KR100835611B1 - Positive-working resist composition - Google Patents

Abstract

The present invention provides a positive electron beam or X-ray resist composition which has high sensitivity, high resolution, can provide excellent rectangular profile patterns, and is excellent in PCD, PED stability, and applicability.

The present invention also provides a positive electron beam or X-ray comprising (a1) a compound which generates an acid by irradiation with an electron beam or X-ray, and (b) a nitrogen-containing compound having one or more specific substructures in the molecule. It consists of a resist composition.

Description

Positive Resist Composition {POSITIVE-WORKING RESIST COMPOSITION}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electron beam or an X-ray resist composition, in particular, having an excellent pattern profile obtained by irradiating an electron beam or X-ray, an excellent resolution at high sensitivity, and particularly an electron beam having excellent time-lapse stability (PCD, PED) in a standing state. It relates to an X-ray resist composition.

In addition, the present invention relates to an electron beam resist composition for manufacturing a mask, in particular, a pattern profile obtained by irradiating electron beams, in particular, excellent footing prevention, high resolution at high sensitivity, and time-lapse stability in a standing state (PCD) , PED) relates to an electron beam resist composition for producing a mask.

Here, the PCD (Post Coating Delay) stability is a coating film stability when the resist composition is applied to a substrate and then left in the irradiation apparatus or outside the apparatus, and the PED (Psot Exposure Delay) stability is used when heating is performed after irradiation. Film stability in the case of being left in the irradiation apparatus or the apparatus in between.

The degree of integration of integrated circuits is increasing, and in the manufacture of semiconductor substrates such as ultra-LSIs, processing of ultra-fine patterns having line widths of 1/2 micron or less is required. In order to satisfy the necessity, the wavelength of use of the irradiation apparatus used for photolithography is gradually shortened, and at the present stage, ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) have been examined. Further, finer pattern formation has been examined by electron beams or X-rays.

In particular, electron beams or X-rays are located in the next generation or the next generation of pattern formation technology, and development of positive and negative resist compositions capable of achieving high sensitivity, high resolution, and rectangular profile shapes is required.

The processing precision of this lithographic technique depends on the dimensional accuracy of the photomask, which fulfills the negative role of the printed circuit. Therefore, obtaining a mask pattern having a rectangular cross-sectional shape and good dimensional accuracy has become an important problem in terms of improving productivity in manufacturing semiconductor integrated circuits.

In the more advanced exposure technique, since the pattern size below the wavelength of light is printed on the semiconductor substrate, a phase shift mask is required in which a shifter for inverting the phase of light is provided in part of the photomask. As a result, even in photomasks, microfabrication of about 1/4 micron level is required, and development of mask fabrication technology capable of realizing high resolution is required.

BACKGROUND ART As a lithography technique for manufacturing a photomask, a technique of exposing with an electron beam drawing apparatus excellent in micromachinability is generally used. However, currently available electron beam resists for masks cannot be manufactured with high aspect ratios of excimer laser exposure masks that require high precision and resolution, and the organic solvent is used as a developer. There is a problem that is difficult to do.

Therefore, a high resolution and highly sensitive electron beam resist using industrially advantageous aqueous alkali solution is required.

As a resist material which solves these, the composition containing the highly reactive medium under acid catalyst and the acid generator which generate | occur | produces an acid by irradiation of an activating line, Unexamined-Japanese-Patent No. 3779778, Unexamined-Japanese-Patent No. 59-45439, Japan The composition etc. which are described in Unexamined-Japanese-Patent No. 2-25850 etc. are known.

According to such a conventional example, the compound or polymer which contains acid-decomposable groups, such as an acetal group and t-butoxycarbonyl group, as a highly reactive medium is disclosed. Examples of the acid generator include a diaryl iodonium salt, a triarylsulfonium salt, a trialkylsulfonium salt, an ester of a compound containing a plurality of phenolic hydroxy groups, an alkyl sulfonic acid, and a sulfonic acid ester of N-hydroxyimide. This type of resist is called chemically amplified resist.

In addition, in the case of positive electron beam or X-ray resist, it is easy to be affected by basic pollutants in the atmosphere or fading into and out of the irradiation apparatus (drying of the coating film). (The surface becomes a T-shape), and in the case of a contact hole pattern, there is a problem that the surface becomes a capping shape (shade formed on the contact hole surface).

In addition, in the case of negative electron beam or X-ray resist, the surface is hard to be hardened by the influence of basic pollutants in the air or fading inside and outside the irradiation apparatus (drying of the coating film), and in the case of the line pattern, the round top shape ( The surface is rounded).

Then, the stability (PCD, PED) in the time period inside or outside the irradiation apparatus is also deteriorated, resulting in a problem that the pattern dimension is changed.

In addition, an unusual pattern profile due to the loss of activation of the acid has been observed in the vicinity of the film interface when a chemical amplification resist is used on the chromium oxide film formed on the quartz substrate of the photomask. In this case, in the case of a positive resist, a resist pattern is observed in a skirt shape in order for the acid in the resist film to react with or diffuse into the film. In addition, in the case of a negative resist, the resist pattern is observed in the eroded shape.

The same phenomenon has been confirmed to occur even when a resist pattern is formed on a silicon wafer substrate on a film such as an oxide film (SiO ₂ ), an aluminum film, or a nitride film (TiN, Si ₃ N ₄ ). This pattern profile abnormality is called footing in the positive resist, and the resist pattern is observed in the eroded shape in the negative resist.

An object of the present invention is not only to have high sensitivity and high resolution, but also to impart an excellent pattern profile of a rectangle, and also to provide excellent PCD and PED stability, and also excellent coating property (in-plane uniformity) to an electron beam or X-ray resist composition. To provide.

Another object of the present invention is to solve the problem that the shape of the resist pattern is deteriorated on a film that is highly reactive to an acid catalyst, such as chromium oxide of a photomask, to maintain a high sensitivity and high resolution, and to provide an excellent pattern profile of a rectangular shape. It is possible to provide an electron beam resist composition for manufacturing a mask that can be provided and has excellent PCD and PED stability as well as excellent coating property (in-plane uniformity).

That is, according to this invention, the following electron beam or X-ray resist composition or the electron beam resist composition for mask manufacture is provided, and the said objective of this invention is achieved.

First, a positive resist composition is described.

(1) a compound which generates an acid by (a1) electron beam or X-ray irradiation,

(b) A positive electron beam or X-ray resist composition containing a nitrogen-containing compound having at least one substructure represented by the following general formula (X) in a molecule.

(2) The positive electron beam or X-ray resist composition according to (1), wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (Ia).

In general formula (Ia), Ra represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group which may have a substituent.

Rb represents a hydrogen atom, an aryl group which may have a substituent, -C (= O) -Ra, or -N = N-Ra. Ra and Rb may combine with each other to form a ring.

(3) The positive electron beam or X-ray resist composition of (1), wherein the (b) nitrogen-containing compound is a compound represented by the following general formula (IIa).

In general formula (IIa), R represents the C1-C20 monovalent organic residue.

(4) The positive electron beam or X-ray resist composition of (1), wherein the (b) nitrogen-containing compound is a compound represented by the following general formula (IIb).

[In Formula (IIb), R ₅₀₁ to R ₅₁₀ are the same or different and represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, a hydroxyalkyl group, a cycloalkyl group, or an aryl group.]

(5) The positive electron beam or X-ray resist composition according to any one of (1) to (4), further comprising (c) a compound having a cationically polymerizable function.

(6) The positive electron beam in any one of said (1)-(5) containing 1 or more types of compounds chosen from (c ') vinyl compound, a cycloalkane compound, a cyclic ether compound, a lactone compound, and an aldehyde compound. Or X-ray resist composition.

(7) a compound which generates an acid by irradiation of an (a1 ') electron beam,

(b) Positive electron beam resist composition for mask manufacture containing the nitrogen-containing compound which has 1 or more partial structure represented by following General formula (X) in a molecule | numerator.

(8) The positive electron beam resist composition for mask manufacture according to (7), wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (Ia).

In general formula (Ia), Ra represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group which may have a substituent.

Rb represents a hydrogen atom, an aryl group which may have a substituent, -C (= O) -Ra, or -N = N-Ra. Ra and Rb may combine with each other to form a ring.

(9) The positive electron beam resist composition for mask manufacture according to (7), wherein the (b) nitrogen-containing compound is a compound represented by the following general formula (IIa).

In general formula (IIa), R represents the C1-C20 monovalent organic residue.

(10) The positive electron beam resist composition for mask manufacture according to (7), wherein the (b) nitrogen-containing compound is a compound represented by the following general formula (IIb).

[In Formula (IIb), R ₅₀₁ to R ₅₁₀ are the same or different and represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, a hydroxyalkyl group, a cycloalkyl group, or an aryl group.]

(11) The positive electron beam resist composition for mask manufacture according to any one of (7) to (10), further comprising (c) a compound having a cationically polymerizable function.

(12) For mask production according to any one of (7) to (11), containing (c ') a vinyl compound, a cycloalkane compound, a cyclic ether compound, a lactone compound, and at least one compound selected from an aldehyde compound Positive electron beam resist composition.

Below, a preferable structure is described.                     

(13) The positive resist composition as described in the above (6) or (12), wherein the compound (c ') is a compound represented by the general formula (A).

R ' _a , R' _b , R '_C; These may be the same or different and represent an alkyl group or an aryl group which may have a hydrogen atom or a substituent, and two of them may combine to form a saturated or olefinically unsaturated ring.

R ' _d : represents an alkyl or substituted alkyl group.

(14) The resin according to any one of (1) to (13), wherein the resin (d) has a group that can be decomposed by acid, and the solubility in an alkaline developer is increased by the action of an acid, or (f A positive resist composition having a group capable of being decomposed by an acid, having a solubility in an alkaline developer increased by the action of an acid, and containing at least one of a low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less.

(15) The compound which generates an acid by irradiation of (a1) electron beam or X-ray in any one of said (1)-(6) and (13) or (14) is the following general formula (I)-general Positive resist composition containing 1 or more of the compound represented by Formula (III).

(Wherein, R ₁ ~ R ₃₇ are the same or different and represent a hydrogen atom, a straight-chain, branched or cyclic alkyl, straight chain, branched or cyclic alkoxy group, a hydroxy group, a halogen atom, or -SR _38. R ₃₈ is A linear, branched or cyclic alkyl group or an aryl group, and two or more of R ₁ to R ₁₅ , R ₁₆ to R ₂₇ , and R ₂₈ to R ₃₇ combine to form a single bond, carbon, oxygen, sulfur, And a ring containing one or two or more selected from nitrogen.

X ^- is an anion of sulfonic acid.)

(16) In the above (15), X ⁻ is

One or more fluorine atoms,

Linear, branched or cyclic alkyl groups substituted with one or more fluorine atoms,

Linear, branched or cyclic alkoxy groups substituted with one or more fluorine atoms,

Acyl groups substituted with one or more fluorine atoms,

An acyloxy group substituted with one or more fluorine atoms,

Sulfonyl groups substituted with one or more fluorine atoms,

Sulfonyloxy groups substituted with one or more fluorine atoms,

Sulfonylamino groups substituted with one or more fluorine atoms,

Aryl groups substituted with one or more fluorine atoms,

An aralkyl group substituted with one or more fluorine atoms, and

A positive resist composition which is an anion of benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid having at least one selected from alkoxycarbonyl groups substituted with at least one fluorine atom.

(17) The compound which generates an acid by irradiation of (a1) electron beam or X-ray in any one of said (1)-(6) and (13)-(16) is a general thing as described in said (14). It contains one or more of the compounds represented by formula (I)-general formula (III), and

(d) has a group that can be decomposed by an acid, a resin whose solubility in an alkaline developer is increased by the action of an acid, or (e) a group that can be decomposed by an acid, and a solubility in an alkaline developer A positive resist composition which is increased by the action of an acid and contains at least one of low molecular weight dissolution inhibiting compounds having a molecular weight of 3000 or less.

(18) The compound which generates an acid by irradiation of (a1 ') electron beam in any one of (7)-(14) is 1 in the compound represented by following General formula (I)-General formula (III). A positive resist composition containing more than two.

(Wherein, R ₁ ~ R ₃₇ are the same or different and represent a hydrogen atom, a straight-chain, branched or cyclic alkyl group, a straight-chain, branched or cyclic alkoxy group, a hydroxy group, a halogen atom, or -SR _38. R ₃₈ Represents a linear, branched or cyclic alkyl group or an aryl group, and two or more of R ₁ to R ₁₅ , R ₁₆ to R ₂₇ , and R ₂₈ to R ₃₇ bond to each other to form a single bond, carbon, oxygen, or sulfur; You may form the ring containing 1 type (s) or 2 or more types selected from and nitrogen.

X ^- is an anion of sulfonic acid.)

(19) In the above (18), X ⁻ is

One or more fluorine atoms,

Linear, branched or cyclic alkyl groups substituted with one or more fluorine atoms,

Linear, branched or cyclic alkoxy groups substituted with one or more fluorine atoms,

Acyl groups substituted with one or more fluorine atoms,

An acyloxy group substituted with one or more fluorine atoms,

Sulfonyl groups substituted with one or more fluorine atoms,

Sulfonyloxy groups substituted with one or more fluorine atoms,

Sulfonylamino groups substituted with one or more fluorine atoms,

Aryl groups substituted with one or more fluorine atoms,

An aralkyl group substituted with one or more fluorine atoms, and

A positive resist composition which is an anion of benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid having at least one selected from alkoxycarbonyl groups substituted with at least one fluorine atom.

(20) The item according to any one of (7) to (14) and (18) or (19),

(a1 ') The compound which generate | occur | produces an acid by irradiation of an electron beam contains one or more of the compounds represented by general formula (I)-general formula (III) as described in said (17), and

(d) has a group that can be decomposed by an acid, a resin whose solubility in an alkaline developer is increased by the action of an acid, or (e) a group that can be decomposed by an acid, and a solubility in an alkaline developer A positive resist composition which is increased by the action of an acid and contains at least one of low molecular weight dissolution inhibiting compounds having a molecular weight of 3000 or less.

(21) The positive resist composition as described in any one of said (1)-(20) which mainly contains propylene glycol monomethyl ether acetate as a solvent.

(22) The positive resist composition according to any one of (1) to (21), further comprising (f) an organic basic compound.

(23) The positive resist composition according to any one of (1) to (22), further comprising (g) a fluorine-based and / or silicon-based surfactant.

Moreover, this invention also includes the mask blank which coat | covered the positive electron beam resist composition for mask manufacture of this invention.

Next, the negative resist composition is described.

(24) A compound which generates an acid by irradiation of (a2) electron beam or X-ray,

(b) a nitrogen-containing compound having at least one substructure represented by the following general formula (X) in a molecule,

(h) alkali-soluble resins, and

(i) An electron beam or X-ray chemically amplified negative resist composition containing a crosslinking agent crosslinked by an acid.

(25) The chemically amplified negative resist composition for electron beams or X rays according to (24), wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (Ia).

In general formula (Ia), Ra represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group which may have a substituent.

Rb represents a hydrogen atom, an aryl group which may have a substituent, -C (= O) -Ra, or -N = N-Ra. Ra and Rb may combine with each other to form a ring.

(26) The chemically amplified negative resist composition for electron beams or X rays according to (24), wherein the (b) nitrogen-containing compound is a compound represented by the following general formula (IIa).

In general formula (IIa), R represents the C1-C20 monovalent organic residue.

(27) The chemically amplified negative resist composition for electron beams or X rays according to (24), wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (IIb).

[In Formula (IIb), R ₅₀₁ to R ₅₁₀ are the same or different and represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, a hydroxyalkyl group, a cycloalkyl group, or an aryl group.]

(28) The item according to any one of (24) to (27), wherein the alkali-soluble resin of (h) includes a structural unit represented by the following General Formula (1), and has a weight average molecular weight of more than 3,000. And an electron beam or X-ray chemically amplified negative resist composition which is an alkali-soluble resin having 300,000 or less.

In formula (1), R <_1a> represents a hydrogen atom or a methyl group.

(29) The item according to any one of (24) to (27), wherein the alkali-soluble resin of (h) has a weight average molecular weight of more than 3,000 and is 300,000 or less, and the following conditions (a1) and (b1) A chemically amplified negative resist composition for electron beams or X-rays, which is a satisfactory alkali-soluble resin.

