CN1690856A - Chemical amplification positive photoresist compositions - Google Patents

Chemical amplification positive photoresist compositions Download PDF

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Publication number
CN1690856A
CN1690856A CNA200510067313XA CN200510067313A CN1690856A CN 1690856 A CN1690856 A CN 1690856A CN A200510067313X A CNA200510067313X A CN A200510067313XA CN 200510067313 A CN200510067313 A CN 200510067313A CN 1690856 A CN1690856 A CN 1690856A
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China
Prior art keywords
composition
alkali
novolac resin
resin
molecular
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Inventor
宫城贤
馆俊聪
新仓聪
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Tokyo Ohka Kogyo Co Ltd
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Tokyo Ohka Kogyo Co Ltd
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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
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • 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
    • 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)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

This invention provides a photoresist composition with which a resist pattern shape does not deform and occurrence of a sublimation substance is reduced during a high temperature heat treatment and which has excellent heat resistance . The chemically amplified positive photoresist composition contains (A) a resin component, (C) a compound which produces an acid component by irradiation, and an organic solvent, and the solubility of the composition with an alkali aqueous solution increases by the effect of the acid component produced from the component (C). The component (A) contains a resin component (a1) obtained by subjecting a resin hardly soluble or insoluble with an alkali to a process of separating and removing a low molecular weight fraction, wherein the resin is prepared by protecting a part of the whole phenolic hydroxyl groups in an alkali soluble novolac resin with acid dissociable dissolution inhibiting groups.

Description

Chemically amplified posative opto-corrosionproof agent composition
Technical field
The present invention relates to chemically amplified posative opto-corrosionproof agent composition.
Background technology
So far, in fields such as preparation semiconductor element, liquid crystal display cells (LCD), galley, projection formations, magnetic head, generally uses with alkali soluble resin and contain the compound (PAC) of quinone diazido for the g～i line photo-corrosion-resisting agent composition of major component, with the compound (resin) that contains the acid dissociation group and light acid propellant (PAG) as the i line of major component use, KrF uses, ArF uses or electron ray chemical amplification type photo-corrosion-resisting agent composition etc.
As the chemical amplification type photo-corrosion-resisting agent composition, the composition of putting down in writing in the known following patent documentation 1～4 etc.
In patent documentation 1, to have put down in writing and contained the composition that resinous principle and PAG form, this resinous principle is to suppress base with the part protection of the hydrogen atom of the hydroxyl of polycarboxylated styrene and form with the acid dissociation dissolving.
In patent documentation 2,3, put down in writing the chemically amplified posative opto-corrosionproof agent composition that side chains such as containing novolac resin has alkali soluble resin, specific cross linker and the acid-producing agent of hydroxyl.
In patent documentation 4, to have put down in writing and contained the composition that partial cross-linked polymkeric substance and PAG form, this partial cross-linked polymkeric substance is to make the polymkeric substance of hydroxyl and polyvinylether prepared in reaction in the presence of acid catalyst.
Patent documentation 1: the spy opens flat 10-97074 communique
Patent documentation 2: the spy opens flat 6-148889 communique
Patent documentation 3: the spy opens flat 6-230574 communique
Patent documentation 4: special table 2002-529552 communique
Be accompanied by development of technology in each field, because of the difference of purposes has proposed stable on heating requirement to photo-corrosion-resisting agent composition.
For example, as follow-on LCD, expectation on 1 sheet glass substrate with the display part form simultaneously the integrated circuit part of driver, DAC (digital analog converter), image processor, image controller, RAM etc. the high-performance LCD that is called what is called " system LCD " (the semiconductor FPD world 2001.9, pp.50-67).
In the TFT of the LCD of this system (thin film transistor (TFT)), because the resistance ratio amorphous silicon is little, mobility ratio amorphous silicon height, the low-temperature poly-silicon that therefore especially preferably adopts the low temperature process below 600 ℃ to form.
In order to prepare the TFT that constitutes by low-temperature poly-silicon, need with low temperature process after forming poly-silicon fiml on the glass substrate, P, B etc. to be thrown in this low-temperature poly-silicon film, promptly in so-called " injection process ", throw the very high impurity of concentration into.This injection process carries out under the condition of condition of high vacuum degree, but owing to squeeze into the heating functioin that impurity produces, resist pattern on the substrate is heated, thereby there is the change of shape cause the resist pattern, the composition that perhaps exists in resist pattern gasification and make the problem of the vacuum tightness reduction process chamber in.
As the means that address this problem, the heating treatment step that is called " back baking " before injection process is effective, this back baking is under the approaching temperature conditions of the temperature of heating when injecting, for example under the high temperature more than 180 ℃, carry out, therefore when this heat treated, there are the change of shape of above-mentioned resist pattern and the pollution problems of the process chamber inwall that gasification (generation of sublimate) is produced.
Resinous principle as photo-corrosion-resisting agent composition; because novolac resin is very cheap; and thermotolerance is also excellent; therefore preferably this novolac resin is used for the design of the chemically amplified posative opto-corrosionproof agent composition of raw material; but present inventor etc. learn by experiment, suppress the resinous principle of base with the part protection of the hydrogen atom of the hydroxyl of this novolac resin with the acid dissociation dissolving; or the resinous principle that conduct makes this novolac resin and specific cross linker react the resultant of reaction that obtains has caused stable on heating remarkable reduction when hydroxyl reduces.
Therefore, although novolac resin is very excellent material, but in the chemically amplified posative opto-corrosionproof agent composition that its hydroxyl need be shielded, be difficult to obtain the resist pattern of excellent heat resistance, therefore with the practicability difficulty of this novolac resin as the chemically amplified posative opto-corrosionproof agent composition of raw material.
Summary of the invention
The present invention In view of the foregoing proposes, and purpose is to provide uses the alkali-soluble novolac resin as raw material, the chemically amplified posative opto-corrosionproof agent composition of excellent heat resistance.
To achieve these goals, the present invention adopts following formation.
Chemically amplified posative opto-corrosionproof agent composition, it contains (A) resinous principle, (C) produce sour composition by the irradiation of radioactive ray compound and organic solvent, has effect by the sour composition that produces by described (C) composition, character for the dissolubility of aqueous alkali increases is characterized in that:
Described (A) composition contains resinous principle (a1); resinous principle (a1) is with the part protection of acid dissociation dissolving inhibition base with whole phenol hydroxyls of alkali-soluble novolac resin, and the alkali slightly solubility or the insoluble resin that form are implemented the processing that the separation of low-molecular-weight body is removed is obtained.
Chemically amplified posative opto-corrosionproof agent composition, it contains (A) resinous principle, (C) produce sour composition by the irradiation of radioactive ray compound and organic solvent, has effect by the sour composition that produces by described (C) composition, character for the dissolubility of aqueous alkali increases is characterized in that:
Described (A) composition contains alkali slightly solubility or insoluble resin (a2), and resin (a2) is to suppress base with the acid dissociation dissolving will implement the low-molecular-weight body to be separated the part protection of whole phenol hydroxyls of removing the alkali-soluble novolac resin after the processing of handling and form.
Chemically amplified posative opto-corrosionproof agent composition, it contains (A) resinous principle, (C) produce sour composition by the irradiation of radioactive ray compound and organic solvent, has effect by the sour composition that produces by described (C) composition, character for the dissolubility of aqueous alkali increases is characterized in that:
Described (A) composition contains resinous principle (a3), and resinous principle (a3) is to make alkali-soluble novolac resin and (B) reaction of the crosslinking chemical shown in the following general formula (I), the resultant of reaction enforcement that obtains is separated the low-molecular-weight body to remove to handle obtaining,
H 2C＝CH-O-R 1-O-CH＝CH 2???????????????(I)
In the formula, R 1Expression can have any of group shown in the alkylidene of substituent carbon number 1-10 or the following general formula (Ia),
Figure A20051006731300071
In the formula, R 4Expression can have the alkylidene of substituent carbon number 1-10, and m represents 0 or 1.
