KR20090002865A - Chemical amplification type positive resist composition - Google Patents
Chemical amplification type positive resist composition Download PDFInfo
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- KR20090002865A KR20090002865A KR1020070067190A KR20070067190A KR20090002865A KR 20090002865 A KR20090002865 A KR 20090002865A KR 1020070067190 A KR1020070067190 A KR 1020070067190A KR 20070067190 A KR20070067190 A KR 20070067190A KR 20090002865 A KR20090002865 A KR 20090002865A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
- C07C381/12—Sulfonium compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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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
- G03F7/004—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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- Materials For Photolithography (AREA)
Abstract
Description
TECHNICAL FIELD The present invention relates to a chemically amplified positive resist composition, and in particular, to a resist composition suitable for photolithography or the like acting by high energy radiation such as far ultraviolet rays (including excimer lasers, etc.), electron beams, X-rays or radiated light. It is about.
In recent years, as the degree of integration of integrated circuits has increased, submicron pattern formation has been required. In particular, photolithography using an excimer laser from fluoride krypton (KrF) or argon fluoride (ArF) has been noted in that it enables the production of 64M DRAM to 1G DRAM. As a resist suitable for a photolithography process using such an excimer laser, a so-called chemically amplified resist using an acid catalyst and a chemical amplification effect is adopted. When a chemically amplified resist is used, the acid generated from the photoacid generator in the irradiation section of the radiation is diffused by subsequent heat treatment, and the solubility in the alkaline developer of the irradiation section is changed by a reaction using the generated acid as a catalyst. Or a negative pattern is obtained.
Chemically amplified positive type resists, particularly positive type resists for KrF excimer laser photolithography, are poly (hydroxystyrene) resins in which some of their phenolic hydroxyl groups are dissociated by the action of an acid. Protected resins are often used in combination with photoacid generators. In addition, as a group dissociated by the action of these acids, it is well known that resins having a specific structure of adamantane-based polymer units and specific high polar polymer units are effective in achieving adhesion to the substrate, etching resistance, and good resolution. have. However, even resins with such good performance show limitations in the profile, such as increasing the amplitude of standing waves or swing curves at different film thicknesses and conditions.
The present invention solves the problems of the prior art as described above, and has various performances such as sensitivity, resolution, coating property, and the like, and particularly, in order to form a pattern under a film thickness condition in which standing waves or reverse tapers appear. In this case, an object of the present invention is to provide a chemically amplified positive resist composition having an improved profile and having an effect of reducing the amplitude of a swing curve to reduce the variation in line width at various film thicknesses.
The present invention,
(A) The structural units represented by the following formula (1) and the structural units represented by the formula (2) are linearly arranged in a molar ratio of 2-5: 5-8, with a glass transition temperature (Tg) of 150-170 ° C and a molecular weight of 9,000 Resin of ˜11,000;
(B) at least one resin selected from the group consisting of the following general formulas (3), (4) and (5); And
(C) Provides a chemically amplified positive resist composition comprising a photoacid generator represented by the formula (6).
Where
R 1 is a hydrogen atom or a methyl group,
R <2> is a C1-C10 linear, branched or cyclic alkyl group.
In the above formula,
R 3 is a hydrogen atom or a methyl group,
R 4 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms
R 5 is hydrogen, methyl, ethyl, propyl, Br, Cl, F or NO 2 ,
c, d and e are mole fractions of each polymerized unit, c + d + e = 1,
0.1 ≦ [(d + e) / (c + d + e)] ≦ 0.5 or 0.05 ≦ [e / (c + d + e)] ≦ 0.4.
In the above formula,
R 3 is a hydrogen atom or a methyl group,
R 4 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms,
R 5 is hydrogen, methyl, ethyl, propyl, Br, Cl, F or NO 2 ,
f, g and h are mole fractions of each polymerized unit, f + g + h = 1,
0.1 ≦ [(g + h) / (f + g + h)] ≦ 0.5 or 0.05 ≦ [h / (f + g + h)] ≦ 0.4.