(a1) Having at least one repeating unit derived from an aromatic ring having 6 to 20 carbon atoms and a monomer having an ethylenically unsaturated group bonded directly or via a linking group to the aromatic ring.

(b1) The following relationship holds between the number of electrons of the lone electron of the aromatic ring and the unshared electron pair of the aromatic ring substituent.

(Nπ represents the total number of π electrons, and N _lone is a non-shared covalent linear, branched or cyclic alkoxy group, alkenyloxy group, aryloxy group, aralkyloxy group, or hydroxy group having 1 to 12 carbon atoms as the substituent). The total number of electrons of an electron pair is shown, and two or more alkoxy groups or a hydroxyl group may combine with two adjacent one another to form a 5-membered ring or more ring structure.)

(30) In the above-mentioned (29), the alkali-soluble resin of (h) is for electron beam or X-ray, which contains one or more of the repeating units represented by the following general formulas (3) to (7) as a component: Chemical Amplification Negative Resist Composition.

In General Formulas (3) to (7), R ₁₀₁ represents a hydrogen atom or a methyl group. L represents a divalent linking group. Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, and Rl are each independently a linear, branched, or cyclic alkyl group, alkenyl group, aryl group, aral having 1 to 12 carbon atoms A kill group or a hydrogen atom is represented. In addition, they may be linked to each other to form a ring having 5 or fewer members having 24 or less carbon atoms.

l, m, n, p, q, r, s, t, u, v, w, x represent integers from 0 to 3, l + m + n = 2, 3, p + q + r = 0 , 1, 2, 3, s + t + u = 0, 1, 2, 3, v + w + x = 0, 1, 2, 3.

(31) The compound which generates an acid by irradiation of (a2) electron beam or X-ray in any one of said (24)-(30) is represented by following General formula (I)-General formula (III) A chemical amplification negative resist composition for electron beams or X-rays containing at least one of the compounds.

[In the general formula (I) ~ the general formula _{(III), R 1 ~ R} 37 is a group represented by a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, or -SR _38. R ₃₈ in -SR ₃₈ represents an alkyl group or an aryl group. R ₁ to R ₃₈ may be the same or different. In the case of R ₁ to R ₁₅ , two or more selected from them may be bonded directly to each other or through an element selected from oxygen, sulfur and nitrogen to form a ring structure. In the case of R ₁₆ to R ₂₇ , a ring structure may be similarly formed. In the case of R ₂₈ to R ₃₇ , a ring structure may be similarly formed.

X ⁻ is an anion of sulfonic acid.]

(32) a compound which generates an acid by (a2 ') electron beam or X-ray irradiation,

(b) a nitrogen-containing compound having at least one substructure represented by the following general formula (X) in a molecule,

(h) alkali-soluble resins, and

(i) Electron negative resist composition for mask manufacture containing the crosslinking agent bridge | crosslinked by acid.

(33) The electron beam negative resist composition for mask manufacture according to (32), wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (Ia).

In general formula (Ia), Ra represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group which may have a substituent.

Rb represents a hydrogen atom, an aryl group which may have a substituent, -C (= O) -Ra, or -N = N-Ra. Ra and Rb may combine with each other to form a ring.

(34) The electron beam negative resist composition for mask manufacture according to (32), wherein the (b) nitrogen-containing compound is a compound represented by the following general formula (IIa).

In general formula (IIa), R represents the C1-C20 monovalent organic residue.

(35) The electron beam negative resist composition for mask manufacture according to (32), wherein the (b) nitrogen-containing compound is a compound represented by the following general formula (IIb).

[In Formula (IIb), R ₅₀₁ to R ₅₁₀ are the same or different and represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, a hydroxyalkyl group, a cycloalkyl group, or an aryl group.]

(36) The item according to any one of (32) to (35), wherein the alkali-soluble resin of (h) includes a structural unit represented by the following General Formula (1), and has a weight average molecular weight greater than 3,000. And an electron beam negative resist composition for manufacturing a mask, which is an alkali-soluble resin having 300,000 or less.

In formula (1), R <_1a> represents a hydrogen atom or a methyl group.

(37) The item according to any one of (32) to (35), wherein the alkali-soluble resin of (h) has a weight average molecular weight of more than 3,000 and 300,000 or less, and the following conditions (a1) and (b1) Electron negative resist composition for mask manufacture which is satisfied alkali-soluble resin.

(a1) Having at least one repeating unit derived from an aromatic ring having 6 to 20 carbon atoms and a monomer having an ethylenically unsaturated group bonded directly or via a linking group to the aromatic ring.

(b1) The following relationship holds between the number of electrons of the unshared electron pair of the aromatic ring and the? electron of the aromatic ring.

(Nπ represents the total number of π electrons, and N _lone is a non-shared covalent linear, branched or cyclic alkoxy group, alkenyloxy group, aryloxy group, aralkyloxy group, or hydroxy group having 1 to 12 carbon atoms as the substituent). The total number of electrons of an electron pair is shown, and two or more alkoxy groups or hydroxy groups may combine with two adjacent groups to form a 5-membered ring or more ring structure.)

(38) The electron beam negative for mask manufacture according to (37), wherein the alkali-soluble resin of (h) holds one or more of the repeating units represented by the following general formulas (3) to (7) as a component: Resist composition.

In General Formulas (3) to (7), R ₁₀₁ represents a hydrogen atom or a methyl group. L represents a divalent linking group. Ra, Rb, and Rc each independently represent a linear, branched or cyclic alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms. Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk and Rl are each independently a linear, branched or cyclic alkyl, alkenyl, aryl, aralkyl or hydrogen atom having 1 to 12 carbon atoms. Indicates. In addition, they may be linked to each other to form a 5-membered or more ring having 24 or less carbon atoms.

l, m, n, p, q, r, s, t, u, v, w, x represent integers from 0 to 3, l + m + n = 2, 3, p + q + r = 0 , 1, 2, 3, s + t + u = 0, 1, 2, 3, v + w + x = 0, 1, 2, 3.

(39) The compound which generates an acid by irradiation of the (a2 ') electron beam in any one of said (32)-(38) is a compound represented by the following general formula (I)-general formula (III). Electron negative resist composition for mask manufacture containing 1 or more types of these.

[In the general formula (I) ~ the general formula _{(III), R 1 ~ R} 37 is a group represented by a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, or -SR _38. R ₃₈ in -SR ₃₈ represents an alkyl group or an aryl group. R ₁ to R ₃₈ may be the same or different. In the case of R ₁ to R ₁₅ , two or more selected from them may be bonded directly to each other, or may be bonded through an element selected from oxygen, sulfur, and nitrogen to form a ring structure. In the case of R ₁₆ to R ₂₇ , a ring structure may be similarly formed. In the case of R ₂₈ to R ₃₇ , a ring structure may be similarly formed.

X ⁻ is an anion of sulfonic acid.]

In addition, the preferable structure of this invention is shown below.

(40) The crosslinking agent crosslinked with the acid (i) according to any one of the items (24) to (39) contains 3 to 5 benzene ring atom groups in the molecule, the molecular weight is 1200 or less, and The negative resist composition which is a phenol derivative which has two or more oxymethyl groups and / or an alkoxy methyl group in the benzene ring atom group.

(41) The negative resist composition as described in any one of said (24)-(40) containing (f) organic basic compound.

(42) The electron beam negative resist composition for mask manufacture in any one of said (24)-(41) containing (g) fluorine type and / or silicone type surfactant.

(43) The negative resist composition as described in any one of said (24)-(42) whose molecular weight distribution (Mw / Mn) of alkali-soluble resin of said (h) is 1.0-1.4.

Moreover, this invention includes the mask blank which provided the electron beam negative resist composition for mask manufacture of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, the electron beam or X-ray resist composition of this invention and the electron beam resist composition for mask manufacture are demonstrated.

[I] (b) nitrogen-containing compounds

The nitrogen-containing compound of (b) used in the present invention is a nitrogen-containing compound having at least one partial structure represented by the following general formula (X) in a molecule.

As a compound containing the partial structure of general formula (X), the compound represented by the following general formula (Ia) is preferable.

Here, Ra represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group which may have a substituent.

Rb represents a hydrogen atom, an aryl group which may have a substituent, -C (= O) -Ra, or -N = N-Ra. Ra and Rb may combine with each other to form a ring.

Such alkyl groups include those having 1 to 10 carbon atoms, preferably having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group.

Although an aryl group has a C6-C20 thing, it is preferable that it is C6-C14 like phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group, anthracenyl group.

Examples of the alkenyl group include one to four carbon atoms, and specific examples thereof include vinyl group, propenyl group, allyl group, and butenyl group.

Substituents for the alkyl group, alkenyl group or aryl group for Ra include a halogen atom, a nitro group, a cyano group and a hydroxy group.                     

Examples of the ring formed by bonding Ra and Rb to each other include the structures of the following (C-4) to (C-7).

It is preferable that the nitrogen-containing compound of following (b) is a compound represented with the following general formula (IIa).

In general formula (IIa), R represents the C1-C20 monovalent organic residue.

Examples of the monovalent organic residue having 1 to 20 carbon atoms include an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent, and an aralkyl group which may have a substituent. Indicates.

Although there are some C1-C10 alkyl groups, it is preferable that they are C1-C4, such as a methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, and t-butyl group.

Although a C3-C15 thing may exist as a cycloalkyl group, C3-C10 things, such as a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and an adamantyl group, are preferable.

Although an aryl group has C6-C20, It is preferable that it is C6-C14 like phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group, anthracenyl group.

Although an aralkyl group may be C7-20, It is preferable that it is C7-15, such as a substituted or unsubstituted benzyl group and a substituted or unsubstituted phenethyl group.

Substituents of such alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups include alkyl groups, alkoxy groups, hydroxy groups, halogen atoms, nitro groups and acyl groups.                     

In addition, the nitrogen-containing compound of (b) is preferably a compound represented by the following general formula (IIb).

[In Formula (IIb), R ₅₀₁ to R ₅₁₀ are the same or different and represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, a hydroxyalkyl group, a cycloalkyl group, or an aryl group.]

As an alkyl group in the said general formula (IIb), it is preferable that it is C1-C4 like methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, t-butyl group, and a cycloalkyl group is a cyclopropyl group It is preferable to have 3 to 10 carbon atoms such as cyclobutyl group, cyclohexyl group, and adamantyl group, and the aryl group may be 6 to 14 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthracenyl group. desirable.

As an alkoxy group, C1-C4 like methoxy group, an ethoxy group, hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group Personal is desirable.

Halogen atoms include fluorine, chlorine, bromine and iodine atoms.

The hydroxyalkyl group is preferably one having 1 to 4 carbon atoms such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group.

Specific examples of the nitrogen-containing compound (b) used in the present invention include compounds (Ia-1) to (Ia-12) and (b-1) to (b-9) shown below. However, it is not limited to this.

In the present invention, the addition amount of the nitrogen-containing compound (b) is generally used in the range of 0.001 to 40% by weight, preferably 0.01 to 20% by weight, more preferably 0.05 to 20% by weight, based on the solid content in the composition. It is used in the range of 15% by weight.

If the addition amount of the nitrogen-containing compound (b) of the present invention is less than 0.001% by weight, it is not sufficient to improve the line edge roughness. In addition, when the added amount is more than 40% by weight, the resist profile is deteriorated, which is not preferable.

[II] (c) Cationic Polymerizable Compound

In the present invention, cationic polymerizable compounds are preferably used.

In the present invention, cationic polymerization refers to addition polymerization in which the growth chain is a cation such as carbonium ions or oxonium ions. In the present invention, such a monomer capable of cationic polymerization is referred to as a compound having a cation polymerization function. Taking a vinyl compound as an example, the cationic polymerizability of the vinyl monomer can be discussed by the Q-e value used for radical polymerization. In other words, when the e value is less than about -0.3, it is known to exhibit cationic polymerization.

In addition, the structural characteristics of the cationically polymerizable compound include (1) a carbon-carbon unsaturated bond, which may be a π-donor, and 2) a hetero, which may be an n-donor, which is seen as a heterocyclic compound of some species (in most cases, saturated). It possesses a single bond containing carbon so that it can become an σ-donor even under special conditions so that it can be seen as an unshared electron pair of atoms (oxygen, sulfur, nitrogen, phosphorus), ③ alkanes.

(1) In addition to vinyl compounds, there are vinylidene compounds and vinylene compounds. Examples of (2) include oxazolines, aziridines, cyclic siloxanes, and the like in addition to lactone compounds and cyclic ether compounds. For example, isobutene, isoprene, butadiene, cyclopentadiene, cyclohexadiene, norbornadiene, styrene, indene, acenaphthylene, benzofuran, p-methoxystyrene, α-methylstyrene, vinyl ether, N-vinyl Carbazole, N-vinylpyrrolidone.

Among these, a vinyl compound is used preferably.

As addition amount of the compound of (c) in the resist composition of this invention, 0.5-50 weight% is preferable with respect to composition whole quantity (solid content), More preferably, it is 3-30 weight%.

[II '] (c') One or more compounds selected from vinyl compounds, cycloalkane compounds, cyclic ether compounds, lactone compounds, aldehyde compounds

In this invention, a (c ') vinyl compound, a cycloalkane compound, a cyclic ether compound, a lactone compound, and an aldehyde compound are used preferably.

As a vinyl compound, the following vinyl ether, styrene, (alpha) -methylstyrene, m-methoxy styrene, p-methoxy styrene, o-chloro styrene, m-chloro styrene, p-chloro styrene, o-nitro styrene, m -Styrenes such as nitrostyrene, p-bromostyrene, 3,4-dichlorostyrene, 2,5-dichlorostyrene, p-dimethylaminostyrene, 2-isopropenfuran, 2-vinylbenzofuran, 2-vinyl Vinylfurans such as dibenzofuran, vinylthiophenes such as 2-isopropenylthiophene and 2-vinylphenoxatine, N-vinylcarbazoles, vinylnaphthalin, vinylanthracene, acenaphthylene and the like can be used. have.

Examples of the cycloalkane compound include phenylcyclopropane, spiro [2,4] heptane, spiro [2,5] octane, spiro [3,4] octane, 4-methylspiro [2,5] octane and spiro [2,7 ] Decane and the like can be used.

As the cyclic ether compound, compounds such as dioxanes such as 4-phenyl-1,3-dioxane, oxetanes such as 3,3-bischloromethyl oxetane, trioxane and 1,3-dioxane Can be used. Moreover, glycidyl ethers, such as allyl glycidyl ether and phenyl glycidyl ether, glycidyl esters, such as glycidyl acrylate and glycidyl methacrylate, and the bisphenol A marketed as a brand name of epicoat Compounds such as a type epoxy resin, tetrabromobisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin and cresol novolak type epoxy resin can be used.

As the lactone compound, propiolactone, butyrolactone, valerolactone, caprolactone, β-methyl-β-propiolactone, α, α-dimethyl-β propiolactone, α-methyl-β-propiolactone Compounds, such as these, can be used.

As an aldehyde compound, Aliphatic saturated aldehyde compounds, such as a barrel aldehyde, a hexanal, a heptanol, an octanal, a nonanal, a decanal, a cyclohexane carbaldehyde, and a phenylacetaldehyde, a metacrolein, a crotonaldehyde, 2-methyl-2 Aliphatic unsaturated aldehyde compounds such as butenal, 2-butenal and safuranal, aromatic aldehyde compounds such as benzaldehyde, tolualdehyde, cinnamic aldehyde, tribromoacetaldehyde, 2,2,3-trichlorobutylaldehyde, chloro Halogen substituted aldehyde compounds such as benzaldehyde, glyceraldehyde, aldol, salylaldehyde, m-hydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, piperonal and the like Amino and nitro substituted aldehyde compounds, such as oxy and alkoxy substituted aldehyde compounds, aminobenzaldehyde, nitrobenzaldehyde, succinaldehyde Dialdehyde compounds such as hydride, glutaraldehyde, phthalaldehyde, terephthalaldehyde, ketoaldehyde compounds such as phenylglyoxal and benzoylacetaldehyde and derivatives thereof can be used.

The relationship between said (c) cationically polymerizable compound, (c ') vinyl compound, a cycloalkane compound, a cyclic ether compound, a lactone compound, and an aldehyde compound is a relationship in any one of following a) -c).