Chemically amplified posative opto-corrosionproof agent composition, it contains (A) resinous principle, (C) produce sour composition by the irradiation of radioactive ray compound and organic solvent, has effect by the sour composition that produces by described (C) composition, character for the dissolubility of aqueous alkali increases is characterized in that:
Described (A) composition contains resultant of reaction (a4), resultant of reaction (a4) make after the processing of having implemented the low-molecular-weight body separate to remove is handled the alkali-soluble novolac resin and (B) reaction of crosslinking chemical shown in the above-mentioned general formula (I) obtain.
According to the present invention, by carrying out that in the operation of modulation (A) composition the low-molecular-weight body is separated the processing of removing, the content of the low-molecular-weight body in the chemically amplified posative opto-corrosionproof agent composition is reduced, the chemically amplified posative opto-corrosionproof agent composition of excellent heat resistance can be provided.
Embodiment
[the 1st embodiment]
◆ (A) composition
In the 1st embodiment of chemically amplified posative opto-corrosionproof agent composition of the present invention; (A) composition contains resinous principle (a1); resinous principle (a1) is with the part protection of acid dissociation dissolving inhibition base with whole phenol hydroxyls of alkali-soluble novolac resin, and the alkali slightly solubility or the insoluble resin that form are implemented the processing that the separation of low-molecular-weight body is removed is obtained.
As above-mentioned alkali-soluble novolac resin, there is no particular restriction, can preferably enumerate the novolac resin that makes aromatic hydroxy compound and aldehydes or ketone condensation reaction and obtain from positive light anti-etching agent composition, forming selection arbitrarily in the normally used material of material as tunicle.
As the above-mentioned aromatic hydroxy compound of use in novolac resin synthetic, can enumerate for example phenol; Cresols classes such as metacresol, paracresol, orthoresol; 2,3-xylenols, 2,5-xylenols, 3,5-xylenols, 3, dimethylbenzene phenols such as 4-xylenols; M-ethylphenol, paraethyl phenol, o-ethyl phenol, 2,3,5-pseudocuminol, 2,3,5-triethyl phenol, 4-tert-butyl phenol, 3-tert-butyl phenol, 2-tert-butyl phenol, the 2-tert-butyl group-4-methylphenol, the 2-tert-butyl group-induced by alkyl hydroxybenzene such as 5-methylphenol; P methoxy phenol, meta-methoxy phenol, to thanatol, m-oxethyl phenol, to alkoxy phenols such as propoxyl group phenol, propoxyl group phenol; Adjacent isopropenyl phenol, to isopropenyl phenol, 2-methyl-4-isopropenyl phenol, 2-ethyl-isopropenyl phenols such as 4-isopropenyl phenol; Aryl phenols such as phenylphenol; 4, polyhydroxy phenols such as 4 '-dihydroxybiphenyl, bisphenol-A, resorcinol, quinhydrones, 1,2,3,-thrihydroxy-benzene etc.These may be used alone, two or more kinds can also be used in combination.
As the synthetic middle above-mentioned aldehydes that uses of novolac resin, can enumerate for example formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionic aldehyde, butyraldehyde, trimethyl-acetaldehyde, acryl aldehyde, crotonaldehyde, hexamethylene alkanal, furfural, furylacrolein, benzaldehyde, o-phthalaldehyde(OPA), phenyl acetaldehyde, α-hydrocinnamicaldehyde, beta-phenyl propionic aldehyde, salicylaldhyde, m-hydroxybenzaldehyde, parahydroxyben-zaldehyde, o-methyl-benzene formaldehyde, a tolyl aldehyde, p-tolyl aldehyde, o-chlorobenzaldehyde, m chlorobenzaldehyde, 4-chloro-benzaldehyde, lauryl aldehyde etc.These may be used alone, two or more kinds can also be used in combination.
In these aldehydes, owing to obtain easily, therefore preferred formaldehyde improves in order to make thermotolerance, especially preferably hydroxy benzaldehyde class and formaldehyde is used in combination.
As the synthetic middle above-mentioned ketone that uses of novolac resin, can enumerate for example acetone, methyl ethyl ketone, diethyl ketone, benzophenone etc.These may be used alone, two or more kinds can also be used in combination.More preferably aldehydes and ketone appropriate combination are used.
Novolac resin can be by in the presence of acidic catalyst, and the employing known method makes above-mentioned aromatic hydroxy compound and aldehydes or ketone condensation reaction and prepares.Acidic catalyst as this moment can use hydrochloric acid, sulfuric acid, formic acid, oxalic acid, p-toluenesulfonic acid etc.
The preferable range of the polystyrene conversion matter average molecular weight (Mw) of alkali-soluble novolac resin before suppressing the base protection with the acid dissociation dissolving is 2000-50000, more preferably 4000-30000 in the present embodiment.If this Mw is littler than above-mentioned scope, the possible variation of coating is if surpass above-mentioned scope, resolution deterioration.
It is to decompose by acid catalyzed reaction that the acid dissociation dissolving suppresses base, becomes the group of alkali-soluble.
Suppress base as this acid dissociation dissolving, can be the group that dissociates owing to the acid that aftermentioned (C) composition produces, can enumerate for example alkoxyalkyls such as ethoxymethyl, 1-ethoxyethyl, the third oxygen methyl, the 1-third oxygen ethyl, positive fourth oxygen methyl, isobutyl oxygen methyl, uncle's fourth oxygen methyl; Alkoxycarbonyl alkyls such as tertbutyloxycarbonyl, tertiary butyloxycarbonyl ylmethyl, tertbutyloxycarbonyl ethyl; Tetrahydrofuran base; THP trtrahydropyranyl; A straight chain shape or a chain acetal radical; The cyclic acetal base; Trialkylsilkls such as trimethyl silyl, triethylsilyl, triphenyl silicyl.
Wherein, from the photo-corrosion-resisting agent composition that can obtain the resolution excellence, the tertbutyloxycarbonyl shown in ethyl vinyl (ethoxyethyl) shown in the preferred following chemical formula (II-1) and the following chemical formula (II-2), preferred especially ethyl vinyl.
Figure A20051006731300091
Figure A20051006731300092
Constituting the alkali slightly solubility of (a1) composition or insoluble resinous principle can synthesize by above-mentioned alkali-soluble novolac resin with the addition reaction that above-mentioned acid dissociation dissolving suppresses basic suitable compound.
Suppressed by the acid dissociation dissolving to be preferably about the 10-50 mole % of whole phenol hydroxyls in the resinous principle (a1) of ratio (protection ratio) after low-molecular-weight body described later is removed processing of the basic phenol hydroxyl of protecting.
Resinous principle (a1) is by implementing the processing that the separation of low-molecular-weight body is removed is prepared to alkali slightly solubility or insoluble resin with acid dissociation dissolving inhibition base.
Low-molecular-weight body in this instructions comprises (monomer and 2-3 nucleomes etc.) such as the dimer of for example residual monomer, monomer 2 molecule combinations, the tripolymers of 3 molecule combinations.
Method for separating and processing as the low-molecular-weight body, be not particularly limited, for example, can use spent ion exchange resin to the method that has the acid dissociation dissolving and suppress the alkali slightly solubility of base or insoluble resin purification, use the good solvent (alcohol etc.) of this resin and the known lock out operation of poor solvent (water etc.).The method that adopts the former can also be removed sour composition, metal ingredient when the low-molecular-weight body is removed.
Remove in the processing scope of the preferred 50-95 quality of the yield % of resinous principle (a1) in the separation of this low-molecular-weight body.When less than 50 quality %, the caused dissolution velocity for aqueous alkali of effect of the sour composition that is produced by (C) described later composition increases and becomes insufficient.Its result: the difference of the dissolution velocity between exposed portion and the unexposed portion reduces, and resolution reduces.On the other hand, when surpassing 95 quality %, can not fully obtain to separate the effect that removal produces.