In the above formula,
R 3 is a hydrogen atom or a methyl group,
R 4 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms,
R 5 is hydrogen, methyl, ethyl, propyl, Br, Cl, F or NO 2 ,
i, j and k are the mole fraction of each polymerized unit i + j + k = 1,
0.1 ≦ [(j + k) / (i + j + k)] ≦ 0.5 or 0.05 ≦ [k / (i + j + k)] ≦ 0.4.
In the above formula,
R 6 and R 7 are each independently hydroxyl, amino or C 3 -C 8 straight alkyl unsubstituted or substituted with alkoxy having 1 to 6 carbon atoms; Branched alkyl of 3 to 8 carbon atoms unsubstituted or substituted with hydroxyl, amino or alkoxy having 1 to 6 carbon atoms; Cyclic alkyl of 3 to 8 carbon atoms unsubstituted or substituted with hydroxyl, amino or alkoxy of 1 to 6 carbon atoms; Or an aryl group having 6 to 10 carbon atoms substituted with alkyl or alkoxy.
The present invention also provides a chemically amplified positive resist composition in which a part of the hydroxy group of the hydroxystyrene polymerized unit of the resin of Formula 1 is protected with a dissociable protecting group by an acid.
The present invention also provides a resist film comprising the chemically amplified positive resist composition.
The chemically amplified positive resist composition of the present invention has various performances such as sensitivity, resolution, and applicability, and is particularly improved when a pattern is formed under a film thickness condition in which standing waves or reverse tapers appear. It has a profile and reduces the amplitude of the swing curve, which is effective in reducing the variation in line width at various film thicknesses.
Hereinafter, the present invention will be described in detail.
In general, chemically amplified resists have a higher light transmittance at an exposure wavelength than the novolak / diazo naphthoquinone type resists used for g-ray and i-ray lithography, and the incident light reflects the reflected light reflected from the substrate. As a cause of standing waves or reverse tapers caused by interference, dimensional fluctuations such as line widths of patterns, collapse of shapes, etc. are likely to occur. As a method of suppressing such standing waves and reverse taper, in general, an antireflection film is applied to the base of the resist. When there is no use of the base antireflection film in an ion implantation process or the like, a light absorber or the like is used to reduce the light transmittance of the resist. There is a way to. However, when the light transmittance of a resist is reduced, there exists a fault that it is easy to impair basic performances, such as a sensitivity and a resolution.
The resins of Chemical Formulas 3, 4, and 5 have a benzene ring in themselves, thereby degrading light transmittance upon exposure. Accordingly, the present invention prevents standing waves and inverse taper phenomenon caused by the film change of resist, exhibits high sensitivity and high resolution, and in particular, prevents performance degradation of profile and depth of focus, and provides an improved chemically amplified positive resist composition. . In addition, the present invention provides a chemically amplified positive resist composition that is effective in reducing the amplitude of a swing curve to reduce the variation in line width at various film thicknesses.
The resin (A) used in the resist composition of the present invention is a resin which is originally insoluble or poorly soluble in an aqueous alkali solution, but becomes soluble in an aqueous alkaline solution after dissociation of a functional group unstable with an acid by the action of an acid.
(A) The structural units represented by the following formula (1) and the structural units represented by the formula (2) are linearly arranged in a molar ratio of 2-5: 5-8, with a glass transition temperature (Tg) of 150-170 ° C and a molecular weight of 9,000 ~ 11,000.
[Formula 1]
Where
R 1 is a hydrogen atom or a methyl group,
R <2> is a C1-C10 linear, branched or cyclic alkyl group.
[Formula 2]
The resin (A) is one structural unit represented by the formula (1) and 2 to 6 structural units represented by the formula (2) are alternately arranged in a line in a molar ratio of 2-5: 5-8, glass transition temperature (Tg) Is 150-170 degreeC, and the resin whose molecular weight is 9,000-11,000 is more preferable.
It is preferable that (A) resin used by this invention is 1.4-1.6 in dispersion degree.
The resin (A) used in the present invention preferably has a protection ratio of 20 to 35% in the acrylate polymerized unit in adjusting the overall properties of the resist. In addition, a part of the hydroxy group of the hydroxystyrene polymerized unit may be dissociated with an acid. Can be protected with protectors.
