KR20020042503A - Positive resist composition - Google Patents

Abstract

PURPOSE: To provide a positive resist composition suitable to be used for an exposure light source at < =160 nm wavelength, especially for F2 excimer laser light (157 nm), that is a positive resist composition having enough transparency when a 157 nm light source is used and exhibiting sufficient coating property and no developing defect, and moreover, and that can form a pattern with good sensitivity and resolution and excellent durability against oxygen plasma. CONSTITUTION: The positive resist composition contains (A) a resin which has a structure of a polymer skeleton with fluorine atoms substituted in the main chain and/or side chains and contains a repeating unit having a silicon group and which decomposes by the effect of acid to increase the solubility with an alkali developer, and (B) a compound which produces acid by irradiation of active rays or radiation.

Description

Positive Resist Composition {POSITIVE RESIST COMPOSITION}

The present invention relates to a positive resist composition which is preferably used for microlithography processes such as the production of ultra-LSI and high capacity microphone chips, and other photopublishing processes. More particularly, the present invention relates to a positive resist composition capable of forming a highly precise and refined pattern using vacuum ultraviolet light of 160 nm or less. In particular, it is related with the positive resist composition used suitably as an upper layer resist of a two-layer resist method.

Integrated circuits have increased the degree of integration, and in the manufacture of semiconductor substrates such as ultra-LSI, the processing of ultra-fine patterns having a line width of 1/4 micron or less has been required. As one of means for miniaturizing a pattern, shortening of the exposure light source used at the time of pattern formation of a resist is known. This is Rayleigh's equation representing the resolution (line width) R of the optical system.

R = kλ / NA

Where? Is the wavelength of the exposure light source, NA is the numerical aperture of the lens, and k is the process constant. It can be seen from this equation that the wavelength? Of the exposure light source should be shortened to achieve high resolution, that is, to reduce the value of R.

For example, i-line (365 nm), such as a high-pressure mercury lamp, has been used as a light source in the manufacture of semiconductor devices having an integration degree of up to 64 M bits. As a positive resist corresponding to this light source, many compositions containing a noblock resin and a naphthoquinone diazide compound as a photosensitive material were developed, and sufficient results were obtained in the processing of the line width to about 0.3 micrometer. In addition, KrF excimer laser light (248 nm) has been adopted as an exposure light source in the manufacture of semiconductor devices with an integration degree of 256 M bits or more. In addition, in order to manufacture semiconductors with an integration degree of 1 Gbit or more, in recent years, the use of ArF excimer laser light (193 nm), which is a short wavelength light source, and in order to form a pattern of 0.1 μm or less, F ₂ excimer laser light (157 nm) The use of is being considered.

In accordance with the shortening of these light sources, the constituent components of the resist material and the compound structure thereof are also greatly changed. That is, in the resist containing the conventional noblock resin and the naphthoquinone diazide compound, since the absorption in the extra-atomic region of 248 nm is large, the light hardly reaches the bottom of the resist, and only a tapered pattern can be obtained with low sensitivity. Did. In order to solve such a problem, a compound which generates acid by irradiation with ultraviolet light using poly (hydroxystyrene) having low absorption in the 248 nm region as a main skeleton and a resin protected by an acid decomposer as a main component. The composition which combined (photoacid generator) and what is called chemically amplified resist came to be developed. The chemically amplified resist can form a highly sensitive and high-resolution pattern because the solubility in the developer is changed by the catalytic component reaction of the acid generated in the exposed portion. For acid-decomposable resins and photoacid generators effective for these, Polym. Eng. Sci., Vol. 23, p. 1012 (1983), ACS. Sym., 242, 11 (1984), Macromolecules, 21, 1475 (1988), Journal of the Korean Society for Organic Chemistry, 49, 437 (1991), Microprocessing and Resist (Koritz Publishing, 1987). And many papers and patents. In addition, when ArF excimer laser light (193 nm) was used, the chemically amplified resist did not obtain sufficient performance because the compound having an aromatic group essentially had a large absorption in the 193 nm wavelength region. In response to this problem, instead of an acid-decomposable resin having an alicyclic structure having no absorption at 193 nm having a poly (hydroxystyrene) as a backbone in the main chain or side chain of the polymer, Improvement is planned. About these alicyclic acid-decomposable resins, Unexamined-Japanese-Patent No. 4-39665, 7-234511, 9-731773, 7-199467, 8-259626, 9-221519 10-10739, 9-230595, 10-111569, 10-218947, 10-153864, WO-97 / 33198 and the like.

In addition, for the F ₂ excimer laser light (157 nm), the absorption in the 157 nm region was also large in the alicyclic resin, and it was found to be insufficient to obtain a target pattern of 0.1 μm or less. In contrast, it was found that the resin containing fluorine atom (perfluoro structure) retained sufficient transparency at 157 nm in Proc. SPIE. Vol. 3678. Reported on page 13 (1999), the structure of a valid fluororesin is described in Proc. SPIE. Vol. 3999. 330 (200), 357 (2000), 365 (2000), WO-00 / 17712, etc. have been proposed. However, the resist having these fluorine resins is not necessarily dry etching resistance, and due to the unique water and oil repellent properties derived from the perfluoro structure, the coating property (uniformity of the coating surface) is improved and the development defect is suppressed. Was also desired.

On the other hand, many of these problems have been found to be solved by using a multilayer resist system. The multilayer resist system is disclosed in Solid State Technology 74 (1981) (Solid State Technology, 74 (1981)), but many other studies on this system have been published.

Generally, the multilayer resist method includes a three-layer resist method and a two-layer resist method. In the three-layer resist method, an organic flattening film is applied on a stepped substrate, and the inorganic intermediate layer and the resist are overlaid and patterned on the resist, followed by dry etching of the inorganic intermediate layer as a mask, and the organic flattening film as an inorganic intermediate layer as a mask. _{2 It} is a method of patterning by RIE (reactive ion etching). Although this method was examined early from the conventional technique because the conventional technique can be used, the process is very complicated, or because the organic layer, the inorganic layer, and the organic layer differ from each other in the three-layer physical properties, the cracks are formed in the intermediate layer. It is a problem that pinholes are likely to occur.

In the three-layer resist method, the two-layer resist method uses a resist having both the properties of the three-layer resist method and the inorganic intermediate layer, that is, a resist having oxygen plasma resistance, thereby suppressing the occurrence of cracks and pinholes. Moreover, since it becomes three to two layers, a process is simplified. However, in the three-layer resist method, the conventional resist can be used for the upper layer resist, but the two-layer resist method has a problem that a resist having oxygen plasma resistance must be newly developed.

Accordingly, it is an object of the present invention to provide a positive resist composition suitable for use of an exposure light source of 160 nm or less, in particular F ₂ excimer laser light (157 nm), specifically exhibiting sufficient transmittance when using a light source of 157 nm, Moreover, it is providing the positive resist composition which satisfy | fills applicability | paintability and image development defect.

In addition, the present invention provides a positive resist composition having a good sensitivity and resolution, and having excellent oxygen plasma resistance.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining all the said characteristics, the present inventors discovered that the objective of this invention was outstandingly achieved by using the following specific composition, and reached this invention.

That is, this invention has the following structures.

(1) (A) It contains a repeating structural unit having a structure substituted with a fluorine atom in the main chain and / or side chain of the polymer backbone, and also contains a silicon group, decomposes by the action of an acid to increase the solubility in the alkaline developer And (B) a positive resist composition comprising a compound which generates an acid by irradiation with actinic light or radiation.

(2) at least one of the repeating units represented by the general formulas (I) to (VI), at least one of the repeating units represented by the general formulas (VII) and (VIII), and the general formula ( (IX) The positive resist composition according to the above (1), which is a resin having at least one of the repeating units represented by (IX) and (X).