In addition, the preferable range of the polystyrene conversion matter average molecular weight (Mw) of gained resin is 5000-100000, more preferably 7000-60000 after this separating treatment.By making this Mw is more than 5000, and the stable on heating raising effect of resist pattern is given full play to.If Mw surpasses 100000, there is the tendency of coating variation, therefore not preferred.In addition, Mw is that the content of the low-molecular-weight body below 500 is preferably below 15% on GPC figure, more preferably below 12%.By being below 15%, the thermotolerance of resist pattern improves effect and is achieved, and the effect of the generation of sublimate also is achieved when suppressing heat treated simultaneously.
(C) composition
Be not particularly limited as (C) composition; can use in the past the known light acid propellant of material, for example sulfonyl diazomethane class acid-producing agent, salt acid-producing agent, oxime sulfonates class acid-producing agent etc. as the positive light anti-etching agent composition of chemical amplification type.
In the present invention, be not particularly limited, be raw material from using novolac resin for the wavelength of the light source that in photoengraving, uses, preferred i line (365nm), when this i line is used for light source, from sour luminous efficiency height for the i line exposing, the compound that preferred use is for example following.
Compound shown in following general formula (III), (IV).
Figure A20051006731300111
(in the formula, m ' expression 0 or 1; X represents 1 or 2; R 1Expression can be by the C more than 1 or 1 1-C 12The phenyl that alkyl replaces, heteroaryl etc., or m ' also represented C at 0 o'clock 2-C 6Alkoxy carbonyl group, carbobenzoxy, CN etc.; R 1' expression C 2-C 12Alkylidene etc.; R 2With R 1Synonym etc.; R 3Expression C 1-C 18Alkyl etc.; R 3' when X=1 and R 3Synonyms etc. are represented C when X=2 2-C 12Alkylidene, phenylene etc.; R 4, R 5Represent hydrogen atom, halogen, C independently 1-C 6Alkyl etc.; A represents S, O, NR 6Deng; R 6Expression hydrogen atom, phenyl etc.) shown in compound (USP6004724).Particularly, can enumerate the oxime sulfonates that contains thiorene shown in for example following formula (V) etc.
In addition, following formula (VI)
Figure A20051006731300122
(in the formula, R 6, R 7The alkyl of representing carbon number 1-3 separately.) shown in two (trichloromethyl) triaizine compounds or this compound (VI) and following formula (VII)
The combination (spy opens flat 6-289614 communique, the spy opens flat 7-134412 communique) of two (trichloromethyl) triaizine compounds shown in (in the formula, Z represents 4-alkoxyphenyl radical etc.).
As triaizine compounds (VI), specifically can enumerate for example 2-[2-(3, the 4-Dimethoxyphenyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(3-methoxyl-4-ethoxyl phenenyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(3-methoxyl-4-propoxyl group phenyl) vinyl]-4,6-two (trichloromethyl)-1,3,5-triazines, 2-[2-(3-ethoxy-4-methoxyphenyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(3,4-diethoxy phenyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(3-ethoxy-4-propoxyl group phenyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(3-propoxyl group-4-methoxyphenyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(3-propoxyl group-4-ethoxyl phenenyl) vinyl]-4,6-two (trichloromethyl)-1,3,5-triazines, 2-[2-(3,4-dipropoxy phenyl) vinyl]-4,6-two (trichloromethyl)-1,3,5-triazines etc.These triaizine compounds may be used alone, two or more kinds can also be used in combination.
On the other hand, as the above-mentioned triaizine compounds (VII) that is used in combination with above-mentioned triaizine compounds (VI) as required, can enumerate for example 2-(4-methoxyphenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-ethoxyl phenenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-propoxyl group phenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-butoxy phenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-methoxyl naphthyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-ethoxy naphthyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-propoxyl group naphthyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-butoxy naphthyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-methoxyl-6-carboxyl naphthyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(4-methoxyl-6-hydroxyl naphthyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(2-furyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(5-methyl-2-furyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(5-ethyl-2-furyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(5-propyl group-2-furyl) vinyl]-4,6-two (trichloromethyl)-1,3,5-triazines, 2-[2-(3, the 5-Dimethoxyphenyl) vinyl]-4,6-two (trichloromethyl)-1,3,5-triazines, 2-[2-(3-methoxyl-5-ethoxyl phenenyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(3-methoxyl-5-propoxyl group phenyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(3-ethoxy-5-methoxyphenyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(3,5-diethoxy phenyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(3-ethoxy-5-propoxyl group phenyl) vinyl]-4,6-two (trichloromethyl)-1,3,5-triazines, 2-[2-(3-propoxyl group-5-methoxyphenyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(3-propoxyl group-5-ethoxyl phenenyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(3,5-dipropoxy phenyl) vinyl]-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-(3, the 4-methylenedioxyphenyl)-4,6-two (trichloromethyl)-1,3, the 5-triazine, 2-[2-(3, the 4-methylenedioxyphenyl) vinyl]-4,6-two (trichloromethyl)-1,3,5-triazine etc.These triaizine compounds can use a kind, also can be used in combination more than 2 kinds.
In addition, can enumerate following formula (VIII)
(in the formula, Ar represents to replace or unsubstituted phenyl, naphthyl; R represents C 1-C 9Alkyl; N represents 2 or 3 integer.) shown in compound.These compounds may be used alone, two or more kinds can also be used in combination.In above illustrative compound, owing to sour luminous efficiency excellence for the i line, so compound shown in the preferred especially above-mentioned formula (V) and the compound shown in the following formula (IX).
Figure A20051006731300142
In the present embodiment, (C) composition can mix use more than a kind or 2 kinds.
(C) use level of composition is the 1-30 mass parts with respect to (A) composition 100 mass parts, is preferably the 1-20 mass parts.
(D) composition
In the chemically amplified posative opto-corrosionproof agent composition of present embodiment, in order to improve mounting ageing stability (post exposure stability of the latent imageformed by the pattern wise exposure of the resist layer), preferably cooperate alkali compounds (preferred amine) as (D) composition.
As this compound, can be for have the material of compatibility for photo-corrosion-resisting agent composition, there is no particular restriction, can enumerate for example special compound of putting down in writing in the flat 9-6001 communique of opening.
Particularly by cooperate the higher specific alkali compounds (d1) of bulk density shown in the following general formula (X), also have be suppressed in the resist composition through the time by-product the effect of amount of sour composition, the long preservation stability of resist composition is improved.
Figure A20051006731300151
In general formula (X), (preferred more than 2, most preferably 3) is for being selected from the group of following (1)-(4) among X, Y, the Z more than 1: (1) carbon number alkyl, (2) carbon number naphthenic base, (3) phenyl, (4) aralkyl more than 3 more than 4.
In addition, in this X, Y, Z, not group or the atom of group for from the alkyl of (1 ') carbon number below 3, (2 ') hydrogen atom, choosing of above-mentioned (1)-(4).
X, Y, Z can be mutually the same, also can be different, but when being when being selected from the group of above-mentioned (1)-(4) more than 2 among X, Y, the Z, on the stability of effect, identical between the preferably suitable group with them.
(1) alkyl of carbon number more than 4
Under the situation of above-mentioned (1), if carbon number less than 4 is difficult to make mounting ageing stability (post exposure stability of the latent image formed by thepattern wise exposure of the resist layer) to improve.Carbon number more preferably more than 5, is preferably more than 8 especially.Higher limit is not particularly limited, but from confirm through the time stablizing effect and commercial easy acquisition the aspect, be below 20, be below 15 especially.If surpass 20, alkaline intensity weakens, and the effect of storage stability reduces.
Alkyl can be any of straight chain shape, a chain.
Specifically, preference such as positive decyl, n-octyl, n-pentyl etc.
(2) naphthenic base of carbon number more than 3
In this naphthenic base, because in commercial easy acquisition and effect excellence that ageing stability is improved, the therefore naphthenic base of preferred especially carbon number 4-8.Preferred especially carbon number is 6 cyclohexyl.
(4) aralkyl
The group of aralkyl for representing with general formula-R '-P (R ' be alkylidene, P is an aromatic hydrocarbyl).
As P, can enumerate phenyl, naphthyl etc., preferred phenyl.
The carbon number of R ' can be preferably 1-3 for more than 1.
As aralkyl, preference such as benzyl, phenethyl etc.
