CN1550898A - Positive anticorrosive additive composition and anticorrosive pattern forming method - Google Patents
Positive anticorrosive additive composition and anticorrosive pattern forming method Download PDFInfo
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- CN1550898A CN1550898A CNA2004100447100A CN200410044710A CN1550898A CN 1550898 A CN1550898 A CN 1550898A CN A2004100447100 A CNA2004100447100 A CN A2004100447100A CN 200410044710 A CN200410044710 A CN 200410044710A CN 1550898 A CN1550898 A CN 1550898A
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- 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
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
- G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
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- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The positive resist composition for a system LCD contains: (A) an alkali-soluble resin; (B) a quinone diazide group-containing compound; (C) a phenolic hydroxyl group-containing compound having <=1,000 molecular weight (M); and (D) an organic solvent. The solid content in the resist composition has the mass average molecular weight (Mw) in the range of 5,000 to 30,000 in terms of polystyrene by gel permeation chromatography. According to this invention, it can provide a resist composition which can be improved in the heat resistance, resolution, linearity and DOF (depth of focus) characteristics required for the manufacture of a system LCD having an integrated circuit and a liquid crystal display part fabricated on one substrate, without decreasing the sensitivity.
Description
Technical field
The present invention relates on a substrate, to be formed with the eurymeric resist composition of substrate manufacturing usefulness of integrated circuit and liquid-crystal display section and the formation method of using its corrosion-resisting pattern.
Background technology
In the past as the anticorrosive additive material in the liquid crystal display cells manufacturing field of using glass substrate, what mostly use is as alkali soluble resins, with the compound that contains the benzoquinones diazido eurymeric resist composition as photographic composition with novolac resin, this is because it is fit to ghi line exposing and less expensive, and can form the good corrosion-resisting pattern of sensitivity, resolving power and shape, to this existing report (following patent documentation 1～4).
So far, because purpose is to form the pixel parts of display, therefore as long as can form very coarse pattern (as about the 3-5 micron), employed is that polystyrene conversion weight-average molecular weight (Mw) by gel permeation chromatography is at the eurymeric resist composition below 4000.
Patent documentation 1
The spy opens the 2000-131835 communique
Patent documentation 2
The spy opens the 2001-75272 communique
Patent documentation 3
The spy opens the 2000-181055 communique
Patent documentation 4
The spy opens the 2000-112120 communique
At present; as follow-on LCD; for the technological development that on 1 glass substrate, forms integrated circuit part such as driver, DAC (digital analog converter), portrait processor, video recording controller, RAM and the high function LCD display part, that be called what is called " system LCD " simultaneously very active (Semiconductor FPD World 2001.9, pp.50-67).
Below, in this instructions, abbreviate the aforesaid substrate that on 1 substrate, is formed with integrated circuit and liquid-crystal display section as system LCD.
In above-mentioned system LCD, what replace that amorphous silicon uses as substrate is formed low temperature polycrystalline silicon in the sub zero treatment below 600 ℃, and this is little and mobility is high because compare its resistance with amorphous silicon.
Therefore, wish to develop to be fit to be used in the resist composition of low temperature polycrystalline silicon as the manufacturing of the system LCD of substrate, but the anticorrosive additive material report example that does not also have relevant system LCD to use up to now.
If will make by the formed TFT of low temperature polycrystalline silicon, after forming polysilicon film by sub zero treatment on the glass substrate, in this low temperature polycrystalline silicon film, squeeze into the operation of P and B, promptly in so-called " imbedding (inplantation) operation ", requiring to squeeze into the very impurity of high concentration.
This is imbedded in the operation, be to have formed under the state of corrosion-resisting pattern being formed with on the glass substrate on the low temperature polycrystalline silicon glass substrate of low temperature polycrystalline silicon film, under the condition of high vacuum degree condition, carry out, wherein there is following problems, when by the squeezing into the heating functioin that is caused and make corrosion-resisting pattern on the substrate be heated of impurity, the corrosion-resisting pattern shape can change, or some the composition generating gasification in the corrosion-resisting pattern, and the vacuum tightness in the process chamber is descended.
As the means that address this problem, more effectively before imbedding operation, be known as the heating treatment step of " back oven dry ", but because dry this back is under the close temperature conditions of heated temperature when imbedding, for example carry out under the high temperature more than 200 ℃, thereby must form the corrosion-resisting pattern of the high-fire resistance that pattern form does not change in this heat treated.Therefore, if will realize the manufacturing of the LCD of system,, require to have good thermotolerance as the resist composition that is used for wherein.
In addition, in the LCD of system, the pattern dimension of display part is 2～10 μ m, and relative with it, and the integrated circuit part but forms with the fine sizes of 0.5～2.0 μ m.Therefore, for the resist composition that the LCD of system makes usefulness, can be simultaneously form the ability (linearity) of fine pattern and coarse pattern except requiring to have with good shape, also be strict with it and make than in the past LCD and have higher resolution, and the depth of focus width of cloth (DOF) characteristic of fine pattern is good etc. with anticorrosive additive material.
But in the manufacturing field of liquid crystal cell, the sensitivity decline of anticorrosive additive material can cause serious throughput rate to descend, thereby not ideal, therefore wishes under the situation that does not cause sensitivity decline above-mentioned characteristic to be improved.
Summary of the invention
Problem of the present invention is: be provided at and do not make under the situation that sensitivity descends, resist composition that can desired thermotolerance, resolving power, the linearity and DOF characteristic improve when being used to be manufactured on the system LCD that is formed with integrated circuit and liquid-crystal display section on 1 substrate and the formation method of using its corrosion-resisting pattern.
In order to solve described problem, system LCD of the present invention is characterised in that with eurymeric resist composition: containing (A) alkali soluble resins, (B), to contain benzoquinones diazido compound, (C) molecular weight (M) be to contain phenol hydroxyl compound and (D) organic solvent below 1000, and the polystyrene conversion weight-average molecular weight (Mw) of passing through gel permeation chromatography of the solid constituent that is contained in this resist composition is in 5000～30000 scope.
