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
• • 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
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells

Definitions

• the present invention relates to a positive photoresist composition for producing an LCD and a method for forming a resist pattern.
• liquid crystal display elements that form a liquid crystal display part on a glass substrate
• they are relatively inexpensive and can form resist patterns with excellent sensitivity, resolution and shape.
• Positive photoresist materials comprising a nopolak resin-quinonediazide group-containing compound system used in the manufacture of semiconductor devices are often used.
• disc-shaped silicon wafers with a maximum diameter of 8 inches (about 200 mm) to 12 inches (about 300 mm) are used, whereas in the manufacture of LCDs, a minimum is used.
• a square glass substrate of about 36 OmmX 460 mm is used.
• the substrate on which the resist material is applied is, of course, different in terms of material and shape, but in terms of its size, the substrate used in the manufacture of semiconductor elements is used. Is very different.
• resist materials for manufacturing LCDs are required to be able to form a resist pattern having excellent characteristics such as shape and dimensional stability over a wide substrate surface.
• resist materials for LCD production are desired to be inexpensive in addition to the above-mentioned characteristics. ing.
• Patent Documents 1 to 6 There have been many reports as resist materials for LCD manufacturing (for example, Patent Documents 1 to 6 below).
• the resist materials described in Patent Literatures 1 to 6 are inexpensive and have excellent applicability, sensitivity, resolution, shape and dimensional stability for small substrates of, for example, about 36 Omm x 46 Omm.
• a resist pattern can be formed. Therefore, it can be suitably used for the purpose of manufacturing a relatively small LCD.
• the resolution is expressed by the following formula of the following equation:
• R is the resolution limit, is the proportionality constant determined by the resist, process, and image formation method, ⁇ is the wavelength of light used in the exposure process, and ⁇ is the numerical aperture of the lens]
• the resolution can be increased by using a light source having a short wavelength ⁇ or by using a high-speed exposure process.
• a light source having a short wavelength ⁇ instead of the g-line (436 nm) exposure used in conventional LCD manufacturing, photolithography technology using shorter-wavelength i-line (365 nm) exposure is used to increase resolution. Can be raised.
• next-generation LCD integrated circuits such as drivers, DACs (digital-to-analog converters), image processors, video controllers, and RAMs are mounted on a single glass substrate at the same time as the display.
• integrated circuits such as drivers, DACs (digital-to-analog converters), image processors, video controllers, and RAMs are mounted on a single glass substrate at the same time as the display.
• Technology is being actively developed for the high-performance LCDs that are formed, so-called “system LCDs” (Semiconductor FPD World 2001. 9, pp. 50-67).
• the integrated circuit part is formed on the substrate in addition to the display part. Therefore, the substrate tends to be larger. Therefore, it is desirable to perform exposure under a lower NA condition than in normal LCD manufacturing.
• the pattern size of the display portion is about 2 to 10 m
• the integrated circuit portion is formed with a fine size of about 0.5 to 2.0 m. . Therefore, it is preferable to simultaneously form the display portion and the integrated circuit portion having different pattern dimensions under the same exposure condition, and to set the linearity [the same exposure condition (different mask size on the reticle but the same exposure light amount)].
• a resist material that excels in the characteristics of accurately reproducing a resist pattern corresponding to different mask dimensions on a reticle when exposed at a higher resolution than conventional resist materials for LCD manufacturing is desired.
• Patent Literature 6 Japanese Patent Application Laid-Open No. 2001-75272 describes a liquid crystal resist containing a soluble resin and a photosensitive component, but not containing a sensitizer.
• this liquid crystal resist had problems such as being unsuitable for i-line exposure, difficulty in forming a resist pattern of 2.0 or less required for manufacturing system LCDs, and lacking linearity.
• the present invention has excellent linearity under low NA
• the display part and the finer resist pattern of the integrated circuit part can be simultaneously obtained in a good pattern shape. It is an object of the present invention to provide a resist material and a method for forming a resist pattern which are suitable as the above.
