JP3907179B2 - Positive resist composition - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a positive resist composition suitably used in microlithography processes such as the production of VLSI and high-capacity microchips, and other photofabrication processes. More specifically, the present invention relates to a positive resist composition capable of forming a highly refined pattern using vacuum ultraviolet light of 160 nm or less.
[0002]
[Prior art]
Integrated circuits have been increasingly integrated, and in manufacturing semiconductor substrates such as VLSI, processing of ultrafine patterns having a line width of less than a quarter micron has been required. As one of means for miniaturizing a pattern, it is known to shorten the wavelength of an exposure light source used in forming a resist pattern. This is the Rayleigh equation representing the resolution (line width) R of the optical system,
R = k · λ / NA
(Where λ is the wavelength of the exposure light source, NA is the numerical aperture of the lens, and k is the process constant). From this equation, it can be seen that in order to achieve a high resolution, that is, to reduce the value of R, it is sufficient to shorten the wavelength λ of the exposure light source.
[0003]
For example, in the manufacture of a semiconductor device having a degree of integration of up to 64 Mbits, i-line (365 nm) of a high-pressure mercury lamp has been used as a light source until now. As a positive resist corresponding to this light source, a number of compositions containing a novolak resin and a naphthoquinonediazide compound as a photosensitive material have been developed, and have achieved sufficient results in processing line widths of up to about 0.3 μm. . Further, in the manufacture of a semiconductor device having an integration degree of 256 Mbit or more, KrF excimer laser light (248 nm) has been adopted as an exposure light source instead of i-line.
Furthermore, for the purpose of manufacturing a semiconductor having a degree of integration of 1 Gbit or more, the use of ArF excimer laser light (193 nm), which is a light source with a shorter wavelength in recent years, and further to form a pattern of 0.1 μm or less.₂The use of excimer laser light (157 nm) has been studied.
[0004]
In accordance with the shortening of the wavelength of these light sources, the constituent components of the resist material and the compound structure thereof have also changed greatly. That is, in the conventional resist containing novolak resin and naphthoquinonediazide compound, since absorption in the far ultraviolet region of 248 nm is large, it becomes difficult for light to reach the bottom of the resist sufficiently, and only a taper-shaped pattern with low sensitivity can be obtained.
In order to solve such a problem, a compound that generates an acid by irradiation with far ultraviolet light using, as a main component, a resin having a poly (hydroxystyrene) having a low absorption in the 248 nm region as a basic skeleton and protected by an acid-decomposable group ( A composition combining a photoacid generator), a so-called chemically amplified resist, has been developed. Since the chemically amplified resist changes the solubility in the developer by the catalytic decomposition reaction of the acid generated in the exposed area, a highly sensitive and high resolution pattern can be formed.
[0005]
For effective acid-decomposable resins and photoacid generators for these, Polym. Eng. Sci., 23, 1012 (1983), ACS. Sym., 242, 11 (1984), Macromolecules, 21 1475 (1988), Journal of the Society of Synthetic Organic Chemistry, Japan, 49, 437 (1991), “Microfabrication and Resist” (Kyoritsu Shuppan, 1987), and many other papers and patents. Further, when ArF excimer laser light (193 nm) was used, a compound having an aromatic group essentially has a large absorption in the wavelength region of 193 nm, and thus sufficient performance was not obtained even with the above chemically amplified resist.
[0006]
To solve this problem, an acid-decomposable resin having poly (hydroxystyrene) as a basic skeleton is replaced with an acid-decomposable resin in which an alicyclic structure having no absorption at 193 nm is introduced into the main chain or side chain of the polymer. Improvement of the amplification type resist is attempted.
About these alicyclic acid-decomposable resins, for example, JP-A-4-39665, 7-234511, 9-73173, 7-199467, 8-259626, 9-221519, 10-10739, 9-230595, 10-1111569, 10-218947, 10-153864, WO-97 / 33198, and the like.
[0007]
F₂With respect to excimer laser light (157 nm), it was found that the alicyclic resin also has a large absorption in the 157 nm region, which is insufficient to obtain a target pattern of 0.1 μm or less. On the other hand, Proc. SPIE. Vol. 3678. page 13 (1999) reported that a resin introduced with fluorine atoms (perfluoro structure) has sufficient transparency at 157 nm. Proc. SPIE. Vol. 3999. 330 (2000), 357 (2000), 365 (2000), WO-00 / 17712, etc.
However, these fluororesins do not necessarily have sufficient dry etching resistance, and because of their unique water- and oil-repellent properties derived from the perfluoro structure, they improve coating properties (uniformity of the coated surface). In addition, suppression of development defects has also been desired.
[0008]
[Problems to be solved by the invention]
Therefore, the object of the present invention is 160 nm or less, particularly F₂It is to provide a positive resist composition suitable for use with an exposure light source of excimer laser light (157 nm). Specifically, it exhibits sufficient transparency when using a light source of 157 nm, and satisfies coating properties and development defects. And providing a positive resist composition.
It is another object of the present invention to provide a positive resist composition that forms a pattern with good sensitivity and resolution and is excellent in dry etching resistance.
[0009]
[Means for Solving the Problems]
As a result of intensive investigations while paying attention to the above characteristics, the present inventors have found that the object of the present invention can be achieved brilliantly by using the following specific composition, and have reached the present invention.
That is, the present invention has the following configuration.
[0010]
(1) (A) a resin having at least one repeating unit represented by the following general formula (I), which decomposes by the action of an acid and increases the solubility in an alkali developer, and (B) irradiation with actinic rays or radiation A positive resist composition containing a compound capable of generating an acid.
[0011]
[Chemical 7]
[0012]
  Where R₁Represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl or haloalkyl group which may have a substituent. R₂, R_ThreeMay be the same or different, and may be a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group, or an optionally substituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group or aryl. Represents a group. R_Four IsEven if it has a substituentGood alkoxyRepresents a carbonylmethyl group or a group of formula (II).
[0013]
[Chemical 8]
[0014]
R_Five, R₆May be the same or different and each represents a hydrogen atom, an alkyl group or a cycloalkyl group which may have a substituent. R₇Represents an alkyl group, perfluoroalkyl group, cycloalkyl group, perfluorocycloalkyl group, aralkyl group or aryl group which may have a substituent. R_Five~ R₇May be combined to form a ring.