The present invention also provides the formation method of corrosion-resisting pattern in addition, and it comprises following operation: (1) is coated with above-mentioned positive light anti-etching agent composition on substrate, forms the operation of filming; (2) carry out heat treated (prebake) to being formed with described substrate of filming, on substrate, form the operation of resist tunicle; (3) use and to describe the following corrosion-resisting pattern of 2.0 μ m and form with mask pattern and the corrosion-resisting pattern that surpasses 2.0 μ m and form, the operation that described resist tunicle is optionally exposed with the two mask of mask pattern; (4) the resist tunicle after the described selectivity exposure is implemented the operation of heat treated (drying after the exposure); (5) with aqueous alkali the resist tunicle after described heat treated (exposure back oven dry) is carried out development treatment, forming the operation that pattern dimension is the corrosion-resisting pattern used of the integrated circuit below the 2.0 μ m and the corrosion-resisting pattern used above the liquid-crystal display section of 2.0 μ m on the described substrate simultaneously.
The value that the value of weight-average molecular weight in this instructions (Mw) is to use following GPC system to be measured.
Device name: SYSTEM11 (goods name, clear and electrician society system)
Pre-column: KF-G (goods name, Shodex society system)
Post: KF-805, KF-803, KF-802 (goods name, Shodex society system)
Detecting device: UV41 (goods name, Shodex society system) measures at 280nm.
Solvent etc.: the flow that divides with 1.0ml/ flows down tetrahydrofuran, 35 ℃ of mensuration.
Measure the sample modulator approach: the photo-corrosion-resisting agent composition that adjustment will be measured dilutes it so that solid component concentration reaches 30 quality % with tetrahydrofuran, and making solid component concentration is the mensuration sample of 0.1 quality %.This mensuration sample of 20 microlitres is squeezed into described device to be measured.
Embodiment
Below describe the present invention in detail.
[(A) composition]
(A) composition is not particularly limited, can from eurymeric resist composition, can be used as the alkali soluble resins that tunicle forms material usually, at random selects a kind or 2 kinds to use.
For example: make phenols (phenol, metacresol, paracresol, xylenols, pseudocuminol etc.) and aldehydes (formaldehyde, formaldehyde precursor, propionic aldehyde, 2-hydroxy benzaldehyde, 3-hydroxy benzaldehyde, 4-hydroxy benzaldehyde etc.) or/and ketone (MEK, acetone etc.) condensation and novolac resin of obtaining in the presence of acidic catalyst;
The hydroxy styrenes such as multipolymer of the multipolymer of the homopolymer of hydroxy styrenes and hydroxy styrenes and other styrenic monomers, hydroxy styrenes and acrylic or methacrylic acid or derivatives thereof are resin;
The multipolymer of acrylic or methacrylic acid and its derivant is that acrylic or methacrylic acid is resin etc.
Particularly preferably be to make and contain metacresol, paracresol, 3,4-xylenols and 2,3, the phenols of 5-pseudocuminol and the aldehydes that contains formaldehyde carry out condensation reaction and the novolac resin that obtains, and this is because its thermotolerance is good, and it is cheap.
(A) composition can be according to the well-established law manufacturing.
The polystyrene conversion weight-average molecular weight (the following Mw that only is designated as sometimes) of (A) composition by gel permeation chromatography is according to its kind and difference is considered from sensitivity and pattern formation aspect, and is preferred 2000～100000, and more preferably 3000～30000.
[(B) composition]
(B) composition is to contain benzoquinones diazido compound.(B) composition so long as can be used as usually in eurymeric resist composition that the photonasty composition uses contain benzoquinones diazido compound and just can use be not particularly limited, can select arbitrarily a kind or 2 kinds with on use.
When wherein particularly using the compound of non-benzophenone series, be suitable for photoetching process with the i line, and also more satisfactory aspect the high-resolution and the linearity.
As (B) composition of this non-benzophenone series, the carboxylate of phenolic compounds that preferred following general formula (I) is represented and naphthoquinones diazido sulfoacid compound.Preferred 1 as naphthoquinones diazido sulfoacid compound, 2-naphthoquinones diazido-5-sulfonyl compound.
[in the formula, R
1～R
8Represent the alkyl of hydrogen atom, halogen atom, carbon number 1～6, the alkoxy of carbon number 1～6 or the naphthenic base of carbon number 3～6 independently of one another; R
10, R
11Represent the alkyl of hydrogen atom or carbon number 1～6 independently of one another; R
9Can be the alkyl of hydrogen atom or carbon number 1～6, at this moment, Q
1Be the alkyl of hydrogen atom, carbon number 1～6 or the residue shown in the following chemical formula (II)
(in the formula, R
12And R
13Represent the alkyl of hydrogen atom, halogen atom, carbon number 1～6, the alkoxy of carbon number 1～6 or the naphthenic base of carbon number 3～6 independently of one another; C represents 1～3 integer), Q
1Can also and R
9The end combination, at this moment, Q
1And R
9And Q
1And R
9Between carbon atom together represent the naphthenic base of carbochain 3～6; A, b represent 1～3 integer; D represents 0～3 integer; N represents 0～3 integer].
In addition, Q
1And R
9And Q
1And R
9Between carbon atom when forming the naphthenic base of carbochain 3～6 together, Q
1And R
9In conjunction with, the alkylidene of formation carbon number 2～5.