• a positive photoresist composition for an LCD comprises (A) an alkali-soluble nopolak which can be synthesized by a condensation reaction of a phenol containing 3,4-xylenol with an aldehyde. (C) a phenolic hydroxyl group-containing conjugate having a molecular weight of 1000 or less,
• This positive photoresist composition for LCD is preferable as a positive photoresist composition for LCD for an i-ray exposure process.
• a positive photoresist composition for an LCD having an NA of 0.3 or less for an exposure process.
• a positive photoresist composition for LCD for producing LCD in which an integrated circuit and a liquid crystal display portion are formed on one substrate.
• the system LCD refers to “LCD in which an integrated circuit and a liquid crystal display portion are formed on one substrate”.
• the method for forming a resist pattern of the present invention comprises:
• the resist film after the heat treatment is subjected to a development treatment using an alkaline aqueous solution, and a resist pattern for an integrated circuit having a pattern size of 2.0 m or less is formed on the substrate. Simultaneously forming a resist pattern for the liquid crystal display part of
• FIG. 1 shows a positive photoresist composition applied to a glass substrate, baked, dried, and exposed to a pattern for evaluation of linearity under low NA conditions.
• FIG. 5 is an explanatory view showing that liquid is pooled from a substrate end portion X to a substrate end portion Z.
• the component (A) is an alkali-soluble resin component containing an alkali-soluble nopolak resin which can be synthesized by a condensation reaction between a phenol containing 3,4-xylenol and an aldehyde.
• a nopolak resin having excellent linearity and suitable as a resist material for a system LCD can be obtained.
• the heat resistance is good. If the heat resistance of the positive photoresist composition is good, the dimensions of the resist pattern after the heat treatment step Suitable for LCD because of low change rate, and suitable for system LCD because the rectangular shape of the resist pattern is good for forming integrated circuits.
• the lower limit of the proportion of 3,4-xylenol in the phenols is at least 5 mol%, preferably at least 7 mol%, and the upper limit is at most 40 mol%, preferably at most 30 mol%, more preferably 20 mol% or less. By setting the lower limit or more, a good effect can be obtained.
• the content of 3,4-xylenol in the phenols may be 100 mol%, but if the amount of 3,4-xylenol is too large, the sensitivity may decrease. It is preferable that it is not more than the upper limit.
• phenols one or more arbitrarily selected from those generally used as a nopolak resin material for a positive photoresist composition may be used in addition to 3,4-xylenol. be able to.
• examples thereof include phenols such as m-cresol, ⁇ -cresol, xylenol other than 3,4-xylenol, and trimethylphenol, and among them, m-cresol is preferable in terms of improving sensitivity.
• a positive photoresist composition for LCD In the case of a positive photoresist composition for LCD, a high sensitivity of, for example, about 5 OmJ is considered preferable from the viewpoints of improvement in production efficiency, throughput, and the like. Satisfying things are easily obtained.
• 3,4-xylenol When 3,4-xylenol is combined with phenols other than 3,4-xylenol, the content of 3,4-xylenol is 5 to 30 mol%, preferably 7 to 20 mol%. It is preferable because the effect of phenols other than 3,4-xylenol can be exerted while maintaining the effect of 3,4-xylenol.
• the lower limit or more is effective in terms of resolution and linearity under low NA conditions. Further, heat resistance is also improved, which is preferable in terms of suppressing scum. It is preferable from the viewpoint of sensitivity that the content is not more than the upper limit.
• the proportion of m-cresol in the phenols is preferably 95 to 40 mol%, and more preferably 93 to 60 mol%, from the viewpoint of sensitivity. Sensitivity is improved by setting the content to 40 mol% or more, and the content of 3,4-xylenol can be ensured by setting the content to 95 mol% or less, which is preferable in terms of resolution, linearity, and the like.
• phenols other than 3,4-xylenol and m-cresol can be used as necessary, but other phenols are, in particular, 3,4-xylenol.
• m-cresol When used together with m-cresol, it may be 0 to 30 mol% in the phenols (that is, whether or not other phenols are used is optional), and preferably 5 to 20 mol%. It is preferable in terms of resolution, linearity characteristics, and sensitivity.
• aldehyde one or more arbitrarily selected ones can be used without particular limitation as long as they are generally used for synthesizing a nopolak resin for a positive photoresist composition.