(2) The positive resist composition as described in (1) above, wherein the resin (A) further has at least one repeating unit represented by the following general formula (III).
[0015]
[Chemical 9]
[0016]
Where R₈, R₉May be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl or haloalkyl group which may have a substituent. R_TenIs a hydrogen atom, a halogen atom, an alkyl group or a haloalkyl group which may have a substituent, or -A₁Represents a -CN group. A₁May have a single bond, a substituent, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R.₁₁-, -CO-O-R₁₂-, -CO-N (R₁₃-R₁₄-Represents. R₁₁, R₁₂, R₁₄May be the same or different and each may have a single bond, an ether group, an ester group, an amide group, a urethane group or a ureido group, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group. To express. R₁₃Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, which may have a substituent.
(3) The positive type as described in (1) or (2) above, wherein the resin of (A) further has at least one of repeating units represented by the following general formulas (IV) and (V): Resist composition.
[0017]
Embedded image
[0018]
Where R₁₅Represents a hydrogen atom, an alkyl group, a perfluoroalkyl group, a cycloalkyl group, a perfluorocycloalkyl group, or an aryl group, which may have a substituent.
(4) The resin of (A) further has at least one repeating unit represented by the general formulas (VI) and (VII), according to any one of (1) to (3), Positive resist composition.
[0019]
Embedded image
[0020]
Where R₁₆, R₁₇These may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or haloalkyl group which may have a substituent. R₁₈Is -C (R₁₉) (R₂₀) (R_{twenty one}), -C (R₁₉) (R₂₀) (OR_{twenty two}Or a group represented by formula (VIII). R₁₉~ R_{twenty two}Are the same or different and each represents an alkyl group, monocyclic or polycyclic cycloalkyl group, alkenyl group, aralkyl group or aryl group which may have a substituent. R₁₉, R₂₀, R_{twenty one}2 of R or R₁₉, R₂₀, R_{twenty two}Two of these may combine to form a ring. In formula (VIII), R_{twenty three}Represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, which may have a substituent. Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with a carbon atom.
A₂May have a single bond, a substituent, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R.₁₁-, -CO-O-R₁₂-, -CO-N (R₁₃-R₁₄-Represents. R₁₁, R₁₂, R₁₄May be the same or different and each may have a single bond, an ether group, an ester group, an amide group, a urethane group or a ureido group, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group. To express. R₁₃Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, which may have a substituent.
R₁Represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl or haloalkyl group which may have a substituent. R₂And R_ThreeMay be the same or different, and may be a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group, or an optionally substituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group or Represents an aryl group.
[0021]
Embedded image
R in the formula (VIII)_{twenty three}Represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, which may have a substituent. Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with a carbon atom.
[0022]
(5) The positive resist composition as described in any one of (1) to (4) above, further comprising (C) a compound having a basic nitrogen atom as an acid diffusion inhibitor.
(6) The compound of component (B) generates perfluoroalkyl sulfonic acid having 2 or more carbon atoms, perfluoroaryl sulfonic acid, or aryl sulfonic acid substituted with a perfluoroalkyl group upon irradiation with actinic rays or radiation. The positive resist composition according to any one of (1) to (5), wherein the positive resist composition is selected from a sulfonium salt or an iodonium salt compound.
(7) The component (B) component is selected from an imide-N-sulfonate compound, an oxime-N-sulfonate compound, or a disulfone compound, according to any one of (1) to (6) above A positive resist composition.
(8) The positive resist composition as described in any one of (1) to (7) above, wherein vacuum ultraviolet light of 160 nm or less is used as an exposure light source.
[0023]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the compounds used in the present invention will be described in detail.
[1] Resin of the present invention (A)
The resin in the present invention (A) is a hexafluoro-2-propanol group represented by the general formula (I) or a group obtained by protecting the OH group of the hexafluoro-2-propanol group with an acid-decomposable group. A resin having at least one repeating unit of a styrene derivative substituted with Preferably, the resin further decomposes by the action of an acid having at least one repeating unit represented by the general formula (III) and increases the solubility in an alkali developer. Further, if necessary, in order to control physical properties such as hydrophilicity / hydrophobicity, glass transition point, and transparency to exposure light of the resin of the present invention (A), or to control the polymerizability at the time of polymer synthesis, the general formula (IV ) To (VII) at least one repeating unit.
[0024]
In the general formula, R₁Represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl or haloalkyl group which may have a substituent. R₂, R_ThreeMay be the same or different, and may be a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group, or an optionally substituted alkyl group, cycloalkyl group, alkenyl group, aralkyl group or aryl. Represents a group.
R_FourIs a hydrogen atom, an optionally substituted alkyl group, a perfluoroalkyl group, a monocyclic or polycyclic cycloalkyl group, an acyl group, an alkoxycarbonyl group, an alkoxycarbonylmethyl group, or the general formula (II) ) Group.
[0025]
R_Five, R₆May be the same or different and each represents a hydrogen atom, an optionally substituted alkyl group or a cycloalkyl group. R₇Represents an alkyl group, perfluoroalkyl group, cycloalkyl group, perfluorocycloalkyl group, aralkyl group or aryl group which may have a substituent. R_Five~ R₇May be combined to form a ring.
R₈, R₉May be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl or haloalkyl group which may have a substituent. R_TenIs a hydrogen atom, a halogen atom, an alkyl group or a haloalkyl group which may have a substituent, or -A₁Represents a -CN group.
A₁And A₂Is a single bond, an optionally substituted divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R.₁₁-, -CO-O-R₁₂-, -CO-N (R₁₃-R₁₄-Represents.
[0026]
R₁₁, R₁₂, R₁₄May be the same or different and each may have a single bond, an ether group, an ester group, an amide group, a urethane group or a ureido group, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group. To express. R₁₃Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, which may have a substituent. R₁₅Represents a hydrogen atom, an alkyl group, a perfluoroalkyl group, a cycloalkyl group, a perfluorocycloalkyl group, or an aryl group, which may have a substituent.
R₁₆, R₁₇It may be the same or different, and represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or haloalkyl group which may have a substituent. R₁₈Is -C (R₁₉) (R₂₀) (R_{twenty one}), -C (R₁₉) (R₂₀) (OR_{twenty two}Or a group of the general formula (VIII). R₁₉~ R_{twenty two}Are the same or different and each represents an alkyl group, monocyclic or polycyclic cycloalkyl group, alkenyl group, aralkyl group or aryl group which may have a substituent.