Preferred protecting groups for the hydroxy group are t-butyloxycarbonyl, ethyl benzene, tetrahydropyranyl, 1-ethoxyethyl, and isopropyl The protection is preferably 10% to 50% in adjusting the overall properties of the resist.
Resin similar to the resin (A) used in the prior art (glass transition temperature (Tg) less than 150 ℃) is a hydrophilic, hydrophobic group gathered separately in the molecular unit, unlike the separation according to the characteristics of the present invention, (A) resin with glass transition temperature (Tg) of 150 ~ 170 ℃ is uniformly distributed from the molecular unit to each other to improve the properties of resist (defect defect, standing wave, profile, residual film ratio, etc.). Has an advantageous structure.
The characteristics of the compounds of Formulas 3, 4 and 5 constituting the resin (B) included in the photoresist composition of the present invention are as follows.
[Formula 3]
In the above formula,
R 3 is a hydrogen atom or a methyl group,
R 4 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms
R 5 is hydrogen, methyl, ethyl, propyl, Br, Cl, F or NO 2 ,
c, d and e are mole fractions of each polymerized unit, c + d + e = 1,
0.1 ≦ [(d + e) / (c + d + e)] ≦ 0.5 or 0.05 ≦ [e / (c + d + e)] ≦ 0.4.
If the value of [d + e / (c + d + e)] (or [e / (c + d + e)]) is less than 0.1 (or 0.05), the effect of lowering the light transmittance upon exposure is minimal. If there is a standing wave or reverse taper and exceeds 0.5 (or 0.4), it will cause a problem of degrading the resolution, making it difficult to implement a smaller pattern.
More preferably, c, d and e have a value of 0.20 ≦ [(d + e / (c + d + e)] ≦ 0.40 or 0.05 ≦ [e / (c + d + e)] ≦ 0.35 .
On the other hand, [(d + e) / (c + d + e)] × 100 is a protection ratio of the resin, and the protection ratio of the resin is preferably 10% to 50%.
[Formula 4]
In the above formula,
R 3 is a hydrogen atom or a methyl group,
R 4 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms,
R 5 is hydrogen, methyl, ethyl, propyl, Br, Cl, F or NO 2 ,
f, g and h are mole fractions of each polymerized unit, f + g + h = 1,
0.1 ≦ [(g + h) / (f + g + h)] ≦ 0.5 or 0.05 ≦ [h / (f + g + h)] ≦ 0.4.
When the value of [(g + h) / (f + g + h)] (or [h / (f + g + h)) is less than 0.1 (or 0.05), the effect of deteriorating light transmittance upon exposure is insignificant. If standing wave or reverse taper is present and exceeds 0.5 (or 0.4), it causes a problem of lowering resolution, making it difficult to realize a smaller pattern.
More preferably, f, g and h have a value of 0.20 ≦ [(g + h / (f + g + h)] ≦ 0.40 or 0.05 ≦ [h / (f + g + h)] ≦ 0.35 .
On the other hand, [(g + h) / (f + g + h)] × 100 is a protection ratio of the resin, and the protection ratio of the resin is preferably 10% to 50%.
[Formula 5]
In the above formula,
R 3 is a hydrogen atom or a methyl group,
R 4 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms,
R 5 is hydrogen, methyl, ethyl, propyl, Br, Cl, F or NO 2 ,
i, j and k are the mole fraction of each polymerized unit i + j + k = 1,
0.1 ≦ [(j + k) / (i + j + k)] ≦ 0.5 or 0.05 ≦ [k / (i + j + k)] ≦ 0.4.
If the value of [j + k / (i + j + k)] (or [k / (i + j + k)]) is less than 0.1 (or 0.05), the effect of lowering the light transmittance upon exposure is negligible. If there is a standing wave or reverse taper, and if it exceeds 0.5 (or 0.4), it causes a problem of degrading the resolution, which makes it difficult to realize a smaller pattern.
More preferably, i, j and k have values of 0.2 ≦ [(j + k / (i + j + k)] ≦ 0.4 or 0.05 ≦ [k / (i + j + k)] ≦ 0.35 .
On the other hand, [(j + k) / (i + j + k)] × 100 is a protection ratio of the resin, and the protection ratio of the resin is preferably 10% to 50%.