(C) A cationically polymerizable compound and not a (c ') vinyl compound, a cycloalkane compound, a cyclic ether compound, a lactone compound, or an aldehyde compound.

B) (c ') A vinyl compound, a cycloalkane compound, a cyclic ether compound, a lactone compound, an aldehyde compound, and not a (c') cationically polymerizable compound.

C) a cation-polymerizable compound, and a (c ') vinyl compound, a cycloalkane compound, a cyclic ether compound, a lactone compound, an aldehyde compound.

Therefore, although the said three types can be mentioned as a preferable compound in this invention, all of these have the effect equivalent to this invention.

However, as described below, the effect of the vinyl compound is remarkable.

As said (c ') compound, since the effect of this invention becomes remarkable, a vinyl compound is preferable, A vinyl ether compound is more preferable, The compound represented by general formula [A] is especially preferable.

In the general formula (A), R _'a, R' _b and R ', where _c is an aryl group, generally has from 4 to 20 carbon atoms, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an acyloxy It may be substituted by the time period, the alkyl mercapto group, the aminoacyl group, the carboalkoxy group, the nitro group, the sulfonyl group, the cyano group, or the halogen atom.

Here, as a C4-C20 aryl group, a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthryl group, a phenanthryl group etc. are mentioned, for example.

When R ' _a , R' _b and R ' _c represent an alkyl group, a saturated or unsaturated linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms represents a halogen atom, cyano group, ester group, oxy group, alkoxy. It may be substituted by the group, the aryloxy group, or the aryl group. Here, as a C1-C20 saturated or unsaturated linear, branched or alicyclic alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, an isobutyl group, t-butyl group, a pentyl group, and an isopentyl group , Neopentyl, hexyl, isohexyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, vinyl, propenyl, butenyl, 2-bute Neyl group, 3-butenyl group, isobutenyl group, pentenyl group, 2-pentenyl group, hexenyl group, heptenyl group, octenyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclo An octyl group, a cyclopentenyl group, a cyclohexenyl group, etc. are mentioned.

Further, R _'a, R' _b, and R _'c which two are saturated to form the bond or an olefin of the unsaturated ring, in particular is a cycloalkane or cycloalkene is generally from 3 to 8, preferably from 5 Or 6-membered ring.

In the present invention, it is preferred in the general formula (I) R _'a, R' _b, and R 'and _c some a methyl group or an ethyl group wherein the remainder is a hydrogen atom enol ether group, more preferably R _a, R _b, And R _c are the following general formula [A-1], wherein all are hydrogen.

General formula [A-1] CH ₂ = CH-OR (R: alkyl, substituted alkyl)

Here, an alkyl group is a C1-C30 linear, branched or cyclic alkyl group.

A substituted alkyl group is a C1-C30 linear, branched or cyclic substituted alkyl group.

In the above description, as a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, an ethyl group, a linear, branched or cyclic propyl group, a butyl group, a pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group.

In the above, preferred examples of the other substituents of the alkyl group include a hydroxy group, an alkyl group, an alkoxy group, an amino group, a nitro group, a halogen atom, a cyano group, an acyl group, an acyloxy group, a sulfonyl group, a sulfonyloxy group, a sulfonylamino group, and an aryl group. , Aralkyl group, imide group, hydroxymethyl group, -OR ₅₁ , -C (= O) -R ₅₂ , -OC (= O) -R ₅₃ , -C (= O) -OR ₅₄ , -SR ₅₅ ,- And substituents such as C (= S) -R ₅₆ , -OC (= S) -R ₅₇ , and -C (= S) -OR ₅₈ . Wherein R ₅₁ to R ₅₈ are each independently a linear, branched or cyclic alkyl group, an alkoxy group, an amino group, a nitro group, a halogen atom, a cyano group, an acyl group, a sulfonyl group, a sulfonyloxy group, a sulfonylamino group, Imide group,-(CH ₂ CH ₂ -O) _n -R ₅₉ (wherein n represents an integer of 1 to 20, R ₅₉ represents a hydrogen atom or an alkyl group), an aryl group which may have a substituent Or an aralkyl group (wherein the substituents are linear, branched or cyclic alkyl groups, alkoxy groups, amino groups, nitro groups, halogen atoms, cyano groups, acyl groups, aryl groups, aralkyl groups and the like).

As a compound represented by general formula (A), although what was shown below is preferable, it is not limited to these.

As a synthesis method of the compound represented by the said general formula [A-1], it is Stephen. By the methods described in C. Lapin, Polymers Paint Color Journal, 179 (4237), 321 (1988), that is, reactions of alcohols or phenols with acetylene, or reactions of alcohols or phenols with halogenated alkylvinyl ethers. Can be synthesized. Moreover, it can synthesize | combine also by reaction of a carboxylic acid compound and a halogenated alkyl vinyl ether.

As addition amount of the compound (c ') (preferably compound represented with the said General formula (A)) in the resist composition of this invention, 0.5-50 weight% is preferable with respect to the composition total weight (solid content), More preferably, it is 3-30 weight%.

[III] A compound which generates an acid by irradiation of an electron beam (or X-ray) used in the resist composition of the present invention

The compound which generate | occur | produces an acid by irradiation of the electron beam (or X-ray) used by this invention is classified as follows.

(1) In a positive electron beam or X-ray resist composition, (a1) a compound which generates an acid by irradiation of an electron beam or X-ray.

(2) In the positive resist composition for mask production, a compound which generates an acid by irradiation of (a1 ') electron beam

(3) In the chemically amplified negative resist composition for electron beams and / or X-rays, (a2) a compound that generates an acid by irradiation with an electron beam or X-ray.

(4) The compound which generates an acid by irradiation of (a2 ') electron beam or X-ray in the electron beam negative resist composition for mask manufacture.

Below, it describes about each.

[III-A] (a1) A compound that generates an acid by irradiation with an electron beam or X-ray (hereinafter referred to as "component (a1)")                     

Although it describes below about a component (a1), about the compound which generate | occur | produces an acid by irradiation of said (a1 ') electron beam (henceforth a component (a1')), in the (a1) component described below The compound which generate | occur | produces an acid by irradiation of the electron beam is mentioned.

As a component (a1), although any can be used as long as it is a compound which generate | occur | produces an acid by irradiation of an electron beam or X-ray, the compound represented by general formula (I)-(III) is preferable.

[III-A-1] Compounds represented by General Formulas (I) to (III)

In the general formulas (I) to (III), as the linear or branched alkyl group of R ₁ to R ₃₈ , a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, which may have a substituent, There exists a C1-C4 thing like t-butyl group. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group which may have a substituent.

As a linear, branched alkoxy group of R ₁ to R ₃₇ , for example, methoxy, ethoxy, hydroxyethoxy, propoxy group, n-butoxy, isobutoxy, sec-butoxy, t-butoxy group There are one to four carbon atoms.

Examples of the cyclic alkoxy group include a cyclopentyloxy group and a cyclohexyloxy group.

As a halogen atom of R <_1> -R <_37> , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

As an aryl group of R <_38> , there exist some C6-C14 which may have substituents, such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group, for example.

Preferred examples of such a substituent include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom and an iodine atom), a 6 to 10 carbon atom aryl group, a 2 to 6 carbon alkenyl group, a cyano group, a hydroxyl group, a carboxyl group, An alkoxycarbonyl group, a nitro group, and the like.

Moreover, 1 type (s) or 2 or more types chosen from single bond, carbon, oxygen, sulfur, and nitrogen which two or more combine and form among R <_1> -R <_15> , R <_16> -R <_27> and R <_28> -R <_37> . Examples of the ring containing include a furan ring, dihydrofuran ring, pyran ring, trihydropyran ring, thiophene ring, pyrrole ring and the like.

In formulas (I) to (III), X ⁻ is an anion of sulfonic acid.

Moreover, what is preferable as X <^-> is an anion of benzene sulfonic acid, naphthalene sulfonic acid, or anthracene sulfonic acid which has 1 or more types chosen from a following formula.

One or more fluorine atoms,

Linear, branched or cyclic alkyl groups substituted with one or more fluorine atoms,

Linear, branched or cyclic alkoxy groups substituted with one or more fluorine atoms,

Acyl groups substituted with one or more fluorine atoms,

An acyloxy group substituted with one or more fluorine atoms,

Sulfonyl groups substituted with one or more fluorine atoms,

Sulfonyloxy groups substituted with one or more fluorine atoms,

Sulfonylamino groups substituted with one or more fluorine atoms,

Aryl groups substituted with one or more fluorine atoms,

An aralkyl group substituted with one or more fluorine atoms, and                     

Alkoxycarbonyl groups substituted with one or more fluorine atoms

As said linear, branched or cyclic alkyl group, it is preferable that carbon number is 1-12 and is substituted by 1-25 fluorine atoms. Specifically, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, heptafluoroisopropyl group, perfluorobutyl group, perfluorooctyl group, Perfluoro dodecyl group, a perfluoro cyclohexyl group, etc. are mentioned. Of these, preferred are perfluoroalkyl groups substituted with all fluorine atoms.

As said linear, branched or cyclic alkoxy group, it is preferable that carbon number is 1-12 and is substituted by 1-25 fluorine atoms. Specifically, trifluoromethoxy group, pentafluoroethoxy group, heptafluoroisopropyloxy group, perfluorobutoxy group, perfluorooctyloxy group, perfluorododecyloxy group, perfluorocyclohex And siloxy groups. Among them, a perfluoroalkoxy group having 1 to 4 carbon atoms substituted with all fluorine atoms is preferable.

The acyl group preferably has 2 to 12 carbon atoms and is substituted with 1 to 23 fluorine atoms. Specifically, there are a trifluoroacetyl group, a fluoroacetyl group, a pentafluoropropionyl group, a pentafluorobenzoyl group, and the like.

The acyloxy group preferably has 2 to 12 carbon atoms and is substituted with 1 to 23 fluorine atoms. Specifically, there are a trifluoroacetoxy group, a fluoroacetoxy group, a pentafluoropropionyloxy group, a heptafluorobenzoyloxy group, and the like.

The sulfonyl group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specifically, trifluoromethanesulfonyl group, pentafluoroethanesulfonyl group, perfluorobutanesulfonyl group, perfluorooctanesulfonyl group, pentafluorobenzenesulfonyl group, 4-trifluoromethylbenzenesulfonyl group, etc. have.

The sulfonyloxy group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specifically, there are a trifluoromethanesulfonyloxy group, a perfluorobutanesulfonyloxy group, a 4-trifluoromethylbenzenesulfonyloxy group, and the like.

The sulfonylamino group preferably has 1 to 12 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specifically, a trifluoromethanesulfonylamino group, a perfluorobutanesulfonylamino group, a perfluorooctanesulfonylamino group, a perfluorobenzenesulfonylamino group, etc. are mentioned.

The aryl group preferably has 6 to 14 carbon atoms and is substituted with 1 to 9 fluorine atoms. Specifically, a pentafluorophenyl group, 4-trifluoromethylphenyl group, heptafluoronaphthyl group, nonafluoro anthranyl group, 4-fluorophenyl group, 2, 4- difluorophenyl group, etc. are mentioned.

As said aralkyl group, it is preferable that carbon number is 7-10, and is substituted by 1-15 fluorine atoms. Specifically, pentafluorophenylmethyl group, pentafluorophenylethyl group, perfluorobenzyl group, perfluorophenethyl group, etc. are mentioned.

The alkoxycarbonyl group preferably has 2 to 13 carbon atoms and is substituted with 1 to 25 fluorine atoms. Specifically, there are a trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, pentafluorophenoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorooctyloxycarbonyl group, and the like.

Most preferred X ⁻ is fluorine-substituted benzenesulfonate anion, of which pentafluorobenzenesulfonate anion is particularly preferred.

In addition, the benzene sulfonic acid, naphthalene sulfonic acid, or anthracene sulfonic acid which has the said fluorine-containing substituent is a linear, branched or cyclic alkoxy group, acyl group, acyloxy group, sulfonyl group, sulfonyloxy group, sulfonylamino group, and aryl group. , An aralkyl group, an alkoxycarbonyl group (the carbon number range is the same as described above), a halogen (except fluorine), a hydroxyl group, a nitro group and the like may be further substituted.

The specific example of the compound represented by general formula (I) is shown below.

The specific example of the compound represented by general formula (II) is shown below.

The specific example of the compound represented by general formula (III) is shown below.

You may use the compound represented by general formula (I)-(III) together using 1 type (s) or 2 or more types.

The compounds of the general formulas (I) and (II) react with the sulfonic acid and the salt of the triarylsulfonium halide obtained by, for example, reacting a substituted or unsubstituted phenyl sulfoxide with an aryl Grignard reagent such as aryl magnesium bromide. Exchange method, substituted or unsubstituted phenylsulfoxide and the corresponding aromatic compound are condensed and salt exchanged using an acid catalyst such as methanesulfonic acid / diphosphate or aluminum chloride, or diaryliodonium salt and diarylsulfoxide It can synthesize | combine by the method of condensation, salt exchange, etc. using catalysts, such as copper acetate.

The compound of formula (III) can be synthesized by reacting an aromatic compound with a periodate.

In addition, the sulfonic acid or sulfonic acid salt used for salt exchange can be obtained by hydrolyzing commercially available sulfonic acid chloride, reacting an aromatic compound with chlorosulfonic acid, reacting an aromatic compound with sulfamic acid, and the like.

In the following detail, the synthesis | combining method of the specific compound of general formula (I)-(III) is demonstrated.

(Synthesis of pentafluorobenzenesulfonic acid tetramethylammonium salt)

25 g of pentafluorobenzenesulfonyl chloride was dissolved in 100 ml of methanol under ice cooling, and 100 g of 25% aqueous tetramethylammonium hydroxide solution was slowly added thereto. It stirred at room temperature for 3 hours and obtained the solution of the pentafluorobenzene sulfonate tetramethylammonium salt. This solution was used for salt exchange with sulfonium salts and iodonium salts.

(Synthesis of triphenylsulfonium pentafluorobenzenesulfonate: synthesis of detailed example (I-1))

50 g of diphenyl sulfoxide was dissolved in 800 ml of benzene, and 200 g of aluminum chloride was added thereto, and the mixture was refluxed for 24 hours. The reaction solution was slowly poured into 2 liters of water, and 400 ml of concentrated hydrochloric acid was added thereto, followed by heating at 70 캜 for 10 minutes. The aqueous solution was washed with 500 ml of ethyl acetate, filtered and 200 g of ammonium iodide dissolved in 400 ml of water was added.

The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate and dried to obtain 70 g of triphenylsulfonium iodide.

30.5 g of triphenylsulfonium iodide was dissolved in 1000 ml of methanol, 19.1 g of silver oxide was added to this solution, and the mixture was stirred at room temperature for 4 hours. The solution was filtered and an excess solution of the synthesized pentafluorobenzenesulfonic acid tetramethylammonium salt was added thereto. The reaction solution was concentrated and dissolved in 500 ml of dichloromethane, and the solution was washed with 5% aqueous tetramethylammonium hydroxide solution and water. The organic phase was dried over anhydrous sodium sulfate and concentrated to give triphenylsulfonium pentafluorobenzenesulfonate.

(Synthesis of triarylsulfonium pentafluorobenzenesulfonate: Synthesis of mixture of detailed example (I-9) and (II-1))

50 g of triarylsulfonium chloride (Fluka, 50% aqueous solution of triphenylsulfonium chloride) was dissolved in 500 ml of water, and an excess solution of pentafluorobenzenesulfonate tetramethylammonium salt was added thereto to precipitate an oily substance. . Only the supernatant was removed by decantation, and the resulting oily substance was washed with water and dried to obtain triarylsulfonium pentafluorobenzenesulfonate (Detailed Example (I-9) and (II-1) as main components).