[0027]
R₁₉, R₂₀, R_{twenty one}2 of R or R₁₉, R₂₀, R_{twenty two}Two of these may combine to form a ring. R_{twenty three}Represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, which may have a substituent. Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with a carbon atom.
[0028]
The alkyl group is, for example, an alkyl group having 1 to 8 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, 2 Preferred examples include -ethylhexyl group and octyl group. The cycloalkyl group may be monocyclic or polycyclic. The monocyclic type has 3 to 8 carbon atoms, and preferred examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The polycyclic type has 6 to 20 carbon atoms, and includes, for example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group, An androstanyl group etc. can be mentioned preferably.
[0029]
As the perfluoroalkyl group, for example, those having 1 to 12 carbon atoms, specifically, a trifluoromethyl group, a pentafluoroethyl group, a 2,2,2-trifluoroethyl group, a heptafluoropropyl group, 2,2,3,3,3-pentafluoro-1-propyl group, 2,2,3,4,4,4-hexafluoro-1-butyl group, 2,2,3,3,4,4, 4-heptafluoro-1-butyl group, 2,2,3,3,4,4,5,5-octafluoro-1-pentyl group, perfluorobutyl group, perfluorohexyl group, perfluorohexylethyl group, A perfluoroheptylmethyl group, a perfluorooctyl group, a perfluorooctylethyl group, a perfluorodecylethyl group and the like can be preferably exemplified.
[0030]
The perfluorocycloalkyl group is a monocyclic or polycyclic cycloalkyl group in which a plurality of fluorine groups are substituted. The monocyclic type has 3 to 8 carbon atoms, and preferred examples include a perfluorocyclopropyl group, a perfluorocyclopentyl group, and a perfluorocyclohexyl group. The polycyclic type has 6 to 20 carbon atoms, such as perfluoroadamantyl group, perfluoronorbornyl group, perfluoroisobornyl group, perfluorotricyclodecanyl group, perfluorotetracyclododecyl. Preferred examples include groups. As the haloalkyl group, for example, a haloalkyl group having 1 to 4 carbon atoms, specifically, a chloromethyl group, a chloroethyl group, a chloropropyl group, a chlorobutyl group, a bromomethyl group, a bromoethyl group and the like can be preferably exemplified.
[0031]
As the aryl group, for example, an aryl group having 6 to 15 carbon atoms, specifically, phenyl group, tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, anthryl group, Preferable examples include 9,10-dimethoxyanthryl group. As the aralkyl group, for example, an aralkyl group having 7 to 12 carbon atoms, specifically, a benzyl group, a phenethyl group, a naphthylmethyl group, and the like can be preferably exemplified.
[0032]
As an alkenyl group, it is a C2-C8 alkenyl group, for example, Specifically, a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group can be mentioned preferably. Examples of the alkoxy group include an alkoxy group having 1 to 8 carbon atoms, and specifically include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a butoxy group, a pentoxy group, an allyloxy group, and an octoxy group. Preferred examples include groups.
[0033]
As the acyl group, for example, an acyl group having 1 to 10 carbon atoms, specifically, a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, an octanoyl group, a benzoyl group and the like can be preferably exemplified. it can. Examples of the alkoxycarbonyl group include tertiary alkoxycarbonyl groups such as a t-butoxycarbonyl group, a t-amyloxycarbonyl group, and a 1-methyl-1-cyclohexyloxycarbonyl group. Examples of the alkoxycarbonylmethyl group include tertiary alkoxycarbonyl groups such as a t-butoxycarbonylmethyl group, a t-amyloxycarbonylmethyl group, and a 1-methyl-1-cyclohexyloxycarbonylmethyl group.
[0034]
Moreover, as an alkylene group, Preferably it is C1-C8 things, such as a methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group which may have a substituent. The alkenylene group is preferably an alkenylene group having 2 to 6 carbon atoms such as an optionally substituted ethenylene group, propenylene group or butenylene group. Preferred examples of the cycloalkylene group include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group which may have a substituent. The arylene group is preferably an arylene group having 6 to 15 carbon atoms such as a phenylene group, a tolylene group and a naphthylene group which may have a substituent.
[0035]
R_Five~ R₇Or R₁₉~ R_{twenty two}Examples of the ring formed by combining the two are, for example, a 3- to 8-membered ring, specifically a cyclopropane ring, cyclopentane ring, cyclohexane ring, furan ring, pyran ring, dioxonol ring, 1,3-dioxolane. A ring etc. are mentioned. Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group, and the formed alicyclic group is a monocyclic type having 3 to 8 carbon atoms, for example, a cyclopropyl group , A cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The polycyclic type has 6 to 20 carbon atoms, and includes, for example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetocyclododecyl group, Preferred examples include an androstanyl group.
[0036]
Substituents substituted with these groups include those having active hydrogen such as amino group, amide group, ureido group, urethane group, hydroxyl group, carboxyl group, and halogen atoms (fluorine atom, chlorine atom, bromine atom). , Iodine atom), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), acyloxy group (acetoxy group, propanoyloxy group, Benzoyloxy group etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group etc.), cyano group, nitro group and the like.
[0037]
Examples of the group which is decomposed by the action of an acid and shows alkali solubility contained in the resin of the present invention (A) include —O—C (R₁₉) (R₂₀) (R_{twenty one}), -O-C (R₁₉) (R₂₀) (OR_{twenty two}), -O-COO-C (R₁₉) (R₂₀) (R_{twenty one}), -O-C (R₀₁) (R₀₂) COO-C (R₁₉) (R₂₀) (R_{twenty one}), -COO-C (R₁₉) (R₂₀) (R_{twenty one}), -COO-C (R₁₉) (R₂₀) (OR_{twenty two}) And the like. R₁₉~ R_{twenty two}Is as defined above and R₀₁, R₀₂Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group which may have the above-described substituent.
[0038]
Preferable specific examples include t-butyl group, t-amyl group, 1-alkyl-1-cyclohexyl group, 2-alkyl-2-adamantyl group, 2-adamantyl-2-propyl group, 2- (4-methylcyclohexyl). ) Ether group or ester group of tertiary alkyl group such as 2-propyl group, acetal group or acetal ester group such as 1-alkoxy-1-ethoxy group, tetrahydropyranyl group, t-alkyl carbonate group, t-alkyl A carbonylmethoxy group etc. are mentioned preferably. More preferred are acetal groups such as a 1-alkoxy-1-ethoxy group and a tetrahydropyranyl group.
