6 0, i.e. monomer 'before and after the treatment of the area ratio of the molecular weight region in the above trimmer also only dimer content of 6% or less, B 2 ZB ⁇ 0. 9 5 or more and medium molecular region Is preferably not substantially removed.
- the boundary value between the medium molecular region B and the high molecular region A is about 12,000 ⁇ 10% under predetermined GPC measurement conditions.
- the boundary value between the middle molecular region B containing the trimer and the monomer's monomer region C is about 160 ⁇ 10%, which was measured using a 28-nm detector of novolak resin. No, obtained by GPC.
- the ranges indicated by A, B, and C in FIG. 1 correspond to the high molecular region, the medium molecular region, and the monomer-dimer region of the novolak resin, respectively.
- the molecular weight of the novolak resin after the treatment is preferably from 2,000 to 2,500, in terms of polystyrene equivalent weight average molecular weight.
- the weight average molecular weight of Noporakku resin after thin film distillation treatment is 2, 0 0 0 smaller than film retention and coatability pattern Ichin decreases, 2 5, 0 0 0 by weight, the sensitivity you decrease c
- the dissolution rate of the novolak resin treated by the thin film distillation method in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide is preferably 100 AZ sec or more. If the dissolution rate of the novolak resin treated by the thin-film distillation method falls below 100 AZ s, the decrease in sensitivity will be large. It is difficult to use for practical use because the pattern forming ability is reduced or the alkaline development time is long, and the heat resistance tends to deteriorate when a low molecular compound is added in order to prevent such a problem.
- the monomer and the dimer are separated by a thin film distillation method so that the medium molecular weight region is not removed, so that a solvent separation treatment such as that disclosed in Japanese Patent Application Laid-Open No. 3-230164 is used.
- a solvent separation treatment such as that disclosed in Japanese Patent Application Laid-Open No. 3-230164 is used.
- this decrease in sensitivity can be prevented by adding a low-molecular compound as a dissolution promoter, but heat resistance will be reduced if the addition amount is too large. It is difficult to balance sensitivity and heat resistance.
- the alcohol-soluble novolak resin used as a raw material of the radiation-sensitive resin composition of the present invention is obtained, for example, by using at least one phenol and an aldehyde such as formalin with oxalic acid as a catalyst. It may be produced by any conventionally known method such as a method of polycondensation.
- phenols used for producing this soluble novolak resin include olesols such as o-cresole, p-cresole, and m-cresol; —Xylenol, 2,5 —xylenol, 2,3-xylenol, 3,4-xylenol, etc., 2,3,4 — trimethylphenol, 2,3,5 —trimethylphenol, 2 , 4,5—Trimethylenophenol, 3,4,5—Trimethylphenols such as trimethylinophenol, 2-t-butylphenol, 3-t-butylphenol, 4 — T-Butyl phenols such as t-butyl phenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxy Phenoenole, 2,3—Dimethoxyphenol, 2,5—Dimethoxyphenol, 3,5—Methoxyphenols such as dimethoxyphenol, 2-ethylfurenol, 3—Ethynolephenol, 4-Echinolephenol Nore, 2, 3-
- Parahonolemaldehyde, acetate aldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde and the like can be used alone or as a mixture of plural kinds.
- the residence time of the novolak resin is controlled by a thin-film distillation apparatus such as a centrifugal thin-film distillation apparatus under the conditions of a pressure of 5 to 10 Torr (Torr) and a temperature of 260 to 280 ° C, Mainly removes monomer and dimer components.
- a thin-film distillation apparatus such as a centrifugal thin-film distillation apparatus under the conditions of a pressure of 5 to 10 Torr (Torr) and a temperature of 260 to 280 ° C, Mainly removes monomer and dimer components.
- Torr Torr
- the thin-film distillation method has conventionally been applied to various polymer systems for the purpose of removing unreacted monomers, low-molecular-weight substances, volatile components, and the like. It is the same as the method in principle.
- the monomer of the novolak resin after treatment Dimer content was below 6%, yet it will control port Lumpur to not Rubeku such a trimmer or more sediment Goma removal, i.e. before and after processing of the area ratio of the molecular weight region in the above trimer, 8 2 8 1 0.95 or more is desirable for achieving the object of the present invention.
- any of the known sensitizers conventionally used in quinonediazide-novolak resists can be used.
- an acid halide such as naphthoquinonediazide sulfonic acid chloride and benzoquinonediazide sulfonic acid chloride, and a functional group capable of undergoing a condensation reaction with these acid halides are used as the photosensitive agent.