In the resist composition of the present invention, the weight ratio of the resin (A) and the resin (B) is preferably 1: 9 to 9: 1 in terms of solid content.
In the photoresist composition of the present invention, based on 100 parts by weight (A) of the resin (in terms of solid content), (B) the resin should be included in the range of 10 to 90 parts by weight of the standing wave by the effect of deteriorating the light transmittance ( The problem of a standing wave or reverse taper is solved.
The photoacid generator in the resist composition of the present invention is a substance that generates an acid by irradiating the material itself or a resist composition containing such material with high energy radiation such as far ultraviolet rays, electron beams, X-rays, or radiant light. In a chemically amplified positive resist composition, the acid generated from the photoacid generator acts on the resin described above to dissociate the group that is unstable with the acid present in the resin.
In the present invention, a compound of the formula (6) is used as a photoacid generator.
[Formula 6]
In the above formula,
R 6 and R 7 are each independently hydroxyl, amino or straight alkyl having 3 to 8 carbon atoms unsubstituted or substituted with alkoxy having 1 to 6 carbon atoms; Branched alkyl of 3 to 8 carbon atoms unsubstituted or substituted with hydroxyl, amino or alkoxy having 1 to 6 carbon atoms; Cyclic alkyl of 3 to 8 carbon atoms unsubstituted or substituted with hydroxyl, amino or alkoxy having 1 to 6 carbon atoms; Or an aryl group having 6 to 10 carbon atoms substituted with alkyl or alkoxy.
Specific examples of the compound of Formula 6 include that R 6 and R 7 are n-propyl group, n-butyl group, n-octyl group, toluyl group, 2,4,6-trimethylphenyl group, 2,4,6- And triisopropylphenyl group, 4-dodecylphenyl group, 4-methoxyphenyl group, 2-naphthyl group, benzyl group.
In the resist composition of the present invention, other photoacid generators other than the photoacid generator of Formula 6 may be used together. Such other photoacid generators include onium salt compounds, s-triazine-based organic halogen compounds, sulfone compounds, sulfonate compounds and the like, and these may be used alone or in combination of two or more.
When the photoacid generator of Chemical Formula 6 and other photoacid generators are used together as the photoacid generator, the mixing ratio is preferably 50:50 to 90:10, and the photoacid generator of Chemical Formula 6 is less than 50%. In this case, the upper part of the profile is thickened, causing the profile to collapse, and when exceeding 90%, the effect of mixing the other photoacid generators is not obtained.
The other photoacid generators specifically include diphenyl iodonium trifluoromethanesulfonate, 4-methoxyphenylphenyl iodonium hexafluoroantimonate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluoroantimo Nate, Bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfo Nitrate, 4-methylphenyldiphenylsulfonium perfluorobutanesulfonate, 4-methylphenyldiphenylsulfonium perfluorooctanesulfonate, 4-methoxyphenyldiphenylsulfonium hexafluoroantimonate, -methoxyphenyl Diphenylsulfonium tripleru Romethanesulfonate, p-tolyldiphenylsulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium tri Fluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphate, 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 1- (2-naphtolylmethyl) thiolanium hexafluoro Roantimonate, 1- (2-naphtolylmethyl) thiolanium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium hexafluoroantimonate, 4-hydroxy-1- Naphthyldimethylsulfoniumtrifluoromethanesulfonate, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2,4,6-tris (trichloromethyl) -1 , 3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl ) -1,3-5-triazine, 2- (4-meth Ciphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy-1-naphthyl) -4,6-bis (trichloromethyl) -1 , 3,5-triazine, 2- (benzo [d] [1,3] dioxolan-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (Trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2-methoxystyryl) -4,6-bis (trichloro Methyl) -1,3,5-triazine, 2- (4-butoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-pentyloxy Styryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 1-benzoyl-1-phenylmethyl p-toluenesulfonate (commonly referred to as benzoin tosylate), 2- Benzoyl-2-hydroxy-2-phenylethyl p-toluenesulfonate (usually α-meth Thiolbenzoin tosylate), 1,2,3-benzenetolyl trimethanesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfonate, 4-nitrobenzyl p -Toluenesulfonate, diphenyl disulfone, di-p-tolyl disulfone, dis (phenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) dia Crude methane, bis (4-tert-butylphenylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, (benzoyl) (phenyl Sulfonyl) diazomethane, N- (phenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N -(Trifluoromethylsulfonyloxy) -5-norbornene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthalimide, N- (10-camphorsul Ponyloxy) naphthalimide, 4-methoxy-α-[[[(4-methyl Carbonyl) sulfonyl] oxy] it is already include no] benzene acetonitrile.