• acetoaldehyde propionaldehyde, salicylaldehyde, formaldehyde, formaldehyde precursor, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, and the like.
• formaldehyde are preferred, and those in which both are combined are particularly preferred.
• propionaldehyde it is preferable to use 5% by mole or more, preferably 15% by mole or more of aldehydes, since resolution is good and a rectangular resist pattern tends to be obtained.
• formaldehyde When formaldehyde is used, it is preferable to use 50 mol% or more, preferably 60 mol% or more of aldehydes from the viewpoint of sensitivity.
• the molar ratio of ropionaldehyde: formaldehyde is 10:90 to 30:70, Preferably it is 25:75. Within this range, the effects of high sensitivity, high resolution, and high heat resistance can be obtained.
• an alkali-soluble nopolak resin that can be synthesized using a phenol containing 3,4-xylenol and m-cresol.
• the aldehydes include an alcohol-soluble novolak resin that can be synthesized using an aldehyde containing one or both (preferably both) of propionaldehyde and formaldehyde.
• alkali-soluble nopolak resins that can be synthesized using phenols containing 3,4-xylenol and m-cresol, and aldehydes containing propionaldehyde and formaldehyde. At this time, it is more preferable to satisfy the conditions of 5 to 30 mol% of 3,4-xylenol, 95 to 40 mol% of m-cresol, and 0 to 30 mol% of other phenols in the phenol.
• the alkali-soluble nopolak resin can be synthesized according to a conventional method, for example, by subjecting a phenol and an aldehyde to a condensation reaction in the presence of an acid catalyst.
• the molar ratio of the phenols to the aldehydes is, for example, 1: 0.5 to 1: 0.95, preferably 1: 0.6 to 1: 0.9.
• the mass-average molecular weight (Mw) of the alkali-soluble nopolak resin is 3000 to 30,000, preferably 4000 to 20000 in terms of polystyrene by GPC (gel permeation chromatography) from the viewpoint of coating properties and heat resistance.
• the alkali-soluble nopolak resin may be used alone or in combination of two or more. Can be used.
• the component (A) may contain, in addition to the essential alkali-soluble nopolak resin, other alcohol-soluble resins.
• the compounding amount of the other alkali-soluble resin in the component (A) is, for example, 50% by mass or less, preferably 30% by mass or less (the lower limit is not particularly limited, but may be 0% by mass). . Within this range, the effect of the essential alkali-soluble nopolak resin is not likely to be impaired, which is preferable.
• any other alcohol-soluble resin that can be blended can be used without particular limitation as long as it is generally used in a positive photoresist composition.
• hydroxystyrene such as a homopolymer of hydroxystyrene, a copolymer of hydroxystyrene and another styrene monomer, and a copolymer of hydroxystyrene and acrylic acid or methacrylic acid or a derivative thereof.
• Acrylic acid or methacrylic acid resin which is a copolymer of acrylic acid or methacrylic acid and a derivative thereof.
• the component (B) is a naphthoquinonediazide esterified product.
• the component (B) is not particularly limited as long as it is generally used as a photosensitive component in a positive photoresist composition, and one or more components can be arbitrarily selected and used.
• RR 8 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms.
• R 1Q and R 11 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; when R 9 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q 1 represents a hydrogen atom or a carbon atom;
• R 12 and R 13 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms.
• c a is an integer of 1 to 3
• Q 1 is bonded with the end end of R 9 is, Q 1 is R 9 and, together with the carbon atoms between Q 1, R 9,
• A, b represents an integer of 1 to 3
• d represents an integer of 0 to 3
• n represents an integer of 0 to 3]
• the esterified product of a phenolic compound and a naphthoquinonediazidosulfonic acid compound represented by the formula is suitable for photolithography using i-line and forms a fine resist pattern of 2.0 m or less under low NA conditions with good shape It is suitable for trying. That is, it is preferable in terms of high resolution and also in terms of linearity.
• Q 1 and R 9 and the carbon atom between Q 1 and R 9 form a cycloalkyl group having a carbon chain of 3 to 6
• Q 1 and R 9 combine to form a carbon atom It forms 2 to 5 alkylene groups.