(Synthesis of di (4-t-amylphenyl) iodonium pentafluorobenzenesulfonate: synthesis of detailed example (III-1))

60 g of t-amylbenzene, 39.5 g of potassium iodide, 81 g of acetic anhydride, and 170 ml of dichloromethane were mixed, and 66.8 g of concentrated sulfuric acid was slowly added dropwise thereto under ice cooling. The mixture was stirred for 2 hours under ice cooling, and then for 10 hours at room temperature. 500 ml of water was added to the reaction solution under ice cooling, and this was extracted with dichloromethane, and the organic phase was washed with sodium bicarbonate and water, and then concentrated to give di (4-t-amylphenyl) iodium sulfate. This sulfate was added to the solution of excess pentafluorobenzenesulfonic acid tetramethylammonium salt. 500 ml of water was added to the solution, which was extracted with dichloromethane, the organic phase was washed with 5% aqueous tetramethylammonium hydroxide solution and water, and concentrated to give (4-t-amylphenyl) iodiumpentafluorobenzenesulfo. Nate was obtained.

Other compounds can also be synthesized using the same method as above.

[III-A-2] Acid generator usable as component (a1)

In this invention, the compound which decomposes | disassembles by irradiation of the following electron beam or X-ray and produces | generates an acid can be used as a component (a1).

In the present invention, in addition to the compound represented by the above general formulas (I) to (III) as the component (a1), a compound which is decomposed by the following electron beam or X-ray irradiation to generate an acid is used in combination. Also good.

In this invention, the usage-amount of the photo-acid generator which can be used together with the compound represented by said general formula (I)-general formula (III) is molar ratio (compound / represented by general formula (I)-general formula (III) /). Other acid generators), generally 100/0 to 20/80, preferably 100/0 to 40/60, and more preferably 100/0 to 50/50.

The total content of component (a1) is generally 0.1 to 20% by weight, preferably 0.5 to 10% by weight, still more preferably 1 to 1, based on the solids of the total composition of the positive electron beam or X-ray resist composition of the present invention. 7% by weight.

The total content of component (a1 ') is generally 0.1 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 1, based on the solids of the entire composition of the positive electron beam resist composition for mask manufacture of the present invention. ˜7% by weight.

Such acid generators are known compounds which generate acids by irradiation with electron beams or X-rays used in photoinitiators of photocationic polymerization, photoinitiators of photoradical polymerization, photochromic agents of pigments, photochromic agents, or microresists. And mixtures thereof may be appropriately selected and used.

See, eg, SI Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), TS Bal et al., Polymer , 21, 423 (1980), etc., diazonium salts, US Pat. Nos. 4,069,055, 4,069,056 and Re27,992, JP-A 3- Ammonium salts described in US 140140 et al., DC Necker et al., Macromolecules , 17, 2468 (1984), CS Wen et al., Teh, Proc.conf. Rad. Phosphonium salts described in Curing ASIA , p. 478, Tokyo, Oct. (1988), US Pat. Nos. 4, 069, 055 and 4,069,056, JV Crivello et al., Macromolecules , 10 (6) 1307 (1977) , Chem. & Eng. News , Nov. 28, p. 31 (1988), European Patent No. 104,143, US Patent No. 339,049, and US Patent Nos. 410, 201, JP-A 2-150848, JP-A-2-296514, 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., Macromolecules , 14 (5), 1141 (1981), JV Crivello et al., J. Polymer Sci., Polymer Chem. Ed. , 17, 2877 (1979), European Patents 370,693, US Patents 3,902,114, 233,567, 297,443, 297,442, 4,933,377, 161,811, 410,201, 339,049, 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, JV Crivello et al., Macromolecules , 10 (6), 1307 (1977), JV Crivello et al., J. Polymer Sci., Polymer Chem. Ed. , 17, 1047 (1979) et al. And selenium salts and CS Wen et al., Teh, Proc. Conf. Rad. Curing ASIA , p. 478, Tokyo, Oct. Onium salts such as arzonium salts described in (1988) and the like; U.S. Patent No. 3,905,815, Patent Publication 46-4605, Patent Publication 48-36281, Patent Publication 55-32070, Patent Publication 60-239736, Patent Publication 61-169835, Patent Publication 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), TP Gill et al., Inorg. Chem. , 19, 3007 (1980), D. Astruc, Acc, Chem. Res. , Organometallic / organic halides as described in (19), (12), 377 (1896), JP-A 2-161445; S. Hayase et al., J. Polymer Sci. , 25, 753 (1987), E. Reichmanis et al., J. Polymer Sci., Polymer Chem. Ed. , 23, 1 (1985), QQ Zhu et al., J. Photochem. , 36, 85, 39, 317 (1987), B. Amit et al., Tetrahedron Lett. , (24) 2205 (1973), DH R 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), PM Collins et al., J. Chem. Soc., Chem. Commun. , 532 (1972), S. Hayase et al., Macromolecules , 18, 1799 (1985), E. Reichmanis et al., J. Eletrochem. Soc., Solid State Sci. Technol. , 130 (6), FM Houlihan et al., Macromolecules , 21, 2001 (1988), European Patent Nos. 0,290,750, 046,083, 156,535, 271,851, and 0,388,343, US Patent 3,901,710 and Photoacid generators having o-nitrobenzyl-type protecting groups described in US Pat. No. 4,181,531, Patent Publication No. 60-198538, Patent Publication No. 53-133022, and the like; 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 Nos. 0,199,672, 84,515, 199,672, 044,115, 0,101,122 Photolyzed by iminosulfonates such as those described in 618,564 and U.S. Patent Nos. 4,371,605 and 4,431,774, Patent Publication No. 64-18143, Patent Publication No. 2-245756, and Patent Publication No. The compound which produces a sulfonic acid, and the disulfone compound of Unexamined-Japanese-Patent No. 61-166544 are mentioned.

In addition, a compound in which an acid or a compound which generates an acid by irradiation of such electron beam or X-ray is introduced into the main chain or side chain of the polymer, for example, 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 No. 3,849,137, German Patent No. 3914407, Patent Publication No. 63-26653, Patent Publication No. 55-164824, Patent Publication No. 62-69263, Patent Publication 63 The compounds described in -146038, Patent Publication No. 63-163452, Patent Publication No. 62-153853, Patent Publication No. 63-146029 and the like can be used.

See also V. N. R. Pillai, Synthesis, (1), 1 (1980), A. Abad et al, Tetra hedron Lett., (47), 4555 (1971), D. H. R. Barton et al, J. Chem. Soc., (C), 329 (1970), U.S. Patent No. 3,779,778, European Patent No. 126,712 and the like can also be used compounds which generate an acid by light.

Among the compounds which decompose by irradiation of the above-mentioned electron beam or X-ray which can be used together and generate an acid, a particularly effective use will be 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).

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 are mentioned in detail, 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).

R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group and an 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 alkoxy groups having 1 to 8 carbon atoms, alkyl groups having 1 to 8 carbon atoms, nitro groups, carboxyl groups, hydroxyl groups and halogen atoms, and examples of the substituents for alkyl groups include alkoxy groups having 1 to 8 carbon atoms, carboxyl groups, It is an alkoxycarbonyl group.

Z ^- is a pair to present an anion such as CF ₃ SO ₃ ^-, such as perfluoro alkane sulfonic acid anion, condensed naphthalene-1-sulfonic acid anion, such as polynuclear aromatic sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dye, etc. Although it is mentioned, it is not limited to this.

In addition, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ may be bonded via a single bond or a substituent, respectively.
Although the compound shown below is mentioned in detail, it is not limited to these.

The onium salts represented by the general formula (PAG4) are known and are described, for example, in 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), US Pat. Nos. 2,807,648 and 4,247,473, Patent Publication No. 53-101331 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, an aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, arylene group.

Although the compound shown below is a detailed example, it is not limited to this.

In the present invention, a resin having a group that can be decomposed by an acid (d) and whose solubility in an alkaline developer is increased by the action of an acid (hereinafter referred to as "component (d)"), or (e) acid It has a group that can be decomposed by, and the solubility in an alkaline developer is increased by the action of acid, and contains at least one of a low molecular weight dissolution inhibiting compound (hereinafter referred to as "component (e)") having a molecular weight of 3000 or less. It is desirable to.

[III-B] (a2) A compound that generates an acid by irradiation with an electron beam or X-ray (hereinafter referred to as "component (a2)" or "acid generator")

Although the component (a2) is described below, about the compound (henceforth "a component (a2)") which generate | occur | produces an acid by irradiation of said (a2 ') electron beam, in (a2) component described below The compound which generate | occur | produces an acid by irradiation of the electron beam is mentioned.

In the negative resist composition of this invention, an acid generator is used with alkali-soluble resin. Any compound can be used as long as it is a compound which produces | generates an acid by irradiation of a radiation, and the acid generator used with alkali-soluble resin.

Such acid generators include compounds which generate acid by irradiation of known electron beams or X-rays used in photoinitiators of photocationic polymerization, photoinitiators of photoradical polymerization, photochromic agents of pigments, photochromic agents, or microresists; Mixtures of these may be appropriately selected and used.

For example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenium salts, and arzonium salts, organic halogen compounds, organometallic / organohalides, and o-nitrobenzyl protecting groups The compound which photodecomposes | generates and produces a sulfonic acid represented by the acid generator which has having, imino sulfonate, etc., a disulfone compound, etc. are mentioned.

Moreover, the compound which introduce | transduced the group or compound which generate | occur | produces an acid by such light in the main chain or side chain of a polymer, for example, Unexamined-Japanese-Patent No. 63-26653, 55-164824, 62-69263. , 63-146038, 63-163452, 62-153853, 63-146029 and the like can be used.

In addition, a compound which generates an acid by light described in U.S. Patent No. 3,779,778, European Patent No. 126,712 or the like can also be used.

In this invention, the onium salt compound which generate | occur | produces an organic acid is preferable, and a particularly preferable thing is an onium salt compound represented by said general formula (I)-general formula (III).

R ₁ ~ R ₃₇ in the general formula (I) ~ the general formula (III) is a group that can be represented by a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, or -SR _38.

The alkyl group represented by R ₁ to R ₃₇ may be linear, branched or cyclic. As a linear or branched alkyl group, a C1-C4 alkyl group, such as a methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, t-butyl group, is mentioned, for example. As a cyclic alkyl group, there exists a C3-C8 thing, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, for example.

The alkoxy group represented by R ₁ to R ₃₇ may be linear, branched or cyclic. Examples of the linear or branched alkoxy group include methoxy, ethoxy, hydroxyethoxy, propoxy, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy having 1 to 8 carbon atoms. A time period, an octyloxy group, etc. are mentioned. Examples of the cyclic alkoxy group include a cyclopentyloxy group and a cyclohexyloxy group.

The halogen atom represented by R ₁ to R ₃₇ includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

_{R 1 ~ R 37 -SR 38 R} 38 in the shown is an alkyl group or an aryl group. As a range of the alkyl group which R <_38> represents, any of the alkyl groups already listed by the alkyl group which R <_1> -R <_37> represents, for example is mentioned.

The aryl group which R <_38> represents has a C6-C14 thing, such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group.

To the alkyl group or less aryl group represented by R ₁ to R ₃₈ , a substituent may be further bonded to a part of a certain group to increase the carbon number, or may not have a substituent. Moreover, as a substituent which may be couple | bonded, Preferably, a C1-C4 alkoxy group, a C6-C10 aryl group, a C2-C6 alkenyl group is mentioned, A cyano group, a hydroxyl group, a carboxyl group, and an alkoxycarbonyl group And nitro groups. In addition, a halogen atom may be sufficient. For example, a fluorine atom, a chlorine atom, and an iodine atom are mentioned.

The group represented by R <_1> -R <_15> in general formula (I) may combine 2 or more of them, and may form the ring. The ring may be formed by directly bonding the terminals of the groups represented by R ₁ to R ₁₅ . A ring may be formed by directly bonding through one or two or more elements selected from carbon, oxygen, sulfur and nitrogen.

As a ring structure which two or more of R <_1> -R <_15> combine and form, the same structure as ring structure, such as a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, a pyrrole ring, etc. is mentioned. Can be. The same applies to R ₁₆ to R ₂₇ in General Formula (II). Two or more may combine directly or indirectly and may form a ring. The same applies to R ₂₈ to R ₃₇ in General Formula (III).

General formulas (I) to (III) have X ⁻ . X <^-> which general formula (I)-(III) hold is an anion of sulfonic acid. The acid which forms an anion is an acid chosen from alkyl sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid, or anthracene sulfonic acid. It is more preferable if the acid has one or more fluorine atoms substituted. Alternatively, the acid is one selected from an alkyl group, an alkoxy group, an acyl group, an acyloxy group, a sulfonyl group, a sulfonyloxy group, a sulfonylamino group, an aryl group, an aralkyl group, an alkoxycarbonyl group together with or instead of the fluorine atom. It is preferable to have the above organic group, and that organic acid is further substituted by one or more fluorine atoms. The alkyl sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid or anthracene sulfonic acid may be substituted with a halogen atom other than fluorine, a hydroxyl group, a nitro group, or the like.

The alkyl group bonded to benzene sulfonic acid or the like forming an anion of X ⁻ is, for example, an alkyl group having 1 to 12 carbon atoms. The alkyl group may be linear, may be branched, or may be cyclic. One or more fluorine atoms, preferably 25 or less fluorine atoms are substituted. Specifically, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, heptafluoroisopropyl group, perfluorobutyl group, perfluorooctyl group, Perfluoro dodecyl group, a perfluoro cyclohexyl group, etc. are mentioned. Of these, preferred are C 1-4 perfluoroalkyl groups substituted with all fluorine atoms.

The alkoxy group bonded to the benzenesulfonic acid or the like together with the alkyl group or alone is an alkoxy group having 1 to 12 carbon atoms. The alkoxy group may be linear, may be branched, or may be cyclic. It is substituted with one or more fluorine atoms, preferably 25 or less fluorine atoms. Specifically, trifluoromethoxy group, pentafluoroethoxy group, heptafluoroisopropyloxy group, perfluorobutoxy group, perfluorooctyloxy group, perfluorododecyloxy group, perfluorocyclohex A siloxy group etc. are mentioned. Among these, a C 1-4 perfluoroalkoxy group substituted with all fluorine is preferable.

It is preferable that the acyl group couple | bonded with the said benzene sulfonic acid etc. together with an alkyl group or alone is substituted by C2-C12, 1-23 fluorine atoms. Specifically, a trifluoroacetyl group, a fluoroacetyl group, a pentafluoropropionyl group, a pentafluorobenzoyl group, etc. are mentioned.

It is preferable that the acyloxy group couple | bonded with the said benzene sulfonic acid etc. together with an alkyl group or alone is substituted by 2-12 and 1-23 fluorine atoms. Specifically, a trifluoroacetoxy group, a fluoroacetoxy group, a pentafluoro propionyloxy group, a pentafluorobenzoyloxy group, etc. are mentioned.

  It is preferable that the sulfonyl group couple | bonded with the said benzene sulfonic acid etc. together with an alkyl group or alone is substituted with 1-12 carbon atoms and 1-25 fluorine atoms. Specifically, trifluoromethanesulfonyl group, pentafluoroethanesulfonyl group, perfluorobutanesulfonyl group, perfluorooctanesulfonyl group, pentafluorobenzenesulfonyl group, 4-trifluoromethylbenzenesulfonyl group, etc. Can be mentioned.

It is preferable that the sulfonyloxy group couple | bonded with the said benzene sulfonic acid etc. together with an alkyl group or alone is substituted by 1-12 and 1-25 fluorine atoms. Specifically, there are a trifluoromethanesulfonyloxy group, a perfluorobutanesulfonyloxy group, a 4-trifluoromethylbenzenesulfonyloxy group, and the like.

It is preferable that the sulfonylamino group couple | bonded with the said benzene sulfonic acid etc. together with an alkyl group or alone is substituted by 1-12 and 1-25 fluorine atoms. Specifically, there are a trifluoromethanesulfonylamino group, a perfluorobutanesulfonylamino group, a perfluorooctanesulfonylamino group, a pentafluorobenzenesulfonylamino group, and the like.

As the aryl group which is bonded to the benzenesulfonic acid or the like together with the alkyl group or alone, it is preferable that carbon atoms are substituted with 6 to 14 and 1 to 9 fluorine atoms. Specifically, there are pentafluorophenyl group, 4-trifluoromethylphenyl group, heptafluoronaphthyl group, nonafluoroanthranyl group, 4-fluorophenyl group, 2,4-difluorophenyl group and the like.

As the aralkyl group bonded to the benzenesulfonic acid or the like together with the alkyl group or alone, it is preferable that the carbon number is substituted with 7 to 10 and 1 to 15 fluorine atoms. Specifically, there are pentafluorophenylmethyl group, pentafluorophenylethyl group, perfluorobenzyl group, perfluorophenethyl group and the like.