- Compounds obtained by reacting a low-molecular compound or a high-molecular compound having the compound are preferred.
- examples of the functional group that can be condensed with an acid halide include a hydroxyl group and an amino group, and a hydroxyl group is particularly preferable.
- Examples of the compound containing a hydroxyl group condensable with an acid halide include, for example, hydroquinone, resonolecin, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone. , 2,4,6—Trihydroxybenzophenone, 2,4,4'Trihydroxybenzophenone, 2,3,4,4, tetrahydrobenzobenzopheno 2,2 ', 4,4'tetrahydroxybenzophenone, 2,2', 3,4,6'-Hydroxybenzophene such as pentahydroxybenzobenzophenone Nonionics, bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) prononone, etc.
- Phenoinoalkanes 4, 4 ', 3 ", 4" Tetrahydroxy 3, 5, 3 ', 5' - Te door Ramechiru door Li Fuenirume data down, 4, 4 ', 2 ", 3", 4 "A penta human Dorokishi 3, 5, 3', 5 ' And hydroxytriphenylmethanes such as tetramethyltriphenylmethane. These may be used alone or in combination of two or more.
- the amount of the sensitizer containing a quinonediazide group is usually 550 parts by weight, preferably 100 parts by weight, per 100 parts by weight of the alkali-soluble resin.
- the novolak resin of the present invention may be a photosensitive novolak resin.
- a photosensitive novolak resin can be obtained by reacting the above-described soluble novolak resin with a photosensitive agent containing a quinonediazide group, and substituting the hydroxyl group of the novolak resin.
- Examples of the solvent for dissolving the radiation-sensitive resin composition of the present invention include ethylene glycol mono-monoethyl ether ethers, ethylene glycol mono-monoethyl ether ethers, and the like; Guriko Norre mono-methylol Norre ether Roh rare Sete over door, ethylene glycol mono ⁇ Norre kill ether Roh rare Sete over bets such as ethylene Gris Kono Les mono E Chino Les er Teruasete door, professional Pirenguri Kono Les mono-methylol Norre ether Norre, off: (B) Pyrene glycol, such as propylene glycol monolenoethyl ether ethers, etc., propylene glycol, such as propylene glycol cornolemonomethine oleate acetate, propylene glycol, etc.
- Noalkyl Lactic esters such as teracetates, methyl lactate, and ethyl lactate; aromatic hydrocarbons such as toluene and xylene; ketones such as methylethyl ketone, 2-butanone, and cyclohexanone; N, N-dimethylacetamide And amides such as N-methylpyrrolidone and ratatones such as ⁇ -butyrolataton.
- These solvents can be used alone or as a mixture of two or more:
- the radiation-sensitive resin composition of the present invention may contain, if necessary, a conventional radiation-sensitive resin.
- a dye, an adhesion aid, a surfactant and the like used as additives of the composition can be arbitrarily compounded.
- the dye include methyl violet, crystal violet, and malachite green
- examples of the adhesion aid include alkyl imidazoline, butyric acid, alkyl acid, polyhydroxystyrene, and polyvinyl methyl.
- surfactants include ethers, t-platinolenovolac, epoxysilanes, epoxy polymers, and silanes.
- Examples of surfactants include polyglycols such as polypropylene dalicol or polyoxyethylene diaryl ether and the like.
- Derivative nonionic surfactants fluorinated surfactants such as Florard (trade name, manufactured by Sumitomo 3M), Megafac (trade name, manufactured by Dainippon Ink and Chemicals, Inc.), Sulfuron (trade name, Asahi Glass) Organic siloxane surfactants, such as KP 3 4 1 (trade name, Shin-Etsu Chemical Co., Ltd.) ), And the like.
- fluorinated surfactants such as Florard (trade name, manufactured by Sumitomo 3M), Megafac (trade name, manufactured by Dainippon Ink and Chemicals, Inc.), Sulfuron (trade name, Asahi Glass)
- Organic siloxane surfactants such as KP 3 4 1 (trade name, Shin-Etsu Chemical Co., Ltd.) ), And the like.
- the radiation-sensitive resin composition of the present invention may be made of an inorganic antireflection film such as TIN, SIN, or SION, or AZ® BARL i®, AZ® BARL i® II (all manufactured by Clarianto Japan). ) Can be used in combination with an organic antireflection film.
- an inorganic antireflection film such as TIN, SIN, or SION, or AZ® BARL i®, AZ® BARL i® II (all manufactured by Clarianto Japan).