The photoacid generator used in the present invention is preferably included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total resin component in terms of solid content. If the amount of the photoacid generator is less than 0.1 part by weight, the amount of acid generated is not sufficient, so that the resin is not sufficiently soluble, and also does not realize the desired pattern shape. For example, pattern shapes such as scum, notching, and round shapes are generated. If it exceeds 20 parts by weight, the transmittance is deteriorated, so that light is not transmitted to the lower portion of the resist film, so that the resin is not sufficiently soluble. Therefore, an appropriate amount of photoacid generator is necessary to obtain a desired pattern shape.
The resist composition of the present invention may contain other organic base compounds, especially nitrogen-containing basic organic compounds synthesized as quenchers in amounts that do not adversely affect the effects of the present invention. Specific examples of the quencher component include tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, tetra-n-octylammonium hydroxide, phenyltrimethylammonium Hydroxide, 3- (trifluoromethyl) -phenyltrimethylammonium hydroxide, (2-hydroxyethyl) trimethylammonium hydroxide, dicyclohexylmethylamine, 2,6-diisopropylaniline, tris ( 2- (2-methoxyethoxy) ethyl) amine and the like, and further, a hindered amine compound having a piperidine skeleton as described in JP-A-11-52575 may also be used as a quencher. Can be.
The quencher of the resist composition of the present invention preferably contains 0.001 to 10 parts by weight based on 100 parts by weight of the total resin component in terms of solid content. If the content of the quencher is less than 0.001 part by weight, the diffusion of acid is increased so that an abnormality in the exposed area is developed, and thus the pattern profile is deteriorated. The photosensitivity of the resist composition is rather reduced by causing a change in profile accordingly.
In addition, the resist compositions of the present invention may also contain small amounts of various additives such as sensitizers, dissolution inhibitors, other resins, surfactants, stabilizers, dyes, and the like.
Such a resist composition is usually in the form of a resist liquid composition containing components dissolved in a solvent, and is applied onto a substrate such as a silicon wafer by a conventional method.
The solvent used in the present invention can be used as is commonly used in the art as it dissolves the components, exhibits a suitable drying rate and provides a uniform and smooth coating after solvent evaporation. Specific examples thereof include glycol ether esters such as ethylcellosolve acetate, methylcellosolve acetate and propylene glycol monomethyl ether acetate; Esters such as ethyl lactate, butyl acetate, amyl acetate and ethyl pyruvate; Ketones such as acetone, methyl isobutyl ketone, 2-heptanone and cyclohexanone: cyclic esters such as γ-butyrolactone; Alcohols such as 3-methoxy-1-butanol and the like. These solvents may be used alone or in mixture of two or more.
The resist applied and dried on the substrate is subjected to an exposure treatment for pattern formation, followed by heat treatment to promote the protective group removal reaction, and then developed with an alkali developer.
The alkali developer used in the present invention can be selected from various aqueous alkali solutions, and usually tetramethylammonium hydroxide and (2-hydroxyethyl) trimethylammonium hydroxide (commonly referred to as choline) are frequently used. .
Hereinafter, the present invention will be described in more detail with reference to Preparation Examples, Examples, and Comparative Examples, but these Examples are provided to illustrate the present invention, but do not limit the technical scope of the present invention.