In General Formulas (I) to (VI), R ₀ and R ₁ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group, a perfluoroalkyl group, a cycloalkyl group, or an aryl group which may have a substituent. R ₂ , R ₃ and R ₄ each independently represent an alkyl group, a perfluorouroalkyl group, a cycloalkyl group or an aryl group which may have a substituent. In addition, R ₀ and R ₁ , R ₀ and R ₂ , R ₃ and R ₄ may be bonded to each other to form a ring. R ₅ represents a hydrogen atom, an alkyl group which may have a substituent, a perfluoroalkyl group, a monocyclic or polycyclic cycloalkyl group, an acyl group, or an alkoxycarbonyl group. R <_6> , R <_7> and R <_8> may be same or different, and represents the alkyl group, perfluoroalkyl group, and alkoxy group which may have a hydrogen atom, a halogen atom, and a substituent. R ₉ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or haloalkyl group which may have a substituent. A ₁ and A ₂ each independently represent a single bond, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group which may have a substituent, or -O-CO-R _15- , -CO-OR _16- , -CO-N (R ₁₇ ) -R ₁₈ -is indicated. R ₁₅ , R ₁₆ and R ₁₈ are each independently a single bond or a divalent alkylene group, alkenylene group, cycloalkylene group or aryl which may have an ether group, ester group, amide group, urethane group or ureide group. Display the Rengi. R <_17> represents a hydrogen atom, the alkyl group which may have a substituent, a cycloalkyl group, an aralkyl group, or an aryl group. In formula (V), n represents 0 or 1.

In general formula (VII) and (VIII), R <_10> , R <_11> and R <_12> may be same or different, and may have a substituent, an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group, and a trialkyl A silyloxy group is shown. m represents the integer of 0-3. In general formula (VIII), R <_13> and R <_14> may be same or different, and represents the alkyl group or the alkoxy group which may have a hydrogen atom, a halogen atom, and a substituent. R ₁₃ and R ₁₄ may be bonded to each other to form a divalent group formed by combining one or more of an alkylene group, -O-, and -S-.

In General Formula (IX), Z represents -O- or -N (R _Z1 )-. R _Z1 represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group, an aralkyl group or an aryl group.

In the general formula (X), X ₁ and X ₂ is -O-, -S-, -NH- or -NHSO ₂ are each independently - displays. A ₃ and A ₄ each independently represent a single bond, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group which may have a substituent, or -O-CO-R _15- , -CO-OR _16- . , -CO-N (R ₁₇ ) -R ₁₈ -is represented. R ₁₅ , R ₁₆ and R ₁₈ each independently may have a single bond or an ether group, an ester group, an amide group, a urethane group or a ureide group, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an aryl Display the Rengi. R <_17> represents a hydrogen atom, the alkyl group which may have a substituent, a cycloalkyl group, an aralkyl group, or an aryl group. Y ₁ represents a hydrogen atom, a cyano group, -OH, -COOH, -COOR _y1 , -CONH-R _y2 , an alkyl group which may have a substituent, a cycloalkyl group, an alkoxy group, -Q, -COO-Q.

R _y1 and R _y2 each independently represent an alkyl group which may have a substituent. Y ₂ represents -Q, -COO-Q. Provided that when X ₂ is -O- and A ₄ is a single bond, Y ₂ represents -Q. Q represents a group that can be broken down into acids.

(3) The positive resist composition according to the above (2), wherein the resin of (A) further contains one or more repeating units represented by General Formulas (XI) to (XIII).

In formula (XI), R <_20> and R <_21> may be same or different, and represents the alkyl group or haloalkyl group which may have a hydrogen atom, a halogen atom, a cyano group, and a substituent. A ₅ is a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group which may have a single bond, a substituent, -O-CO-R _15- , -CO-OR _16- , or -CO-N (R ₁₇ ) -R ₁₈ -is displayed. R ₁₅ , R ₁₆ and R ₁₈ are each independently a single bond or a divalent alkylene group, alkenylene group, cycloalkylene group or aryl which may have an ether group, ester group, amide group, urethane group or ureide group. Display the Rengi. R <_17> represents a hydrogen atom, the alkyl group which may have a substituent, a cycloalkyl group, an aralkyl group, or an aryl group.

In formula (XII), R <_23> , R <_24> and R <_25> may be same or different, and may have a hydrogen atom, a halogen atom, a cyano group, and a substituent, the alkyl group, perfluoroalkyl group, alkoxy group, -CO- OR ₂₂ is represented. n represents 0 or 1.

In General Formula (XIII), R ₂₆ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or haloalkyl group which may have a substituent. A ₆ is a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group which may have a single bond, a substituent, -O-CO-R _15- , -CO-OR _16- , or -CO-N (R ₁₇ ) -R ₁₈ -is displayed. R ₁₅ , R ₁₆ and R ₁₈ are each independently a single bond or a divalent alkylene group, alkenylene group, cycloalkylene group or aryl which may have an ether group, ester group, amide group, urethane group or ureide group. Display the Rengi. R <_17> represents a hydrogen atom, the alkyl group which may have a substituent, a cycloalkyl group, an aralkyl group, or an aryl group. R ₂₈ and R ₂₉ may be the same or different and are an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl which may be the same or different and may have a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group or a substituent. Display the flag.

In General Formulas (XI) to (XIII), R ₂₂ and R ₂₇ are each independently -C (R ₃₀ ) (R ₃₁ ) (R ₃₂ ), -C (R ₃₀ ) (R ₃₁ ) (OR ₃₃ ) Or a group represented by the formula (XIV).

R <_30> , R <_31> , R <_32> and R <_33> may be same or different and may represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group which may have a substituent. Two of R ₃₀ , R ₃₁ and R ₃₂ , or two of R ₃₀ , R ₃₁ and R ₃₃ may combine to form a ring. R ₃₄ 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. B represents the atomic group which comprises a monocyclic or polycyclic alicyclic group with a carbon atom.

(4) The positive resist composition according to the above (2) or (3), wherein the resin of (A) also has at least one repeating unit represented by General Formula (XV).

In the formula, R ₃₅ represents an alkyl group, cycloalkyl group, aralkyl group or aryl group which may have a substituent.

(5) The positive resist composition as described in any one of said (1)-(4) which further contains (C) silicone type and / or fluorine type surfactant.

(6) The positive resist composition as described in any one of said (1)-(5) which further contains the compound which has a basic nitrogen atom as (D) acid diffusion inhibitor.

(7) The compound of component (B) is a sulfonium salt that generates perfluoroalkylsulfonic acid, perfluoroarylsulfonic acid, or perulloalkyl group-substituted allulsulfonic acid having 2 or more carbon atoms by irradiation with actinic light or radiation. Or the compound of an iodide salt, The positive resist composition as described in any one of said (1)-(6) characterized by the above-mentioned.

(8) The positive resist composition as described in any one of said (1)-(7) characterized by using the vacuum ultraviolet light of 160 nm or less as an exposure light source.

Hereinafter, the compound used for this invention is demonstrated in detail.

[1] Resin having a structure in which a main chain and / or side chain of the polymer skeleton has a fluorine atom substituted therein, and also having a silicon group, which is decomposed by the action of an acid to increase solubility in an alkaline developer ( Fluoro group-containing silicone resin)

The fluorine group-containing silicone resin to be used as the component (A) in the present invention includes a repeating structural unit having a structure in which the fluorine atom is substituted in the main chain and / or the side chain of the polymer, and also having a silicon group. It is a resin which is decomposed | disassembled and increases the solubility to an alkali developing solution, Preferably it has one or more site | parts chosen from a perfluoroalkylene group and a perfluoro arylene group in the principal chain of a polymer skeleton, or Contains a fluorine group having at least one moiety selected from the group protecting the OH group of the alkyl group, perfluoroaryl group, hexafluoro-2-propanol group and hexafluoro-2-propanol group in the side chain of the polymer skeleton. Resin.