In the case of an acetal group, the acid decomposability is large, the range of selection of the acid generating compound to be used in combination is widened, and it is effective in terms of improvement in sensitivity, performance fluctuation over time until post-exposure heating. Particularly preferred is an acetal group containing an alkoxy group derived from the perfluoroalkyl group as the 1-alkoxy component of the acetal group. In this case, short-wave exposure light (for example, F₂The transparency of excimer laser light at 157 nm) can be further improved.
[0039]
The total content of the repeating units represented by the general formula (I) is used in the range of 20 to 100 mol%, preferably 30 to 80 mol%, more preferably 40 to 70 mol% in the total polymer composition.
The content of the repeating unit represented by formula (III) is 0 to 80 mol%, preferably 20 to 60 mol%, more preferably 30 to 50 mol% in the total polymer composition.
The content of the repeating units represented by the general formulas (IV) to (V) is 0 to 50 mol%, preferably 0 to 40 mol%, more preferably 0 to 30 mol% in the total polymer composition. Is done.
The content of the repeating units represented by the general formulas (VI) to (VII) is 0 to 60 mol%, preferably 10 to 50 mol%, more preferably 20 to 40 mol% in the total polymer composition. Is done.
[0040]
In addition to the above repeating structural unit, the resin of the present invention (A) may be copolymerized with other polymerizable monomers for the purpose of further improving the performance of the positive resist of the present invention.
[0041]
Examples of copolymerizable monomers that can be used include those shown below. For example, an addition polymerizable unsaturated bond selected from acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters other than the above. A compound having one.
[0042]
Specifically, for example, acrylic esters, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms) acrylate (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, acrylic Cyclohexyl acid, ethyl hexyl acrylate, octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl Acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) aryl acrylate (eg, phenyl acrylate);
[0043]
Methacrylic acid esters, for example, alkyl (the alkyl group preferably has 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl Methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, Glycidyl methacrylate, furfuryl methacrylate, Tiger like tetrahydrofurfuryl methacrylate), aryl methacrylates (e.g., phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc.);
[0044]
Acrylamides, for example, acrylamide, N-alkyl acrylamide, (the alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl Group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-arylacrylamide (as aryl group, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group, cyanophenyl group, hydroxyphenyl) Group, carboxyphenyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group) Group, etc.), N, N-diaryla (Examples of the aryl group include phenyl group.) Riruamido, N- methyl -N- phenyl acrylamide, N- hydroxyethyl -N- methylacrylamide, etc. N-2- acetamidoethyl -N- acetyl acrylamide;
[0045]
Methacrylamide, for example, methacrylamide, N-alkylmethacrylamide (the alkyl group has 1 to 10 carbon atoms, for example, methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group, cyclohexyl Group, etc.), N-aryl methacrylamide (the aryl group includes phenyl group), N, N-dialkyl methacrylamide (the alkyl group includes ethyl group, propyl group, butyl group, etc.) ), N, N-diarylmethacrylamide (the aryl group includes phenyl group), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N -Phenylmethacrylamide and the like; allyl compounds such as allyl este Class (e.g., allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), and allyl oxyethanol;
[0046]
Vinyl ethers such as alkyl vinyl ethers (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl Vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc., vinyl aryl ethers (for example, vinyl phenyl ether, vinyl tolyl ether, vinyl chloropheny) Ether, vinyl 2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether);
[0047]
Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinylphenyl Acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc .;
[0048]
Styrenes such as styrene, alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoro Dimethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (eg, methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene, etc.), halogen styrene (eg, chloro styrene, dichloro styrene, trichloro styrene). , Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, tri Ruorusuchiren, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene etc.), carboxy styrene, vinyl naphthalene;
[0049]
Crotonic esters such as alkyl crotonic acid (eg butyl crotonate, hexyl crotonate, glycerol monocrotonate); dialkyl itaconates (eg dimethyl itaconate, diethyl itaconate, dibutyl itaconate); Examples thereof include dialkyl esters of acid or fumaric acid (for example, dimethyl maleate, dibutyl fumarate, etc.). In addition, any addition-polymerizable unsaturated compound that is generally copolymerizable may be used.
[0050]
Specific examples of the repeating structural unit represented by the general formula (I) are shown below, but the present invention is not limited thereto.
[0051]
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[0052]
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[0053]
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[0054]
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[0055]
Moreover, although the specific example of the repeating structural unit represented by general formula (III)-(VII) is shown, this invention is not limited to this.
[0056]
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[0057]
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[0058]
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[0059]
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[0060]
The repeating structural units represented by the above specific examples may be used singly or in combination.
The preferred molecular weight of the resin (A) of the present invention having the above repeating structural unit is 1,000 to 200,000 on a weight average, and more preferably 3,000 to 20,000. The molecular weight distribution (weight average molecular weight / number average molecular weight) is 1 to 10, preferably 1 to 3, and more preferably 1 to 2. The smaller the molecular weight distribution, the smoother the resolution, the resist shape, and the side wall of the resist pattern, and the better the roughness. The addition amount of the resin (A) of the present invention is 50 to 99.5% by weight, preferably 60 to 98% by weight, more preferably 65 to 95% by weight, based on the total solid content of the composition. The
[0061]
[2] Compound capable of generating acid upon irradiation with actinic ray or radiation of the present invention (B)
Examples of the compound that decomposes upon irradiation with actinic rays or radiation to be used in the present invention include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, and a photochromic. Known light (400-200 nm ultraviolet light, far ultraviolet light, particularly preferably g-line, h-line, i-line, KrF excimer laser beam), ArF excimer laser beam, electron beam A compound that generates an acid by X-ray, molecular beam, or ion beam and a mixture thereof can be appropriately selected and used.