Production Example 1: Synthesis of Resin A-2
(1) Preparation of t-butoxystyrene / 2-ethyl-2-adamantyl methacrylate / benzoate styrene terpolymer
500 ml of 120 g (0.68 mole) of 4-t-butoxystyrene, 16.74 g (0.08 mole) of 2-ethyl-2-adamantyl methacrylate, 20 g (0.07 mole) of benzoate styrene and 273.49 g of 2-propanol Place in a four-necked flask and heat to 75 ° C. under a nitrogen atmosphere. Individually, a solution was prepared in which 10.45 g of dimethyl 2,2'-azobis (2-methylpropionate) was dissolved in 27.35 g of 2-propanol, and this was carried out over 30 minutes in the monomer solution maintained at 75 ° C. described above. Add it down. The resulting mixture is stirred for 23 hours, further heated and then refluxed for 8 hours. After cooling to room temperature, the reaction mixture is added with stirring to a mixture of 2,688.2 g of methanol and 1,344.1 g of ion-exchanged water.
The reaction mixture is stirred for 3 hours and then filtered to give a white solid. It was dried under reduced pressure to give 134.6 g of 4-t-butoxystyrene / 2-ethyl-2-adamantyl methacrylate / benzoate styrene terpolymer.
(2) Preparation of hydroxystyrene / 2-ethyl-2-adamantyl methacrylate / benzoate styrene terpolymer
120 g of 4-t-butoxystyrene and 2-ethyl-2-adamantyl methacrylate / benzoate styrene terpolymer and 360 g of 2-propanol obtained in the above (1) were added to a 1 L four-necked flask and dissolved. The temperature is raised to less than 75 ° C. To this solution is added a mixed solution of 20.77 g of 36% hydrochloric acid and 20.77 g of 2-propanol. Thereafter, the mixture was hydrolyzed by refluxing at the same temperature for 3 hours, and then cooled to room temperature. This reaction product is added to a mixed solution of 120 g of acetone and 1,200 g of ion-exchanged water, and the solid precipitated therefrom is collected by filtration. The solid is dissolved in 300 g of acetone and the resulting solution is added to 3,600 g of ion-exchanged water. The solid precipitated in this way was collected by filtration, and the operation from dissolution in acetone to filtration collection of the precipitated solid by addition to ion-exchanged water was repeated twice. The solid thus obtained was dried under reduced pressure so that 4-hydroxystyrene and 2-ethyl-2-adamantyl methacrylate /, in which the t-butoxy group in the copolymer was hydrolyzed and converted to a hydroxyl group 86.7 g of benzoate styrene terpolymer are obtained. The weight average molecular weight of this copolymer is 10,000, and dispersion degree is 1.7.
Production Example 2: Synthesis of Resin A-3
(1) Preparation of t-butoxystyrene / 2-ethyl-2-adamantyl methacrylate / phenyl styrene terpolymer
500 g of sand containing 120 g (0.68 mole) of 4-t-butoxystyrene, 16.74 g (0.08 mole) of 2-ethyl-2-adamantyl methacrylate, 20 g (0.07 mole) of phenyl styrene and 273.49 g of 2-propanol Place in flask and heat to 75 ° C. under nitrogen atmosphere. Individually, a solution was prepared in which 10.45 g of dimethyl 2,2'-azobis (2-methylpropionate) was dissolved in 27.35 g of 2-propanol, and over 30 minutes in a monomer solution maintained at 75 ° C. as described above. Add it down. The resulting mixture is stirred for 23 hours, further heated and then refluxed for 8 hours. After cooling to room temperature, the reaction mixture is added with stirring to a mixture of 2,688.2 g of methanol and 1,344.1 g of ion-exchanged water.
The reaction mixture is stirred for 3 hours and then filtered to give a white solid. It was dried under reduced pressure to give 134.6 g of 4-t-butoxystyrene / 2-ethyl-2-adamantyl methacrylate / phenyl styrene terpolymer.