The fluorine group-containing silicone resin used as the component (A) is preferably one or more repeating units represented by the general formulas (I) to (VI), among the repeating units represented by the general formulas (VII) to (VIII). One or more resins having at least one of the repeating units represented by formulas (IX) to (X), and more preferably at least one repeating unit represented by the formulas (XI) to (XIII). It is a fluorine group-containing silicone resin having an acid-decomposable group.

In addition, the fluorine group-containing silicone resin of the present invention has the general formulas (IX) to (X) for the purpose of controlling physical properties such as hydrophilicity and glass transition point of the resin, or controlling the polymerizability at the time of resin synthesis. Or one or more repeating units derived from maleic anhydride or vinyl ether represented by (XV).

Each substituent in the said general formula is explained in full detail.

As an alkyl group as each substituent, it is a C1-C12 alkyl group, for example, A methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, and octyl group are preferable, for example. I can lift it.

The cycloalkyl group may be monocyclic or polycyclic. The ring structure may also contain heteroatoms. As monocyclic group, it is C3-C8 thing, for example, A cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, tetrahydropyranyl group is mentioned preferably, for example. As a polycyclic group, it is C6-C20, for example, Specifically, an adamantyl group, a norbornyl group, an isobonyl group, a campanyl group, a dicyclopentyl group, the (alpha) -finel group, a tricyclo decanyl group, a tetracyclo dodecyl group Andandrostanyl group etc. can be illustrated preferably. The cycloalkyl group may also contain heteroatoms such as oxygen atoms in the ring.

Examples of the perfluoroalkyl group include 4 to 12 carbon atoms, specifically, a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perfluorooctylethyl group, a perfluorododecyl group, and the like. Preferred is mentioned.

As a haloalkyl group, it is a C1-C4 haloalkyl group, specifically, a chloromethyl group, a chloroethyl group, a chloropropyl group, a chlorobutyl group, a bromomethyl group, a bromoethyl group etc. can be illustrated preferably.

As an aryl group, it is a C6-C15 aryl group, for example, A phenyl group, a tril group, a dimethylphenyl group, 2,4,6- trimethylphenyl group, a naphthyl group, anthryl group, 9,10- dimethoxyan A tril group etc. are mentioned preferably.

As an aralkyl group, it is a C7-12 aralkyl group, For example, a benzyl group, a phenethyl group, a naphthyl methyl group, etc. are mentioned preferably.

As an alkenyl group, it is a C2-C8 alkenyl group, for example, A vinyl group, an allyl group, butenyl group, and a cyclohexenyl group are mentioned specifically ,.

As an alkoxy group, it is a C1-C8 alkoxy group, Specifically, a methoxy, ethoxy group, n-propoxy group, iso-propoxy group, butoxy type, pentoxy group, allyloxy group, octoxy group etc. Preferred is mentioned.

As an acyl group, as a C1-C10 acyl group, a horyl group, an acetyl group, a propofanoyl group, butanoyl group, a pihaloyl group, an octanoyl group, a benzoyl group, etc. are mentioned specifically ,.

As an alkoxycarbonyl group, it is a C2-C9 alkoxycarbonyl group, for example, i-propoxycarbonyl group, t-butoxycarbonyl group, t-amioxycarbonyl group, 1-methyl-1- cyclohexyloxycarbonyl group, etc. are preferable. Preferably, a secondary, more preferably tertiary alkoxycarbonyl group is mentioned.

As a trialkylsilyl group, it is a C3-C9 trialkylsilyl group, for example, a trimethylsilyl group, a triethylsilyl group, and a tripropylsilyl group are mentioned specifically ,.

As a trialkylsilyloxy group, it is a C3-C9 trialkylsilyloxy group, for example, A trimethylsilyloxy group, a triethylsilyloxy group, and a tripropylsilyloxy group are specifically, mentioned.

Moreover, as an alkylene group, Preferably, methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group,

There are 1-12 carbon atoms, and the like.

As an alkenylene group, Preferably, there are C2-C6 things, such as an ethenylene group, a propenylene group, butenylene group. As a cycloalkylene group, Preferably, there are C5-C8 things, such as a cyclopentylene group and a cyclohexylene group.

As an arylene group, Preferably, there are C6-C15 things, such as a phenylene group, a triylene group, a naphthylene group.

Moreover, as a ring formed by combining R <_0> and R <_1> , R <_0> and R <_2> , R <_3> and R <_{4>, it} is a 5-7 membered ring, for example, the pentane ring, hexane ring, and fran ring which substituted fluorine specifically, , Dioxonol ring, 1,3-dioxolane ring, and the like.

As a ring formed by combining two of R <_30> -R <_32> and two of R <_30> -R <_31> and R <_33> , it is a 3-8 membered ring, Specifically, a cyclopropane ring, a cyclopentane ring, a cyclohexane ring, Preferred ring, pyran ring, etc. are mentioned preferably.

Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group, and the alicyclic group formed is monocyclic having 3 to 8 carbon atoms, for example cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, Cyclooctyl group is mentioned preferably. As a polycyclic type, it is C6-C20, For example, an adamantyl group, a norbornyl group, an isobornyl group, a campanyl group, a dicyclopentyl group, a-pinel group, a tricyclo decanyl group, a tetracyclo dodecyl group, andro A stanyl group etc. are mentioned preferably.

In addition, each of the substituents may further have a substituent. New substituents include active hydrogens such as amine groups, amide groups, ureide groups, urethane groups, hydroxyl groups and carboxyl groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms) and alkoxy groups ( Preferably C1-C10, for example, a methoxy group, an ethoxy group, a propoxy group, butoxy group, a cyclohexyl ethyleneoxy group, etc., a perfluoro alkoxy group (preferably C1-C10), a thioether group , Acyl group (acetyl group, propanoyl group, benzoyl group, etc.), acyloxy group (acetoxy group, propanoyloxy group, benzoyloxy group, etc.), alkoxycarbonyl group (preferably having 2 to 10 carbon atoms, for example, Oxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group and the like), cyano group, nitro group and the like.

The fluorine group-containing silicone resin of the present invention is a resin which decomposes under the action of an acid to increase alkali solubility, and contains a group (acid decomposable group) which decomposes under the action of an acid and exhibits alkali solubility. In addition to the acid-decomposable group having a repeating unit represented by formulas (X) and (XI) to (XIII) described above, in any repeating unit (for example, as R ₅ of formulas (IV) to (VI)) You may have an acid-decomposable group.

Examples of such acid-decomposable groups include -OC (R ₃₀ ) (R ₃₁ ) (R ₃₂ ), -OC (R ₃₀ ) (R ₃₁ ) (R ₃₃ ), -O-COO-C (R ₃₀ ) (R ₃₁ ) (R ₃₂ ), -OC (R ₀₁ ) (R ₀₂ ) COO-C (R ₃₀ ) (R ₃₁ ) (R ₃₂ ), -COO-C (R ₃₀ ) (R ₃₁ ) (R ₃₂ ), -COO-C (R ₃₀ ) (R ₃₁ ) (R ₃₃ ) and the like. R <_30> -R <_33> is as above-mentioned, R <_01> , R <_02> represents the hydrogen atom, the alkyl group, cycloalkyl group, alkenyl group, aralkyl group, or aryl group which may have the substituent shown above. The detail of these groups is as follows.

As a preferable specific example, t-butyl group, t-amyl group, 1-alkyl-1-cyclohexyl group, 2-alkyl-2-adamantyl group, 2-adamantyl-2-propyl group, 2- (4- Acetal or acetal ester groups such as ether groups or ester groups of tertiary alkyl groups such as methylcyclohexyl) -2-propyl group, 1-alkoxy-1-ethoxy group and tetrahydropyranyl group, t-alkylcarbonate group, t -Alkylcarbonylmethoxy group and the like are preferably exemplified.