In X, Y, Z, not group or the atom of group for from above-mentioned (1 '), (2 '), choosing of above-mentioned (1)-(4).
(1 ') can be any of straight or branched.Special preferable methyl, ethyl.
As (d1) composition, preferably constitute the material of tertiary amine, in X, Y, Z, not that the group of above-mentioned (1)-(4) is preferably chosen from (1 ').Particularly, can enumerate for example three n-Decylamines, methyl two n-octyl amines, tri-n-amyl amine, N, N-dicyclohexyl methylamine, tribenzylamine etc.
Wherein, preferably from three n-Decylamines, methyl two n-octyl amines, tri-n-amyl amine, choose more than a kind, preferred especially three n-Decylamines.
In the present embodiment, (D) composition can use mixing use more than a kind or 2 kinds.
From the effect aspect, (D) composition preferably cooperates the 0.01-5.0 mass parts with respect to resist solid constituent 100 mass parts, cooperates in the scope particularly preferably in the 0.1-1.0 mass parts.
Organic solvent
As the organic solvent in the photo-corrosion-resisting agent composition of present embodiment, if the organic solvent that can use in the positive light anti-etching agent composition of chemical amplification type then can use without particular limitation.
Can enumerate for example esters solvent such as propylene-glycol monoalky lether acetic acid esters (for example propylene glycol monomethyl ether (PGMEA) etc.), lactate (for example ethyl lactate etc.), ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; Polyalcohols and derivants thereof such as ethylene glycol, propylene glycol, diglycol or their monomethyl ether, single ethylether, single propyl ether, single-butyl ether or single phenyl ether; The ring type ethers that diox is such; Etc. non-esters solvent.Therefore esters solvent contains the organic carboxyl acid as free acid owing to be the resultant of reaction of organic carboxyl acid and alcohol.Therefore, at the photo-corrosion-resisting agent composition that does not cooperate above-mentioned (d1) composition or do not cooperate in the photo-corrosion-resisting agent composition of preserving stabilizer described later, preferably do not contain the non-esters solvent of this free acid, preferred especially ketone (solvent of ketone).Wherein, from the dissolubility aspect of filming property, (C) composition, preferred 2-heptanone.
Esters solvent and non-esters solvent sometimes all through the time decompose and by-product acid, but in the presence of above-mentioned (d1) composition or preserving stabilizer described later in the presence of, this decomposition reaction is inhibited.Particularly in esters solvent, its effect is remarkable, in the presence of this (d1) composition, preserving stabilizer, and preferred on the contrary esters solvent, preferred especially PGMEA.
As because above-mentioned decomposition and the sour composition of by-product for example under the situation of 2-heptanone, confirm to generate formic acid, acetate, propionic acid etc.
Organic solvent can use to mix more than a kind or 2 kinds and use.
Be not particularly limited, from the coating aspect, organic solvent preferably with the concentration of solid constituent be 10-50 quality %, the use level that is preferably 20-45 quality % uses.The solid constituent of positive light anti-etching agent composition (resist solid constituent) is not for comprising the composition of above-mentioned organic solvent, is equivalent to (A), (C) composition and the summation of other compositions of using as required.
Other compositions
In the chemically amplified posative opto-corrosionproof agent composition of present embodiment, the preserving stabilizer below preferred as required in addition the cooperation.
As this preserving stabilizer, if having the material of the decomposition reaction effect that suppresses organic solvent, then be not particularly limited, can enumerate for example special antioxidant of putting down in writing in the clear 58-194834 communique of opening.As antioxidant, known phenolic compound and aminated compounds, preferred especially phenolic compound, wherein, from effective,, and preserve the excellent aspect of stablizing effect and set out at commercial easy acquisition and low price for the deterioration of esters solvent, ketones solvent, preferred 2,6-two (tert-butyl group)-paracresol and derivant thereof.Particularly the anti-degradation effects for propylene-glycol monoalky lether acetic acid esters, 2-heptanone is extremely excellent.
In addition, in the scope of not damaging purpose of the present invention, can make as required in the photo-corrosion-resisting agent composition of present embodiment and contain additive with compatibility, for example be used to improve additional resin, plastifier, stabilizing agent, the surfactant of the performance etc. of resist film, be used to make the more visual colouring matter of picture of development, be used to habitual additives such as the sensitizer that the sensitizing effect is further improved, anti-halation dyestuff, adherence improving agent.
The preparation method of positive light anti-etching agent composition
The positive light anti-etching agent composition of present embodiment can prepare by (A) composition, (C) composition and other compositions as required are dissolved in the organic solvent.
When dissolving other compositions of (A), (C) composition and use as required,, preferably the use amount of organic solvent is suitably adjusted in order to obtain the positive light anti-etching agent composition of homogeneous.As mentioned above, preferably be 10-50 quality %, more preferably use under the situation of 20-45 quality % at solid component concentration.
The formation method of resist pattern
Below the photo-corrosion-resisting agent composition that uses present embodiment is formed the resist method of patterning a preferred example describe.
At first, with (A) composition and (C) composition and the various compositions that add as required be dissolved in the solvent, with spinner etc. it is applied to form on the substrate and films.Substrate can suitably be selected silicon substrate, glass substrate etc. according to purposes.
Then, carry out heat treated (prebake conditions), remaining solvent is removed, form the resist tunicle having formed this substrate of filming.As the prebake conditions method, be not particularly limited, can enumerate make between hot plate and the substrate keep the gap near baking, do not keep the direct baking in gap etc., but when using glass substrate as substrate, especially preferably make keep between hot plate and the substrate gap near toasting.In the present embodiment, the heating condition during prebake conditions preferably sets at 80-150 ℃, 60-300 about second.
Then, by mask above-mentioned resist tunicle is carried out the selectivity exposure.
As light source used herein,, preferably use i line (365nm) in order to form fine pattern.
Then, the resist tunicle after the selectivity exposure is implemented heat treated (postexposure bake: PEB).As the PEB method, there is no particular restriction, can enumerate make between hot plate and the substrate keep the gap near baking, do not keep the direct baking in gap etc., but when using glass substrate as substrate, in order not make substrate produce warpage, obtain the diffusion effect that PEB produces, preferably after carrying out, carry out the method for direct baking near baking.In the present embodiment, the heating condition during PEB preferably sets at 80-150 ℃, 60-300 about second.
Use developer solution, for example the resist tunicle of the such aqueous alkali of 1-10 quality % tetramethylammonium hydroxide aqueous solution after to above-mentioned PEB implemented development treatment, the exposed portion dissolving can be removed, and forms the resist pattern simultaneously on substrate.
Then, wash off, can form the resist pattern by the developer solution that will remain in the resist patterned surfaces with leacheates such as pure water.
The positive light anti-etching agent composition of present embodiment shows the function of chemical amplification type, obtain good resolution and sensitivity, because resinous principle (A) is to remove the operation modulation through low-molecular-weight separation, therefore the thermotolerance as positive light anti-etching agent composition improves simultaneously.
In the thermotolerance here as positive light anti-etching agent composition, the inhibition effect that the anti-change in size effect of the anti-deformation effect of resist pattern, resist pattern, sublimate produce when comprising high-temperature heating treatment etc.
Use the chemically amplified posative opto-corrosionproof agent composition of present embodiment to form the resist pattern, even in the high-temperature heating treatment of the back baking processing for example before injection process etc., also can prevent the distortion of resist pattern form etc., also can suppress the generation of sublimate.
Especially, low, the easy acquisition of novolac resin price, but dispersion degree is wide usually, produces the sublimate of low-molecular-weight body (low molecular compound) during heat treated, is easy to generate the problem of polluting in the oven.Adopt the positive light anti-etching agent composition of present embodiment,, solved this problem, the positive light anti-etching agent composition of low price, excellent heat resistance can be provided because the low-molecular-weight body is removed.