• the phenolic compounds corresponding to the general formula include tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, and bis (4-hydroxy-2,3,5-trimethylphenyl).
• 2-Hydroxyphenylmethane bis (4-hydroxy-1,3,5-dimethylphenyl) 1,4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -1,3-hydroxyphenylmethane, bis ( 4-Hydroxy-1,3,5-dimethylphenyl-1-hydroxyphenylmethane, bis (4-hydroxy 2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5) 1-hydroxyphenylmethane, bis (4-hydroxy-1,2,5-dimethylphenyl) 1,2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) 1,3,4-dihydroxyphenylme
• Examples include condensed phenol compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane.
• a photoresist composition containing one or more (preferably these three types) naphthoquinonediazide ester of a phenol compound is a resist having high sensitivity, high resolution, and good shape. This is preferable in that a pattern can be formed.
• the amount of the component (B) is preferably at least 10% by mass, more preferably at least 15% by mass.
• the compounding amount of (B1) is 50 to 90% by mass, preferably 60 to 80% by mass.
• the amount of (B2) is 5 to 20% by mass, preferably 10 to 15% by mass, and the amount of (B3) is 5 to 20% by mass, preferably 10 to 15% by mass.
• a compound represented by the above general formula (I) and naphthoquinone-1-1 A predetermined amount of 2-diazido 4 (or 5) -sulfonyl chloride is dissolved in an organic solvent such as dioxane, n-methylpyrrolidone, dimethylacetamide, and tetrahydrofuran, and tritylamine, triethanolamine, pyridine, and carbonic acid are dissolved therein.
• One or more basic catalysts such as alkali and alkali bicarbonate can be added and reacted, and the resulting product can be prepared by washing with water and drying.
• component (B) as described above, other naphthoquinone diazide esterified compounds may be used in addition to the preferred exemplified naphthoquinone diazide esterified compounds.
• an esterification reaction product of a phenolic compound such as polyhydroxybenzophenone-alkyl gallate and a naphthoquinonediazidosulfonic acid compound may be used.
• the use amount of these other naphthoquinonediazide esterified compounds is preferably 80% by mass or less, particularly 50% by mass or less in the component (B), from the viewpoint of improving the effects of the present invention.
• the amount of the component (B) in the photoresist composition is 20 to 70% by mass, preferably 25 to 60% by mass, based on the total amount of the component (A) and the following component (C). .
• the amount of the component (B) By setting the amount of the component (B) to be not less than the above lower limit, an image faithful to the pattern can be obtained, and transferability is improved.
• the content is not more than the above upper limit, the sensitivity can be prevented from deteriorating, the uniformity of the formed resist film can be improved, and the resolution can be improved.
• the component (C) is a phenolic hydroxyl group-containing compound.
• the material suitable for LCD can be obtained.
• the molecular weight of the component (C) is preferably 100 or less, preferably 700 or less, substantially 200 or more, and preferably 300 or more, from the viewpoint of the above effects.
• phenolic water generally used in a photoresist composition is used.
• the acid group-containing compound is not particularly limited as long as it satisfies the above-mentioned molecular weight condition, and one or more kinds can be arbitrarily selected and used.
• the following general formula (III) is not particularly limited as long as it satisfies the above-mentioned molecular weight condition, and one or more kinds can be arbitrarily selected and used.
• RU to R 18 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms.
• R 2Q and R 21 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; when R 19 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Q 2 represents a hydrogen atom;
• R 22 and R 23 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms.
• the expressed; g a is an integer of 1 to 3
• Q 2 is bonded with the terminal of R 19 is, Q 2 is R 19, and, together with the carbon atoms between Q 2 and R 19, carbon Chain represents a cycloalkyl group of 3 to 6
• e, f represents an integer of 1 to 3
• h represents 0
• n represents an integer of 0 to 3]
• the phenol compound represented by the following is preferable because it shows the above characteristics well.
• the phenol compound used in the naphthoquinonediazide esterified product of the phenol compound exemplified in the above-mentioned component (B) can be preferably used.
• Isopropyl]-4-[1,1 _bis (4-hydroxyphenyl) ethyl] benzene is preferred.