The sum total of the content of the repeating unit represented by general formula (I)-(VI) is 10-70 mol%, Preferably it is 15-60 mol%, More preferably, 20-55 mol% in the whole polymer composition. Used in the range of.

The content of the repeating units represented by General Formulas (VII) to (VIII) is generally in the range of 10 to 60 mol%, preferably 15 to 55 mol%, more preferably 20 to 50 mol% in the total polymer composition. Used as

The content of the repeating unit represented by the general formulas (IX) to (X) is generally in the range of 5 to 60 mol%, preferably 10 to 50 mol%, more preferably 15 to 40 mol% in the total polymer composition. Used as

The content of the repeating unit represented by General Formulas (XI) to (XIII) is 0 to 70 mol%, preferably 10 to 60 mol%, more preferably 15 to 50 mol% in the total polymer composition. do.

The content of the repeating unit represented by general formula (XV) is used in the range of 0-50 mol%, preferably 0-40 mol%, More preferably, 5-30 mol% in the whole polymer composition.

The total amount of the repeating units represented by the formulas (X), (XI) to (XIII), and other repeating units having other acid-decomposable groups in the overall polymer composition is generally 1 mol% or more, preferably 5 to 70 mol% More preferably, it is used in 10-50 mol%.

Although the resin of this invention (B) may be resin which consists only of the said specific repeating structural unit, you may copolymerize another polymerizable monomer for the purpose of further improving the performance of the resist of this invention.

As a copolymerizable monomer which can be used, what is shown below is contained. For example, addition polymerization property selected from acrylic esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters and the like other than the above It is a compound which has one unsaturated bond.

Specifically, for example, acrylic esters such as alkyl (preferably having 1 to 10 carbon atoms in the alkyl group), acrylate (e.g., methyl acrylate, ethyl acrylate, propyl acrylate, t-butyl acrylate, amyl acrylate, acrylic acid Cyclohexyl, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chlorethyl acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylol Propane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate and the like), aryl acrylates (e.g., phenyl acrylate, etc.);

Methacrylic acid esters such as alkyl (preferably having 1 to 10 carbon atoms in the alkyl group), methacrylates (e.g., methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate) , t-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorbenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4 Hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycy Dimethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, and the like, aryl methacrylate (e.g., phenyl methacrylate, cresylmeth) Methacrylate, naphthyl methacrylate, etc.);

Acrylamides, such as acrylamide, N-alkylacrylamide, (as an alkyl group, those having 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group and octyl group , Cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-aryl acrylamide (Aryl group is, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group, cyanophenyl group, hydroxyphenyl group , Carboxyphenyl group, and the like.), N, N-dialkylacrylamide (The alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group) Etc.), N, N-diarylacrylamide (Aryl group includes, for example, a phenyl group, etc.), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N 2-acetamidoethyl-N-acetylacrylamide and the like;

Methacrylamides such as methacrylamide and N-alkyl methacrylamide (as the alkyl group, those having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl and cyclo Hexyl group etc.), N-aryl methacrylamide (Aryl group has a phenyl group etc.), N, N- dialkyl methacrylamide (The alkyl group is an ethyl group, a propyl group, a butyl group, etc.). .), N, N-diaryl methacrylimide (Aryl group has a phenyl group etc.), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenyl methacrylamide, N -Ethyl-N-phenylmethacrylamide and the like; Allyl compounds such as allyl esters (eg, allyl acetate, allyl caprolate, allyl caprylic acid, allyl laurate, allyl palmitate, allyl stearic acid, allyl benzoate, allyl acetic acid, allyl lactate, etc.), allyloxymethanol, and the like. ;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chlorethyl 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 and the like), vinyl aryl ether (e.g., vinyl phenyl ether, vinyl tolyl ether, vinyl chlorphenyl ether, vinyl-2,4-dichlorphenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.) );

Vinyl ethers such as vinyl butyrate, vinyl isobutylate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl varate, vinyl caproate, vinyl chlor acetate, vinyl dichlor acetate, vinyl methoxy acetate, vinyl butoxy acetate , Vinyl phenyl acetate, vinyl aceto acetate, vinyl lactate, vinyl-β-phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salutate, vinyl chlorate, vinyl tetrachlorate, vinyl nattoate Etc;

Styrene, such as styrene, alkyl styrene (e.g. ethyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chlormethyl Styrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrenes (e.g., methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrenes (e.g., chlorine) Styrene, dichlorostyrene, trichlorstyrene, terrachlorstyrene, pentachlorstyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-brom-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene and the like), carboxystyrene, vinylnaphthalene;

Crotonic acid esters such as alkyl crotonate (eg, butyl crotonate, hexyl crotonate, glycerin monocrotonate, etc.); Dialkyl itaconic acid (for example, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc.); Dialkyl esters of maleic acid or fumaric acid (for example, dimethyl maleate, dibutyl fumarate, etc.), maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleylonitrile and the like. In addition, generally, what is necessary is just the copolymerizable addition-polymerizable unsaturated compound.

Although the specific example of the repeating structural unit represented by General Formula (I)-(X) is shown below, this invention is not limited to these.

Moreover, although the specific example of the repeating structural unit represented by General Formula (XI)-(XIII) is shown, this invention is not limited to this.

One type of repeating structural unit represented by the said specific example may be used, respectively, and a plurality may be used in mixture.

Preferable molecular weight of resin (A) of this invention which has the said repeating structural unit is 1,000-200,000 by weight average, More preferably, it is used in the range of 3,000-20,000. Molecular weight distribution (Mw / Mn) is 1-10, Preferably it is 1-3, More preferably, the thing of the range of 1-2 is used. The smaller the molecular weight distribution is, the smoother the sidewall of the resolution, the resist shape and the resist pattern, and the better the edge roughness are.

The addition amount of resin (A) of this invention is used in 50-99 weight%, Preferably it is 60-98 weight%, More preferably, it is 65-95 weight% based on the total solid of a composition.

[2] a compound which generates an acid by irradiation with actinic light or radiation according to the invention (B)

As a compound which decomposes | dissolves by irradiation of actinic light or radiation used in this invention, an acid is produced, it is used for the photoinitiator of photocationic polymerization, the photoinitiator of photoradical polymerization, the photochromic agent of pigments, a photochromic agent, a microresist, etc. Acids are known by known light (ultraviolet rays of 400 to 200 nm, far ultraviolet rays, particularly preferably g rays, h rays, i rays, KrF excimer laser light), ArF excimer laser light, electron beams, X rays, molecular rays or ion beams. The compound and the mixture which generate | occur | produce can be used suitably selecting.