The represented phenolic compounds of this general formula (I) can be listed below: three (4-hydroxy phenyl) methane, two (4-hydroxy-3-methyl phenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-2,3, the 5-trimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-4-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-3-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-4-hydroxy phenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-3-hydroxy phenyl methane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyls-3, the 5-3,5-dimethylphenyl)-3,4-dihydroxy benzenes methylmethane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-3,4-dihydroxy benzenes methylmethane, two (4-hydroxyls-2, the 5-3,5-dimethylphenyl)-2,4-dihydroxy benzenes methylmethane, two (4-hydroxy phenyl)-3-methoxyls-4-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-4-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-3-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-2-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-3, triphenol type compounds such as 4-dihydroxy benzenes methylmethane;
2, two (3,5-dimethyl-4-the hydroxybenzyl)-5-hydroxyl phenols, 2 of 4-, two (2,5-dimethyl-4-the hydroxybenzyl)-line style 3 nucleome phenolic compounds such as 4-methylphenol of 6-; 1, two [3-(2-hydroxy-5-methyl base benzyl)-4-hydroxyl-5-cyclohexyl phenyl] the different propane of 1-, two [2,5-dimethyl-3-(4-hydroxy-5-methyl base benzyl)-4-hydroxy phenyl] methane, two [2,5-dimethyl-3-(4-hydroxybenzyl)-4-hydroxy phenyl] methane, it is two that [3-(3,5-dimethyl-4-hydroxybenzyl)-and 4-hydroxy-5-methyl base phenyl] methane, it is two that [3-(3,5-dimethyl-4-hydroxybenzyl)-and 4-hydroxyl-5-ethylphenyl] methane, it is two that [3-(3,5-diethyl-4-hydroxybenzyl)-and 4-hydroxy-5-methyl base phenyl] methane, it is two that [3-(3,5-diethyl-4-hydroxybenzyl)-and 4-hydroxyl-5-ethylphenyl] methane, two [2-hydroxyl-3-(3,5-dimethyl-4-hydroxybenzyl)-and the 5-aminomethyl phenyl] methane, two [2-hydroxyl-3-(2-hydroxy-5-methyl base benzyl)-5-aminomethyl phenyl] methane, two [4-hydroxyl-3-(2-hydroxy-5-methyl base benzyl)-5-aminomethyl phenyl] methane, line style 4 nucleome phenolic compounds such as two [2,5-dimethyl-3-(2-hydroxy-5-methyl base benzyl)-4-hydroxy phenyl] methane; 2, two [2-hydroxyl-3-(4-hydroxybenzyl)-5-the methyl-benzyl]-6-cyclohexylphenol, 2 of 4-, two [4-hydroxyl-3-(4-hydroxybenzyl)-5-the methyl-benzyl]-6-cyclohexylphenol, 2 of 4-, two [2,5-dimethyl-3-(2-hydroxy-5-methyl base benzyl)-4-the hydroxybenzyl]-line style polyphenolic substances such as line styles such as 4-methylphenol 5 nucleome phenolic compounds of 6-;
Two (2,3,4-trihydroxy phenyl) methane, two (2, the 4-dihydroxy phenyl) methane, 2,3,4-trihydroxy phenyl-4 '-hydroxy phenyl methane, 2-(2,3,4-trihydroxy phenyl)-2-(2 ', 3 ', 4 '-the trihydroxy phenyl) propane, 2-(2, the 4-dihydroxy phenyl)-2-(2 ', 4 '-dihydroxy phenyl) propane, 2-(4-hydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, 2-(3-fluoro-4-hydroxy phenyl)-2-(3 '-fluoro-4 '-hydroxy phenyl) propane, 2-(2, the 4-dihydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, 2-(2,3,4-trihydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, 2-(2,3,4-trihydroxy phenyl)-2-(4 '-hydroxyl-3 ', 5 '-3,5-dimethylphenyl) bisphenol type compound such as propane; 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene, 1-[1-(3-methyl-4-hydroxy phenyl) isopropyl]-4-[1, two (3-methyl-4-hydroxy phenyl) ethyls of 1-] benzene, etc. multinuclear ramiform compound; 1, condensed type phenolic compounds such as 1-bis(4-hydroxyphenyl)cyclohexane etc.
They can be used in combination more than a kind or 2 kinds.
Wherein, when being major component with triphenol type compound, more satisfactory aspect high sensitivityization and resolving power, preferred especially two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-3,4-dihydroxy benzenes methylmethane [being designated hereinafter simply as (B1 ')], two (4-hydroxyl-2,3, the 5-trimethylphenyl)-2-hydroxy phenyl methane [being designated hereinafter simply as (B3 ')].In addition, reach the resist composition of good equilibrium on the whole in order to adjust resist characteristics such as resolving power, sensitivity, thermotolerance, DOF characteristic, linearity, preferably with line style polyphenolic substance, bisphenol type compound, multinuclear ramiform compound and condensed type phenolic compounds etc. and described triphenol type compound and usefulness, particularly also using the bisphenol type compound, wherein also with two (2, the 4-dihydroxy phenyl) during methane [being designated hereinafter simply as (B2 ')], can adjust the resist composition that reaches good equilibrium generally.
In addition, below abbreviate described (B1 '), (B2 '), (B3 ') naphthoquinones diazido carboxylate separately as (B1), (B2), (B3).
When using (B1), (B3), (B) use level in the composition is respectively preferably more than 10 quality %, more preferably more than the 15 quality %.
Have again, (B1), (B2), (B3) when all using, are considered from the effect aspect, use level separately is: (B1) be 50～90 quality %, preferred 60～80 quality % (B2) are 5～20 quality %, preferred 10～15 quality % (B3) are 5～20 quality %, preferred 10～15 quality %.
Can implement according to well-established law carrying out naphthoquinones diazido sulfonic acid esterification method by all or part of of the phenol hydroxyl of the represented compound of described general formula (I).
For example: can make naphthoquinones diazido sulfonic acid chloride and obtain by the represented compound condensation of described general formula (I).
Specifically can modulate: with compound and the naphthoquinones-1 shown in a certain amount of described general formula (I) by following method, 2-diazido-5-sulfonic acid chloride is dissolved in the organic solvents such as diox, n-methyl pyrrolidone, dimethyl acetamide, tetrahydrofuran, to wherein adding base catalysts such as triethylamine more than a kind, triethanolamine, pyridine, carbonic acid alkali metal salt, bicarbonate alkali metal salt, make their reactions, with product washing and the drying that obtains.
As (B) composition, except the preferred naphthoquinones diazido carboxylate that is as above exemplified, can also use other naphthoquinones diazido carboxylate, for example: esterification reaction product of phenolic compounds such as polyhydroxy benzophenone and gallic acid alkane ester and naphthoquinones diazido sulfoacid compound etc.