• the amount of the component (C) is in the range of 10 to 70% by mass, preferably 20 to 60% by mass, based on the component (A) from the viewpoint of the effect.
• component (D) one or more kinds can be selected and used without particular limitation as long as they are general ones used in a photoresist composition, and propylene glycol monoalkyl ether acetate, And those containing Z or 2-heptanone are preferred because they have excellent coatability and excellent uniformity of the thickness of a resist film on a large glass substrate.
• both propylene daricol monoalkyl ether acetate and 21-heptane can be used, but the spin coat method or the like, when used alone or in combination with another organic solvent, is used. In many cases, it is preferable in terms of the uniformity of the film thickness at the time of coating.
• the propylene glycol monoalkyl ether acetate preferably contains 50 to 100% by mass of the component (D).
• Propylene dalycol monoalkyl ether acetate has, for example, a linear or branched alkyl group having 1 to 3 carbon atoms.
• PGMEA propylene glycol monomethyl ether acetate
• 2-hepno-non is not particularly limited, but as described above, (B) It is a suitable solvent when combined with a non-benzophenone-based photosensitive component as a futoquinone diester.
• 2-Heptane-non is a very preferable solvent because it has excellent heat resistance as compared with PGMEA and has the property of giving a resist composition with reduced scum generation.
• other solvents can be mixed with these preferable solvents.
• an alkyl lactate such as methyl lactate or ethyl lactate (preferably ethyl lactate) is blended, a resist pattern having excellent uniformity in the thickness of the resist film and excellent shape can be formed.
• the mass ratio is 0.1 to 10 times, preferably 1 to 5 times the mass ratio of propylene glycol monoalkyl ether acetate to propylene glycol monoalkyl ether acetate. It is desirable to mix twice the amount of alkyl lactate.
• Organic solvents such as carboxylactone and propylene glycol monobutyl ether can also be used.
• arptyrolactone When arptyrolactone is used, it is added in an amount of 0.01 to 1 times by mass, preferably 0.05 to 0.5 times by mass with respect to propylene glycol monoalkyl ether acetate. It is desirable to do.
• organic solvents that can be blended include the following.
• ketones such as acetone, methyl ethyl ketone, cyclohexanone, and methyl isoamyl ketone; ethylene glycol, propylene glycol, ethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, and monomers thereof.
• Polyhydric alcohols such as tyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; and methyl acetate, ethyl acetate, butyl acetate, Esters such as methyl ruvinate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate.
• the content is not more than 50% by mass in the component (D).
• the positive photoresist composition of the present invention contains compatible additives as necessary, for example, an additional resin and a plasticizer for improving the performance of the resist film, as long as the object of the present invention is not impaired.
• compatible additives for example, an additional resin and a plasticizer for improving the performance of the resist film, as long as the object of the present invention is not impaired.
• Conventional additives can be included.
• Antihalation dyes include ultraviolet absorbers (eg, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dimethylamino-2', 4,1-dihydroxybenzophenone, 5-amino-3- Methyl-11-phenyl-1-41- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-methylethyl-4'-ethoxyazobenzene, 4-ethylethylaminoazobenzene, curcumin Etc.) can be used.
• ultraviolet absorbers eg, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dimethylamino-2', 4,1-dihydroxybenzophenone, 5-amino-3- Methyl-11-phenyl-1-41- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-methylethyl-4'-ethoxyazobenzen
• the surfactant can be added, for example, to prevent striation.
• Florad FC-430, FC431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), EFTOP EF 122A, EF 122B, EF 122C, EF 126 (trade name, manufactured by Tochem Products Co., Ltd.) and R-08 (trade name, manufactured by INHIKIN INK CHEMICAL INDUSTRIES, LTD.).
• the positive photoresist composition of the present invention is preferably prepared by dissolving the component (A), the component (B), the component (C) and, if necessary, other components in the organic solvent (D). be able to.
• the amount of the component (D) is preferably adjusted appropriately so as to dissolve the components (A) to (C) and other components used as necessary, and to obtain a uniform positive photoresist composition. I can do it.
• the solid content [components (A) to (C) and other components used as needed] is 10 to 50% by mass, more preferably 20 to 35% by mass.