[the 2nd embodiment]
(A) composition
(A) composition in the present embodiment contains alkali slightly solubility or the insoluble resin (a2) with acid dissociation dissolving inhibition base.The difference that is somebody's turn to do (a1) composition in (a2) composition and the 1st embodiment is: before suppressing the phenol hydroxyl protection of base with the alkali-soluble novolac resin with the acid dissociation dissolving; the alkali-soluble novolac resin is implemented the low-molecular-weight body is separated the processing of removing; and thereafter; make the alkali-soluble novolac resin of handling of preparation and have the compound reaction that the acid dissociation dissolving suppresses base, suppress the part protection of whole phenol hydroxyls of the alkali-soluble novolac resin after base will be handled with the acid dissociation dissolving.
The alkali-soluble novolac resin that uses in the present embodiment is identical with the 1st embodiment.
In the present embodiment, the alkali-soluble novolac resin is to implement processing is removed in the separation of low-molecular-weight body, uses as the alkali-soluble novolac resin after handling.
Implement the scope that the low-molecular-weight body separates the preferred 2000-50000 of matter average molecular weight that removes the alkali soluble resin before handling, more preferably the scope of 4000-30000.
As the method for separating and processing of low-molecular-weight body, for example, the method that can use spent ion exchange resin that the alkali-soluble novolac resin is made with extra care.Adopt this method when the low-molecular-weight body is removed, sour composition, metal ingredient can also be removed.
In addition, can adopt the alkali-soluble novolac resin is dissolved in good solvent, for example alcohol such as methyl alcohol, ethanol, ketone such as acetone, methyl ethyl ketone, in ethylene glycol monoethyl ether acetate, the tetrahydrofuran etc., inject water then and make methods such as its precipitation, the low-molecular-weight body is separated remove.
In addition, can in the synthetic reaction way of alkali-soluble novolac resin, for example carry out steam distillation, make low nucleome content minimizings (opening the 2000-13185 communique) such as 2 nucleomes with reference to the spy.
This low-molecular-weight body separates the yield of removing in handling, for the reason identical with the 1st embodiment, and the scope of preferred 50-95 quality %.
In addition, the preferable range of the polystyrene conversion matter average molecular weight (Mw) of gained alkali-soluble novolac resin is 5000-100000, more preferably 5500-60000 after this separating treatment.By making this Mw is more than 5000, and the stable on heating raising effect of resist pattern is given full play to.If Mw surpasses 100000, there is the tendency of coating variation, therefore not preferred.In addition, Mw is that the content of the low-molecular-weight body below 500 is preferably below 15% on GPC figure, more preferably below 12%.By being below 15%, the thermotolerance of resist pattern improves effect and is achieved, and the effect of the generation of sublimate also is achieved when suppressing heat treated simultaneously.
(a2) composition can synthesize by the alkali-soluble novolac resin after the above-mentioned processing and the addition reaction of the compound that is equivalent to acid dissociation dissolving inhibition base.It is identical with the 1st embodiment that the acid dissociation dissolving suppresses base.
, in (a2) composition, be preferably about the 10-50 mole % of whole phenol hydroxyls by the ratio (protection ratio) of the phenol hydroxyl of acid dissociation dissolving inhibition base protection.
(C) composition of present embodiment, (D) composition, organic solvent are identical with the 1st embodiment with other compositions.
The positive light anti-etching agent composition of present embodiment is identical with the 1st embodiment, can prepare by (A) composition, (C) composition and other compositions as required are dissolved in the organic solvent.
Use the photo-corrosion-resisting agent composition formation resist method of patterning of present embodiment identical with the 1st embodiment.
The positive light anti-etching agent composition of present embodiment is identical with the 1st embodiment, has good resolution, sensitivity, simultaneously excellent heat resistance.In addition, the generation of sublimate also is inhibited during heat treated.
[the 3rd embodiment]
◆ (A) composition
In the 3rd embodiment of chemically amplified posative opto-corrosionproof agent composition of the present invention, (A) composition contains resinous principle (a3), resinous principle (a3) is to make alkali-soluble novolac resin and the reaction of (B) described later crosslinking chemical, the resultant of reaction that obtains is implemented that the low-molecular-weight body is separated the removal processing obtain.
Alkali-soluble novolac resin in the present embodiment is not if the alkali-soluble novolac resin that can use in positive light anti-etching agent composition then can have especially restrictedly and uses.Preferably use the alkali-soluble novolac resin that in above-mentioned the 1st embodiment, uses in the modulation of (a1) composition.The alkali-soluble novolac resin can use a kind or use material more than 2 kinds.
When using novolac resin as the alkali soluble resin in the present embodiment, from sensitivity characteristic aspect, the preferred 2000-50000 of its Mw is more preferably about 3000-20000.The scope of preferred Mw is 4000-15000.If littler than above-mentioned scope, the possible variation of coating, if surpass above-mentioned scope, resolution might reduce.
When using novolac resin,, preferred and with above-mentioned (d1) composition, preserving stabilizer from the viewpoint of the long preservation stability of resist composition.
◆ (B) composition
(B) composition is the compound shown in the following general formula (I), plays a role as crosslinking chemical.
H 2C＝CH-O-R 1-O-CH＝CH 2??????????????(I)
In the formula, R 1Expression can have any of group shown in the alkylidene of substituent carbon number 1-10 or the following general formula (Ia),
In the formula, R 4Expression can have the alkylidene of substituent carbon number 1-10, and m represents 0 or 1.
In above-mentioned general formula (I), R 1Substituent for having, chain, the alkylidene of straight chain shape or the group shown in the above-mentioned general formula (Ia) of carbon number 1-10.This alkylidene can contain aerobic key (ehter bond) on main chain.In general formula (Ia), R 4Also substituent for having, the chain of carbon number 1-10, the alkylidene of straight chain shape, this alkylidene can contain aerobic key (ehter bond) on main chain.As R 1, preferred-C 4H 8-,-C 2H 4OC 2H 4-,-C 2H 4OC 2H 4OC 2H 4-and general formula (Ia) shown in group etc.Wherein, group shown in the preferred formula (Ia), preferred especially R 4Carbon number be 1, m is 1.
(B) composition can use to mix more than a kind or 2 kinds and use.
Alkali-soluble novolac resin composition and (B) composition reaction obtain having the resultant of reaction of following structural unit: (B) vinyl of composition end is attached on the phenol hydroxyl of for example side chain of alkali-soluble novolac resin composition.
As the concrete example of this structural unit, can enumerate the structural unit shown in the following general formula (1A).
In addition, alkali-soluble novolac resin composition and (B) composition reaction, obtain existing the resultant of reaction as the lower part: (B) vinyl of two of composition ends is attached to respectively on 2 phenol hydroxyls of for example side chain in the alkali-soluble novolac resin composition.As the concrete example of this structural unit, can enumerate the intermolecular cross-linking part shown in the following general formula (1B).
What had (B) composition usually is the structural unit (for example (1A)) of single terminal combination and both resultant of reaction (a3) of part (for example (1B)) of two terminal combinations.
R 1Same as described above, R 2, R 3For what in the related record of above-mentioned novolac resin, illustrate, from the group of phenols, aldehydes, ketone etc.
At the alkali-soluble novolac resin with (B) in the reaction of composition, even owing to do not use acid catalyst, reaction also can be carried out, therefore need not use acid catalyst, be present in the reaction system as the tartaric acid composition, make the storage stability deterioration after resist is modulated on the contrary, therefore not preferred.
As the method for removing of sour composition, can enumerate known method, for example can make the washing of spent ion exchange resin, pure water, with in the alkali and etc. method.
In addition, (B) concentration of the sour composition in the alkali-soluble novolac resin composition before composition and the reaction is preferably below the 0.1ppm, is preferably below the 0.01ppm especially.
This resultant of reaction (a3) combines with the hydroxyl of the side chain of alkali-soluble novolac resin by above-mentioned (B) composition, compares with the alkali-soluble novolac resin, for the dissolubility reduction of alkaline aqueous solution.In addition, this photo-corrosion-resisting agent composition is applied to back heating on the substrate, the terminal ethylenyl groups reaction of the phenol hydroxyl of the side chain of alkali-soluble novolac resin and said structure unit (1A), the formation of cross-linked structure is carried out, therefore the dissolubility for alkaline aqueous solution further reduces, and the alkaline aqueous solutions such as alkaline developer that use when forming for the resist pattern are slightly solubility.