Above-mentioned other the use amount of naphthoquinones diazido carboxylate is below the 80 quality % in (B) photonasty composition, considers from improving effect of the present invention aspect, below the preferred especially 50 quality %.
The use level of (B) composition in the resist composition is 20～70 quality % when being benchmark with the total amount of (A) composition and following (C) composition, preferred 25～60 quality %.
The use level of (B) composition is set at more than the described lower limit, can accesses the image of being loyal to pattern, improve transfer printing.And be set at below the described higher limit, can prevent the sensitivity variation, improve the homogenieity and the resolving power of formed resist film.
[(C) composition]
(C) composition is to contain the phenol hydroxyl compound.Should can obtain good sensitivity raising effect by (C) composition by using.
(C) molecular weight of composition (M) preferably below 700, considers that lower limit is in fact more than 200, preferably more than 300 below 1000 from described effect aspect.
(C) composition is usually to contain the phenol hydroxyl compound as what sensitivity improved that material or sensitizer be used for the resist composition, so long as can satisfy the material of described molecular weight condition, just is not particularly limited, can at random select a kind or 2 kinds with on use.Wherein, when using the compound of non-benzophenone series, improve effect except obtaining good sensitivity, in handling, the i line exposing also can access high sensitivity, high-resolution, therefore be particularly suitable for adopting the manufacturing of the LCD that the i line exposing handles and the manufacturing of the LCD of system, can realize the higher levels of resolution and the linearity.
As (C) composition of this non-benzophenone series, the represented phenolic compounds of preferred following general formula (III).
[in the formula, R
21～R
28Represent the alkyl of hydrogen atom, halogen atom, carbon number 1～6, the alkoxy of carbon number 1～6 or the naphthenic base of carbon number 3～6 independently of one another; R
30, R
31Represent the alkyl of hydrogen atom or carbon number 1～6 independently of one another; R
29Can be the alkyl of hydrogen atom or carbon number 1～6, at this moment, Q
2Be the alkyl of hydrogen atom, carbon number 1～6 or the residue shown in the following chemical formula (IV)
(in the formula, R
32And R
33Represent the alkyl of hydrogen atom, halogen atom, carbon number 1～6, the alkoxy of carbon number 1～6 or the naphthenic base of carbon number 3～6 independently of one another; G represents 0～3 integer), Q
2Can also and R
29The end combination, at this moment, Q
2And R
29And Q
2And R
29Between carbon atom represent the naphthenic base of carbochain 3～6 together; E, f represent 1～3 integer; H represents 0～3 integer; M represents 0～3 integer].
Particularly, except cited in described (B) composition, beyond the phenolic compounds that uses in the naphthoquinones diazido carboxylate of phenolic compounds, can also be suitable for following compound: two (3-methyl-4-hydroxy phenyl)-4-cumene methylmethanes, two (3-methyl-4-hydroxy phenyl)-phenylmethanes, two (2-methyl-4-hydroxy phenyl)-phenylmethanes, two (3-methyl-2-hydroxy phenyl)-phenylmethanes, two (3,5-dimethyl-4-hydroxy phenyl)-phenylmethane, two (3-ethyl-4-hydroxy phenyl)-phenylmethanes, two (2-methyl-4-hydroxy phenyl)-phenylmethanes, two (the 2-tert-butyl group-4,5-dihydroxy phenyl)-triphenol type compounds such as phenylmethane.Wherein, preferred two (2-methyl-4-hydroxy phenyl)-phenylmethanes, 1-[1-(4-hydroxy phenyl) isopropyl]-4-[1, two (4-hydroxy phenyl) ethyls of 1-] benzene.
Considering from the effect aspect, is 10～70 quality % when (C) use level of composition is benchmark with (A) composition, preferred 20～60 quality %.
[(D) composition]
(D) composition is so long as can be used for the general organic solvent of resist composition and just can use, be not particularly limited, can select more than a kind or 2 kinds, film thickness uniformity wherein good and the resist tunicle on large-size glass substrate from coating good aspect consider, preferably contain propylene glycol list alkane ether acetic acid ester or/and the material of 2-heptanone.
In addition, can use simultaneously propylene glycol list alkane ether acetic acid ester and 2-heptanone the two, but use respectively separately or when mixing use with other organic solvent, more satisfactory usually aspect the film thickness uniformity when utilizing method of spin coating etc. to be coated with.
Propylene glycol list alkane ether acetic acid ester preferably accounts for 50～100 quality % in (D) composition.
Propylene glycol list alkane ether acetic acid ester is the material that has as the alkyl of the straight or branched of carbon number 1～3, when wherein using propylene glycol methyl ether acetate (being designated hereinafter simply as PGMEA), the film thickness uniformity of the resist tunicle on large-size glass substrate is very good, thereby desirable especially.
On the other hand, the use of 2-heptanone is not particularly limited, and when containing benzoquinones diazido compound and use the photonasty composition of the represented non-benzophenone series of described general formula (I) as (B), is the comparison The suitable solvent.
The 2-heptanone is compared with PGMEA, excellent heat resistance, has the characteristic that can obtain the less resist composition of scum silica frost (scum), is very desirable solvent.
The 2-heptanone mixes when using separately or with other organic solvent, preferably contains 50～100 quality % in (D) composition.
In addition, can mix other solvent in the above-mentioned preferred solvent uses.
When for example cooperating the lactic acid alkane ester of methyl lactate, ethyl lactate etc. (preferred ethyl lactate), can form the corrosion-resisting pattern that film thickness uniformity is good and shape is good of resist tunicle, thus more satisfactory.
Mixing when using propylene glycol list alkane ether acetic acid ester and lactic acid alkane ester, is benchmark with propylene glycol list alkane ether acetic acid ester, and the use level of lactic acid alkyl ester is 0.1～10 times of amount by quality ratio, preferred 1～5 times of amount.
In addition, can also use organic solvents such as gamma-butyrolacton or propylene glycol monobutyl ether.