• the above-mentioned positive photoresist composition of the present invention is applied to a substrate using a spinner or the like to form a coating film.
• a glass substrate is preferred as the substrate.
• Amorphous silica is usually used as the glass substrate, but low temperature polysilicon or the like is preferable in the field of system LCD.
• the composition of the present invention since the composition of the present invention has excellent resolution under low NA conditions, it is large in size of 50 O mm x 60 O mm or more, especially 55 O mm X 65 O mm or more. Substrate can be used.
• the glass substrate on which the coating film is formed is subjected to a heat treatment (prebaking) at, for example, 100 to 140 ° C. to remove the residual solvent, thereby forming a resist coating film.
• prebaking it is preferable to perform proximity baking in which a gap is provided between the hot plate and the substrate.
• the resist film is selectively exposed using a mask on which a mask pattern is drawn.
• i-line As a light source, it is preferable to use i-line (365 nm) in order to form a fine pattern.
• the exposure process employed in this exposure is preferably a low NA exposure process having an NA of 0.3 or less, preferably 0.2 or less, and more preferably 0.15 or less.
• a mask pattern for forming a resist pattern when a system LCD is manufactured, in the step of performing the selective exposure, a mask pattern for forming a resist pattern of 2.0 m or less, It is preferable to use a mask on which both the resist pattern forming mask patterns are drawn.
• the resist film after the selective exposure is subjected to a heat treatment (post-exposure bake: PEB).
• PEB method there are a proximity bake where a gap is provided between the hot plate and the substrate, and a direct bake where no gap is provided. Then, in order to obtain a diffusion effect by PEB without causing the substrate to be warped, a method of performing direct baking after performing proximity baking is preferable.
• the heating temperature is 90 ⁇ : L 40 ° C, especially 110 ⁇ 130 preferable.
• a developing solution for example, an alkaline aqueous solution such as a 1 to 10% by mass aqueous solution of tetramethylammonium hydroxide (TMAH)
• TMAH tetramethylammonium hydroxide
• the exposed portions are dissolved and removed.
• a resist pattern is formed.
• a mask on which both the resist pattern forming mask pattern of 2.0 or less and the resist pattern forming mask pattern of more than 2.0 m are drawn is used, the resist pattern for the integrated circuit and the liquid crystal are formed on the substrate.
• a resist pattern for the display portion is simultaneously formed.
• the resist pattern can be formed by washing the developing solution remaining on the resist pattern surface with a rinse solution such as pure water.
• the positive photoresist composition for LCD of the present invention has excellent linearity, a resist pattern that faithfully reproduces both rough and fine mask patterns can be obtained. Therefore, when a step of simultaneously forming a resist pattern using a mask on which both are drawn is performed, a resist pattern for an integrated circuit having a pattern size of 2.0 m or less and a resist pattern of more than 2.0 m are formed on the substrate.
• the resist pattern for the liquid crystal display portion can be formed at the same time.
• the positive photoresist composition of the present invention is suitable for an exposure process under low NA conditions. It is also suitable for i-line exposure processes. Therefore, in the manufacture of LCD, a resist pattern of at least a display portion can be obtained with high resolution.
• the positive photoresist composition of the present invention is excellent in linearity under low NA conditions, a rough pattern and a fine pattern can be formed on one substrate under the same exposure conditions. Therefore, even under a low NA condition, a resist pattern for a display portion of a system LCD and a finer integrated circuit portion can be obtained at a high resolution at the same time, which is suitable for manufacturing a system LCD.
• an alcohol-soluble nopolak resin containing 3,4-xylenol as the component (A) heat resistance is improved, and the residual film property after alkali development is improved. Furthermore, since the resolution is good, the system Suitable for LCD.
• the positive photoresist composition for LCD it is necessary that the width of the depth of focus (DOF) is large to some extent from the viewpoint of production efficiency, easy control of production conditions, and the like.
• the positive photoresist composition for LCD can realize a range of depth of focus (for example, 15 / m or more) that can be practically used for LCD.
• the positive photoresist composition for LCDs of the present invention can provide high resolution under low NA conditions (a uniform and good resolution can be obtained even when a large area is exposed) and a linearity. It is also preferable, and can be preferably used as a general positive photoresist composition for LCDs, and is particularly suitable for system LCDs.