If play a role from the acid that (C) composition produces by exposure, this cross-linked structure cracking, therefore the dissolubility for the alkaline aqueous solution of resist pattern (photo-corrosion-resisting agent composition) increases.
From aspects such as thermotolerances, make the alkali soluble resin and (B) the preferred 10000-100000 of matter average molecular weight (Mw) of the resultant of reaction of composition prepared in reaction, preferred especially 20000-60000.
(B) use amount of composition is 1-15 quality % with respect to this alkali-soluble novolac resin, the ratio of preferred 4-8 quality %.If less than 1 quality %, the film of resist pattern unexposed portion reduces and increases, the tendency that has the contrast reduction of resist pattern, if surpass 15 quality %, the tendency that has remarkable deterioration for the dissolubility of developer solution (aqueous alkali), it is poor to produce sensitivity, and pattern is problem such as exploring not.
(a3) composition is to make alkali-soluble novolac resin and (B) composition reaction, the resultant of reaction enforcement that obtains is separated the low-molecular-weight body to remove to handle obtaining.
Method for separating and processing as the low-molecular-weight body is not particularly limited, and is identical with the 1st embodiment, can use method that spent ion exchange resin makes with extra care, use the known lock out operation of good solvent (alcohol etc.) and poor solvent (water etc.).The method that adopts the former can also be removed sour composition, metal ingredient when the low-molecular-weight body is removed.
For the reason same with the 1st embodiment, the scope of the preferred 50-95 quality of the yield % in handling is removed in the separation of this low-molecular-weight body.
In addition, the preferable range of the polystyrene conversion matter average molecular weight (Mw) of gained resin is 10000-100000, more preferably 20000-60000 after this separating treatment.By making this Mw is more than 10000, and the stable on heating raising effect of resist pattern is given full play to.If Mw surpasses 100000, there is the tendency of coating variation, therefore not preferred.In addition, Mw is that the content of the low-molecular-weight body below 500 is preferably below 15% on GPC figure, more preferably below 12%.By being below 15%, the thermotolerance of resist pattern improves effect and is achieved, and the effect of the generation of sublimate also is achieved when suppressing heat treated simultaneously.
(C) composition of present embodiment, (D) composition, organic solvent are identical with the 1st embodiment with other compositions.
In the present embodiment, preferred especially above-mentioned (d1) conduct (D) composition that uses.
The positive light anti-etching agent composition of present embodiment is identical with the 1st embodiment, can prepare by (A) composition, (C) composition and other compositions as required are dissolved in the organic solvent.
Use the photo-corrosion-resisting agent composition formation resist method of patterning of present embodiment to carry out according to the order identical with the 1st embodiment.In addition, preferably the i line is used for exposure.But in the present embodiment, the heating condition during prebake conditions is preferably set to 80-150 ℃, 60-300 about second.In addition, the heating condition during PEB is preferably set to 80-150 ℃, 60-300 about second.
The positive light anti-etching agent composition of present embodiment is identical with the 1st embodiment, has good resolution, sensitivity, simultaneously excellent heat resistance.In addition, the generation of sublimate also is inhibited during heat treated.
[the 4th embodiment]
◆ (A) composition
(A) composition in the present embodiment contains the resultant of reaction (a4) of alkali-soluble novolac resin and above-mentioned (B) composition.The difference that is somebody's turn to do (a3) composition in (a4) composition and the 3rd embodiment is: before making the alkali-soluble novolac resin and (B) composition reacts, the alkali-soluble novolac resin is implemented the low-molecular-weight body is separated the processing of removing, and thereafter, make the alkali-soluble novolac resin of handling of preparation and (B) composition reaction, on the alkali-soluble novolac resin that crosslink unit is added to handle.
The alkali-soluble novolac resin that uses in the present embodiment is identical with the 3rd embodiment.
In the present embodiment, the alkali-soluble novolac resin is to implement processing is removed in the separation of low-molecular-weight body, uses as the alkali-soluble novolac resin after handling.
The method for separating and processing of low-molecular-weight body is identical with the 2nd embodiment.
For the reason same with the 1st embodiment, the scope of the preferred 50-95 quality of the yield % of alkali-soluble novolac resin during the separation of low-molecular-weight body is removed and handled in the present embodiment.
In addition, the preferable range of the polystyrene conversion matter average molecular weight (Mw) of gained resin is 10000-100000, more preferably 20000-60000 after this separating treatment.By making this Mw is more than 10000, and the stable on heating raising effect of resist pattern is given full play to.If Mw surpasses 100000, there is the tendency of coating variation, therefore not preferred.In addition, Mw is that the content of the low-molecular-weight body below 500 is preferably below 15% on GPC figure, more preferably below 12%.By being below 15%, the thermotolerance of resist pattern improves effect and is achieved, and the effect of the generation of sublimate also is achieved when suppressing heat treated simultaneously.
(B) composition is identical with the 3rd embodiment, and (B) use amount of composition is also identical with the 3rd embodiment.
(C) composition of present embodiment, (D) composition, organic solvent are identical with the 3rd embodiment with other compositions.
The positive light anti-etching agent composition of present embodiment is identical with the 3rd embodiment, can prepare by (A) composition, (C) composition and other compositions as required are dissolved in the organic solvent.
Use the photo-corrosion-resisting agent composition formation resist method of patterning of present embodiment identical with the 3rd embodiment.
The positive light anti-etching agent composition of present embodiment is identical with the 1st embodiment, has good resolution, sensitivity, simultaneously excellent heat resistance.In addition, the generation of sublimate also is inhibited during heat treated.
Especially, the 1st, the 3rd embodiment is compared with the 2nd, the 4th embodiment, and is big for each molecular weight that separates solvent deliquescent difference down, thus can be with high yield, efficiently the low-molecular-weight body is removed.
[embodiment]
Below enumerate embodiment the present invention is described in more detail, but the present invention is not limited to following embodiment.
[evaluation method of positive light anti-etching agent composition]
Adopt the evaluation method of following each rerum natura (1)-(4) as follows for the positive light anti-etching agent composition of following embodiment or comparative example.
(1) sensitivity evaluation: use spinner that positive light anti-etching agent composition is applied on the silicon substrate, on the hot plate, under 90 ℃ (in embodiment 5,6 and comparative example 3, being 140 ℃), be dried 90 seconds (prebake conditions), form the resist tunicle of thickness 1.48 μ m then.
Then, pass through L﹠amp; S is 1: 1 1.5 μ m resist pattern corresponding mask (net mould), uses Mirror Projection aligner MPA-600FA (Canon Inc.'s preparation; Ghi line exposing device), can verily reproduce 1.5 μ mL﹠amp; The exposure of S (Eop exposure) is carried out the selectivity exposure to this film.
Then, implementing the PEB (heating of exposure back) in 90 seconds down 110 ℃ (being 140 ℃) in embodiment 5,6 and comparative example 3 handles.
Then, use 2.38 quality %TMAH aqueous solution (tetramethylammonium hydroxide aqueous solution down at 23 ℃; The preparation of goods name NMD-3, Tokyo Applied Chemistry Industrial Co., Ltd.) carries out the development treatment in 90 seconds, carry out drip washing in 30 seconds with pure water then, be rotated drying.
As the index that sensitivity is estimated, 1.5 μ mL﹠amp can be verily reproduced in use; Exposure (Eop, the unit: mJ/cm of the resist pattern of S 2).
(2) resolution evaluation: the limit exploring degree of obtaining above-mentioned Eop exposure.
(3) thermotolerance evaluation: in above-mentioned Eop exposure, will describe 1.5 μ mL﹠amp; The substrate of S is statically placed in 300 seconds on the hot plate that is set at 140 ℃, then, observes cross sectional shape.Its result: 1.5 μ mL﹠amp; The size changing rate of S is designated as zero for ± 3% with interior, is the △ that is designated as in 3～10% or-10～-3% the scope, surpass ± 10% be designated as *.