[0062]
Other compounds that generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), TS Bal et al, Polymer, 21 , 423 (1980), U.S. Pat.Nos. 4,069,055, 4,069,056, Re 27,992, Ammonium salts described in JP-A-3-140140, DC Necker et al, Macromolecules, 17, 2468 (1984), CS Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, 4,069,056, etc. , 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent Nos. 104,143, 339,049, 410,201, JP 2-150848, JP Iodonium salts described in Kaihei 2-96514, etc., JV Crivello et al, Polymer J. 17, 73 (1985), JV Crivello et al., J. Org. Chem., 43, 3055 (1978), WR Watt et al, J. Polymer Sci. , Polymer Chem. Ed., 22, 1789 (1984), JV Crivello et al, Polymer Bull., 14, 279 (1985), JV Crivello et al, Macromorecules, 14 (5), 1141 (1981), JV Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patent Nos. 370,693, 161,811, 410,201, 339,049, 233,567, 297,443, and 297,442 Sulfonium salts described in U.S. Pat. , 10 (6), 1307 (1977), JV Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), etc., selenonium salts, CS Wen et al, Teh, Proc. Onium salts such as arsonium salts described in Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 3,905,815, JP-B 46-4605, JP-A 48-36281, JP-A 55 -32070, JP-A-60-239736, JP-A-61-169835, Organohalogen compounds described in JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243, JP-A-63-298339, etc., K. Meier et al, J. Rad. Curing, 13 (4), 26 (1986), TP Gill et al, Inorg. Chem., 19, 3007 (1980), D. Astruc, Acc. Chem. Res., 19 (12 ), 377 (1896), and organometallic / organic halides described in JP-A-2-16145, S. Hayase et al, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al, J Pholymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQ Zhuetal, J. Photochem., 36, 85, 39, 317 (1987), B. Amit et al, Tetrahedron Lett., (24) 2205 (1973), DHR Barton et al, J. Chem Soc., 3571 (1965), PM Collins et al, J. Chem. Soc., Perkin I, 1695 (1975), M. Rudinstein et al, Tetrahedron Lett. , (17), 1445 (1975), JW Walker et al, J. Am. Chem. Soc., 110, 7170 (1988), SC Busman et al, J. Imaging Technol., 11 (4), 191 (1985) ), HM Houlihan et al, Macromolecules, 21, 2001 (1988), PMCollins et al, J. Chem. Soc., Chem. Commun., 532 (1972), S. Hayase et al, Macromolecules, 18, 1799 (1985), E. Reichmanis et al, J. Electrochem. Soc., Solid State Sci. Technol., 130 (6), FM Houlihan et al, Macromolcules, 21,2001 (1988), European Patent Nos. 0290,750, 046,083, 156,535, 271,851, 0,388,343, U.S. Patents 3,901,710, 4,181,531, JP 60-198538 , Photoacid generators having a 0-nitrobenzyl-type protecting group described in JP-A-53-133022, etc., M.TUNOOKA et al, Polymer Preprints Japan, 35 (8), G. Berner et al, J. Rad Curing, 13 (4), WJ Mijs et al, Coating Technol., 55 (697), 45 (1983), Akzo, H. Adachi et al, Polymer Preprints, Japan, 37 (3), European Patent No. 0199, No. 672, No. 84515, No. 044,115, No. 618,564, No. 0101,122, U.S. Pat.Nos. 4,371,605, 4,431,774, JP-A No. 64-18143, JP-A No. 2-245756, JP-A No. 3-245 Compounds that generate sulfonic acid by photolysis, such as iminosulfonate described in No. 140109 etc. It can be exemplified disulfone compounds described in JP-61-166544 Patent like.
[0063]
Further, a group that generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, for example, ME Woodhouse et al, J. Am. Chem. Soc., 104, 5586 (1982), SP Pappas et al, J. Imaging Sci., 30 (5), 218 (1986), S. Kondo et al, Makromol. Chem., Rapid Commun., 9, 625 (1988), Y. Yamada et al, Makromol. Chem., 152, 153, 163 (1972), JV Crivello et al, J. Polymer Sci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.No. 3,849,137, Korea Japanese Patent No. 3914407, Japanese Patent Publication No. 63-26653, Japanese Patent Publication No. Sho 55-164824, Japanese Patent Publication No. Sho 62-69263, Japanese Patent Publication No. Sho 63-146038, Japanese Patent Publication Sho 63-163452, Japanese Patent Publication Sho 62-153853 And compounds described in JP-A-63-146029 can be used.
[0064]
Furthermore, VNR Pillai, Synthesis, (1), 1 (1980), A. Abad et al, Tetrahedron Lett., (47) 4555 (1971), DHR Barton et al, J. Chem. Soc., (C), 329 (1970), US Pat. No. 3,779,778, European Patent 126,712 and the like, compounds that generate an acid by light can also be used.
[0065]
Of the compounds that decompose upon irradiation with actinic rays or radiation to generate an acid, those that are particularly effective are described below.
(1) An oxazole derivative represented by the following general formula (PAG1) substituted with a trihalomethyl group or an S-triazine derivative represented by the general formula (PAG2).
[0066]
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[0067]
Where R²⁰¹Is a substituted or unsubstituted aryl group, alkenyl group, R²⁰²Is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, -C (Y)_ThreeIndicates. Y represents a chlorine atom or a bromine atom.
Specific examples include the following compounds, but are not limited thereto.
[0068]
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[0069]
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[0070]
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[0071]
(2) An iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the general formula (PAG4).
[0072]
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[0073]
Where the formula Ar¹, Ar²Each independently represents a substituted or unsubstituted aryl group. Preferable substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.
[0074]
R²⁰³, R²⁰⁴, R²⁰⁵Each independently represents a substituted or unsubstituted alkyl group or aryl group. Preferred are aryl groups having 6 to 14 carbon atoms, alkyl groups having 1 to 8 carbon atoms, and substituted derivatives thereof. Preferred substituents for the aryl group are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group, a nitro group, a carboxyl group, a mercapto group, a hydroxy group, and a halogen atom. And an alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, or an alkoxycarbonyl group.
[0075]
Z^-Represents an anion, specifically, an alkyl sulfonic acid, cycloalkyl sulfonic acid, perfluoroalkyl sulfonic acid or aryl sulfonic acid which may have a substituent (for example, benzene sulfonic acid which may have a substituent) , Naphthalenesulfonic acid, anthracenesulfonic acid) and the like.
[0076]
Z^-Is preferably a perfluoroalkylsulfonic acid anion having 2 or more carbon atoms, a perfluoroarylsulfonic acid anion, or an arylsulfonic acid anion substituted with a perfluoroalkyl group.