(2) Preparation of hydroxystyrene / 2-ethyl-2-adamantyl methacrylate / phenyl styrene terpolymer
120 g of 4-t-butoxystyrene and 2-ethyl-2-adamantyl methacrylate / phenyl styrene terpolymer and 360 g of 2-propanol obtained in (1) above were added to a 1 L four-necked flask, It raises below 75 degreeC. To this solution is added a mixed solution of 20.77 g of 36% hydrochloric acid and 20.77 g of 2-propanol. Thereafter, the mixture was hydrolyzed by refluxing at the same temperature for 3 hours, and then cooled to room temperature. This reaction product is added to a mixed solution of 120 g of acetone and 1,200 g of ionic exchange, and the solid precipitated therefrom is collected by filtration. The solid is dissolved in 300 g of acetone and the resulting solution is added to 3,600 g of ion-exchanged water. The solid precipitated in this way was collected by filtration, and the operation from dissolution in acetone to filtration collection of the precipitated solid by addition to ion-exchanged water was repeated twice. The solid thus obtained was dried under reduced pressure so that 4-hydroxystyrene and 2-ethyl-2-adamantyl methacrylate /, in which the t-butoxy group in the copolymer was hydrolyzed and converted to a hydroxyl group 86.7 g of phenyl styrene terpolymer are obtained. The weight average molecular weight of this copolymer is 10,000, and dispersion degree is 1.7.
Production Example 3: Synthesis of Resin A-4
(1) Preparation of t-butoxystyrene / 2-ethyl-2-adamantyl methacrylate / phenoxy styrene terpolymer
500 ml of 120 g (0.68 mol) of 4-t-butoxystyrene, 16.74 g (0.08 mol) of 2-ethyl-2-adamantyl methacrylate, 20 g (0.07 mol) of phenoxy styrene, and 273.49 g of 2-propanol In a four-necked flask and heated to 75 ° C. under a nitrogen atmosphere. Individually, a solution was prepared in which 10.45 g of dimethyl 2,2'-azobis (2-methylpropionate) was dissolved in 27.35 g of 2-propanol, and over 30 minutes in a monomer solution maintained at 75 ° C. as described above. Add it down. The resulting mixture is stirred for 23 hours, further heated and then refluxed for 8 hours. After cooling to room temperature, the reaction mixture is added with stirring to a mixture of 2,688.2 g of methanol and 1,344.1 g of ion-exchanged water.
The reaction mixture is stirred for 3 hours and then filtered to give a white solid. It was dried under reduced pressure to give 134.6 g of 4-t-butoxystyrene / 2-ethyl-2-adamantyl methacrylate / phenoxy styrene terpolymer.
(2) Preparation of hydroxystyrene / 2-ethyl-2-adamantyl methacrylate / phenoxy styrene terpolymer
120 g of 4-t-butoxystyrene and 2-ethyl-2-adamantyl methacrylate / phenoxy styrene terpolymer and 360 g of 2-propanol obtained in the above (1) were added to a 1 L four-necked flask and dissolved. The temperature is raised to less than 75 ° C. To this solution is added a mixed solution of 20.77 g of 36% hydrochloric acid and 20.77 g of 2-propanol. Thereafter, the mixture was hydrolyzed by refluxing at the same temperature for 3 hours, and then cooled to room temperature. This reaction product is added to a mixed solution of 120 g of acetone and 1,200 g of ion-exchanged water, and the solid precipitated therefrom is collected by filtration. The solid is dissolved in 300 g of acetone and the resulting solution is added to 3,600 g of ion-exchanged water. The solid precipitated in this way is collected by filtration, and the operation from dissolution of acetone to filtration of the precipitated solid by addition of ion-exchanged water is repeated twice. The solid thus obtained was dried under reduced pressure so that 4-hydroxystyrene and 2-ethyl-2-adamantyl methacrylate /, in which the t-butoxy group in the copolymer was hydrolyzed and converted to a hydroxyl group 86.7 g of phenoxy styrene terpolymer are obtained. The weight average molecular weight of this copolymer is 10,000, and dispersion degree is 1.7.
Example 1 to 5 and Comparative example 1 to 3: chemically amplified positive Resist Preparation of the composition
The components shown in Table 1 and components except for the solvent were mixed and dissolved in 1030 parts by weight of propylene glycol monomethyl ether acetate, and then filtered through a fluorine resin filter having a pore diameter of 0.2 μm to prepare a resist solution. The resist solution prepared here includes a resin containing a degree of protection of about 15% to 25%.