As an alkoxycarbonyl group couple | bonded with the said benzene sulfonic acid etc. independently or together with an alkyl group, it is preferable that carbon number is substituted by 2-13 and 1-25 fluorine atoms. Specifically, there are a trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, pentafluorophenoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorooctyloxycarbonyl group, and the like.

Of these anions, most preferred X ⁻ is fluorine-substituted benzenesulfonate anion, and among these, pentafluorobenzenesulfonate anion is particularly preferred.

In addition, alkyl sulfonic acid, benzene sulfonic acid, naphthalene sulfonic acid, or anthracene sulfonic acid having a fluorine-containing substituent, linear, branched or cyclic alkoxy group, acyl group, acyl oxy group, sulfonyl group, sulfonyloxy group, sulfonylamino group, An aryl group, an aralkyl group, an alkoxycarbonyl group (the carbon number range is the same as described above), a halogen (except fluorine), a hydroxy group, a nitro group and the like may be further substituted.

Although the compound and other specific examples shown by such general formula (I)-(III) are shown below, it is not limited to these.                     

The specific example of the compound represented by general formula (I) is shown below.

The specific example of the compound represented by general formula (II) is shown below.

The specific example of the compound represented by general formula (III) is shown below.

Specific examples of compounds other than the compounds represented by formulas (I) to (III) are shown below.

Compounds of general formula (I) and general formula (II) can be synthesized by the following method. For example, an aryl grignard reagent such as aryl magnesium bromide and phenyl sulfoxide are reacted, and the resulting triarylsulfonium halide is salt exchanged with the corresponding sulfonic acid. There is another method, for example, a method in which phenyl sulfoxide and the corresponding aromatic compound are condensed and salt exchanged using an acid catalyst such as methanesulfonic acid / diphosphate or aluminum chloride. In addition, the diaryl iodonium salt and the diaryl sulfide can be synthesized by condensation and salt exchange using a catalyst such as copper acetate. In any of the above methods, the phenyl sulfoxide may have a substituent substituted with a benzene ring, and may not have such a substituent.

The compound of general formula (III) can be synthesize | combined by making an aromatic compound react using a periodate.

As for content of the acid generator used for this invention, 0.1-20 weight% is suitable with respect to solid content of the whole negative resist composition, Preferably it is 0.5-10 weight%, More preferably, it is 1-7 weight%.

[III-B-2] (Other Photoacid Generator)

In the present invention, in addition to the compounds represented by the above general formulas (I) to (III), or with these, other compounds that decompose upon irradiation with radiation to generate an acid can be used.

When using other compounds which decompose by irradiation with radiation to generate an acid together with the compounds represented by formulas (I) to (III), the ratio of other compounds that decompose by irradiation with radiation to generate an acid The molar ratio is 100/0 to 20/80, preferably 90/10 to 40/60, and more preferably 80/20 to 50/50.

[IV] Resin having a group which can be decomposed by (d) acid, and solubility in alkaline developing solution is further increased by the action of acid.

Component (d) used in the positive resist composition of the present invention is a resin having a group that can be decomposed in an acid in the main chain or the side chain, or both the main chain and the side chain of the resin. Of these, resins having groups in the side chain that can decompose in acids are more preferred.

Preferable groups as the group which can be decomposed in an acid are -C0O-A ⁰ and -OB ⁰ groups, and examples of the group further including these groups include -R ⁰ -COOA ⁰ or -A _r -OB ⁰ .

Wherein A ⁰ is -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), Si- (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), or -C (R ⁰⁴ ) (R ⁰⁵ ) -OR ⁰⁶ Group. B ⁰ represents an A ⁰ or -C ⁰ -OA ⁰ group (R ⁰ , R ⁰¹ to R ⁰⁶ , and Ar are the same as below).

The acid-decomposable group is preferably a silyl ether group, cumyl ester group, acetal group, tetrahydropyranyl ether group, enol ether group, enol ester group, tertiary alkyl ether group, tertiary alkyl ester group, tertiary alkyl. Carbonate groups and the like. More preferred are tertiary alkyl ester groups, tertiary alkyl carbonate groups, cumyl ester groups, acetal groups and tetrahydropyranyl ether groups.

Next, an alkali-soluble resin for holding a matrix resin when the group is bonded to a side chain which may be decomposed to such acids are, for side chain -OH or -COOH, preferably -R ⁰ -COOH or a group -A _r -OH to be. For example, the following alkali-soluble resin is mentioned.

It is preferable that the alkali dissolution rate of such alkali-soluble resin is 170 Pa / sec or more as measured (23 degreeC) by 0.261N tetramethylammonium hydroxide (TMAH). It is especially preferable that it is 330 ms / sec or more.

In this respect, particularly preferred alkali-soluble resins are o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly (hydroxystyrene), Part of poly (hydroxystyrene), O-alkylated or O-acylates, styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers and hydrogenated novolak resins.

Component (d) used in the present invention is decomposed in an acid into an alkali-soluble resin, as disclosed in European Patent No. 254853, Japanese Patent Application Laid-Open No. 2-25850, No. 3-223860, No. 4-251259 and the like. It can be obtained by reacting a precursor of a group which can be made, or by copolymerizing a combined alkali-soluble resin monomer of a group that can be decomposed in an acid with various monomers.

Although the specific example of component (d) used for this invention is shown below, it is not limited to this.

The content rate of the group that can be decomposed in the acid is the number of groups (B) which can be decomposed in the acid in the resin and the number (S) of alkali-soluble groups not protected by the group that can be decomposed in the acid, B / ( B + S). The content rate is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, and most preferably 0.05 to 0.40. At B / (B + S)> 0.7, film shrinkage after PEB and adhesion to the substrate are poor or cause scum, which is not preferable. On the other hand, at B / (B + S) <0.01, standing waves are remarkably remaining on the pattern side wall, which is not preferable.

The weight average molecular weight (Mw) of component (d) is preferably in the range of 2,000 to 200,000. If it is less than 2,000, the film reduction tends to be large due to the development of the unexposed portion, and if it exceeds 200,000, the dissolution rate of the alkali-soluble resin itself to alkali will be slowed, and the sensitivity tends to be lowered. More preferably, it is the range of 5,000-100,000, Most preferably, it is the range of 8,000-50,000.
In addition, the molecular weight distribution (Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 2.0, most preferably 1.0 to 1.6, and when the degree of dispersion becomes small, heat resistance and image formability (pattern profile) become It becomes good.

Here, the weight average molecular weight is defined as the polystyrene conversion value of gel permeation chromatography.

In addition, component (d) can also be used in combination of 2 or more type.

[V] (e) Low Molecular Acid Degradable Dissolution Inhibiting Compound ("(e) Component")

In the present invention, the component (e) may be used. (e) A component is a low molecular dissolution inhibiting compound which has a group which can be decomposed | dissolved by an acid, the solubility to alkaline developing solution increases by the action of an acid, and whose molecular weight is 3000 or less.

Preferred (e) component to be blended into the composition of the present invention has at least two groups which can be decomposed in the acid in its structure, and at the position where the distance between the acid-decomposable groups is the lowest, the bonding atoms excluding the acid-decomposable group It is a compound which passes through eight or more.

A more preferable component (e) has at least two groups which can be decomposed in an acid in its structure, and at least ten bond atoms excluding the acid-decomposable group at a position where the distance between the acid-decomposable groups is the least, preferably A compound having at least 11, more preferably at least 12, or at least 3 acid-decomposable groups, and at least 9 binding atoms excluding the acid-decomposable group at a position where the distance between the acid-decomposable groups is the least; Is a compound having at least 10, more preferably at least 11. The upper limit of the number of the binding atoms is preferably 50, more preferably 30.

When the acid-decomposable dissolution inhibiting compound (e) has three or more acid-decomposable groups, preferably four or more, and even when the acid-decomposable groups contain two acid-decomposable groups, the acid-decomposable groups are separated from each other by a predetermined distance or more There exists a tendency for the dissolution inhibition property to alkali-soluble resin to increase significantly.

In addition, the distance between acid-decomposable groups is represented by the number of bonding atoms passing through, except for the acid-decomposable group. For example, in the following compounds (1) and (2), the distance between the acid-decomposable groups is four bonding atoms, and in compound (3), the bonding atoms are 12 bonding atoms.

The acid-decomposable dissolution inhibiting compound of the component (e) preferably has a plurality of acid-decomposable groups on one benzene ring, but is preferably composed of a skeleton having one acid-decomposable group on one benzene ring. Compound. The molecular weight of the acid-decomposable dissolution inhibiting compound of the present invention is 3,000 or less, preferably 300 to 3,000, and more preferably 500 to 2,500.

In a preferred embodiment of the present invention, a group that can be decomposed by an acid, that is, a group containing a -COOA ⁰ , -OB ⁰ group is represented by -R ⁰ -COO-A ⁰ , or -Ar-OB ⁰ have.

Wherein A ⁰ represents a -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), -Si (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -C (R ⁰⁴ ) (R ⁰⁵ ) -OR ⁰⁶ groups Display. B ⁰ represents an A ⁰ or -CO-OA ⁰ group.

R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ may be the same or different, respectively, and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, and R ⁰⁶ represents an alkyl group or an aryl group. However, two or more of R ⁰¹ to R ⁰³ may be a group other than a hydrogen atom, and two groups of R ⁰¹ to R ⁰³ and R ⁰⁴ to R ⁰⁶ may combine to form a ring. R <^0> represents the bivalent or more aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- represents the bivalent or more aromatic group which may have a monocyclic or polycyclic substituent.

Here, the alkyl group preferably has 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, and cycloalkyl group is cyclopropyl group, cyclobutyl group, cyclohex. It is preferable that it is C3-C10 like a real group and an adamantyl group, As an alkenyl group, it is preferable that it is C2-C4 like vinyl group, a propenyl group, an allyl group, butenyl group, As an aryl group, a phenyl group, a xylyl group, It is preferable that they are C6-C14, such as a toluyl group, cumenyl group, a naphthyl group, and anthracenyl group.

As the substituent, a hydroxy group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, Alkoxy groups such as alkoxy groups such as n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, and aralkyl jade Acyloxy groups, such as acyl groups, such as a formyl group, an acetyl group, butyryl group, a benzoyl group, a cyanyl group, and a bareryl group, and an acyloxy group, such as butyryloxy group, the said alkenyl group, vinyloxy group, propenyloxy group, and allyloxy group Alkenyloxy groups, such as a butenyloxy group, aryloxy groups, such as the said aryl group and phenoxy group, and aryloxycarbonyl groups, such as a benzoyloxy group, are mentioned.

Preferably, silyl ether group, cumyl ester group, acetal group, tetrahydropyranyl ether group, enol ether group, enol ester group, tertiary alkyl ether group, tertiary alkyl ester group, tertiary alkyl carbonate group, etc. There is this. More preferably, there is a tertiary alkyl ester group, tertiary alkyl carbonate group, cumyl ester group, and tetrahydropyranyl ether group.

Preferable examples of (e) component include Patent Publication Nos. 1-289946, 1-289947, 2-2560, 3-128959, 3-158855, 3-179353, and 3- 191351, East 3-200251, East 3-200252, East 3-200253, East 3-200254, East 3-200255, East 3-259149, East 3-279958, East 3-279959 , East 4-1650, East 4-1651, East 4-11260, East 4-12356, East 4-12357, Patent Application No. 3-33229, East 3-230790, East 3-320438 , Polyhydroxy described in the specification such as 4-25157, 4-52732, 4-103215, 4-104542, 4-107885, 4-107889, 4-152195, etc. Some or all of the phenolic OH groups of the compound are bonded to the group, -R ⁰ -COO-A ⁰ or B ⁰ group, and the compound protected.

More preferably, Japanese Patent Application Laid-Open No. 1-289946, No. 3-128959, No. 3-158855, No. 3-179353, No. 3-200251, No. 3-200252, No. 3-200255, No. 3-259149, east 3-279958, east 4-1650, east 4-11260, east 4-12356, east 4-12357, patent application 4-25157, east 4-103215, east The polyhydroxy compound described in the specification of 4-104542, 4-107885, 4-107889, and 4-152195 is used.

More specifically, there exist a compound represented by general formula [I]-[XVI].                     

Here, R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ , R ^{130 may be the} same or different, and a hydrogen atom, -R ⁰ -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), except that R ⁰ , R ⁰¹ , R ⁰² and R ⁰³ are defined as above.

R ¹⁰⁰ : -CO-, -COO-, -NHCONH-, -NHCOO-, -O-, -S-, -SO-, -SO _2- , -SO _3- , or

Where, G = 2 ~ 6, if inde, provided that, G = 2 days, at least one of R ^150, R ¹⁵¹ is an alkyl group,

R ¹⁵⁰ , R ¹⁵¹ : may be the same or different, hydrogen atom, alkyl group, alkoxy group, -OH, -COOH, -CN, halogen atom, -R ¹⁵² -COOR ¹⁵³ or -R ¹⁵⁴ -OH,

R ¹⁵² , R ¹⁵⁴ : alkylene group,

R ¹⁵³ : hydrogen atom, alkyl group, aryl group, or aralkyl group,

R ⁹⁹ , R ¹⁰³ to R ¹⁰⁷ , R ¹⁰⁹ , R ¹¹¹ to R ¹¹⁸ , R ¹²¹ to R ¹²³ , R ¹²⁸ to R ¹²⁹ , R ¹³¹ to R ¹³⁴ , R ¹³⁸ to R ¹⁴¹ and R ¹⁴³ : may be the same or different, Hydrogen atom, hydroxy group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, halogen atom, nitro group, carboxyl group, cyano group, or -N (R ¹⁵⁵ ) ( R ¹⁵⁶ ), wherein R ¹⁵⁵ , R ¹⁵⁶ : H, an alkyl group, or an aryl group

R ¹¹⁰ : single bond, alkylene group, or

R ¹⁵⁷ and R ^{159 may be the} same or different, and are a single bond, an alkylene group, -O-, -S-, -CO-, or a carboxyl group,

R ¹⁵⁸ : a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, a nitro group, a hydroxy group, a cyano group, or a carboxyl group, provided that the hydroxy group is an acid decomposable group (e.g., t-butoxycarbonyl Methyl group, tetrahydropyranyl group, 1-ethoxy-1-ethyl group, 1-t-butoxy-1-ethyl group).

R ¹¹⁹ and R ^{120 may be the} same or different and are a methylene group, a lower alkyl substituted methylene group, a halomethylene group, or a haloalkyl group, except that the lower alkyl group in the present application refers to an alkyl group having 1 to 4 carbon atoms,

R ¹²⁴ to R ¹²⁷ : may be the same or different, a hydrogen atom or an alkyl group,

R ¹³⁵ to R ¹³⁷ : may be the same or different, a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or an acyloxy group,

R ¹⁴² : hydrogen atom, -R ⁰ -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or

R ¹⁴⁴ , R ¹⁴⁵ : the same as or different from each other, a hydrogen atom, a lower alkyl group, a lower haloalkyl group, or an aryl group,

R ¹⁴⁶ to R ¹⁴⁹ : may be same or different, hydrogen atom, hydroxy group, halogen atom, nitro group, cyano group, carbonyl group, alkyl group, alkoxy group, alkoxycarbonyl group, aralkyl group, aralkyloxy group, acyl group, acyloxy group, alke A substituent group of an identical group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group, and four identical symbols may not be the same group.

Y: -CO-, or -SO _2- ,

Z, B: single bond or -O-,

A: methylene group, lower alkyl substituted methylene group, halomethylene group, or haloalkyl group,

E: single bond or oxymethylene group,

a to z, a1 to y1: In the case of a plurality, the groups in parentheses may be the same or different.

a to q, s, t, v, g1 to i1, k1 to m1, o1, q1, s1, u1: an integer of 0 or 1 to 5,

r, u, w, x, y, z, a1 to f1, p1, r1, t1, v1 to x1: an integer of 0 or 1 to 4,                     

j1, n1, z1, a2, b2, c2, d2: 0 or an integer of 1 to 3,

at least one of z1, a2, c2, and d2 is one or more,

y1: an integer from 3 to 8,

(a + b), (e + f + g), (k + l + m), (q + r + s), (w + x + y), (c1 + d1), (g1 + h1 + i1 + j1), (o1 + p1), (s1 + t1) ≥2,

(j1 + n1) ≤ 3,

(r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1 + f1), (p1 + r1), (t1 + v1), (x1 + w1) ≤ 4, except that in the general formula [V], (w + z), (x + a1) ≤5,

(a + c), (b + d), (e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q + t), (s + v), (g1 + k1), (h1 + l1), (i1 + m1), (o1 + q1), and (s1 + u1) ≦ 5.