When using gamma-butyrolacton, be benchmark with propylene glycol list alkane ether acetic acid ester, cooperate 0.01～1 times of amount by mass ratio, the scope of preferred 0.05～0.5 times of amount is more satisfactory.
In addition, other solvent that can cooperate specifically is listed below:
That is ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone; The multivalence alcohols and the derivant thereof of ethylene glycol, propylene glycol, diglycol, ethylene glycol acetate, propylene glycol monoacetate, diglycol monotertiary acetic acid esters or their monomethyl ether, single ether, single propyl ether, monobutyl ether or single phenyl ether etc.; As ring-type ethers such as dioxs; And ester class such as methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid methyl esters, ethoxyl ethyl propionate etc.
When using above-mentioned solvent, in (D) composition, preferably account for below the 50 quality %.
In the scope of harmless the object of the invention, can also make eurymeric resist composition of the present invention contain additive as required with compatibility, for example: be used to improve the performance etc. of resist film additional resin, plastifier, preserving stabilizer, surfactant, make development image more clearly colouring matter, the dyestuff that makes sensitizer that the sensitizing effect improves more and anti-corona usefulness, cohesive improver, etc. habitual adjuvant.
Can use following ultraviolet light absorber as anti-corona with dyestuff, as: 2,2 ', 4,4 '-tetrahydroxybenzophenone, 4-dimethylamino-2 ', 4 '-dihydroxy benaophenonel, 5-amino-3-methyl isophthalic acid-phenyl-4-(4-hydroxy phenyl azo group) pyrazoles, 4-dimethylamino-4 '-hydroxyazobenzene, 4-diethylamino-4 '-ethoxy azobenzene, 4-DEAB, curcumin etc.
In order to prevent streak etc. and can add surfactant, for example can use following surfactant: Off ロ ラ-De FC-430, FC431 (trade name, Sumitomo 3M (strain) system), エ Off ト Star プ EF122A, EF122B, EF122C, EF126 (trade name, ト-ケ system プ ロ ダ Network Star (strain) system) waiting fluorine is surfactant, メ ガ Off ア Star Network R-08 (trade name, big Japanese ink chemical industry (strain) is made) etc.
The preferred modulator approach of eurymeric resist composition of the present invention is: other composition of (A) composition, (B) composition, (C) composition and use as required is dissolved in (D) organic solvent.Can adjust the use amount of (D) composition,, can access uniform eurymeric resist composition with when dissolving other composition of (A)～(C) composition and use as required.Solid component concentration is preferably 10～50 quality %, more preferably 20～35 quality %.In addition, the solid constituent of eurymeric resist composition is equivalent to (A)～(C) composition and the total amount of other composition of using as required.
Eurymeric resist composition of the present invention is modulated into the Mw of the solid constituent that this resist composition contained in 5000～30000 scope, and preferred Mw is 6000～10000.Be set at above-mentioned scope by Mw, can under the situation that sensitivity is descended, realize high-fire resistance, high resolution, can obtain linear and all good eurymeric resist composition of DOF characteristic simultaneously the solid constituent of this resist composition.
When the Mw of the solid constituent of this resist composition was lower than above-mentioned scope, it is not enough that thermotolerance, resolving power, linearity and DOF characteristic become, and when surpassing above-mentioned scope, the decline of sensitivity is obvious, and the coating of resist composition might suffer damage.
In addition, in the system LCD manufacturing, if replace employed g line (436nm) exposure in the manufacturing of LCD in the past, this lithography technology might improve resolving power when using the shorter i line (365nm) of wavelength to expose.Corresponding with it, the compound that particularly uses non-benzophenone series as (B) composition with and/or (C) composition and the resist composition that forms, can suppress because of (B) composition with and/or (C) absorption of the i line that produces of composition, therefore be suitable for the i line exposing and handle, can realize further high-resolutionization.
Comprise the operation that Mw is modulated to above-mentioned preferable range in the modulator approach of eurymeric resist composition of the present invention.For example have as the method for implementing this operation: in order to make the Mw that mixes behind the full composition, before mixing (A) composition is carried out fractionation operation, the Mw of (A) composition is adjusted into suitable scope in advance in above-mentioned scope.
[the formation method of corrosion-resisting pattern]
The method that the is preferably formed example of the corrosion-resisting pattern when below being to use eurymeric resist composition of the present invention to come manufacturing system LCD.
At first, be coated on the substrate with the eurymeric resist composition of spin coater with the invention described above, formation is filmed.As substrate preferred glass substrate.Usually use amorphous silica as glass substrate, and in system LCD field, low temperature polycrystalline silicon etc. are considered to preference.
Then, will be formed with this glass substrate of filming and under 90～140 ℃ temperature, carry out heat drying (prebake), remove remaining solvent, form the resist tunicle.Preferred prebake method is: carry out forming between electric hot plate and substrate spaced contiguous oven dry.
With the mask of describing mask pattern described resist tunicle is optionally exposed then.
In order to form fine pattern, preferably use i line (365nm) as light source.In addition, the exposure-processed that this exposure is adopted is that NA is below 0.3, and is preferred below 0.2, more preferably the exposure-processed under the low NA condition below 0.15.Adopt the exposure-processed under the low NA condition can enlarge the single exposure area, thereby can boost productivity.
Next (dry the exposure back: PEB) the resist tunicle after the selection exposure to be implemented heat treated.For example have as the PEB method: between electric hot plate and substrate, form spaced contiguous oven dry, the not direct oven dry at interval, in order to prevent the warpage of substrate, acquisition is preferably adopted the method for directly drying again by the diffusion effect that PEB produces after being close to oven dry.In addition, heating-up temperature is preferably 90～150 ℃, preferred especially 100～140 ℃.
To the resist tunicle behind the described PEB, with developer solution, for example the aqueous alkalis such as tetramethylphosphonihydroxide hydroxide base amine aqueous solution of 1～10 quality % carry out development treatment, then exposed portion is dissolved removes, and can form the corrosion-resisting pattern that corrosion-resisting pattern that integrated circuit uses and liquid-crystal display section are used on the substrate simultaneously.