A-1: The structural units represented by the formula (1) (R1: methyl group, R2: ethyl group) and the structural units represented by the formula (2) are alternately arranged in a line, the molar ratio of the structural unit is 2.5: 7.5, the glass transition temperature (Tg) is 150 DEG C and has a molecular weight of 9,150 (manufacturer: Dupont, trade name: SRC-D90)
A-2: Resin having a molecular weight of 10,000 and a dispersity of 1.7 containing a benzoate protecting group having d of 0.12 and e of 0.2 in Chemical Formula 2
A-3: Resin having a molecular weight of 10,000 and a dispersity of 1.7 containing a benzyl protecting group having g of 0.12 and h of 0.2 in Formula 3
A-4: Resin having a molecular weight of 10,000 and a dispersity of 1.7 containing a phenyl protecting group having j of 0.12 and k of 0.2 in Formula 4
A-5: Others are the same as those of A-1, and a resin having a glass transition temperature (Tg) of 14 2 ° C (manufacturer: Dupont, trade name: ピ oly GA2)
B-1: Diazodisulfone type photoacid generator wherein R 6 and R 7 in formula (5) are cyclohexyl groups
C-1: 2,6-diisopropylaniline
C-2: tris (2- (2-methoxyethoxy) ethyl) amine
D-1: Propylene Glycol Monomethyl Ether Acetate
Test Example .
The resist solution described above was applied to a silicon wafer treated with hexamethyldisilazane using a spin coater and dried to obtain a film thickness of 0.25 mu m. After applying the resist solution, preheat treatment was performed for 60 seconds on a hot plate at 100 ° C. The wafer having the resist film thus formed is exposed while the exposure dose is gradually changed using a scanning exposure apparatus ['NSR-S203B' manufactured by Nikon Corp., NA = 0.68, sigma == 0.75] having an exposure wavelength of 248 nm (KrF). To form a line and space pattern. The post-exposure heat treatment was then performed at 110 ° C. for 60 seconds on a hot plate. In addition, paddle development was performed for 60 seconds using an aqueous 2.38% tetramethylammonium hydroxide solution. The depth of focus and profile were measured in 0.18 micrometer line and space pattern using the KLA scanning electron microscope after image development. The results are shown in Figure 1 (Example 1) and Figure 2 (Comparative Example 1) and Table 2.
In addition, the light transmittance of a resist film measured the transmittance | permeability of 248 nm light with the ultraviolet-visible powder meter (the Shimadzu product, UV-2401PC), and the result is shown in Table 2.
As confirmed in Table 2, it can be seen that Examples 1 to 5 have a lower transmittance than Comparative Examples 1 to 3. These results indicate that the benzene ring of the benzoate styrene polymerized units (Examples 1-3), the phenyl styrene polymerized units (Example 4), and the phenoxy styrene polymerized units (Example 5) contained in Examples 1 to 5 were reflected light. This means absorption. Therefore, from these results, the resist compositions of Examples 1 to 5 can lower the standing wave by lowering the transmittance and implement a better pattern shape.
Specifically, as shown in Table 2, according to the present invention, benzoate styrene polymerized units (Examples 1-3), phenyl styrene polymerized units (Example 4), and phenoxy styrene polymerized units (Example 5) were contained. It can be seen that the resist compositions of Examples 1 to 5 are superior in profile in comparison with the resist compositions of Comparative Examples 1 and 2 that do not contain such polymerized units (see FIGS. 1 and 2). In the case of including such a polymerized unit, a resin (A-5) having a conventional glass transition temperature (Tg) of less than 150 ° C. is used instead of the resin (A-1) used in Examples 1 to 5 of the present invention (Comparative Example). 3) confirmed that the profile is not good.
In addition, as shown in Table 3, it was confirmed that the resist composition of Examples 1 to 5 is more effective in reducing the amplitude of the swing curve than the resist composition of Comparative Examples 1 to 3.
FIG. 1 is a photograph of a pattern formed of the resist composition of Example 1 and taken of a profile using a KLA scanning electron microscope. FIG.
FIG. 2 is a photograph of a pattern formed of a resist composition of Comparative Example 1 and taken of a profile using a KLA scanning electron microscope. FIG.
Claims (13)
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KR1020070067190A KR20090002865A (en) | 2007-07-04 | 2007-07-04 | Chemical amplification type positive resist composition |
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KR1020070067190A KR20090002865A (en) | 2007-07-04 | 2007-07-04 | Chemical amplification type positive resist composition |
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