Where Z^-The alkyl group possessed by may be linear, branched or cyclic, and is preferably an alkyl group having 2 to 10 carbon atoms. For example, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-amyl group, i-amyl group, t-amyl group, n-hexyl group, A cyclohexyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decanyl group, etc. can be mentioned. The alkyl group may have a substituent such as a halogen atom, a cyano group, a nitro group, a linear, branched or cyclic alkoxy group having 1 to 6 carbon atoms.
Z^-The aryl group possessed by is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. In addition, the aryl group may have a substituent such as the group mentioned as the substituent that the alkyl group may have and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. .
[0077]
R²⁰³, R²⁰⁴, R²⁰⁵Two of them and Ar¹, Ar²May be bonded via a single bond or a substituent.
[0078]
Specific examples include the following compounds, but are not limited thereto.
[0079]
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[0080]
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[0081]
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[0082]
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[0083]
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[0084]
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[0085]
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[0086]
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[0087]
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[0088]
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[0089]
The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JW Knapczyk et al, J. Am. Chem. Soc., 91, 145 (1969), AL Maycok et al, J. Org Chem., 35, 2532, (1970), E. Goethas et al, Bull. Soc. Chem. Belg., 73, 546, (1964), HM Leicester, J. Ame. Chem. Soc., 51, 3587 (1929), JV Crivello et al, J. Polym. Chem. Ed., 18, 2677 (1980), U.S. Pat.Nos. 2,807,648 and 4,247,473, and JP-A-53-101331. be able to.
[0090]
(3) A disulfone compound represented by the following general formula (PAG5) or an imide-N-sulfonate compound represented by the general formula (PAG6).
[0091]
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[0092]
Where Ar^Three, Ar^FourEach independently represents a substituted or unsubstituted aryl group. R²⁰⁶Represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group.
Specific examples include the following compounds, but are not limited thereto.
[0093]
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[0094]
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[0095]
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[0096]
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[0097]
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[0098]
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[0099]
(4) A diazodisulfone derivative represented by the following general formula (PAG7).
[0100]
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[0101]
Here, R represents a linear, branched or cyclic alkyl group, or an aryl group which may be substituted.
Specific examples include the following compounds, but are not limited thereto.
[0102]
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[0103]
(5) An oxime-N-sulfonate compound represented by the following general formula (PAG8).
[0104]
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[0105]
Where R₂₀₇Represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group or aralkyl group. R₂₀₈, R₂₀₉Represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, aralkyl group, cyano group, or acyl group. R₂₀₈, R₂₀₉May combine to form a carbocyclic ring or a heterocyclic ring having an oxygen atom, a nitrogen atom, or a sulfur atom.
Specific examples include the following compounds, but are not limited thereto.
[0106]
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[0107]
The amount of the compound capable of generating an acid upon irradiation with actinic rays or radiation of the present invention (B) is 0.1 to 20% by weight, preferably 0 based on the total solid content of the composition of the present invention. .5 to 10% by weight, more preferably 1 to 7% by weight. These compounds may be used alone or in combination.
[0108]
[3] Acid diffusion inhibitor of the present invention (C)
In the composition of the present invention, performance fluctuations due to aging after irradiation with actinic rays or radiation and heat treatment (pattern T-top shape formation, sensitivity fluctuations, pattern line width fluctuations, etc.) and performance fluctuations over time after application Furthermore, it is preferable to add an acid diffusion inhibitor for the purpose of preventing excessive diffusion (degradation of resolution) of the acid during heat treatment after irradiation with actinic rays or radiation. The acid diffusion inhibitor is an organic basic compound, for example, an organic basic compound containing basic nitrogen, and a compound having a pKa value of a conjugate acid of 4 or more is preferably used.
Specifically, the structures of the following formulas (A) to (E) can be exemplified.
[0109]
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[0110]
Where R²⁵⁰ , R²⁵¹ And R²⁵² May be the same or different and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, or 6 to 20 carbon atoms. Represents a substituted or unsubstituted aryl group, wherein R²⁵¹And R²⁵²May combine with each other to form a ring. R²⁵³ , R²⁵⁴ , R²⁵⁵ And R²⁵⁶ May be the same or different and each represents an alkyl group having 1 to 6 carbon atoms.
Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms of different chemical environments in one molecule, and particularly preferably both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom. Or a compound having an alkylamino group.
[0111]
Preferred examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, imidazole, substituted or unsubstituted Substituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted Aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, and the like. Preferred substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is.
[0112]
Particularly preferred compounds include guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4 , 5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (Aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4- Aminoethylpyridine,
[0113]
3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl)- Examples include 5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine. It is not limited to this.
These nitrogen-containing basic compounds are used alone or in combination of two or more.
[0114]
The use ratio of the acid generator and the organic basic compound in the composition is preferably (acid generator) / (organic basic compound) (molar ratio) = 2.5 to 300. If the molar ratio is less than 2.5, the sensitivity may be low and the resolution may be reduced. If the molar ratio is more than 300, the resist pattern may increase in thickness over time until post-exposure heat treatment, and the resolution may also be reduced. . (Acid generator) / (organic basic compound) (molar ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.
[0115]
[4] Fluorine-based and / or silicon-based surfactant that can be used in the present invention
The positive resist composition of the present invention can contain a fluorine-based and / or silicon-based surfactant. That is, the positive resist composition of the present invention contains any one or two or more of fluorine-based surfactants, silicon-based surfactants, and surfactants containing both fluorine atoms and silicon atoms. Can do. The addition of these fluorine-based and / or silicon-based surfactants is effective for suppressing development defects and improving coating properties.
[0116]
As these surfactants, for example, Japanese Patent Laid-Open Nos. 62-36663, 61-226746, 61-226745, 62-170950, 63-34540, 63-34540, 7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, U.S. Patent 5,405,720, U.S. Patent 5360692, U.S. Patent 5529881, U.S. Patent 5,296,330, U.S. Patent 5436098 , U.S. Pat. No. 5,576,143, U.S. Pat. No. 5,296,143, U.S. Pat. No. 5,945,511, and U.S. Pat. No. 5,842,451. The following commercially available surfactants can also be used as they are.