Then, wash the developer solution that remains in the corrosion-resisting pattern surface off, form corrosion-resisting pattern with rinsing liquids such as pure water.
In the formation method of this corrosion-resisting pattern, when manufacturing system LCD, in the operation of carrying out above-mentioned optionally exposure, can use the corrosion-resisting pattern described below the 2.0 μ m to form as described mask and form with the two mask of mask pattern with mask pattern and the corrosion-resisting pattern that surpasses 2.0 μ m.
Therefore LCD of the present invention has good linearity with eurymeric resist composition, can obtain verily to reproduce the two corrosion-resisting pattern of coarse patterns in the mask pattern and fine pattern.Thus, can form the corrosion-resisting pattern that the integrated circuit of pattern dimension below 2.0 μ m use and surpass the corrosion-resisting pattern that the liquid-crystal display section of 2.0 μ m is used on the substrate simultaneously.
Embodiment
Be described in more detail the present invention with embodiment below, but the present invention is not limited to embodiment.
[evaluation method of eurymeric resist composition]
Eurymeric resist composition to following embodiment or comparative example is estimated its each rerum natura (1)～(5) according to following method.
(1) sensitivity evaluation
With resist-coating device (device name: TR36000 answers in Tokyo chemical industry (strain) system) eurymeric resist composition is coated on silicon chip (after 550mm * 650mm) goes up with large substrate, under 90 ℃, 90 seconds heating condition, carry out prebake by the contiguous oven dry that is about 1mm at interval, forming thickness is the resist tunicle of 1.5 μ m.
Then by describing to be useful on reproduction 1.5 μ m L﹠amp simultaneously; S corrosion-resisting pattern and 3.0 μ m L﹠amp; The Test Drawing mask of the mask pattern of S corrosion-resisting pattern (レ チ Network Le) is with i line exposing device (device name: FX-702J, Nikon society system; And use and verily to reproduce 1.5 μ m L﹠amp NA=0.14); The exposure of S (Eop exposure) is optionally exposed.
Then under 120 ℃, 90 seconds condition, implement PEB by the contiguous oven dry that is spaced apart 0.5mm.
Carry out the development treatment in 60 seconds with 23 ℃, the TMAH aqueous solution of 2.38 quality % then, use 30 seconds of pure water rinsing afterwards, be rotated drying.
As the index that sensitivity is estimated, 1.5 μ m L﹠amp can be verily reproduced in employing; The exposure of the corrosion-resisting pattern of S (Eop, unit: mJ).
(2) DOF evaluating characteristics:
In described Epo exposure, suitably adjust focus up and down, be that unit obtains 1.5 μ mL﹠amp with μ m; The amplitude of the depth of focus (DOF) that S obtains in ± 10% size changing rate scope the time.
(3) thermotolerance evaluation:
In described Epo exposure, 3.0 μ m L﹠amp will have been described; The substrate of S be set to left standstill for 300 seconds on 140 ℃ the electric hot plate after, observe cross sectional shape.Its result, 3.0 μ m L﹠amp; The size changing rate of S ± 3% with interior usefulness zero, in 3～5% or-5～-3% scope with △, surpass usefulness * expression of ± 5%.
(4) resolving power evaluation: calculate the limit resolution in the described Eop exposure.
(5) linear evaluation: observe the 3.0 μ m L﹠amp that obtain with described Eop exposure by SEM (scanning electron microscope) photo; The cross sectional shape of the corrosion-resisting pattern of S is estimated 3.0 μ m L﹠amp; The repeatability of the corrosion-resisting pattern of S.3.0 μ m L﹠amp; The size changing rate of S ± 10% with interior usefulness zero, in 10～15% or-15～-10% scope with △, surpass usefulness * expression of ± 15%.
(embodiment 1～7, comparative example 1～4)
Prepare following material as (A)～(D) composition.
(A) alkali solubility novolac resin:
(a1) with metacresol/3, the mixed phenol 1mol of 4-xylenols=8/2 (mol ratio) and formaldehyde 0.76mol are according to well-established law novolac resin synthetic, Mw=12000, Mw/Mn=4.7
(a2) with metacresol/3, the mixed phenol 1mol of 4-xylenols=8/2 (mol ratio) and formaldehyde 0.8mol are according to well-established law novolac resin synthetic, Mw=17000, Mw/Mn=5
(a3) with metacresol/3, the mixed phenol 1mol of 4-xylenols=8/2 (mol ratio) and formaldehyde 0.82mol are according to well-established law novolac resin synthetic, Mw=20000, Mw/Mn=5.2
(a4) with metacresol/3, the mixed phenol 1mol of 4-xylenols=8.5/1.5 (mol ratio) and formaldehyde 0.85mol are according to well-established law novolac resin synthetic, Mw=25000, Mw/Mn=5.5
(a5) with metacresol/3, the mixed phenol 1mol of 4-xylenols=8.5/1.5 (mol ratio) and formaldehyde 0.87mol are according to well-established law novolac resin synthetic, Mw=30000, Mw/Mn=5.8
(a6) with metacresol/3, the mixed phenol 1mol of 4-xylenols=9/1 (mol ratio) and formaldehyde 0.89mol are according to well-established law novolac resin synthetic, Mw=35000, Mw/Mn=6.1
(a7) with metacresol/3, the mixed phenol 1mol of 4-xylenols=9/1 (mol ratio) and formaldehyde 0.91mol are according to well-established law novolac resin synthetic, Mw=40000, Mw/Mn=6.4
(a8) the mixed phenol 1mol of usefulness metacresol/paracresol=9/1 (mol ratio) and formaldehyde 0.73mol are according to well-established law novolac resin synthetic, Mw=7000, Mw/Mn=3
(a9) the mixed phenol 1mol of usefulness metacresol/paracresol=9/1 (mol ratio) and formaldehyde 0.75mol are according to well-established law novolac resin synthetic, Mw=9000, Mw/Mn=3.2
(a10) the mixed phenol 1mol of usefulness metacresol/paracresol=9.5/0.5 (mol ratio) and formaldehyde 0.92mol are according to well-established law novolac resin synthetic, Mw=45000, Mw/Mn=6.7
(a11) the mixed phenol 1mol of usefulness metacresol/paracresol=9.5/0.5 (mol ratio) and formaldehyde 0.95mol are according to well-established law novolac resin synthetic, Mw=50000, Mw/Mn=7
(B) contain benzoquinones diazido compound:
(B1) two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-3,4-dihydroxy benzenes methylmethane (B1 ') 1mol and 1, the esterification reaction product of 2-naphthoquinones diazido-5-sulfonic acid chloride [being designated hereinafter simply as (5-NQD)] 2mol
(B2) esterification reaction product of two (2, the 4-dihydroxy phenyl) methane (B2 ') 1mol and 5-NQD 2mol
(B3) esterification reaction product of two (4-hydroxyl-2,3,5-trimethylphenyl)-2-hydroxy phenyl methane (B3 ') 1mol and 5-NQD 2mol
(C) contain the phenol hydroxyl compound:
(C1) two (2-methyl-4-hydroxy phenyl)-phenylmethanes
(D) organic solvent: PGMEA
Use described (A)～(C) composition according to the use level shown in the table 1, the gross mass with above-mentioned (A)～(C) composition is a benchmark simultaneously, uses surfactant (the goods name " メ ガ Off ア Star Network R-08 " that is equivalent to the 450ppm amount; Big Japanese ink chemical industry (strain) system), they being dissolved in (D) composition that table 1 puts down in writing, is that the membrane filter of 0.2 μ m filters with the aperture then, modulates eurymeric resist composition.The potpourri that (//) expression mixes with the mass ratio shown in it in the table 1.