- the radiation-sensitive resin composition of the present invention is applied, for example, by spin coating on a silicon wafer substrate provided with an antireflection film.
- the radiation-sensitive resin film is formed on the substrate.
- the substrate on which the radiation-sensitive resin film is formed is exposed to radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and electron beams, and then developed with an alkaline developer to obtain a high-resolution, favorable pattern shape.
- a positive resist pattern is formed.
- m-Resole 58.6 g, p-Resole 42.8 g, 2,5-xylenol 15.8 g, 2,4-xylenole 6.lg, 37% formaldehyde 8.5 g of aqueous solution and 0.986 g of oxalic acid were placed in a 1 liter separable flask equipped with a stirrer, condenser and thermometer, and stirred at 95 to 100 ° C for 5 hours. Reacted. Thereafter, water and unreacted monomer are distilled off over 1 hour while heating to 180 ° C, and further reduced to 1 OmmHg while heating to 195 ° C, and water and unreacted monomers are removed.
- the temperature was returned to around room temperature to recover the nopolak resin.
- the obtained novolak resin A-1 was subjected to gel permeation.chromatography (GPC) at a detection wavelength of 28 O nm under the following “conditions for measuring the molecular weight of nopolak resin”. Obtained. From these measurement results, the weight-average molecular weight (Mw) of the novolak resin A-1 is 10,900, and the area ratio of the molecular regions A], B, and C] is 0.267: 0. 6 35: 0.098.
- the weight average molecular weight (Mw) of the novolak resin A-2 was 14,800, and the area ratio of the molecular weight regions A 2 , B 2 , and C 2 was 0.304: 0 6 4 1: 0.05 5
- 1,2-naphthoquinonediazido 5-sulfonic acid chloride is 3 mole equivalent And dissolved to a 10% concentration.
- 1,1-naphthoquinonediazide — 1.1 mole equivalent of trisulfonic acid chloride of 5-sulfonic acid chloride was added dropwise over 1 hour and stirred for 30 minutes. did.
- the precipitated triethylamine hydrochloride was separated by filtration and poured into a 0.1-fold aqueous solution of 0.1 N hydrochloric acid of the reaction solution. The precipitated solid was filtered, washed with ultrapure water, and dried under vacuum to obtain a naphthoquinonediazidesulfonic acid ester compound B-1 as a photosensitizer.
- Example 1 Comparative Examples 1-2
- the novolak resins A-1 to A-3 and the photosensitizer B-1 obtained in the synthesis examples were mixed in the proportions shown in Table 1 below, respectively, and the surfactant Megafac R-08 (Dai Nippon Ink Chemical Industry) was dissolved in PGMEA. Next, this solution was filtered through a 0.5 ⁇ membrane Teflon filter to obtain radiation-sensitive resin compositions of Example 1, Comparative Examples 1 and 2.
- Each of these radiation-sensitive resin compositions was applied to a 4-inch silicon wafer treated with HMDS (hexamethyldisilazane) by a spin coater (LAR CULTI MA—100,000) manufactured by Lithotech Japan Co., Ltd. C, for 90 seconds, the pre-beta was run on a hot plate, and prepared so as to obtain a resist film of 1.5 ⁇ m.
- the film thickness was measured with a film thickness measuring device (Lambda Ace) manufactured by Dainippon Screen.
- Al force Li developer [AZ® 3 0 0 MIF-development par, 2.3 8 wt 0/0 hydroxide Te tetramethyl ammonium Niu anhydrous solution] 2 3. It was developed by the paddle method for 60 seconds under the condition of C to obtain a resist pattern. After that, the film thickness was measured again.
- the sensitivity, residual film ratio, and heat resistance in the table were evaluated as follows.
- the wafer on which a 1 ⁇ ⁇ ⁇ ⁇ line-and-space (LZS) pattern was formed was heated on a hot plate for 120 seconds while changing the temperature.
- the cross-sectional shape of the line pattern was observed by S ⁇ , and the point where the top of the resist pattern became round was defined as the heat resistance temperature.
- Example 1 ⁇ -2 100 183 B-1 22.5 40.9 51.6 99.1 130 1.01 0.055 Comparative Example 1 A-1 100 415 B-1 22.5 3.1 3.9 58.7 115 0.098 Comparative Example 2 ⁇ - :? 100 95 B 1 22.5 59.2 70.2 98.9 130 0.90 0.055
- the monomer and dimer in the novolak resin are selectively removed by a thin-film distillation method so as to fall within a predetermined range, thereby preventing a decrease in the remaining film ratio and preventing the novolak resin from being removed by a solvent separation method.