R ¹⁶⁰ : organic group, single bond, -S-, -SO- or

R ¹⁶¹ : hydrogen atom, monovalent organic group or

R ¹⁶² to R ^{166 may be the} same or different and represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, -OR ⁰ -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -O- CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), but two or more are -OR ⁰ -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -O-CO-OC (R ⁰¹ (R ⁰² ) (R ⁰³ ). In addition, substituents of four or six identical symbols may not be the same groups.

X: a divalent organic group,

e2: 0 or 1 is displayed.

From here,

R ¹⁶⁷ to R ^{170 may be the} same or different and a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, or an alkenyl group, provided that the substituents of each of 4 to 6 identical symbols may not be the same group.

R ¹⁷¹ , R ¹⁷² : hydrogen atom, alkyl group or

R ¹⁷³ : two or more are -OR ⁰ -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -O-CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), except for hydroxy group to be.

f2, h2: 0 or 1,

g2: The integer of 0 or 1-4 is represented.

From here,

R ¹⁷⁴ to R ¹⁸⁰ : may be the same or different, hydrogen atom, hydroxy group, halogen atom, alkyl group, alkoxy group, nitro group, alkenyl group, aryl group, aralkyl group, alkoxycarbonyl group, arylcarbonyl group, acyloxy group, acyl group, aral A cheloxy group or an aryloxy group, provided that the six substituents of the same symbol may not be the same group.

R ¹⁸¹ : two or more are -OR ⁰ -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -O-CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) groups, except for hydroxy groups Is displayed.

From here,

R ¹⁸² : hydrogen or alkyl, provided that they are not necessarily the same.

R ¹⁸³ to R ¹⁸⁶ : a hydroxyl group, a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group, provided that the substituents of each of the three same symbols may not be the same group.

R ¹⁸⁷ : two or more are -OR ⁰ -COO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) or -O-CO-OC (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) groups; The hydroxyl group is represented.

The specific example of a preferable compound skeleton is shown below.

R in compounds (1) to (44) is a hydrogen atom,

를 표시한다.

Is displayed.

However, two or more or three may be groups other than a hydrogen atom by structure, and each substituent R may not be the same group.

[VI] The positive resist composition of the present invention is a resin which is not dissolved in water as (h ') other components and is soluble in an alkaline developer (hereinafter, "(h') component" or "(h ') alkali-soluble resin"). Can be used).

In the positive resist composition of the present invention, as the (h ') component, a resin insoluble in water and soluble in an aqueous alkali solution can be used. When using (h ') component, it is not necessary to mix | blend resin which has group which decomposes by the action of the acid which is said (h') component, and increases the solubility to alkaline developing solution. Of course, combined use with (h ') component is not excluded.

As (h ') alkali-soluble resin used for this invention, a novolak resin, a hydrogenated novolak resin, acetone- pyrogallol resin, o-polyhydroxy styrene, m-polyhydroxy styrene, p-poly Hydroxystyrene, hydrogenated polyhydroxystyrene, halogen or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, polyhydroxystyrene Some O-alkylates (e.g., 5-30 mole% O-methylate, O- (1-methoxy) ethylate, O- (1-ethoxy) ethylate, O-2 -Tetrahydropyranylide, O- (t-butoxycarbonyl) methylate, etc.) or O-acylide (e.g., 5-30 mol% o-acetylate, O- (t-butoxy) Carbonylide, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing meta Rilgye resin and there can be a derivative thereof, polyvinyl alcohol derivatives, but is not limited in this respect.

Particularly preferred (h ') alkali-soluble resins include novolak resins and o-polyhydroxystyrenes, m-polyhydroxystyrenes, p-polyhydroxystyrenes and copolymers thereof, alkyl substituted polyhydroxystyrenes, and poly Some O-alkylated, or O-acylates, styrene-hydroxystyrene copolymers, α-methylstyrene-hydroxystyrene copolymers of hydroxystyrene. The novolak resin can be obtained by addition condensation with aldehydes in the presence of an acidic catalyst with a predetermined monomer as a main component.

Predetermined monomers include cresols such as phenol, m-cresol, p-cresol and o-cresol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2, Alkyl phenols such as xylenols such as 3-xylenol, m-ethylphenol, p-ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol and 2,3,5-trimethylphenol, p -Methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-prop Alkoxyphenols such as foxyphenol, m-butoxyphenol and p-butoxyphenol, bisalkylphenols such as 2-methyl-4-isopropylphenol, m-chlorophenol, p-chlorophenol, o-chlorophenol, di Although hydroxy aromatic compounds, such as hydroxyphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol, can be used individually or in mixture of 2 or more types, it is not limited to these.

-페닐프로필알데히드,

-페닐프로필알데히드, o-히드록시벤즈알데히드, m-히드록시벤즈알데히드, p-히드록시벤즈알데히드, o-클로로벤즈알데히드, m-클로로벤즈알데히드, p-클로로벤즈알데히드, o-니트로벤즈알데히드, m-니트로벤즈알데히드, p-니트로벤즈알데히드, o-메틸벤즈알데히드, m-메틸벤즈알데히드, p-메틸벤즈알데히드, p-에틸벤즈알데히드, p-n-부틸벤즈알데히드, 푸르푸랄, 클로로아세트알데히드 및 이들의 아세탈체, 예를 들면, 클로로아세트알데히드디에틸아세탈 등을 사용할 수 있지만, 이것들 중에서 포름알데히드를 사용하는 것이 바람직하다.As aldehydes, For example, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde,

Phenylpropylaldehyde,

-Phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-hydroxybenzaldehyde Nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde and their acetals such as chloroacetaldehyde diethyl Although etc. can be used, it is preferable to use formaldehyde among these.

These aldehydes are used individually or in combination of 2 or more types. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

The weight average molecular weight of the novolak resin thus obtained is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film reduction after development of unexposed part becomes large, and if it exceeds 30,000, the developing speed will become small. It is especially preferable that it is the range of 2,000-20,000.

Moreover, the weight average molecular weights of the said polyhydroxy styrene other than novolak resin, its derivative (s), and copolymer are 2,000 or more, Preferably it is 5000-200000, More preferably, it is 5000-100000.

Here, a weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography.

In this invention, you may use these (h ') alkali-soluble resin in mixture of 2 or more types.

Here, although the structural example of the positive resist composition of this invention is shown below, the content of this invention is not limited to this.

1) A positive electron beam or X-ray resist composition comprising said component (a1), said component (b), said component (c) and said component (d).

2) The resist composition for positive electron beam or X-ray containing the said component (a1), the said component (b), the said component (c), the said component (e), and the said component (d).

3) A positive electron beam or X-ray resist composition comprising said component (a1), said component (b), said component (c), said component (d) and said component (e).

4) Positive electron beam resist composition for mask manufacture containing said component (a1 '), the said component (b), the said component (c), and the said component (d).

5) The positive electron beam resist composition for mask manufacture containing the said component (a1 '), the said component (b), the said component (c), the said component (e), and the said component (h').

6) The positive electron beam resist composition for mask manufacture containing the said component (a1 '), the said component (b), the said component (c), the said component (d), and the said component (e).

1) 'A resist composition for positive electron beam or X-ray comprising said component (a1), said component (b), said component (c'), and said component (d).

2) A resist composition for positive electron beams or X-rays comprising said component (a1), said component (b), said component (c '), said component (e) and said component (h).

3) A positive electron beam or X-ray resist composition comprising said component (a1), said component (b), said component (c '), said component (d) and said component (e).

4) 'Positive electron beam resist composition for mask manufacture containing said component (a1'), the said component (b), the said component (c '), and the said component (d).

5) 'Positive electron beam resist composition for manufacturing a mask comprising the component (a1'), the component (b), the component (c '), the component (e) and the component (h').

6 ') Positive electron beam resist composition for mask manufacture containing said phase part (a1'), the said component (b), the said component (c '), the said component (d), and the said component (e).

(c) A cationically polymerizable compound, (c ') vinyl compound, a cycloalkane compound, a cyclic ether compound, a lactone compound, and an aldehyde compound can be used together.

In the above structural example, not only part of (c) can be replaced by (c '), but also part of (c') can be replaced by (c).

In each of the above constituent examples, the amounts used in the compositions of components (d), 2) and 5) of components (d), 2) and 5) and component (d) of 3) and 6), 40-99 weight% is preferable with respect to solid content of, More preferably, it is 50-95 weight%.

As for the usage-amount in the composition of the said component (e), 3-45 weight% is preferable with respect to solid content of the whole composition also in any of said each structural examples, More preferably, it is 5-30 weight%, More preferably, Is 10 to 30% by weight.

[VII] (h) alkali-soluble resin

Alkali-soluble resin in the negative resist composition of this invention is resin (it is called alkali-soluble resin) insoluble in water and soluble in aqueous alkali solution.

The alkali dissolution rate of alkali-soluble resin is measured by 0.261N tetramethylammonium hydroxide (TMAH) (23 degreeC), and it is preferable that it is 20 microseconds / sec or more. It is especially preferable that it is 200 microseconds / sec or more.

(1) One of the preferable structures of alkali-soluble resin in this invention is resin containing the structural unit represented by the said General formula (1).

In addition to the structural unit represented by the general formula (1), other repeating structural units may be included.

Alkali-soluble resin containing the structural unit represented by General formula (1) used for this invention is an alkali-soluble resin made into the objective of the following monomer (8) and the other monomer as needed by radical polymerization, a living anion polymerization method, etc. You can get it.

In the above, when using the monomer which has a hydroxyl group in a molecule | numerator, the method of protecting a hydroxyl group previously and removing a protecting group after superposition | polymerization is preferable. Moreover, also when protecting with an acid-decomposable group, the method of introducing a protecting group after completion | finish of a polymer synthesis is common.

In this invention, content in resin of the repeating structural unit represented by the said General formula (1) should just be an amount by which the effect of this invention can be expressed. Specifically, it is 30-100 mol% with respect to all the repeating units, More preferably, it is 50-90 mol%.

(2) One of the other preferable structures of alkali-soluble resin in this invention satisfy | fills the following conditions (a1) and (b1).

(a1) Having at least one repeating unit derived from an aromatic ring having 6 to 20 carbon atoms, and a monomer having an ethylenically unsaturated group bonded directly or via a linking group to the aromatic ring.                     

(b1) The relationship of the following formula (I) holds between the number of electrons of the lone electron of the aromatic ring and the unshared electron pair of the aromatic ring substituent.

Here, Nπ represents the total number of π electrons, and N _lone is a non-covalent electron pair of a linear, branched or cyclic alkoxy group, alkenyloxy group, aryloxy group, aralkyloxy group, or hydroxy group having 1 to 12 carbon atoms as its substituent. Represents the total number of electrons. Two or more alkoxy groups or hydroxy groups may combine with two adjacent groups to form a 5-membered ring or more ring structure.

In particular, Nπ + (1/2) N _lone in formula (I) is preferably in the range of 10 to 40 because the structure is likely to generate secondary electrons. Preferred aromatic rings include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, biphenyls, and the like. Examples of preferred aromatic ring substituents include hydroxy groups, methoxy groups, ethoxy groups, and isopropyl groups.

If the π-electron total number Nπ is an aromatic ring (eg, an aromatic ring such as a naphthalene ring, anthracene ring, or phenanthrene ring, or biphenyl), the substituent on the aromatic ring does not have a non-covalent electron pair. The group (group which becomes N _lone = 0) may be sufficient, and a hydrogen, a saturated alkyl group, etc. are mentioned, for example.

More specifically, it is preferable that the alkali-soluble resin of this invention hold | maintains the repeating unit represented by General formula (3)-(7) as a component.

In General Formulas (3) to (7), R ₁₀₁ represents a hydrogen atom or a methyl group. L represents a divalent linking group. Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Rl are each independently a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, alkenyl group, aryl group, aralkyl group or Represents a hydrogen atom. In addition, they may be linked to each other to form a 5-membered or more ring having 24 or less carbon atoms. l, m, n, p, q, r, s, t, u, v, w, x represent integers from 0 to 3, where l + m + n = 2,3, p + q + r = 0, 1, 2, 3, s + t + u = 0, 1, 2, 3, v + w + x = 0, 1, 2, 3.

Examples of Ra, Rb and Rc include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group and octyl group , Decyl group, dodecyl group, allyl group, benzyl group, phenyl group, cumyl group and the like. It is also exemplified that they are linked to each other to form a methyl substituted dioxol ring, an ethyl substituted dioxol ring, a phenyl substituted dioxol ring, a dimethyl substituted dioxol ring and a dioxane ring.

Examples of Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk and Rl include hydrogen, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group and neo Pentyl, hexyl, cyclohexyl, octyl, decyl, dodecyl, allyl, benzyl, phenyl, cumyl and the like. Rd-Rf, Rg-Ri, or Rj-Ri can also form a dioxol ring, a methyl substituted dioxol ring, an ethyl substituted dioxol ring, a phenyl substituted dioxol ring, a dimethyl substituted dioxol ring, and a dioxane ring.

An example of L is a single bond, -CH ₂ - and the _{like, -CONH- -, -COO, -COOCH 2} -, -OCH 2 CH 2 O- -OCH 2.

In each of the aromatic rings represented by Y, the position of the bond number bonded to the main chain or the bond number bonded to the substituent may be anywhere in the aromatic ring shape.

These can be obtained by superposition | polymerization of the monomer of (9)-(12), and copolymerization of another monomer as needed.

In the above, R ₁ a, R ₁₀₁ , Ra to Rl, 1, m, n, p, q, r, s, t, u, v, w, x have the same meaning as described above.

Among the above, when using the monomer which has a hydroxyl group in a molecule | numerator, the method of protecting a hydroxyl group previously and removing a protecting group after superposition | polymerization is preferable. Moreover, also when protecting with an acid-decomposable group, the method of introduce | transducing a protecting group after finishing polymer synthesis is common.

Although the specific example of such a structure is shown below, it is not limited to this.

In this invention, alkali-soluble resin can be synthesize | combined by well-known methods, such as radical polymerization, cationic polymerization, and anionic polymerization. Although it is the most simple to perform radical polymerization by combining the corresponding monomer, it can synthesize | combine more preferably when cation polymerization and anion polymerization are used with a monomer. Moreover, when a monomer produces reaction other than superposition | polymerization by superposition | polymerization start type, a desired polymer can be obtained by superposing | polymerizing the monomer which introduce | transduced the suitable protecting group, and deprotecting after superposition | polymerization. Moreover, about the polymer which has alkoxy, a desired polymer can be obtained even if etherification reaction of the hydroxyl group of the polymer which has a corresponding hydroxyl group is carried out. The polymerization method is described in Experimental Chemistry Lecture 28 Polymer Synthesis, New Experimental Chemistry Lecture 19 Polymer Chemistry [I] and the like.

In addition, the molecular weight of alkali-soluble resin (1) and (2) of this invention exceeds 3,000 and is 300,000 or less. It is preferable that the weight average molecular weight exceeds 3,000 and is 100,000 or less. More preferably, the weight average molecular weight exceeds 3,000 and is 50,000 or less.

It is preferable that the molecular weight distribution (Mw / Mn) of alkali-soluble resin which can be synthesize | combined by the said synthesis method is 1.0-1.5, and it can especially make a resist highly sensitive. In addition, alkali-soluble resin of such molecular weight distribution can be synthesize | combined using living anion polymerization by the said synthesis method.

(3) Other alkali-soluble resin which can be used by this invention other than said (1) and (2).