(4) the sublimate amount is estimated: diameter is inverted on 160 ℃ hot plate than the big funnel of wafer (wafer), the pipe of filler tube with the immersion liquid of the trap tube that tetrahydrofuran is housed (trap) is connected, off-gas pump is connected with the pipe that another does not immerse liquid.The wafer of painting erosion resistant agent, prebake conditions, PEB is packed in the funnel, toast and change wafer after 1 minute.Carry out this operation continuously, measure sublimate in the liquid of trap tube with GPC after 25 repeatedly, carry out relatively with the area ratio.
(modulation example 1; (a1) modulation of composition)
With the part protection of tertbutyloxycarbonyl, implement the low-molecular-weight body is separated the processing of removing modulation (a1) composition again with whole phenol hydroxyls of novolac resin.
20 quality % solution [solvent=1 at novolac resin (metacresol/paracresol=6/4 (mol ratio), formalin/salicylide=3/1 (mol ratio), Mw=5500), the 4-diox] add triethylamine 15.6g and di-t-butyl-two carbonic ester 18.1g among the 250g, under 22 ℃, carry out reaction in 2 hours.Then, reactant liquor is injected 1.5 quality % aqueous acetic acid 1000ml, make the reactant precipitation.After the sediment isolated by filtration, the filter thing that obtains is dissolved among the methyl alcohol 250g, make this solution pass through ion exchange resin.Then, solvent exchange is PGMEA, obtains the 25% phenolic resin varnish solution 130g that is protected by tertbutyloxycarbonyl of phenol hydroxyl.
The novolac resin of preparation is modulated to the PGMEA solution of 30 quality %, in this solution, add normal heptane 270g, after the sediment of separating out is taken out, the sediment that obtains is dissolved among the PGMEA, carry out concentration operation normal heptane is removed, obtain (a1) composition.The yield of separating treatment is 79 quality %, and the Mw after the separating treatment is 7950.In addition, the content of the low-molecular-weight body below the Mw500 after the separating treatment (GPC figure is upper and lower together) is 2.9%.
(modulation example 2; (a1) modulation of composition)
With the part protection of ethyl vinyl, implement the low-molecular-weight body is separated the processing of removing modulation (a1) composition again with whole phenol hydroxyls of novolac resin.
20 quality % solution [solvent=1 at novolac resin (metacresol/paracresol=6/4 (mol ratio), formalin/salicylide=3/1 (mol ratio), Mw=5500), the 4-diox] add p-toluenesulfonic acid monohydrate 0.01g and ethyl vinyl ether 9g among the 250g, at room temperature carry out reaction in 2 hours.Then, in reactant liquor, add the triethylamine of 0.01g, be injected among the pure water 1000ml, make the reactant precipitation.After the sediment isolated by filtration, the filter thing (sediment) that obtains is dissolved among the methyl alcohol 250g, make this solution pass through ion exchange resin.Then, solvent exchange is PGMEA, obtains the 30% phenolic resin varnish solution 125g that is protected by ethyl vinyl of phenol hydroxyl.
Similarly carry out lock out operation with modulation example 1, obtain (a1) composition.The yield of separating treatment is 76 quality %, and the Mw after the separating treatment is 7200.In addition, the content of the low-molecular-weight body below the Mw500 after the separating treatment is 3.7%.
(modulation example 3; (a2) modulation of composition)
After the low-molecular-weight body separating treatment with novolac resin, with the part protection of tertbutyloxycarbonyl with its whole phenol hydroxyls, modulation (a2) composition.
In 30% methanol solution 150g of novolac resin (metacresol/paracresol=6/4 (mol ratio), formalin/salicylide=3/1 (mol ratio), Mw=5500), add pure water 115g, make the sediment of separating out be dissolved in 1, in the 4-diox, by it is carried out concentration operation moisture is removed, obtained implementing the phenolic resin varnish solution of separating treatment.The yield of separating treatment is 80 quality %, and the Mw after the separating treatment is 6000.The content of the low-molecular-weight body that the Mw500 after this separating treatment is following is 9.7%.
Add triethylamine 10.0g and di-t-butyl-two carbonic ester 13.1g among 20 quality % solution [solvent=1, the 4-diox] 180g of the novolac resin after the processing that separating treatment obtains, under 22 ℃, carry out reaction in 2 hours.Then, reactant liquor is injected 1.5 quality % aqueous acetic acid 720ml, make the reactant precipitation.After the sediment isolated by filtration, this sediment (filter thing) is dissolved among the methyl alcohol 180g, make this solution pass through ion exchange resin.
Then, solvent exchange is PGMEA, obtains novolac resin (a2) the composition 120g after 25% processing of being protected by tertbutyloxycarbonyl of phenol hydroxyl.Mw is 7800, and the content of the low-molecular-weight body that Mw500 is following is 4.9%.
(modulation example 4; (a2) modulation of composition)
After the low-molecular-weight body separating treatment with novolac resin, with the part protection of ethyl vinyl with its whole phenol hydroxyls, modulation (a2) composition.
20 quality % solution [solvent=1 of the novolac resin (Mw=6000) after the processing that separating treatment obtains in modulation example 3, the 4-diox] add p-toluenesulfonic acid monohydrate 0.01g and ethyl vinyl ether 6.5g among the 180g, under 22 ℃, carry out reaction in 2 hours.
Then,, be injected in the 1000ml pure water, make the reactant precipitation adding the triethylamine of 0.01g in the reactant liquor.After the sediment isolated by filtration with preparation, this sediment (filter thing) is dissolved among the methyl alcohol 250g, makes this solution pass through ion exchange resin.Then, solvent exchange is PGMEA, obtains 30% novolac resin of being protected by ethoxyethyl group, i.e. (a2) composition 120g of phenol hydroxyl.Mw is 7100, and the content of the low-molecular-weight body that Mw500 is following is 6.7%.
(modulation example 5; (a3) modulation of composition)
Make novolac resin and (B) composition reaction, implement the low-molecular-weight body is separated the processing of removing, modulation (a3) composition for the resultant of reaction that obtains.
In 30 quality % solution [solvent=methyl isobutyl ketone] 200g of novolac resin (metacresol/paracresol=6/4 (mol ratio), formalin/salicylide=3/1 (mol ratio), Mw=5500), add cyclohexanedimethanol divinyl ether 4g as (B) composition, reacted 24 hours down at 100-110 ℃, at room temperature continue then to stir 12 hours.
In the resultant of reaction of preparation, add normal heptane 240g, the sediment of separating out is taken out by decant.This sediment is dissolved among the PGMEA,, obtains (a3) composition of separating treatment by remaining methyl isobutyl ketone decompression is removed.The yield of separating treatment is 83 quality %, and the Mw after the separating treatment is 23700.In addition, the content of the low-molecular-weight body below the Mw500 after the separating treatment is 6.1%.
(modulation example 6; (a4) modulation of composition)
After the low-molecular-weight body separating treatment with novolac resin, with (B) composition reaction modulation (a4) composition.Add cyclohexanedimethanol divinyl ether 3.8g among 30 quality % solution [solvent=methyl isobutyl ketone] 160g of the novolac resin (Mw=6000) in modulation example 3 after the processing of separating treatment preparation, reacted 24 hours down at 100-110 ℃, at room temperature continue then to stir 12 hours.
It is PGMEA that reaction finishes the back solvent exchange, obtains (a4) composition 135g.Mw is 25000, and the content of the low-molecular-weight body that Mw500 is following is 8.1%.
(comparative example modulation example 1)
In modulation example 1, except not carrying out the separating treatment, similarly obtain 25% novolac resin of being protected by tertbutyloxycarbonyl of phenol hydroxyl.
(comparative example modulation example 2)
In modulation example 2, except not carrying out the separating treatment, similarly obtain 30% novolac resin of being protected by ethyl vinyl of phenol hydroxyl.
(comparative example modulation example 3)
In modulation example 5, except not carrying out the separating treatment, similarly obtain making the novolac resin and (B) resultant of reaction (resinous principle) of composition reaction.