- a radiation-sensitive resin composition having well-balanced characteristics could be obtained without lowering the sensitivity.
- the radiation-sensitive resin composition of the present invention is excellent in various properties required for photo resists, such as sensitivity, pattern, heat resistance, and the like, and these properties are well-balanced.
- the radiation-sensitive resin composition of the present invention is extremely useful as a resist material for producing semiconductors such as LSI, producing display surfaces for LCD panels, and producing circuit boards such as thermal heads.
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00906656A EP1085378A4 (en) | 1999-04-02 | 2000-03-03 | RADIATION SENSITIVE RESIN COMPOSITION |
US09/701,851 US6384103B1 (en) | 1999-04-02 | 2000-03-03 | Radiation-sensitive resin composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11/96352 | 1999-04-02 | ||
JP9635299A JP4068260B2 (ja) | 1999-04-02 | 1999-04-02 | 感放射線性樹脂組成物 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000060416A1 true WO2000060416A1 (fr) | 2000-10-12 |
Family
ID=14162614
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/001259 WO2000060416A1 (fr) | 1999-04-02 | 2000-03-03 | Composition de resine sensible au rayonnement |
Country Status (8)
Country | Link |
---|---|
US (1) | US6384103B1 (ja) |
EP (1) | EP1085378A4 (ja) |
JP (1) | JP4068260B2 (ja) |
KR (1) | KR100705302B1 (ja) |
CN (1) | CN1226669C (ja) |
MY (1) | MY122637A (ja) |
TW (1) | TWI250380B (ja) |
WO (1) | WO2000060416A1 (ja) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10084285T1 (de) * | 1999-12-27 | 2002-04-11 | Polyplastics Co | Flammwidrige Harzzusammensetzung |
JP4554122B2 (ja) * | 2001-08-06 | 2010-09-29 | 東京応化工業株式会社 | 化学増幅型ポジ型液晶素子用レジスト組成物 |
KR100512171B1 (ko) * | 2003-01-24 | 2005-09-02 | 삼성전자주식회사 | 하층 레지스트용 조성물 |
JP3977307B2 (ja) * | 2003-09-18 | 2007-09-19 | 東京応化工業株式会社 | ポジ型フォトレジスト組成物及びレジストパターン形成方法 |
JP4929733B2 (ja) * | 2005-01-28 | 2012-05-09 | 住友ベークライト株式会社 | ノボラック型フェノール樹脂の製造方法 |
US20170082923A1 (en) * | 2014-06-12 | 2017-03-23 | Dic Corporation | Photosensitive composition for permanent films, resist material and coating film |
JP6621233B2 (ja) * | 2014-07-25 | 2019-12-18 | 東京応化工業株式会社 | 有機el表示素子における絶縁膜形成用の感光性樹脂組成物 |
TWI678596B (zh) * | 2018-09-13 | 2019-12-01 | 新應材股份有限公司 | 正型光阻組成物及圖案化聚醯亞胺層之形成方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4918994A (ja) * | 1972-06-13 | 1974-02-19 | ||
US4812551A (en) * | 1986-11-08 | 1989-03-14 | Sumitomo Chemical Company, Limited | Novolak resin for positive photoresist |
US5019479A (en) * | 1986-03-28 | 1991-05-28 | Japan Synthetic Rubber Co., Ltd. | Positive type radiation-sensitive resin composition comprising a photosensitizer and a novolak resin |
JPH03230164A (ja) * | 1990-02-05 | 1991-10-14 | Toray Ind Inc | ポジ型フォトレジスト組成物 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5884814A (ja) * | 1981-11-17 | 1983-05-21 | Dainippon Ink & Chem Inc | ノボラツク型フエノ−ル系樹脂の製造法 |
US5753406A (en) * | 1988-10-18 | 1998-05-19 | Japan Synthetic Rubber Co., Ltd. | Radiation-sensitive resin composition |
CA2023791A1 (en) * | 1989-08-24 | 1991-02-25 | Ayako Ida | Radiation-sensitive positive resist composition |
US5132376A (en) * | 1989-09-08 | 1992-07-21 | Ocg Microelectronic Materials, Inc. | Process for selective removal of dimeric species from phenolic polymers |
-
1999
- 1999-04-02 JP JP9635299A patent/JP4068260B2/ja not_active Expired - Fee Related
-
2000
- 2000-03-03 WO PCT/JP2000/001259 patent/WO2000060416A1/ja not_active Application Discontinuation