• a high-resolution resist pattern can be formed even in an exposure process under a low NA condition suitable for LCD production.
• a resist pattern for an integrated circuit with a pattern size of 2.0 m or less, for example, and a resist pattern for a liquid crystal display portion with a pattern size of more than 2.0 m, for example, can be simultaneously formed on a substrate. It can be used favorably in the manufacture of LCDs.
• Glass substrate (55 OmmX 65 Omm) on which a Ti film is formed using a positive photoresist composition by a resist coating device for large substrates (apparatus name: TR3600 manufactured by Tokyo Ohka Kogyo Co., Ltd.)
• the temperature of the hot plate is set to 100 ° C
• the first drying is performed for 90 seconds by a proximity bake with an interval of about lmm
• the temperature of the hot plate is set to 90 ° C
• the second drying was performed for 90 seconds by a proximity bake with an interval of 0.5 mm to form a resist film having a thickness of 1.5 ⁇ .
• the temperature of the hot plate is set to 120 ° C, a heat treatment is performed for 30 seconds by a proximity bake at intervals of 0.5 mm, and then a direct bake is performed at the same temperature without any space. Heat treatment was performed for 60 seconds.
• a 23.degree. C., 2.38 mass% TMAH aqueous solution was developed using a developing device (device name: TD-3900, demonstration machine, manufactured by Tokyo Ohka Kogyo Co., Ltd.) having a slit nozzle.
• TD-3900 demonstration machine, manufactured by Tokyo Ohka Kogyo Co., Ltd.
• the cross-sectional shape of the obtained resist pattern was observed by SEM (scanning electron microscope) photograph, and the reproducibility of the 1.5 mL & S resist pattern was evaluated.
• the focus was shifted up and down as appropriate, and the width of the depth of focus (DOF) obtained in 1.5 mL & S within the range of the dimensional change rate of 10% of the soil was obtained in units of / zm.
• the substrate surface on which 1.5 mL & S was drawn was observed with an SEM to check for scum.
• the substrate on which 1.5 mL & S is drawn is left on a hot plate set at 140 for 300 seconds, and then left in an oven set at 200 ° C for 30 minutes. did.
• ⁇ indicates that the dimensional change rate of 1.5 mL & S was more than 100% to 105% or less
• 105 indicates that the dimensional change rate was more than 105% to 110% or less
• X indicates that the rate of change was more than 110%.
• B 2 Esterification reaction product of 1 mol of B 2 ′ and 4 mol of 5-NQD
• B 3 Esterification reaction product of 1 mol of B 3 ′ and 2 mol of 5—NQD (C) phenolic hydroxyl group
• C phenolic hydroxyl group
• PGMEA surfactant product name "R-08”; equivalent to 450 ppm based on the total weight of components (A) to (C) and components (A) to (C)) (Nippon Dainippon Ink and Chemicals Co., Ltd.) is dissolved in PGMEA, which is the component (D), and the solid content [total of (A) to (C) components] is adjusted to 25 to 28% by mass. This was filtered using a membrane filter having a pore size of 0.2 to prepare a positive photoresist composition.
• a positive photoresist composition was prepared in the same manner as in Example 1 except that the components (A) to (D) were changed to those shown in Table 1 below. table 1
• B 1 / B 2 / B 3 (6/1/1) means that B 1 / B 2 / B 3 is mixed at a mass ratio of 6/1/1 as described above. Indicates that it was used.
• A2-8, C2, and D2-3 are as follows.
• Mw / Mn 3.05 nopolak resin
• Heat resistance and sensitivity are commonly required for LCDs and system LCDs.
• the composition of Comparative Example 2 has a very low sensitivity of 100 mJ because the component (A) is different from that of the present invention, and is adopted in the field of LCD manufacturing where high sensitivity of about 5 OmJ is required. Was a very difficult material.
• the composition of Comparative Example 3 has a linearity because the component (A) is different from that of the present invention. Was bad.
• Comparative Example 4 was inferior in linearity and narrow in the depth of focus (DOF) because the component (A) was different from that of the present invention. Industrial applicability

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