As other alkali-soluble resin which can be used by this invention, a novolak resin, hydrogenated novolak resin, acetone- pyrogallol resin, o-polyhydroxy styrene, p-polyhydroxy styrene, hydrogenated polyhydroxy styrene, for example Some O-alkylates for the hydroxy groups of halogen or alkyl-substituted polyhydroxystyrenes, hydroxystyrene-N-substituted maleimide copolymers, o / p-hydroxystyrene copolymers, polyhydroxystyrenes (e.g., 5-30 mol% O-methylate, O- (1-methoxy) ethylate, O- (1-ethoxy) ethylate, O-2-tetrahydropyranylate, O- (t-butoxy Carbonyl) methylate, etc.) or O-acylates (e.g., 5-30 mole% o-acetylate, (O- (t-butoxy) carbonylate, etc.), styrene-maleic anhydride copolymer, Styrene-hydroxy styrene copolymer, (alpha) -methylstyrene-hydroxy styrene copolymer, carboxyl group-containing methacryl-type resin and its There can be a derivative, it is not limited in this respect.

Particularly preferred other alkali-soluble resins are novolak resins and o-polyhydroxystyrenes, p-polyhydroxystyrenes and copolymers thereof, alkyl substituted polyhydroxystyrenes, some O-alkylated or O- of polyhydroxystyrenes. Acylates, styrene-hydroxystyrene copolymers, and α-methylstyrene-hydroxystyrene copolymers. The novolak resin can be obtained by addition condensation with aldehydes in the presence of an acidic catalyst with the following predetermined monomer as a main component.

Predetermined monomers include cresols such as phenol, m-cresol, p-cresol and o-cresol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2, Alkyl phenols such as xylenols such as 3-xylenol, m-ethylphenol, p-ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol and 2,3,5-trimethylphenol, p -Methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-prop Alkoxyphenols such as foxyphenol, m-butoxyphenol and p-butoxyphenol, bisalkylphenols such as 2-methyl-4-isopropylphenol, m-chlorophenol, p-chlorophenol, o-chlorophenol, di Although hydroxy aromatic compounds, such as hydroxy biphenyl, bisphenol A, phenyl phenol, resorcinol, naphthol, can be used individually or in mixture of 2 or more types, it is not limited to these.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, and the like. p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-hydroxybenzaldehyde , p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde and acetals thereof, such as chloroacetaldehyde diethylacetal, can be used, but among these, it is preferable to use formaldehyde. Do.

These aldehydes are used individually or in combination of 2 or more types. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

The weight average molecular weight of the novolak resin thus obtained is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film | membrane reduction after image development of an exposure part will become large, and if it exceeds 30,000, the developing speed will become small easily. Especially preferable is the range of 2,000-20,000.

Moreover, the weight average molecular weights of said polyhydroxy styrene, its derivatives, and copolymers other than a novolak resin are 2,000 or more, Preferably it is 2000-30000, More preferably, it is 2000-20000.

Here, a weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography.

It is preferable that the weight average molecular weight of alkali-soluble resin obtained in this way is 1,000 to 30,000. If it is less than 1,000, the film | membrane reduction after image development of an exposure part will become large, and if it exceeds 30,000, the developing speed will become small easily. More suitable are 2,000-200,000.

The weight average molecular weight of especially preferable alkali-soluble resin is the range of 2,000-9,000 in the point which a sensitivity becomes especially excellent, More preferably, it is the range of 2,500-9,000, More preferably, it is 3,000-9,000.

The molecular weight distribution (Mw / Mn) of the alkali-soluble resin is preferably 1.0-1.5 (monodisperse polymer) because the developing residue becomes smaller. In particular, since the sensitivity becomes especially excellent, the molecular weight distribution (Mw / Mn) of alkali-soluble resin is 1.0-1.4, More preferably, it is 1.0-1.3, More preferably, it is 1.0-1.2.

Here, a weight average molecular weight is defined with the polystyrene conversion value of gel permeation chromatography.

The usage-amount of all alkali-soluble resin is 30 to 90 weight% normally, Preferably it is 50 to 80 weight% based on the total weight (excluding a solvent) of a resist composition.

[VIII] (i) Crosslinking Agent Crosslinked With Acid

In the negative resist composition of the present invention, a compound crosslinked by an acid (hereinafter, appropriately referred to as an acid crosslinking agent or simply a crosslinking agent) is used together with the alkali-soluble resin and the acid generator.

(3) -1 A crosslinking agent can use a phenol derivative.

Preferably, the molecular weight is 1,200 or less, contains 3 to 5 benzene rings in the molecule, and retains two or more hydroxymethyl groups or alkoxymethyl groups in combination, and at least one benzene ring of the hydroxymethyl group and the alkoxymethyl group. And phenol derivatives formed by concentrating on or dividing and binding. By using such a phenol derivative, the effect of this invention can be made more remarkable.

As an alkoxy methyl group couple | bonded with the benzene ring, it is preferable that it is C6 or less. Specifically, methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethyl group, i-butoxymethyl group, sec-butoxymethyl group, t-butoxymethyl group are preferable. . And like a 2-methoxyethoxy and 2-methoxy-1-propyl group, the alkoxy substituted alkoxy group is preferable.

Among these phenol derivatives, particularly preferred ones are listed below.

(Wherein L ¹ to L ⁸ may be the same or different and represent a hydroxymethyl group, methoxymethyl group or ethoxymethyl group.)

The phenol derivative having a hydroxymethyl group can be obtained by reacting a phenol compound (a compound in which L ¹ to L ⁸ is a hydrogen atom in the above formula) and formaldehyde under a base catalyst, without having a corresponding hydroxymethyl group. At this time, in order to prevent resination or gelation, it is preferable to perform reaction temperature at 60 degrees C or less. Specifically, it can synthesize | combine by the method described in Unexamined-Japanese-Patent No. 6-282067, Unexamined-Japanese-Patent No. 7-64285, etc.

A phenol derivative having an alkoxymethyl group can be obtained by reacting a phenol derivative having a corresponding hydroxymethyl group with an alcohol under an acid catalyst. At this time, in order to prevent resination or gelation, it is preferable to perform reaction temperature at 100 degrees C or less. Specifically, it can synthesize | combine by the method described in European patent EP632003A1 etc.

The phenol derivative having a hydroxymethyl group or an alkoxymethyl group thus synthesized is preferable in view of stability during storage, while the phenol derivative having an alkoxymethyl group is particularly preferred in view of stability during storage.

These phenol derivatives having two or more in combination with a hydroxymethyl group or an alkoxymethyl group and being concentrated or divided into any one benzene ring may be used alone or in combination of two or more thereof. good.

(3) -2 In addition to the phenol derivatives, the following compounds (i) and (ii) can be used as the crosslinking agent.

(i) a compound having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group

(ii) epoxy compounds

Such a crosslinking agent is demonstrated in detail below.

(i) Compounds having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group include European Patent Publication Nos. 0,133,216 (hereinafter referred to as "EP-A") and German Patent No. 3,634,671 , Benzoguanamine-formaldehyde condensates described in the monomers and oligomer-melamine-formaldehyde condensates and urea-formaldehyde condensates described in US Pat. No. 3,711,264, the alkoxy substituted compounds described in EP-A No. 0,212,482 and the like. .

More preferred examples include melamine-formaldehyde derivatives having, for example, two or more free N-hydroxymethyl groups, N-alkoxymethyl groups, or N-acyloxymethyl groups, among which N-alkoxymethyl derivatives are particularly preferred. Do.

(ii) The epoxy compound includes one or more epoxy groups, and includes monomers, dimers, oligomers, and polymer epoxy compounds. For example, the reaction product of bisphenol A and epicrohydrin, the reaction product of low molecular weight phenol-formaldehyde resin and epicrohydrin, etc. are mentioned. In addition, the epoxy resin described and used by US Patent No. 4,026,705 and British Patent 1,539,192 is mentioned.

In this invention, the said phenol derivative is preferable.

In addition to the said phenol derivative, the other crosslinking agents (i) and (ii) mentioned above can be used together, for example.

The ratio of the crosslinking agent which can be used in addition to the said phenol derivative is 100 / 0-20 / 80 by molar ratio, Preferably it is 90 / 10-40 / 60, More preferably, it is 80 / 20-50 / 50.

The crosslinking agent is used in the range of 3 to 70% by weight, preferably 5 to 50% by weight in the total resist composition solids. If the addition amount of the crosslinking agent is less than 3% by weight, the residual film ratio is lowered. If the amount of the crosslinking agent is more than 70% by weight, the resolution decreases, and it is not very preferable in terms of stability during storage of the resist liquid.

[IX] (f) Organic Basic Compounds

Preferable organic basic compounds which can be used in the present invention are compounds which are more basic than phenol. Of these, nitrogen-containing basic compounds are preferred.

Among these, a nitrogen-containing basic compound containing a structure represented by the following (A) to (E) is preferable.

Where R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and include a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an aminoalkyl group of 1 to 6 carbon atoms, a hydroxyalkyl group of 1 to 6 carbon atoms, or a substituted or unsubstituted aryl of 6 to 20 carbon atoms. Group, where R ²⁵¹ and R ²⁵² may combine with 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.

Particularly preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, particularly preferably compounds containing both substituted and unsubstituted amino groups and ring structures containing nitrogen-containing atoms, or It is a compound which has an alkylamino group.

Preferred detailed examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted imidazole, substituted or substituted Unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted pipepe Razin, substituted or unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, and the like. Preferable 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, hydroxy group and cyano group.

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, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperi Dine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) -pyrrolidine, pyra Sol, 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, diazabicyclononene, diazabicyclo undecene, etc. are mentioned, It is not limited to these.

Such an (f) organic basic compound may be used alone or in combination of two or more. (F) The amount of the organic basic compound used in the positive resist composition may generate an acid by (a1) electron beam or X-ray irradiation of the present invention. It is generally 0.01-10 mol%, preferably 0.1-5 mol% with respect to the compound to generate | occur | produce an acid by irradiation of the compound or (a1 ') electron beam.

If it is less than 0.01 mol%, the addition effect thereof is not obtained. On the other hand, when 10 mol% is exceeded, there exists a tendency for the fall of a sensitivity and the developability of a non-irradiation part to deteriorate.

In addition, (f) the amount of the organic basic compound used in the negative composition can be expressed by the ratio of the acid generator and the organic basic compound in the negative resist composition. The ratio of the acid generator and the organic basic compound in the composition is It is preferable that it 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 it exceeds 300, the size of the resist pattern may become very large over time until the post-exposure heat treatment, and the resolution may also decrease.

(Acid generator) / (organic basic compound) (molar ratio) becomes like this. Preferably it is 5.0-200, More preferably, it is 7.0-150. The addition of such a nitrogen-containing basic compound has the effect of improving the time-lapse stability (PCD stability and PED stability) in the state of leaving the resist film.

Here, PCE (Post Coating Delay) stability is the film stability when the resist composition is applied to the substrate and then left in the irradiation apparatus or outside the apparatus, and PED (Post Exposure Delay) stability is the heating operation after irradiation. Film stability in the case of being left in the irradiation apparatus or the apparatus in the meantime until

[X] (g) Fluorine and / or Silicone Surfactants

As the surfactant usable in the resist composition of the present invention, fluorine-based and / or silicon-based surfactants are suitably used, and any one or two of fluorine-based surfactants, silicone-based surfactants and surfactants containing both fluorine and silicon atoms can be used. It may contain more than one species.

As such surfactant, for example, Patent Publication Nos. 62-36663, 61-226746, 61-226745, 62-170950, 63-34540, Patent Publication No. 7-230165, 8 Interfaces described in -62834, 9-54432, 9-5988, U.S. Patent 5405720, 5360692, 5529881, 5296330, 5436098, 5576143, 5294511, 5824451 Although an active agent is mentioned, the following commercially available surfactant can also be used as it is.

Commercially available surfactants that can be used are, for example, Eftop EF301 and EF303 (manufactured by Shin Akita Kasei Co., Ltd.), Florad FC430 and 431 (manufactured by Sumitomo 3M Corporation), Megafac F171, F173, F176, F189 and R08. (Dainippon Ink Co., Ltd.), Surflon S-382, SC101, 102, 103, 104, 105, and 106 (Asahi Glass Co., Ltd.), Troisol S-366 (Troy Chemical Co., Ltd.), etc. Fluorine-based surfactants or silicone-based surfactants. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) may also be used as the silicone surfactant. In the present invention, (g) fluorine-based and / or silicone-based surfactants can be used.

Surfactants other than a fluorine type and / or silicone type surfactant can be used together. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl Polyoxyethylene alkylallyl ethers such as phenol ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan tri Sorbitan fatty acid esters such as oleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan triol Latex, polyoxyethylene sorbitan tristeare Nonionic surfactants, such as polyoxyethylene sorbitan fatty acid esters, such as a nitrate, acrylic acid type, or methacrylic acid type (co) polymerization polyflow No. 75, no. 95 (manufactured by Kyoei Oil Industries, Ltd.).

The compounding quantity of such (g) surfactant is 2 weight% or less normally with respect to solid content of the whole composition in the composition of this invention, Preferably it is 1 weight% or less.

These surfactants may be added alone, or may be added in combination of 2% by weight or more. By adding such a surfactant, the in-plane uniformity of the resist film is increased, and the resolution is improved.

[XI] other ingredients used in the present invention

If necessary, the resist composition of the present invention may contain a dye, a pigment, a plasticizer, a photosensitizer, and a compound having two or more phenolic OH groups for promoting solubility in a developer.

[XI] -1 dye

Suitable dyes are oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (above, Orient Close Up) High school, KK), crystal violet (CI42555), methyl violet (CI42535), rotamine B (CI45170B), malachite green (CI42000), methylene blue (CI52015), etc. are mentioned.

[XI] -2 compounds having two or more phenolic OH groups                     

The compound having two or more phenolic OH groups usable in the present invention is preferably a phenol compound having a molecular weight of 1,000 or less. In addition, although it is necessary to have two or more phenolic hydroxy groups in the molecule, if it exceeds 10, the effect of improving development latitude is lost. Moreover, when the ratio of a phenolic hydroxyl group and an aromatic ring is less than 0.5, there exists a tendency for dependence on film thickness to become large, or developing latitude narrows. When this ratio exceeds 1.4, the stability of the composition is deteriorated, and it becomes difficult to obtain high resolution and good film thickness dependency, which is not preferable.

The preferable addition amount of this phenolic compound is 2-50 weight% with respect to alkali-soluble resin, More preferably, it is 5-30 weight%. At an added amount exceeding 50% by weight, developing defects deteriorate, or new defects such as deformation of the pattern at the time of development occur, which is also undesirable.

Such phenolic compounds having a molecular weight of 1000 or less, for example, with reference to the methods described in Japanese Patent Application Laid-Open No. 4-122938, Japanese Patent Application Laid-Open No. 2-28531, US Patent No. 4916210, European Patent No. 219294, etc. It can be easily synthesized by those skilled in the art.

Although the specific example of a phenol compound is shown below, the compound which can be used for this invention is not limited to these.

Resorcin, fluoroglucin, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,3 ', 4', 5'- Hexahydroxybenzophenone, acetone-pyrogallol condensation resin, fluorogluside, 2,4,2 ', 4'-biphenylterol, 4,4'-thiobis (1,3-dihydroxy) benzene , 2,2, ', 4,4'-tetrahydroxydiphenylether, 2,2', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2 ', 4,4'-tetrahydroxy Sidiphenylsulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4- (α-methylbenzylidene) bisphenol, α, α ', α "- Tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α ', α "-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 1,2 , 2-tris (hydroxyphenyl) propane, 1,1,2-tris (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) Hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) butane, La [α, α, α ', α'- tetrakis (4-hydroxyphenyl) - there is a xylene and the like.

The resist composition of this invention is melt | dissolved in the solvent which melt | dissolves each said component, and apply | coats on a support body. Here, as a solvent used, 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 monomethyl ether acetate, propylene glycol monomethyl ether propionate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, Ethoxy propionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents may be used alone or in combination. have.

In the present invention, as the coating solvent, propylene glycol monomethyl ether acetate is particularly preferable, and the in-plane uniformity is thereby excellent.                     

As semiconductors become more advanced, high-performance compositions are required from various viewpoints such as sensitivity, coating property, minimum coating amount, adhesion to substrate, heat resistance, and storage stability of the composition, in addition to the performance of intrinsic high resolution of resists. It is becoming.

Recently, there is a tendency to manufacture devices using large diameter wafers to increase the absolute amount of finished chips.

However, since application | coating to a large diameter is concerned about the fall of applicability | paintability, especially in-plane film thickness uniformity, the improvement of the film thickness in-plane uniformity with respect to a large diameter wafer is calculated | required.