Examples of such commercially available surfactants include F-top EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Florard FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFuck F171, F173, F176, F189 R08 (Dainippon Ink Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.) Fluorine-based surfactants or silicon-based surfactants such as Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon surfactant.
[0117]
The compounding amount of the surfactant is usually 0.001% to 2% by weight, preferably 0.01% to 1% by weight, based on the solid content in the composition of the present invention. These surfactants may be added alone or in some combination.
[0118]
The composition of the present invention is dissolved in a solvent that dissolves each of the above components and coated on a support. Solvents used here include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahi Preferably such Rofuran, the use of these solvents alone or in combination.
[0119]
In the manufacture of precision integrated circuit elements, the pattern forming process on the resist film is carried out by applying the positive resist composition of the present invention on a substrate (eg, a transparent substrate such as a silicon / silicon dioxide covering, a glass substrate, an ITO substrate). A good resist pattern can be formed by applying an object, then irradiating with an actinic ray or radiation drawing apparatus, heating, developing, rinsing and drying.
[0120]
Examples of the developer for the positive resist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, ethylamine, n-propylamine and the like. Monoamines, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethyl Aqueous solutions of alkalis such as quaternary ammonium salts such as ammonium hydroxide and choline, cyclic amines such as pyrrole and piperidine, and the like can be used. Furthermore, an appropriate amount of an alcohol such as isopropyl alcohol or a nonionic surfactant may be added to the alkaline aqueous solution.
Among these developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and choline are more preferable.
[0121]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, the content of this invention is not limited by this.
[0122]
[Synthesis Example 1]
13.5 g (0.05 mol) of 4- [bis (trifluoromethyl) -hydroxymethyl] styrene and 3.4 g (0.05 mol) of methacrylonitrile are dissolved in 60 ml of 1-methoxy-2-propanol and polymerized. As an initiator, 0.25 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd .; trade name V-65) was added. This solution was added dropwise to 10 ml of 1-methoxy-2-propanol heated to 70 ° C. under a nitrogen stream over 2 hours with stirring. Stirring was continued for 4 hours after the addition. Thereafter, the reaction solution was charged into 1 L of methanol / ion exchange water (1/1) with vigorous stirring. The precipitated resin was washed with ion-exchanged water, filtered, and dried under vacuum to obtain 14.8 g of a white resin. It was confirmed by NMR measurement that this resin was a resin of Structural Example (I-1) / (III-2) = 52/48 and GPC measurement confirmed that the weight average molecular weight (polystyrene standard) was 8,900. . This resin was dissolved in 100 ml of THF, 2.9 g (0.04 mol) of ethyl vinyl ether was added, a catalytic amount of p-toluenesulfonic acid was added, and the mixture was stirred at room temperature for 8 hours. Triethylamine was added to the reaction solution twice as much as the p-toluenesulfonic acid catalyst to stop the reaction, and the mixture was poured into 3 L of ion-exchanged water with vigorous stirring. The precipitated resin was separated by filtration and dried to obtain 15.3 g of the resin (1) of the present invention. According to GPC measurement, the molecular weight of the resin (1) was 9,100 in terms of weight average (Mw). Moreover, when the composition of resin (1) was investigated by H-NMR, C-NMR, and IR measurement, it was structural example (I-1) / (I-4) / (III-2) = 10/42 by molar ratio. / 48.
In the same manner, the resins of the present invention shown in Table 1 were synthesized.
[0123]
[Table 1]
[0124]
[Example 1 (Measurement of transmittance)]
For the resins (1) to (6) shown in Table 1, 0.02 g of triphenylsulfonium nonaflate salt (PAG4-3) and 0.02 g of imidosulfonate compound (PAG6-19) were added to 1.36 g of each resin. In addition, dissolved in 8.5 g of propylene glycol monomethyl ether acetate, 0.005 g of dicyclohexylmethylamine and 0.01 g of MegaFac R08 (manufactured by Dainippon Ink Co., Ltd.) as a fluorosurfactant were added thereto. The resist composition of the invention was prepared. For the resins (7) to (12), 0.04 g of triphenylsulfonium nonaflate salt (PAG4-3) was added to 1.36 g of each resin, and dissolved in 8.5 g of propylene glycol monomethyl ether acetate, and dicyclohexylmethyl was added thereto. The resist composition of the present invention was prepared by adding 0.005 g of amine and 0.01 g of Megafac R08 (Dainippon Ink Co., Ltd.) as a fluorosurfactant.
[0125]
Each sample solution was filtered through a 0.1 μm Teflon filter, then applied onto a calcium fluoride disk by a spin coater, and heated and dried at 120 ° C. for 5 minutes to obtain a resist film having a thickness of 0.1 μm. The absorption of the coating film was measured with an Acton CAMS-507 spectrometer, and the transmittance at 157 nm was calculated. The results are shown in Table 2.
[0126]
[Table 2]
[0127]
From the results shown in Table 2, it can be seen that the measured transmittance of the coating film using the composition of the present invention exceeds approximately 50% and has sufficient transmittance at 157 nm.
[0128]
[Example 2 (Evaluation of coating properties and development defects)]
The surfactant in Example 1 was changed to the following W-1 to W-4 to prepare a resist composition of the present invention. The surfactants used are shown in Table 5.
[0129]
As surfactant,
W1: Megafuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
W3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
W4: Polyoxyethylene nonylphenyl ether
Represents.
[0130]
Each sample solution was filtered through a 0.1 μm Teflon filter, and then applied to a silicon wafer subjected to hexamethyldisilazane treatment by a spin coater, and heated and dried on a vacuum contact hot plate at 110 ° C. for 90 seconds. A resist film having a thickness of 0.3 μm was obtained. The resulting resist film was exposed to an image using a Canon KrF excimer stepper (FPA-3000EX5), post-heated at 110 ° C. for 90 seconds, and then developed with a 0.262 N TMAH aqueous solution to obtain a resist film of 0. A 5 μL L / S pattern was formed.
[0131]
Development defects and coatability were evaluated as follows.
[Number of development defects]: For the resist pattern obtained as described above, the number of development defects was measured with a KLA-Tencor KLA-2112 machine, and the obtained primary data value was defined as the number of development defects. .