(embodiment 1,2)
(a1) composition for preparing respectively in the above-mentioned modulation example 1,2: 100 mass parts
(C) composition [compound of above-mentioned formula (IX)]: 3 mass parts
(D) composition [three n-Decylamines]: 0.2 mass parts
These each compositions are dissolved among the PGMEA, cooperate XR-104 (preparation of big Japanese ink company) 500ppm as surfactant again, after being adjusted into the solution of 25 quality % concentration, use the membrane filter of aperture 0.2 μ m that it is filtered, the modulation photo-corrosion-resisting agent composition.
Carry out the evaluation of physical property of above-mentioned (1)-(4) for this photo-corrosion-resisting agent composition.
It the results are shown in following table 1.
(embodiment 3,4)
(a2) composition for preparing respectively in the above-mentioned modulation example 3,4: 100 mass parts
(C) composition [compound of above-mentioned formula (IX)]: 3 mass parts
(D) composition [three n-Decylamines]: 0.2 mass parts
These each compositions are dissolved among the PGMEA, cooperate XR-104 (preparation of big Japanese ink company) 500ppm as surfactant again, after being adjusted into the solution of 25 quality % concentration, use the membrane filter of aperture 0.2 μ m that it is filtered, the modulation photo-corrosion-resisting agent composition.
Carry out the evaluation of physical property of above-mentioned (1)-(4) for this photo-corrosion-resisting agent composition.
It the results are shown in following table 1.
(embodiment 5)
(a3) composition of preparation in the above-mentioned modulation example 5: 100 mass parts
(C) composition [compound of above-mentioned formula (IX)]: 3 mass parts
(D) composition [three n-Decylamines]: 0.2 mass parts
These compositions are dissolved among the PGMEA, cooperate XR-104 (preparation of big Japanese ink company) 500ppm as surfactant again, after being adjusted into the solution of 20 quality % concentration, use the membrane filter of aperture 0.2 μ m that it is filtered, the modulation photo-corrosion-resisting agent composition.
Carry out the evaluation of physical property of above-mentioned (1)-(4) for this photo-corrosion-resisting agent composition.
It the results are shown in following table 1.
(embodiment 6)
(a4) composition of preparation in the above-mentioned modulation example 6: 100 mass parts
(C) composition [compound of above-mentioned formula (IX)]: 3 mass parts
(D) composition [three n-Decylamines]: 0.2 mass parts
These compositions are dissolved among the PGMEA, cooperate XR-104 (preparation of big Japanese ink company) 500ppm as surfactant again, after being adjusted into the solution of 20 quality % concentration, use the membrane filter of aperture 0.2 μ m that it is filtered, the modulation photo-corrosion-resisting agent composition.
Carry out the evaluation of physical property of above-mentioned (1)-(4) for this photo-corrosion-resisting agent composition.
It the results are shown in following table 1.
(comparative example 1-2)
The above-mentioned resinous principle for preparing respectively among the routine 1-2 of relatively modulating: 100 mass parts
(C) composition [compound of above-mentioned formula (IX)]: 3 mass parts
(D) composition [three n-Decylamines]: 0.2 mass parts
These compositions are dissolved among the PGMEA, cooperate XR-104 (preparation of big Japanese ink company) 500ppm as surfactant again, after being adjusted into the solution of 25 quality % concentration, use the membrane filter of aperture 0.2 μ m that it is filtered, the modulation photo-corrosion-resisting agent composition.
Carry out the evaluation of physical property of above-mentioned (1)-(4) for this photo-corrosion-resisting agent composition.
It the results are shown in following table 1.
(comparative example 3)
The above-mentioned resinous principle for preparing respectively in the example 3 of relatively modulating: 100 mass parts
(C) composition [compound of above-mentioned formula (IX)]: 3 mass parts
(D) composition [three n-Decylamines]: 0.2 mass parts
These compositions are dissolved among the PGMEA, cooperate XR-104 (preparation of big Japanese ink company) 500ppm as surfactant again, after being adjusted into the solution of 20 quality % concentration, use the membrane filter of aperture 0.2 μ m that it is filtered, the modulation photo-corrosion-resisting agent composition.
Carry out the evaluation of physical property of above-mentioned (1)-(4) for this photo-corrosion-resisting agent composition.
It the results are shown in following table 1.
Table 1
Sensitivity (mJ/cm 2) Resolution (μ m) Thermotolerance Sublimate
Embodiment 1 ??50 ?1.2 ??△ ??25
??2 ??25 ?1.2 ??△ ??30
??3 ??50 ?1.2 ??△ ??25
??4 ??25 ?1.2 ??△ ??30
??5 ??50 ?1.2 ??○ ??30
??6 ??50 ?1.2 ??○ ??40
Comparative example 1 ??50 ?1.2 ??× ??100
??2 ??25 ?1.2 ??× ??100
??3 ??50 ?1.2 ??× ??100
Can see that from the result of table 1 the embodiment 1-6 that has carried out the separating treatment of low-molecular-weight body compares with the comparative example 1-3 that does not carry out this separating treatment, sensitivity, resolution are equal, and thermotolerance improves.And the generation of sublimate significantly reduces.

Claims (4)

1. chemically amplified posative opto-corrosionproof agent composition, it contains (A) resinous principle, (C) produce sour composition by the irradiation of radioactive ray compound and organic solvent, has effect by the sour composition that produces by described (C) composition, character for the dissolubility of aqueous alkali increases is characterized in that:
Described (A) composition contains resinous principle (a1); resinous principle (a1) is with the part protection of acid dissociation dissolving inhibition base with whole phenol hydroxyls of alkali-soluble novolac resin, and the alkali slightly solubility or the insoluble resin that form are implemented the processing that the separation of low-molecular-weight body is removed is obtained.
2. chemically amplified posative opto-corrosionproof agent composition, it contains (A) resinous principle, (C) produce sour composition by the irradiation of radioactive ray compound and organic solvent, has effect by the sour composition that produces by described (C) composition, character for the dissolubility of aqueous alkali increases is characterized in that:
Described (A) composition contains alkali slightly solubility or insoluble resin (a2), and resin (a2) suppresses base, the part protection of having implemented the low-molecular-weight body is separated whole phenol hydroxyls of removing the alkali-soluble novolac resin after the processing of handling is formed with the acid dissociation dissolving.
3. chemically amplified posative opto-corrosionproof agent composition, it contains (A) resinous principle, (C) produce sour composition by the irradiation of radioactive ray compound and organic solvent, has effect by the sour composition that produces by described (C) composition, character for the dissolubility of aqueous alkali increases is characterized in that:
Described (A) composition contains resinous principle (a3), and resinous principle (a3) is to make alkali-soluble novolac resin and (B) reaction of the crosslinking chemical shown in the following general formula (I), the resultant of reaction enforcement that obtains is separated the low-molecular-weight body to remove to handle obtaining,
H 2C＝CH-O-R 1-O-CH＝CH 2????????????(I)
In the formula, R 1Expression can have any of group shown in the alkylidene of substituent carbon number 1-10 or the following general formula (Ia),
Figure A2005100673130003C1
In the formula, R 4Expression can have the alkylidene of substituent carbon number 1-10, and m represents 0 or 1.
4. chemically amplified posative opto-corrosionproof agent composition, it contains (A) resinous principle, (C) produce sour composition by the irradiation of radioactive ray compound and organic solvent, has effect by the sour composition that produces by described (C) composition, character for the dissolubility of aqueous alkali increases is characterized in that:
Described (A) composition contains resultant of reaction (a4), resultant of reaction (a4) make after the processing of having implemented the low-molecular-weight body separate to remove is handled the alkali-soluble novolac resin and (B) reaction of crosslinking chemical shown in the following general formula (I) obtain,
H 2C＝CH-O-R 1-O-CH＝CH 2????????????(I)
In the formula, R 1Expression can have any of group shown in the alkylidene of substituent carbon number 1-10 or the following general formula (Ia),
Figure A2005100673130003C2
In the formula, R 4Expression can have the alkylidene of substituent carbon number 1-10, and m represents 0 or 1.
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