Moreover, as a compound which generate | occur | produces an acid by irradiation of actinic light or radiation used for other this invention, S.I. Schlesnger, Photogr. Sci. Eng., 18, 387 (1974), T.S. Diazonium salts described in Bal et al., Polymer, 21, 423 (1980), etc., ammonium salts described in US Pat. Nos. 4,069,055, 4,069,056, Re27,992, Japanese Patent Application Laid-Open No. 3-140140, and the like. Necker et al., Macromolecules, 17, 2468 (1984), C.S. Wen et al ,. Teh, Proc. Conf. Rad. Curing ASIA, p. 478, Tokyo. Phosphonium salts described in Oct (1988), US Pat. No. 4,069,055, US Pat. No. 4,069,056, etc., J.V. Crivello etat ,. Macromolecules, 10 (6) 1307 (1977), Chem. & Eng. News, Nov. 28, p. 31 (1988), iodine salts described in European Patent 104,143, 339,049, 410,201, Japanese Patent Laid-Open No. 2-150848, Japanese Patent Laid-Open No. 2-296514, J.V. Crivello etat ,. Polymer J., 17, 73 (1985), J.V. Crivello et al., J. Org. Chem., 43, 3055 (1978), W. R. Watt et al., J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), J.V. Crivello et al., Polymer Bull., 14, 279 (1985), J.V. Crivello et al., Macromolecules, 14 (5), 1141 (1981), J.V. Crivello et al., J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patents 370,693, 233,567, 297,443, 297,442, 161,811, 410,201 and 339,049, US Patents 3,902,114, 4,933,377, 4,760,013 Sulfonium salts described in US Pat. Nos. 4,734,444 and 2,833,827, German Patents 2,904,626, 3,604,580 and 3,604,581, etc. Crivello et al., Macromolecules, 10 (6), 1307 (1977), J. V. Crivello et al., J. Polymer Sci., Polymer Chem. Selenium, described in Ed., 17, 1047 (1979), and the like. Wen et al., Teh. Proc. Conf. Rad. Curing ASIA, p. 478, Tokyo. Arsonium salts described in Oct (1988) and the like; US Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Patent Publication No. 48-36281, Patent Publication No. 55-32070, Patent Publication No. 60-239736, Patent Publication No. 61-169835, Patent Publication No. 61 Organic halogen compounds described in -169837, Patent Publication No. 62-58241, Patent Publication No. 62-212401, Patent Publication No. 63-70243, Patent Publication No. 63-298339 and the like; K. Meier et al., J. Rad. Curing, 13 (4), 26 (1986), T.P. Gill et al., Inorg. Chem., 19, 3007 (1980), D. Astruc. Acc. Chem. Organometallic / organic halides described in Res., 19 (12), 377 (1896), Japanese Patent Laid-Open No. 2-161445 and the like; S. Hayase et al., J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al., J. Polymer Sci., Polymer Chem. Ed., 23, 1 (1985), Q. Q. Zhu et al., J. Photochem., 36, 85, 39, 317 (1987), B. Amit et al., Tetrahedron Lett., (24) 2205 (1973), D.H.R. Barton et al., J. Chem. Soc., 3571 (1965), P.M. Collins et al., J. Chem. Soc., Perkin I, 1695 (1975), M. Rudinstein et al., Tetrahedron Lett., (17), 1445 (1975), J.W. Walker et al., J. Am. Chem. Soc., 110, 7170 (1988), S.C. Busman et al., J. Imaging Technol., 11 (4), 191 (1985), H.M. Houlihan et al., Macromolecules, 21, 2001 (1988), P.M. Collins et al., J. Chem. Soc., Chem. Commun., 532 (1972), S. Hayase et al., Macromolecules, 18, 1799 (1985), E. Reichamanis et al., J. Electrochem. Soc., Solid State Sci. Technol., 130 (6), F.M. Houlihan et al., Macromolecules, 21, 2001 (1998), European Patents 0,290,750, 046,083, 156,535, 271,851 and 0,388,343, US Patent 3,901,710, 4,181,531, and Japanese Patent Application Publication No. 60-198538 Photoacid generators having an o-nitrobenzyl-type protecting group described in Japanese Patent Application Laid-Open No. 53-133022 and the like; M. TUNOOKA et al ,. Polymer Preprints Japan, 35 (8), G. Berner et al., J. Rad. Curing, 13 (4), W.J. Mijs et al., Coating Technol., 55 (697), 45 (1983), Akzo, H. Adachi et al., Polymer Preprints, Japan, 37 (3), European Patent No. 0.199,672, No. 84,515, No. 199,672 No. 044,115, 618,564, 0,101,122, U.S. Patent 4,371,605, 4,431,774, Japanese Patent Publication No. 64-18143, Patent Publication No. 2-245756, Patent Application No. 3-140109, etc. The compound which produces | generates sulfonic acid by photolysis represented by sulfonate, the disulfone compound as described in Unexamined-Japanese-Patent No. 61-166544, etc. can be mentioned.

Moreover, the compound which introduce | transduced the group or compound which generate | occur | produces an acid by irradiation of these actinic rays or a radiation to the main chain or side chain of a polymer, such as M.E. Woodhouse et al., J. Am. Chem. Soc., 104, 5586 (1982), S.P. 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), J.V. Crivello et al., J. Polymer Sci., Polymer Chem. Ed., 17, 3845 (1979), US Patent 3,849,137, German Patent 3,914,407, Japanese Patent Publication No. 63-26653, Japanese Patent Publication No. 55-164824, Japanese Patent Publication No. 62-69263, Japanese Patent Application Publication The compounds described in 146038, Patent Publication No. 63-163452, Patent Publication No. 62-153853, Patent Publication 63-146029 and the like can be used.

See also V.N.R.Pillai, Synthesis, (1), 1 (1980), A. Abab et al, Tetrahedron Lett., (47) 4555 (1971), D. H. R. Barton et al, J. Chem. Compounds which generate an acid by light described in Soc., (C), 329 (1970), US Pat. No. 3,779,778, EP 126,712 and the like can also be used.

Among the compounds that decompose upon irradiation with actinic light or radiation to generate an acid, particularly effective use will be described below.

(1) The oxazole derivative represented by the following general formula (PAG1) substituted with the trihalomethyl group, or the S-triazine derivative represented by general formula (PAG2).

In the formula, R ²⁰¹ represents a substituted or unsubstituted aryl group, alkenyl group, and R ²⁰² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group, or -C (Y) ₃ . Y represents a chlorine atom or a bromine atom.

Although the following compounds can be enumerated specifically, it is not limited to these.

(2) Iodonium salt represented by the following general formula (PAG3), or sulfonium salt represented by the general formula (PAG4).

The formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include alkyl, haloalkyl, cycloalkyl, aryl, alkoxy, nitro, carboxyl, alkoxycarbonyl, hydroxy, mercapto and halogen atoms.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group and an aryl group. Preferably they are a C6-C14 aryl group, a C1-C8 alkyl group, and their substituted derivatives. As a preferable substituent, about an aryl group, a C1-C8 alkoxy group, a C1-C8 alkyl group, a cycloalkyl group, a nitro group, a carboxyl group, and a mercapto group. It is a hydroxyl group and a halogen atom, and it is a C1-C8 alkoxy group, a carboxyl group, and the alkoxycarbonyl group about an alkyl group.

Z <^-> represents an anion and specifically, alkylsulfonic acid, cycloalkylsulfonic acid, perfluoroalkanesulfonic acid, and arylsulfonic acid which may have a substituent (for example, benzene sulfonic acid, naphthalene sulfonic acid, anthracene sulfonic acid which may have a substituent). Each anion.

In addition, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ , and Ar ¹ and Ar ² may be bonded via a single bond or a substituent.

Specifically, the compound shown below is enumerated, but it is not limited to these.

The onium salts represented by the formulas (PAG3) and (PAG4) are known and are described, for example, in J. W. Knapczyk etal, J. Am. Chem. Soc., 91, 145 (1969), A. L. Maycok et al, J. Org. Chem., 35, 2532 (1970), E. Goethas et al, Bull. Soc. Chem. Belg., 73, 546 (1964), H. M. Leicester J. Ame. Chem. Soc., 51, 3587 (1929), J. V. Crivello et al, J. Polym. Chem. Ed., 18, 2677 (1980), US Pat. Nos. 2,807,648 and 4,247,473, US Patent Publication Nos. 53-101,331 and the like.

(3) The disulfone derivative represented by the following general formula (PAG5) or the iminosulfonate derivative represented by the general formula (PAG6).

In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, arylene group.

Although the compound shown below can be enumerated specifically, it is not limited to these.

(4) Diazodisulfone derivatives represented by the following general formula (PAG7).

R represents a straight chain, a branched or cyclic alkyl group, or the aryl group which may be substituted here.

Although the compound shown below is mentioned as a specific example, It is not limited to these.

The addition amount of the compound which generate | occur | produces an acid by irradiation of actinic light or radiation of this invention (B) is 0.1-20 weight% based on the total solid of the composition of this invention, Preferably it is 0.5-10 weight%, More preferably, it is 1-7 weight%. Moreover, these compounds may be used independently and may be used in mixture of multiple.