Resulting eurymeric resist composition is estimated projects of described (1)～(5) respectively.Its result is as shown in table 2.
Table 1
| The Mw of resist composition | A composition (use level) | B composition (use level) | C composition (use level) | D composition (use level) | |
| Embodiment 1 | ??5000 | ????a1 ????(15) | B1/B2/B3 [75/12.5/12.5 (mol ratio)] 5.5 | ????C1 ????(4.5) | ????PGMEA ????(75) |
| Embodiment 2 | ??7000 | ????a2 ????(15) | The same | The same | The same |
| Embodiment 3 | ??10000 | ????a3 ????(15) | The same | The same | The same |
| Embodiment 4 | ??15000 | ????a4 ????(15) | The same | The same | The same |
| Embodiment 5 | ??20000 | ????a5 ????(15) | The same | The same | The same |
| Embodiment 6 | ??25000 | ????a6 ????(15) | The same | The same | The same |
| Embodiment 7 | ??30000 | ????a7 ????(15) | The same | The same | The same |
| Comparative example 1 | ??3000 | ????a8 ????(15) | The same | The same | The same |
| Comparative example 2 | ??4000 | ????a9 ????(15) | The same | The same | The same |
| Comparative example 3 | ??35000 | ????a10 ????(15) | The same | The same | The same |
| Comparative example 4 | ??40000 | ????a11 ????(15) | The same | The same | The same |
Table 2
| Sensitivity (mJ) | DOF(μm) | Thermotolerance | Resolving power (μ m) | Linear | |
| Embodiment 1 | ????40 | ????16 | ????△ | ????1.3 | ????○ |
| Embodiment 2 | ????50 | ????17 | ????△ | ????1.2 | ????○ |
| Embodiment 3 | ????70 | ????17 | ????○ | ????1.2 | ????○ |
| Embodiment 4 | ????90 | ????16 | ????○ | ????1.2 | ????○ |
| Embodiment 5 | ????110 | ????16 | ????○ | ????1.3 | ????○ |
| Embodiment 6 | ????130 | ????16 | ????○ | ????1.3 | ????○ |
| Embodiment 7 | ????150 | ????16 | ????○ | ????1.3 | ????○ |
| Comparative example 1 | ????10 | ????10 | ????× | ????1.5 | ????× |
| Comparative example 2 | ????20 | ????12 | ????× | ????1.5 | ????× |
| Comparative example 3 | ????250 | ????11 | ????○ | ????1.4 | ????△ |
| Comparative example 4 | ????350 | ????10 | ????○ | ????1.4 | ????△ |
Good and the excellent heat resistance of aforesaid its sensitivity of eurymeric resist composition of the present invention can obtain high-resolution, therefore makes applicable to the LCD of system, can boost productivity.
In addition, because of having good linearity, coarse pattern and fine pattern can formed on a substrate under the same conditions of exposure.Therefore, can be simultaneously obtain the display part of the LCD of system and than the corrosion-resisting pattern of fine integrated circuit part, thereby be suitable for the manufacturing of the LCD of system with high-resolution.
In addition, use in the eurymeric resist composition at the LCD of system, the amplitude ratio of depth of focus (DOF) is bigger, and this is extremely important at the aspects such as control easiness of making efficient, create conditions, according to the present invention, can realize can be used as the LCD of system and use and the depth of focus width of cloth (for example more than the 15 μ m) of practical application.
Claims (6)
1. eurymeric resist composition, it is the substrate manufacturing eurymeric resist composition that on a substrate, is formed with integrated circuit and liquid-crystal display section, it is characterized in that: wherein contain (A) alkali soluble resins, (B) and contain benzoquinones diazido compound, (C) molecular weight (M) and containing phenol hydroxyl compound and (D) organic solvent below 1000, the polystyrene conversion weight-average molecular weight (Mw) of passing through gel permeation chromatography of the contained solid constituent of this resist composition is in 5000～30000 scope.