[0132]
[Applicability (in-plane uniformity)]: Each resist solution is applied on an 8-inch silicon wafer, and the same process as the application of the resist layer as described above is performed to form a resist coating film for in-plane uniformity measurement. Obtained. This was measured with Lambda A manufactured by Dainippon Screen Co., Ltd., and the coating film thickness was measured uniformly at 36 locations so as to form a cross along the wafer diameter direction.
The standard deviation of each measured value was taken, and the evaluation was evaluated as ◯ when 3 times less than 50 and x when 50 or more.
The performance evaluation results are shown in Table 3.
[0133]
[Table 3]
[0134]
From the results shown in Table 3, it can be seen that the composition of the present invention to which fluorine and / or silicon-based surfactant is added has a large coating property and development defects are significantly reduced as compared with a comparative example without the same component. .
[0135]
[Example 3 (Evaluation of image formability)]
A resist solution was prepared in the same manner as in Example 1 using the resin of the present invention. Each trial
After the material solution was filtered through a 0.1 μm Teflon filter, it was applied onto a silicon wafer subjected to hexamethyldisilazane treatment by a spin coater, and heated and dried on a vacuum contact hot plate at 110 ° C. for 90 seconds. A resist film having a thickness of 0.1 μm was obtained. Using the 157 nm laser exposure / dissolution behavior analyzer VUVES-4500 (manufactured by RISOTEC Japan), the dissolution contrast of the exposed and unexposed portions by 157 nm exposure was measured for the obtained resist film.
The results are shown in Table 4.
[0136]
[Table 4]
[0137]
From the results in Table 4, it can be seen that the composition of the present invention has a dissolution contrast equivalent to that of a resist practically used for the KrF excimer of the comparative example, that is, has an image forming property.
[0138]
【The invention's effect】
The positive resist composition of the present invention is a positive resist composition that has sufficient transparency and image-forming property even at a short wavelength of 157 nm, and has improved coating properties based on fluororesin and development defects. Can be provided.

Claims (9)

(A) A resin having at least one repeating unit represented by the following general formula (I), which decomposes by the action of an acid and increases the solubility in an alkali developer, and (B) an acid by irradiation with actinic rays or radiation. A positive resist composition containing a compound that generates oxygen.
In the formula, R ₁ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or haloalkyl group which may have a substituent. R ₂ and R ₃ may be the same or different, and may be a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group or an alkyl group, cycloalkyl group or alkenyl group which may have a substituent. Represents an aralkyl group or an aryl group. R ₄ represents an alkoxycarbonylmethyl group which may have a substituent, or a group of the formula (II).
R ₅ and R ₆ may be the same or different and each represents a hydrogen atom or an optionally substituted alkyl group or cycloalkyl group. R ₇ represents an alkyl group, a perfluoroalkyl group, a cycloalkyl group, a perfluorocycloalkyl group, an aralkyl group or an aryl group which may have a substituent. Two of R _{5 to} R ₇ may be bonded to form a ring. The positive resist composition according to claim 1, wherein the resin (A) further has at least one repeating unit represented by the following general formula (III).
In the formula, R ₈ and R ₉ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or haloalkyl group which may have a substituent. R ₁₀ represents a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, or an —A ₁ —CN group, which may have a substituent. A ₁ may have a single bond, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R ₁₁ —, —CO—O—R ₁₂ —, —CO—N (R ₁₃ ) —R ₁₄ — is represented. R ₁₁ , R ₁₂ and R ₁₄ may be the same or different, and may have a single bond, an ether group, an ester group, an amide group, a urethane group or a ureido group, a divalent alkylene group, an alkenylene group. Represents a cycloalkylene group or an arylene group. R ₁₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, which may have a substituent. The positive resist composition according to claim 1 or 2, wherein the resin (A) further has at least one repeating unit represented by the general formulas (IV) and (V).
In the formula, R ₁₅ represents a hydrogen atom, an alkyl group, a perfluoroalkyl group, a cycloalkyl group, a perfluorocycloalkyl group, or an aryl group, which may have a substituent. The positive resist composition according to claim 1, wherein the resin (A) further has at least one repeating unit represented by the general formulas (VI) and (VII).
In the formula, R ₁₆ and R ₁₇ may be the same or different and each represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or haloalkyl group which may have a substituent. R ₁₈ represents —C (R ₁₉ ) (R ₂₀ ) (R ₂₁ ), —C (R ₁₉ ) (R ₂₀ ) (OR ₂₂ ), or a group represented by the formula (VIII). R _{19 to} R ₂₂ may be the same or different and each represents an alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, which may have a substituent. Two of R ₁₉ , R ₂₀ and R ₂₁ , or two of R ₁₉ , R ₂₀ and R ₂₂ may be bonded to form a ring.
A ₂ is a single bond, an optionally substituted divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group, or —O—CO—R ₁₁ —, —CO—O—R ₁₂ —, —CO—N (R ₁₃ ) —R ₁₄ — is represented. R ₁₁ , R ₁₂ and R ₁₄ may be the same or different, and may have a single bond, an ether group, an ester group, an amide group, a urethane group or a ureido group, a divalent alkylene group, an alkenylene group. Represents a cycloalkylene group or an arylene group. R ₁₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group or an aryl group, which may have a substituent.
R ₁ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or haloalkyl group which may have a substituent. R ₂ and R ₃ may be the same or different, and may be a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group, or an optionally substituted alkyl group, cycloalkyl group, alkenyl group. Represents a group, an aralkyl group or an aryl group.
In the formula (VIII), R ₂₃ represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, which may have a substituent. Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with a carbon atom.   The positive resist composition according to claim 1, further comprising (C) a compound having a basic nitrogen atom as an acid diffusion inhibitor.   (B) a sulfonium salt in which the compound of component generates a perfluoroalkylsulfonic acid having 2 or more carbon atoms, a perfluoroarylsulfonic acid or an arylsulfonic acid substituted with a perfluoroalkyl group upon irradiation with actinic rays or radiation, or The positive resist composition according to claim 1, wherein the positive resist composition is selected from iodonium salt compounds.   The positive resist composition according to claim 1, wherein the compound of component (B) is selected from an imide-N-sulfonate compound, an oxime-N-sulfonate compound, or a disulfone compound. .   The positive resist composition according to claim 1, wherein vacuum ultraviolet light of 160 nm or less is used as an exposure light source.   A pattern forming method comprising: forming a resist film from the positive resist composition according to claim 1; and exposing and developing the resist film.