[3] fluorine-based and / or silicone-based surfactants (component (C))

The positive photoresist composition of the present invention preferably contains a fluorine-based and / or silicon-based surfactant. That is, the positive photoresist composition of the present invention contains any one or two or more of a fluorine-based surfactant, a silicone-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom. The addition of these fluorine-based and / or silicone-based surfactants has an effect on suppressing development defects and improving coatability.

As these surfactants, for example, Japanese Patent Laid-Open No. 62-36663, Japanese Patent Laid-Open No. 61-226746, Japanese Patent Laid-Open No. 61-226745, Japanese Patent Laid-Open No. 62-170950, Japanese Patent Laid-Open No. 63-34540 , Patent Publication No. 7-230165, Patent Publication No. 8-62834, Patent Publication No. 9-54432, Patent Publication No. 9-5988, US Patent No. 557520, US Patent No. 5360692, US Patent Surfactants described in 5529881, U.S. Patent No. 5296330, U.S. Patent No. 5436098, U.S. Patent No. 5576143, U.S. Patent No. 5294511, and U.S. Patent No. 5824451, may be enumerated. You can use it as it is.

As such a commercially available surfactant, F-top EF301, EF303, (made by Shin-Aki Takasei Co., Ltd.), Floroid FC430, 431 (made by Sumitomo 3M Co., Ltd.), Megapack F171, F173, F176, F189, R08 (manufactured by Dainippon Inky Co., Ltd.), Asahi Guide AG710, Seflon S-382, SC101, 102, 103, 104, 105, 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Tro Chemical) Fluorine-based surfactants or silicone-based surfactants such as (i) may be enumerated. Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone type surfactant.

The compounding quantity of surfactant is 0.01 weight%-2 weight% normally based on solid content in the composition of this invention, Preferably they are 0.01 weight%-1 weight%. These surfactants may be added alone or in any combination.

[4] acid diffusion inhibitors ((D) component)

The composition of the present invention includes a performance variation (T-top shape formation of the pattern, a sensitivity variation, a pattern line width variation, etc.) due to aging after irradiation with actinic rays or radiation, or a change in time after application, Alternatively, it is preferable to add an acid diffusion inhibitor for the purpose of preventing excessive diffusion (degradation of resolution) during heat treatment after irradiation with actinic light or radiation. As the acid diffusion inhibitor, an organic basic compound, for example, an organic basic compound containing basic nitrogen, and a compound having a pKa value of conjugated acid of 4 or more is preferably used.

Specifically, the following formula (A)-(E) structure can be enumerated.

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and include a hydrogen atom, a C 1-6 alkyl group, a C 1-6 aminoalkyl group, a C 1-6 hydroxyalkyl group or a C 6-20 atom Or a substituted or unsubstituted aryl group, wherein R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ may be the same or different and represent an alkyl group having 1 to 6 carbon atoms.

More preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms of different chemical environments in one molecule, and particularly preferably those containing both substituted or unsubstituted amino groups and ring structures containing nitrogen atoms. Or a compound having an alkylamino group.

Preferred embodiments 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 pyrazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted Substituted 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.

Particularly preferred compounds are 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, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperi Dine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopyridine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole , 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (ami Methyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2 -Aminoethyl) morpholine etc. are mentioned, but it is not limited to these.

These nitrogen-containing basic compounds are used alone or in combination of two or more thereof.

It is preferable that the use role in the composition of an acid generator and an organic basic compound is (acid generator) / (organic basic compound) (molar ratio) = 2.5-300. If the molar ratio is less than 2.5, the resolution may be reduced, and if the resolution exceeds 300, the thickness of the resist pattern may become large and the resolution may also decrease in the time until the post-exposure heat treatment. (Acid generator) / (organic basic compound) (molar ratio) becomes like this. Preferably it is 5.0-200, More preferably, it is 7.0-150.

The composition of this invention is melt | dissolved in the solvent which melt | dissolves each said component, and apply | coats on a support body. As a solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, (gamma) -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 vinate, ethyl pyrvinate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofran and the like are preferable, and these solvents are used alone or in combination.

In the fabrication of a precision integrated circuit device, the pattern forming step onto a resist film is performed by applying the positive photoresist composition of the present invention onto a substrate (e.g., a transparent substrate such as silicon / silicon dioxide coating, a glass substrate, an ITO substrate, etc.). Then, irradiation is performed using an actinic ray or a radiation drawing apparatus, and a good resist pattern can be formed by heating, developing, rinsing and drying.

Examples of the developer of the positive photoresist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia water, first amines such as ethylamine and n-propylamine, diethylamine, Second amines such as di-n-butylamine, third amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide And aqueous solutions of alkalis such as cyclic amines such as quaternary ammonium salts such as choline, pyrrole and piperidine, and the like can be used. Moreover, it is also possible to add the alcohols, such as isopropyl alcohol, and surfactant, such as a nonionic type, to the aqueous solution of the said alkalis, and to use it in an appropriate amount.

Among these developers, quaternary ammonium salts are more preferred, tetramethylammonium hydrooxide and choline.

(Example)

Hereinafter, although an Example demonstrates this invention further in detail, the content of this invention is not limited by this.

Synthesis Example 1

150 ml of a 1,1,2-trichloro-trifluoroethylene solution of 11.4 g (0.10 mol) of trimethylallylsilane and 19.4 g (0.10 mol) of norbornene-2-carboxylic acid t-butyl ester was added to a 1 L autoclave. Pressurized to 200 psi under nitrogen atmosphere. Further 20 g (0.20 mol) of tetrafluoroethylene were injected and heated to 50 ° C under stirring. 15 ml of a 1,1,2-trichloro-trifluoroethylene 15 ml solution of 1.2 g of di (4-t-butylcyclohexyl) peroxydicarbonate was injected into the reaction solution over 20 minutes, and stirring was continued for 20 hours. It was. After completion of the reaction, the reaction solution was poured into 2 L of methanol with vigorous stirring to precipitate a white resin. The precipitated resin was filtered off and dried in vacuo to give 26.4 g of Resin (1) of the present invention. The molecular weight of resin (1) was 5,400 by weight average (Mw) by GPC measurement. In structure the composition irradiation yeotdeoni molar ratio of the resin (1) by C ¹³ -NMR measurement examples (F-1) / (Si-1) / (B-16) was 45 = / 28/27.

Synthesis Example 2

7.2 g (0.02 mol) of the following monomers (a), 2.3 g (0.02 mol) of trimethylallylsilane, 3.9 g (0.04 mol) of maleic anhydride, and 2.6 g (0.02 mol) of t-butyl acrylate were dissolved in 100 ml of MEK, It heated to 70 degreeC under nitrogen stream. As a polymerization initiator, 0.2 g of V-601 (Hwagwang Pure Chemical Industries, Ltd. product) was added, and it stirred for 3 hours. Furthermore, 0.2 g of V-601 was added and stirring was continued for 4 hours. Thereafter, the reaction solution was poured into 1 L of t-butyl methyl ether with vigorous stirring to precipitate a white resin. 9.8 g of Resin (2) of the present invention was obtained after filtration and drying the precipitated resin under vacuum. The molecular weight of resin (2) was 7,800 by weight average (Mw) by GPC measurement. In addition, the composition of the resin (2) was examined by C ¹³ -NMR measurement, and the structural example (F-21) / (Si-1) / (I′-1) / (B-4) = 25/18/36 was determined by the molar ratio. It was / 21.