2. eurymeric resist composition according to claim 1, contain in wherein said (B) composition following formula (I) represented contain phenol hydroxyl compound and 1, the esterification reaction product of 2-naphthoquinones diazido-5-sulfonyl compound,
[in the formula, R
1～R
8Represent the alkyl of hydrogen atom, halogen atom, carbon number 1～6, the alkoxy of carbon number 1～6 or the naphthenic base of carbon number 3～6 independently of one another; R
10, R
11Represent the alkyl of hydrogen atom or carbon number 1～6 independently of one another; R
9Can be the alkyl of hydrogen atom or carbon number 1～6, at this moment, Q
1Be the alkyl of hydrogen atom, carbon number 1～6 or the residue shown in the following chemical formula (II)
(in the formula, R
12And R
13Represent the alkyl of hydrogen atom, halogen atom, carbon number 1～6, the alkoxy of carbon number 1～6 or the naphthenic base of carbon number 3～6 independently of one another; C represents 1～3 integer), Q
1Can also and R
9The end combination, at this moment, Q
1And R
9And Q
1And R
9Between carbon atom represent the naphthenic base of carbochain 3～6 together; A, b represent 1～3 integer; D represents 0～3 integer; N represents 0～3 integer].
3. eurymeric resist composition according to claim 1, contain in wherein said (C) composition following formula (III) represented contain the phenol hydroxyl compound,
[in the formula, R
21～R
28Represent the alkyl of hydrogen atom, halogen atom, carbon number 1～6, the alkoxy of carbon number 1～6 or the naphthenic base of carbon number 3～6 independently of one another; R
30, R
31Represent the alkyl of hydrogen atom or carbon number 1～6 independently of one another; R
29Can be the alkyl of hydrogen atom or carbon number 1～6, at this moment, Q
2Be the alkyl of hydrogen atom, carbon number 1～6 or the residue shown in the following chemical formula (IV)
(in the formula, R
32And R
33Represent the alkyl of hydrogen atom, halogen atom, carbon number 1～6, the alkoxy of carbon number 1～6 or the naphthenic base of carbon number 3～6 independently of one another; G represents 1～3 integer), Q
2Can also and R
29The end combination, at this moment, Q
2And R
29And Q
2And R
29Between carbon atom represent the naphthenic base of carbochain 3～6 together; E, f represent 1～3 integer; H represents 0～3 integer; M represents 0～3 integer].
4. eurymeric resist composition according to claim 1 contains the propylene-glycol monoalky lether acetic acid esters or/and the 2-heptanone in wherein said (D) composition.
5. the formation method of a corrosion-resisting pattern, comprise following operation: (1) is coated with each the described positive light anti-etching agent composition in the claim 1～4 on substrate, forms the operation of filming; (2) carry out heat treated (prebake) to being formed with described substrate of filming, on substrate, form the operation of resist tunicle; (3) use and to describe the following corrosion-resisting pattern of 2.0 μ m and form with mask pattern and the corrosion-resisting pattern that surpasses 2.0 μ m and form with the two mask of mask pattern, the operation of described resist tunicle being carried out the selectivity exposure; (4) the resist tunicle after the described selectivity exposure is implemented the operation of heat treated (drying after the exposure); (5) the resist tunicle after the described heat treated (exposure back oven dry) is used the development treatment of aqueous alkali, forming the operation that pattern dimension is the corrosion-resisting pattern used of the corrosion-resisting pattern used of the integrated circuit below the 2.0 μ m and the liquid-crystal display section that surpasses 2.0 μ m on the described substrate simultaneously.
6. the formation method of corrosion-resisting pattern according to claim 5, wherein said (3) carry out using the i line as light source in the operation of selectivity exposure, are by being that exposure-processed under the low NA condition below 0.3 is carried out at NA.
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| KR100194370B1 (en) * | 1993-04-28 | 1999-06-15 | 마에다 가쯔노스께 | Forged electron beam resist composition and developer for forged electron beam resist |
| JPH06348007A (en) * | 1993-06-07 | 1994-12-22 | Sumitomo Chem Co Ltd | Photosensitive resin composition and production thereof |
| JPH08234423A (en) * | 1995-02-27 | 1996-09-13 | Nippon Zeon Co Ltd | Positive type resist composition |
| JPH0990622A (en) * | 1995-09-22 | 1997-04-04 | Fuji Photo Film Co Ltd | Positive photoresist composition |
| JP3376222B2 (en) * | 1996-10-25 | 2003-02-10 | クラリアント インターナショナル リミテッド | Radiation-sensitive composition |
| JP3978885B2 (en) | 1998-08-19 | 2007-09-19 | Ｊｓｒ株式会社 | Radiation sensitive resin composition |
| JP2000258901A (en) | 1999-03-11 | 2000-09-22 | Jsr Corp | Radiation sensitive resin composition |
| MY133599A (en) * | 1999-10-07 | 2007-11-30 | Az Electronic Mat Japan K K | Photosensitive composition |
| KR100846084B1 (en) * | 2001-01-16 | 2008-07-14 | 주식회사 동진쎄미켐 | Positive photoresist composition |
| JP2002244285A (en) * | 2001-02-20 | 2002-08-30 | Jsr Corp | Radiation sensitive resin composition |
| JP2003195495A (en) | 2001-12-26 | 2003-07-09 | Tokyo Ohka Kogyo Co Ltd | Positive photoresist composition |
-
2003
- 2003-05-19 JP JP2003140576A patent/JP2004341431A/en not_active Withdrawn
-
2004
- 2004-04-23 TW TW093111509A patent/TW200426504A/en unknown
- 2004-05-12 KR KR1020040033351A patent/KR100572544B1/en not_active IP Right Cessation
- 2004-05-17 CN CNB2004100447100A patent/CN100347610C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104710588A (en) * | 2013-12-12 | 2015-06-17 | 罗门哈斯电子材料有限公司 | Aromatic resins for underlayers |
| US9540476B2 (en) | 2013-12-12 | 2017-01-10 | Rohm And Haas Electronic Materials Llc | Aromatic resins for underlayers |
| US9809672B2 (en) | 2013-12-12 | 2017-11-07 | Rohm And Haas Electronic Materials Llc | Aromatic resins for underlayers |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100572544B1 (en) | 2006-04-24 |
| KR20040100912A (en) | 2004-12-02 |
| JP2004341431A (en) | 2004-12-02 |
| CN100347610C (en) | 2007-11-07 |
| TW200426504A (en) | 2004-12-01 |
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