- 2000-03-03 US US09/701,851 patent/US6384103B1/en not_active Expired - Fee Related
- 2000-03-03 KR KR1020007013598A patent/KR100705302B1/ko not_active IP Right Cessation
- 2000-03-03 EP EP00906656A patent/EP1085378A4/en not_active Withdrawn
- 2000-03-03 CN CNB008004498A patent/CN1226669C/zh not_active Expired - Fee Related
- 2000-03-17 MY MYPI20001049A patent/MY122637A/en unknown
- 2000-03-29 TW TW089105837A patent/TWI250380B/zh not_active IP Right Cessation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4918994A (ja) * | 1972-06-13 | 1974-02-19 | ||
US5019479A (en) * | 1986-03-28 | 1991-05-28 | Japan Synthetic Rubber Co., Ltd. | Positive type radiation-sensitive resin composition comprising a photosensitizer and a novolak resin |
US4812551A (en) * | 1986-11-08 | 1989-03-14 | Sumitomo Chemical Company, Limited | Novolak resin for positive photoresist |
JPH03230164A (ja) * | 1990-02-05 | 1991-10-14 | Toray Ind Inc | ポジ型フォトレジスト組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1085378A4 * |
Also Published As
Publication number | Publication date |
---|---|
US6384103B1 (en) | 2002-05-07 |
KR20010043974A (ko) | 2001-05-25 |
CN1226669C (zh) | 2005-11-09 |
CN1297542A (zh) | 2001-05-30 |
JP4068260B2 (ja) | 2008-03-26 |
KR100705302B1 (ko) | 2007-04-11 |
JP2000292919A (ja) | 2000-10-20 |
EP1085378A1 (en) | 2001-03-21 |
EP1085378A4 (en) | 2003-01-02 |
MY122637A (en) | 2006-04-29 |
TWI250380B (en) | 2006-03-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6475693B1 (en) | Positively photosensitive resin composition | |
EP0443820A2 (en) | Radiation-sensitive resin composition | |
JPH06345837A (ja) | 高度にオルソ−オルソ結合したノボラックバインダー樹脂および放射線感受性組成物中のその利用 | |
JP3039048B2 (ja) | ポジ型感放射線性レジスト組成物 | |
JP4068253B2 (ja) | ポジ型感光性樹脂組成物 | |
WO2000060416A1 (fr) | Composition de resine sensible au rayonnement | |
EP1614005A2 (en) | Photoresist compositions | |
JP2010033027A (ja) | ポジ型感放射線性樹脂組成物 | |
TW200307013A (en) | Novolak resin mixtures and photosensitive compositions comprising the same | |
JP2555620B2 (ja) | 感放射線性樹脂組成物 | |
JPH0648382B2 (ja) | 半導体デバイス製造用ポジ型感放射線性樹脂組成物 | |
JP3245207B2 (ja) | 感放射線性樹脂組成物 | |
JP3488332B2 (ja) | ポジ型ホトレジスト塗布液 | |
JP3076523B2 (ja) | ポジ型ホトレジスト組成物 | |
JP3373072B2 (ja) | ポジ型フォトレジスト組成物 | |
JP3028648B2 (ja) | ポジ型レジスト組成物およびパターン形成方法 | |
JP2005010215A (ja) | 1つの基板上に集積回路と液晶ディスプレイ部分が形成された基板製造用ポジ型ホトレジスト組成物およびレジストパターンの形成方法 | |
JP3503916B2 (ja) | ポジ型ホトレジスト組成物 | |
JPH05142770A (ja) | ポジ型フオトレジスト組成物 | |
JP2619050B2 (ja) | ポジ型感光性組成物 | |
JP2626468B2 (ja) | ポジ型感放射線性樹脂組成物 | |
JP3631289B2 (ja) | ポジ型ホトレジスト組成物 | |
JP2004045618A (ja) | ポジ型ホトレジスト組成物およびレジストパターンの形成方法 | |
JPH11255855A (ja) | アルカリ可溶性ノボラック樹脂 | |
JPS61144644A (ja) | ポジ型感放射線樹脂組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 00800449.8 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CN KR SG US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2000906656 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09701851 Country of ref document: US Ref document number: 1020007013598 Country of ref document: KR |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWP | Wipo information: published in national office |
Ref document number: 2000906656 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020007013598 Country of ref document: KR |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 2000906656 Country of ref document: EP |
|
WWR | Wipo information: refused in national office |
Ref document number: 1020007013598 Country of ref document: KR |