Synthesis 3

The following monomer (b) 8.6 g (0.02 mol), 2-methyl-2-adamantane acrylate 4.4 g (0.02 mol), 2-tris (trimethylsilane) silylnorbornene 10.2 g (0.03 mol), maleic anhydride 2.9 g (0.03 mol) was dissolved in 100 mL of MEK, and heated to 70 ° C. under a nitrogen stream. 0.2 g of V-601 (made by Hwagwang Pure Chemical Co., Ltd.) was added as a polymerization initiator, and it stirred for 3 hours. Furthermore, 0.2 g of V-601 was added and stirring was continued for 4 hours. Thereafter, the reaction solution was poured into 1 L of t-butyl methyl ether with vigorous stirring to precipitate a white resin. After drying precipitated resin under reduced pressure, 14.6g of resin (3) of this invention was obtained. When molecular weight was measured by GPC measurement, it was 8,500 by weight average (Mw). In addition, the composition of the resin (3) was examined by C ¹³ -NMR measurement, and the structural example (F-30: acrylate) / (Si-20) / (I'-1) / (B-7: acrylate) Sieve) = 27/29/31/13.

Synthesis Example 4-10

Hereinafter, the resin of this invention (A) shown in Table 1 was synthesize | combined similarly.

Synthesis of Resin (A) of the Present Invention Resin (A) The furtherance (structural unit and molar ratio in resin) Molecular Weight (4) (F-1) / (Si-21) / (B-16) = 43/27/30 6,200 (5) (F-1) / (Si-1) / (I'-1) / (B-4) = 22/21/38/19 7,400 (6) (F-21) / (Si-20) / (I'-1) = 33/20/47 8,500 (7) (F-21) / (Si-4) / (I'-4) = 35/22/43 7,900 (8) (F-20) / (Si-25) / (I-33) / (I'-1) = 31/16/26/27 8,800 (9) (F-30: acrylate) / (Si-21) / (I'-5) = 28/37/35 9,400 10 (F-30) / (Si-1) / (I'-1) / (B-2) = 30/29/32/9 7,200

Example 1 (Measurement of Transmittance)

Dissolve 1.36 g of the resin shown in Table 1 above and 0.04 g of nonaphthalate salt of triphenylsulfonium in 8.5 g of propylene glycol monomethyl ether acetate. 0.01 g of R80 (manufactured by Dainippon Ink & Chemicals Co., Ltd.) was added to adjust the resist composition of the present invention.

After filtering each sample solution with a 0.1 micrometer Teflon filter, it apply | coated on the calcium fluoride disc by a spin coater, and it heat-dried at 120 degreeC for 5 minutes, and obtained the resist film with a film thickness of 0.1 micrometer. The absorption of the coating film was measured with an Acton CAMS-507 spectrometer to calculate the transmittance at 157 nm. The results are shown in Table 2.

Resin of the invention % Transmittance at 157nm (One) 60 (2) 52 (3) 51 (4) 58 (5) 51 (6) 52 (7) 56 (8) 54 (9) 52 10 53 Comparative Example 1 (resist for acetal KrF) 18

From the results in Table 2, it can be seen that the measured transmittance of the coating film using the composition of the present invention exceeds almost 50% and retains sufficient transmittance at 157 nm.

Example 2 (Evaluation of coating property and development defect)

The resist composition of this invention was adjusted like Example 1 except having used resin and surfactant shown in Table 3.

As a surfactant,

W-1: Mega Pack F176 (Dainippon Ink & Chemicals Co., Ltd.) (Fluorine)

W-2: Mega Pack R08 (manufactured by Dainippon Ink & Chemicals Co., Ltd.) (fluorine-based and silicon-based)

W-3: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsukagaku Kogyo Co., Ltd.)

W-4: Polyoxyethylene nonyl phenyl ether

Is displayed.

Each sample solution was filtered through a 0.1 μm Teflon filter, then coated on a silicon wafer subjected to hexamethyldisilazane treatment by a spin coater, and dried on a hot plate of vacuum adhesion for 110 seconds at 90 ° C. to obtain a film thickness. A 0.3 micrometer resist film was obtained. The resulting resist film was subjected to image exposure using a Canon KrF excimer stepper (FPA-3000EX5), post-heated at 110 ° C. for 90 seconds, and then developed with a 0.262N TMAH aqueous solution to form a 0.5 μL / S pattern. I was.

Development defects and applicability were evaluated as follows.

<Development defect>: The development defect function was measured with KLA-2112 by KLA Tencol Co., Ltd. with respect to the resist pattern obtained as mentioned above, and the obtained primary data value was made into the development bond number.

<Coating property (inner surface uniformity)> Each resist solution was apply | coated on an 8-inch silicon wafer, and the process similar to the application of the above-mentioned resist layer was performed, and the resist coating film for in-plane uniformity measurement was obtained. The coating film thickness was measured in 36 places equally so that the cross | cross_length | cross_length | surface may be crosswise along the wafer diameter direction by Dainippon Screen Co., Ltd. LambdaA.

The standard deviation of each measured value was calculated | required, and the thing which was 3 or less times 50 was evaluated as (circle) and 50 or more as x.

The performance evaluation results are shown in Table 3.

Resin (A) of the present invention Used Surfactant Phenomenon Applicability (One) W-1 21 ○ (2) W-2 22 ○ (3) W-2 26 ○ (4) W-3 28 ○ (5) W-1 21 ○ (6) W-2 19 ○ (7) W-3 24 ○ (8) W-3 30 ○ (9) W-2 25 ○ 10 W-2 20 ○ (One) none 1800 × (One) W-4 580 ×

From the results of Table 3, it was found that the composition to which the fluorine-based and / or silicone-based surfactant was added is significantly superior in coating property and very few development defects as compared with the composition without the same component.

Example 3 (Image Formability Evaluation)

The resist liquid was adjusted like Example 1 using resin (1)-(5) of this invention. Each sample solution was filtered through a 0.1 μm Teflon filter, then coated on a silicon wafer subjected to hexamethyldisilazane treatment by a spin coater, and dried on a hot plate of vacuum adhesion for 110 seconds at 90 ° C. to obtain a film thickness. A 0.1 micrometer resist film was obtained. About the obtained resist film, the melt | dissolution contrast of the exposure part and the unexposed part by 157 nm exposure was measured using the 157 nm laser exposure and dissolution behavior analyzer VUVES-4500 (made by Listech Japan). The results are shown in Table 4.

Resin of the invention Dissolution Contrast (tan θ) (One) 6.3 (2) 5.8 (3) 6.4 (4) 5.9 (5) 6.1 Comparative Example 4 (resist for acetal KrF) 5.3 ^*)

*) Value during KrF excimer laser (248 nm) exposure

The results of Table 4 show that the composition of the present invention retains the same dissolution contrast as that of the resist used for the KrF excimer of the comparative example, that is, retains image formability.

Example 4 (Evaluation of Dry Etching Resistance)

The resist liquid was adjusted like Example 1 using resin (6)-(10) of this invention. Each sample solution was filtered through a 0.1 µm Teflon filter, then coated on a silicon wafer subjected to hexamethyldisilazane treatment by a spin coater, dried on a hot plate of vacuum adhesion for 110 seconds at 90 DEG C, and a film thickness of 0.5. A micrometer resist film was obtained. The obtained resist film was etched using an Arbag parallel flat reactive ion etching apparatus with etching gas as oxygen, and subjected to etching treatment under a pressure of 20 mmTorr and an applied power of 100 kW / cm 3. The etching rate of the resist film was obtained from the film thickness change. The ratio with the etching rate determined from the cresol noblock type i-line resist under the same conditions was calculated as the etching selectivity (etch rate of the i-line resist / etch rate of the resist of the present invention). The results are shown in Table 5.

Resin of the invention Etch selectivity (6) 12 (7) 9 (8) 11 (9) 10 10 10

From the results in Table 5, it was found that the composition of the present invention was superior in reactive oxygen ion etching resistance as compared to the i-line resist used as the underlayer resist.

The positive resist composition of the present invention retains sufficient transmittance and image formability even at a short wavelength of 157 nm, and has sufficient etching resistance when used as an upper layer resist of the two-layer resist method. Moreover, the positive resist which the problem of the coating property and image development defect based on fluorine-type resin can be improved can be provided.

Claims (8)

(A) a resin having a structure in which the fluorine atom is substituted in the main chain and / or the side chain of the polymer skeleton, and also contains a repeating structural unit having a silicon group, and decomposed by the action of an acid to increase solubility in an alkaline developer, And (B) a compound that generates an acid by irradiation with actinic light or radiation. The resin of claim 1, wherein the resin of component (A) is at least one of the repeating units represented by general formulas (I) to (VI), at least one of the repeating units represented by the general formulas (VII) and (VIII), and A positive resist composition, which is a resin having at least one of repeating units represented by General Formulas (IX) and (X). In General Formulas (I) to (VI), R ₀ and R ₁ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group, a perfluoroalkyl group, a cycloalkyl group, or an aryl group which may have a substituent. R ₂ , R ₃ and R ₄ each independently represent an alkyl group, a perfluorouroalkyl group, a cycloalkyl group or an aryl group which may have a substituent. In addition, R ₀ and R ₁ , R ₀ and R ₂ , R ₃ and R ₄ may be bonded to each other to form a ring. R ₅ represents a hydrogen atom, an alkyl group which may have a substituent, a perfluoroalkyl group, a monocyclic or polycyclic cycloalkyl group, an acyl group, or an alkoxycarbonyl group. R <_6> , R <_7> and R <_8> may be same or different, and represents the alkyl group, perfluoroalkyl group, and alkoxy group which may have a hydrogen atom, a halogen atom, and a substituent. R ₉ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or haloalkyl group which may have a substituent. A ₁ and A ₂ each independently represent a single bond, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group which may have a substituent, or -O-CO-R _15- , -CO-OR _16- , -CO-N (R ₁₇ ) -R ₁₈ -is indicated. R ₁₅ , R ₁₆ and R ₁₈ are each independently a single bond or a divalent alkylene group, alkenylene group, cycloalkylene group or aryl which may have an ether group, ester group, amide group, urethane group or ureide group. Display the Rengi. R <_17> represents a hydrogen atom, the alkyl group which may have a substituent, a cycloalkyl group, an aralkyl group, or an aryl group. In formula (V), n represents 0 or 1. In general formula (VII) and (VIII), R <_10> , R <_11> and R <_12> may be same or different, and may have a substituent, an alkyl group, a haloalkyl group, a halogen atom, an alkoxy group, a trialkylsilyl group, and a trialkyl A silyloxy group is shown. m represents the integer of 0-3. In general formula (VIII), R <_13> and R <_14> may be same or different, and represents the alkyl group or the alkoxy group which may have a hydrogen atom, a halogen atom, and a substituent. R ₁₃ and R ₁₄ may be bonded to each other to form a divalent group formed by combining one or more of an alkylene group, -O-, and -S-. In General Formula (IX), Z represents -O- or -N (R _Z1 )-. R _Z1 represents a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group, an aralkyl group or an aryl group. In the general formula (X), X ₁ and X ₂ is -O-, -S-, -NH- or -NHSO ₂ are each independently - displays. A ₃ and A ₄ each independently represent a single bond, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an arylene group which may have a substituent, or -O-CO-R _15- , -CO-OR _16- . , -CO-N (R ₁₇ ) -R ₁₈ -is represented. R ₁₅ , R ₁₆ and R ₁₈ each independently may have a single bond or an ether group, an ester group, an amide group, a urethane group or a ureide group, a divalent alkylene group, an alkenylene group, a cycloalkylene group or an aryl Display the Rengi. R <_17> represents a hydrogen atom, the alkyl group which may have a substituent, a cycloalkyl group, an aralkyl group, or an aryl group. Y ₁ represents a hydrogen atom, a cyano group, -OH, -COOH, -COOR _y1 , -CONH-R _y2 , an alkyl group which may have a substituent, a cycloalkyl group, an alkoxy group, -Q, -COO-Q. R _y1 and R _y2 each independently represent an alkyl group which may have a substituent. Y ₂ represents -Q, -COO-Q. Provided that when X ₂ is -O- and A ₄ is a single bond, Y ₂ represents -Q. Q represents a group that can be broken down into acids. The positive resist composition according to claim 2, wherein the resin of (A) further contains at least one repeating unit represented by General Formulas (XI) to (XIII). In formula (XI), R <_20> and R <_21> may be same or different, and represents the alkyl group or haloalkyl group which may have a hydrogen atom, a halogen atom, a cyano group, and a substituent. A ₅ is a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group which may have a single bond, a substituent, -O-CO-R _15- , -CO-OR _16- , or -CO-N (R ₁₇ ) -R ₁₈ -is displayed. R ₁₅ , R ₁₆ and R ₁₈ are each independently a single bond or a divalent alkylene group, alkenylene group, cycloalkylene group or aryl which may have an ether group, ester group, amide group, urethane group or ureide group. Display the Rengi. R <_17> represents a hydrogen atom, the alkyl group which may have a substituent, a cycloalkyl group, an aralkyl group, or an aryl group. In formula (XII), R <_23> , R <_24> and R <_25> may be same or different, and may have a hydrogen atom, a halogen atom, a cyano group, and a substituent, the alkyl group, perfluoroalkyl group, alkoxy group, -CO- OR ₂₂ is represented. n represents 0 or 1. In General Formula (XIII), R ₂₆ represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group or haloalkyl group which may have a substituent. A ₆ is a divalent alkylene group, alkenylene group, cycloalkylene group or arylene group which may have a single bond, a substituent, -O-CO-R _15- , -CO-OR _16- , or -CO-N (R ₁₇ ) -R ₁₈ -is displayed. R ₁₅ , R ₁₆ and R ₁₈ are each independently a single bond or a divalent alkylene group, alkenylene group, cycloalkylene group or aryl which may have an ether group, ester group, amide group, urethane group or ureide group. Display the Rengi. R <_17> represents a hydrogen atom, the alkyl group which may have a substituent, a cycloalkyl group, an aralkyl group, or an aryl group. R ₂₈ and R ₂₉ may be the same or different and are an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl which may be the same or different and may have a hydrogen atom, a hydroxyl group, a halogen atom, a cyano group, an alkoxy group, an acyl group or a substituent. Display the flag. In General Formulas (XI) to (XIII), R ₂₂ and R ₂₇ are each independently -C (R ₃₀ ) (R ₃₁ ) (R ₃₂ ), -C (R ₃₀ ) (R ₃₁ ) (OR ₃₃ ) Or a group represented by the formula (XIV). R <_30> , R <_31> , R <_32> and R <_33> may be same or different and may represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, or an aryl group which may have a substituent. Two of R ₃₀ , R ₃₁ and R ₃₂ , or two of R ₃₀ , R ₃₁ and R ₃₃ may combine to form a ring. R ₃₄ 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. B represents the atomic group which comprises a monocyclic or polycyclic alicyclic group with a carbon atom. The positive resist composition according to claim 2 or 3, wherein the resin of (A) also has at least one repeating unit represented by the general formula (XV). In the formula, R ₃₅ represents an alkyl group, cycloalkyl group, aralkyl group or aryl group which may have a substituent. The positive resist composition according to any one of claims 1 to 4, further comprising (C) a silicon-based and / or fluorine-based surfactant. The positive resist composition according to any one of claims 1 to 5, further comprising (D) a compound having a basic nitrogen atom as an acid diffusion inhibitor. The compound of component (B) is a perfluoroalkylsulfonic acid, a perfluoroarylsulfonic acid or a perfluoroaryl sulfonate having 2 or more carbon atoms by irradiation of actinic light or radiation. A positive resist composition, characterized in that the alkyl group is selected from a sulfonium salt or a compound of iodide salt to generate allulsulfonic acid substituted. The positive resist composition according to any one of claims 1 to 7, wherein vacuum ultraviolet light of 160 nm or less is used as the exposure light source.