By the method which can confirm this uniformity, a film thickness is measured at many points in a wafer, the standard deviation of each measured value is calculated | required, and uniformity can be confirmed by three times its value. Smaller values mean higher in-plane uniformity. As a value, it is preferable that the value of 3 times standard deviation is 100 or less, and it is more preferable that it is 50 or more.

In addition, in the production of masks for lithography, CD linearity is most important, and it is necessary to improve the film thickness surface uniformity in the blank.

By the method which can confirm such a uniformity, a film thickness is measured at many points in a mask blank, the standard deviation of each measured value is calculated | required, and a uniformity can be confirmed by three times its value. Smaller values mean higher in-plane uniformity. The value is preferably 100 or less, more preferably 50 or less, which is three times the standard deviation.                     

The resist composition of the present invention can be filtered after dissolved in a solvent. For this reason, the filter to be used is selected from those used in the field of resist, specifically, the material of the filter containing polyethylene, nylon or polysulfone is used.

More specifically, the MicroGuard, MicroGuard Plus, MicroGuard Minicam-D, Microguard Minicam-D PR, Mirpoa Optimizer DEV / DEV-C, Mirpoa Optimizer 16/14, Polsa Products include Ultipoa N66, Pozidine, and Nylon Falcon.

In addition, the thing confirmed by the following method about the pore size of a filter can be used. In short, the PSL standard particles (polystyrene latex beads particle diameter 0.100㎛) are dispersed in ultrapure water, and the rectifier is continuously flown to the filter primary side with a tube pump, and the challenge concentration is measured by a particle calculator. It can be used as a 0.1 μm filter.

The electron beam or X-ray resist composition of the present invention is applied onto a substrate (e.g., silicon / silicon dioxide coating) used for the manufacture of precision integrated circuit elements by a suitable coating method such as a spinner, a coater, and the like through a predetermined mask. By irradiating, baking and developing, a favorable resist pattern can be formed.

The mask blank of this invention is coat | covered with the electron beam resist composition for mask manufacture. Specifically, the electron beam resist composition for mask production of the present invention is applied onto a substrate for photolithography mask production (e.g., glass / chromium oxide coating) by a suitable coating method such as a spinner, a coater, and dried and coated as necessary. .                     

Here, as dry film thickness, Preferably they are 0.1 micrometer-1.0 micrometer, More preferably, they are 0.2 micrometer-0.8 micrometer. The mask blank of this invention can be irradiated using electron beam drawing politics through a predetermined mask, baked, and developed, and a favorable resist pattern can be obtained.

As a developing solution used for the resist composition of this invention, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, 1st 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 Alkaline aqueous solutions, such as quaternary ammonium salts, such as a seed and choline, cyclic amines, such as a pyrrole and a piperidine, can be used. Moreover, alcohol, such as isopropyl alcohol, surfactant, such as nonionics, can be added and used for the said aqueous solution of alkalis.

Among these developers, preferred are quaternary ammonium salts, particularly preferred are tetramethylammonium hydroxide and choline.

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

(1) positive resist composition

Synthesis Example 1 Synthesis of Poly (p-hydroxystyrene / styrene) Copolymer]

In a general manner, 35.25 g (0.2 mol) of dehydrated and distilled and purified p-tert-butoxystyrene monomer and 5.21 g (0.05 mol) of styrene monomer were dissolved in 100 ml of tetrahydrofuran. Under a nitrogen stream and under stirring, 0.033 g of azobisisobutyronitrile (AIBN) was added three times at an interval of 2.5 hours at 80 ° C, and the polymerization was carried out by continuing stirring for another 5 hours. The reaction solution was poured into 1200 ml of hexane to precipitate white resin. The obtained resin was dried and dissolved in 150 ml of tetrahydrofuran.

To this was added 4N hydrochloric acid, heated to reflux for 6 hours to hydrolyze, re-precipitated in 5 L of ultrapure water, and the resin was filtered off, washed with water and dried. The solution was further dissolved in 200 ml of tetrahydrofuran, and dripped and reprecipitated with vigorous stirring in 5 L of ultrapure water. This reprecipitating operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / styrene) copolymer.

Synthesis Example 2: Synthesis of Resin Example (c-21)

32.4 g (0.2 mol) of p-acetoxy styrene and 7.01 g (0.07 mol) of t-butyl methacrylate were dissolved in 120 ml of butyl acetate and azobisisobutyronitrile (AIBN) at 80 ° C under nitrogen stream and stirring. 0.033 g was added three times at 2.5 hour intervals, and the polymerization reaction was carried out by continuously stirring for another 5 hours. The reaction solution was poured into 1200 ml of hexane to precipitate a white resin. The obtained resin was dried and dissolved in 200 ml of methanol.

An aqueous solution of 7.7 g (0.19 mol) of sodium hydroxide / 50 ml of water was added thereto, and the mixture was heated and refluxed for 1 hour to hydrolyze. Then, 200 ml of water was added thereto, diluted, and neutralized with hydrochloric acid to precipitate a white resin. This resin was filtered off, washed with water and dried. It was further dissolved in 200 ml of tetrahydrofuran, and dripped and reprecipitated in 5 L of ultrapure water with vigorous stirring. This reprecipitating operation was repeated three times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / t-butyl methacrylate) copolymer.

Synthesis Example 3: Synthesis of Resin Example (c-3)

10 g of poly (p-hydroxystyrene) (VP-8000 manufactured by Nippon Stet. Co., Ltd.) was dissolved in 50 ml of pyridine, and 3.63 g of di-t-butyl dicarbonate was added dropwise thereto while stirring at room temperature.

After stirring for 3 hours at room temperature, the mixture was added dropwise to a solution of 1 L of ion-exchanged water / 20 g of concentrated hydrochloric acid. The precipitated powder was filtrated and washed with water to obtain a resin example (c-3).

Synthesis Example 4 Synthesis of Resin Example (c-33)

83.1 g (0.5 mole) of p-cyclohexylphenol was dissolved in 300 ml of toluene, followed by 150 g of 2-chloroethyl vinyl ether, 25 g of sodium hydroxide, and 5 g of tetrabutylammonium bromide. 60 g of triethylamine were added and reacted at 120 degreeC for 5 hours. The reaction solution was washed with water, excess chloroethyl vinyl ether and toluene were distilled off, and the oil thus obtained was purified by distillation under reduced pressure to obtain 4-cyclohexylphenoxyethyl vinyl ether.

20 g of poly (p-hydroxystyrene) (VP-8000 manufactured by Nippon-Jochichi Co., Ltd.) and 6.5 g of 4-cyclohexylphenoxyethyl vinyl ether are dissolved in 80 ml of THF, and 0.01 g of p-toluenesulfonic acid is added thereto. It was added and reacted at room temperature for 18 hours. The reaction solution was added dropwise to 5 liters of distilled water with vigorous stirring, and the precipitated powder was filtered and dried to obtain Resin Example (c-33).

Resin examples (c-4), (c-28) and (c-30) were also synthesized in the same manner using the corresponding main polymer and vinyl ether.

Instead of poly (P-hydroxystyrene) (VP-8000 manufactured by Nippon Hitachi Co., Ltd.), the same operation is performed by using poly (P-hydroxystyrene) (VP-5000 manufactured by Nippon Hitachi Co., Ltd.). , (c-3) ', (c-33)', (c-4) ', (c-28)' and (c-30) '.

In addition, polymers (poly (P-hydroxystyrene / styrene) copolymers (2) and (c-21) ') having a molecular weight of about 6 were controlled by controlling the amount of the initiator.

(Synthesis example-1 of a dissolution inhibiting compound: synthesis of compound example 16)

42.4 g (0.10 mol) of 1- [α-methyl-α- (4'-hydroxyphenyl) ethyl] -4- [α ', α'-bis (4 "-hydroxyphenyl) ethyl] benzene It was dissolved in 300 ml of N-dimethylacetamide, and 49.5 g (0.35 mol) of potassium carbonate and 84.8 g (0.33 mol) of bromoacetic acid cumyl ester were added thereto, followed by stirring at 120 ° C. for 7 hours. The mixture was poured into 2 L of ion-exchanged water, neutralized with acetic acid, and then precipitated with ethyl acetate.The ethyl acetate extract was concentrated and purified to give Compound Example 16 (R is -CH ₂ COOC (CH ₃ ) ₂ C ₆ H _5. Group) 70 g was obtained.

(Synthesis example-2 of a dissolution inhibiting compound: synthesis of compound example 41)

44 g of 1,3,3,5-tetrakis- (4-hydroxyphenyl) pentane are dissolved in 250 ml of N, N-dimethylacetamide, which is 70.7 g of potassium carbonate, followed by 90.3 g of t-butyl bromoacetate. Was added and stirred at 120 ° C. for 7 hours. The reaction mixture was poured into 2 L of ion-exchanged water, and the obtained viscous product was washed with water. This was purified by column chromatography to obtain 87 g of Compound Example 41 (R is -CH ₂ COOC ₄ H ₉ (t)).

(Synthesis example-3 of a dissolution inhibiting compound: synthesis | combination of compound example 43)

20 g of α, α, α ', α', α ", α" -hexakis (4-hydroxyphenyl) -1,3,5-triethylbenzene was dissolved in 400 ml of diethyl ether. 42.4 g of 3,4-dihydro-2H-pyrans and a catalytic amount of hydrochloric acid were added to this solution under nitrogen stream, and the mixture was refluxed for 24 hours. After the reaction was completed, a small amount of sodium hydroxide was added, followed by filtration. The filtrate was concentrated and purified by column chromatography to obtain 55.3 g of Compound 43 (all of which are THP).

(Synthesis example 4 of a dissolution inhibiting compound: synthesis of compound example 43-2)

20 g of α, α, α ', α', α ", α" -hexakis (4-hydroxyphenyl) -1,3,5-triethylbenzene were dissolved in 200 ml of N, N-dimethylacetamide, 28.2 g of potassium carbonate and then 36.0 g of butyl bromoacetate were added thereto, and the mixture was stirred at 120 ° C for 7 hours. The reaction product was poured into 2 L of ion-exchanged water, and the obtained viscous product was washed with water. This was purified by column chromatography to obtain 37 g of Compound 43-2 (R is -CH ₂ COOC ₄ H ₉ (t))).

[Synthesis example of compound represented by general formula (A)]

Synthesis Example-1 Synthesis of A-22 (benzoyloxyethyl vinyl ether)

244 g (2 mol) of benzoic acid are dissolved in 3000 ml of toluene, and then 320 g of 2-chloroethyl vinyl ether are added, followed by the addition of 88 g of sodium hydroxide, 25 g of tetrabutylammonium bromide and 100 g of traethylamine. It stirred for heating by time.

The reaction solution was washed with water and distilled under reduced pressure to remove excess 2-chloroethyl vinyl ether and toluene. From the obtained oil powder, 300 g of benzoyloxyethyl vinyl ether which was a target object were obtained from distillation under reduced pressure.

Synthesis Example-2-8 Synthesis of A-23-A-29                     

In the same manner as in the synthesis of A-22, A-23 to A-29 were synthesized.

Example (1) -1 [Example, Comparative Example]

(1) Resist drawing

The components shown in Table 1 were dissolved in 8.2 g of propylene glycol monomethyl ether acetate, and this was filtered through a 0.1 µm Teflon filter to prepare a resist solution. In the composition of Example 21, 8.2 g of ethyl lactate was used as the solvent.

Each sample solution was applied onto a silicon wafer using a spin coater, dried at 120 ° C. for 90 seconds in a vacuum suction hot plate to obtain a resist film having a thickness of 0.5 μm.

(2) Preparation of resist pattern

This resist film was irradiated using an electron beam drawing apparatus (pressurized voltage 50 KV).

After irradiation, each was heated with a vacuum adsorption hot plate (60 seconds at 110 ° C.), immersed in a 2.38% aqueous tetramethylammonium hydroxide (TMAH) solution for 60 seconds, washed with water for 30 seconds, and dried. The cross-sectional shape of the obtained contact hole pattern and the line and space pattern was observed with a scanning electron microscope.

(3) evaluation of sensitivity and resolution

The limit resolution (minimum diameter of the hole) in the contact hole pattern was defined as the resolution, and the minimum dose that could resolve the limit resolution was defined as the sensitivity.

In addition, the dose of resolving 0.2 μm in the design dimension at 1: 1 in the line and space patterns was regarded as the sensitivity, and the minimum resolvable size at the dose was set as the resolution.

(4) Evaluation of the PCD                     

The resist film obtained by the method of (1) was left to stand for 120 minutes under high vacuum in the electron beam drawing apparatus, and then the resist pattern was formed by the method of (2).

The minimum contact hole size (diameter) or the line and space which can be resolved at the same dose as the sensitivity obtained in the method of (3) (in this case, the irradiation is performed immediately without forming the resist film under high vacuum for 120 minutes). Obtained. The PCD stability is better as this magnitude and the marginal resolution obtained in (3) show a proximity value.

(5) Evaluation of PED

When forming a resist pattern, it carried out by the method similar to (2) except adding the process of leaving to stand for 120 minutes under high vacuum in an electron beam drawing apparatus after irradiation. Find the minimum contact hole size (diameter) or line and space that can be resolved at the same dose as the sensitivity obtained by the method in (3) (in this case, no heating for 120 minutes under high vacuum after irradiation, but heating immediately). It was. As the magnitude and the marginal resolution obtained in (3) show a proximal value, the PED stability is better.                     

Acid generator PAG-1 is as follows.

The composition and physical properties of the binder resin used are as follows.

(c-3): p-hydroxy styrene / p-t-butoxycarboxy styrene copolymer (molar ratio: 80/20), weight average molecular weight (Mw) 13000, molecular weight distribution (Mw / Mn) 1.4

(c-3) ': Mw 8000

(c-4): p-hydroxy styrene / p- (1-ethoxyethoxy) styrene copolymer (molar ratio: 70/30), weight average molecular weight (Mw) 12000, molecular weight distribution (Mw / Mn) 1.3

(c-4) ': Mw 7000

(c-21): p-hydroxy styrene / t-butyl methacrylate copolymer (molar ratio: 70/30), Mw 16000, molecular weight distribution (Mw / Mn) 2.0

(c-21) ': Mw 9500

(c-22): p-hydroxystyrene / p- (1-t-butoxyethoxy) styrene copolymer (molar ratio: 85/15), Mw 12000, molecular weight distribution (Mw / Mn) 1.1

(C-22) ': Mw 7000

(c-28): p-hydroxystyrene / p- (1-phenethyloxyethoxy) styrene copolymer (molar ratio: 85/15), Mw 12000, molecular weight distribution (Mw / Mn) 1.2

(c-28) ': Mw 7000

(c-30) ': p-hydroxy styrene / p- (1-phenoxy ethoxy ethoxy) styrene copolymer (molar ratio: 85/15), Mw 13000, molecular weight distribution (Mw / Mn) 1.2

(c-30) ': Mw 8000

(c-33): p-hydroxystyrene / p- (1-p-cyclohexylphenoxyethoxy) styrene copolymer (molar ratio: 85/15), Mw 13000, molecular weight distribution (Mw / Mn) 1.2

(c-33) ': Mw 8000

(PHS-1): poly (P-hydroxy styrene) (Nippon-Joitachi Co., Ltd., brand name VP-8000)

(PHS-2): poly (P-hydroxy styrene) (Nippon-Joitachi, brand name VP-5000)

(PHS-3): Poly (P-hydroxy styrene) (Toho Chemical Co., Ltd., brand name H-80A)

(PHS-4): Poly (P-hydroxystyrene) (Toho Corporation make, brand name H-60A)

(PHS / St: synthesized in Synthesis Example 1): p-hydroxystyrene / styrene (molar ratio: 80/20), Mw 26000, molecular weight distribution (Mw / Mn) 1.9

(PHS / St2): Mw 15600

About an organic basic compound, it is as follows.

B-1: 2,4,5-triphenylimidazole                     

B-2: 1,5-diazabicyclo [4.3.0] nona-5-ene

B-3: 4-dimethylaminopyridine

B-4: 1,8-diazabicyclo [5.4.0] undec-7-ene

B-5: N-cyclohexyl-N'-morpholinoethylthiourea

About surfactant, it is as follows.

W-1: Troisol S-366 (Troy Chemical Co., Ltd.)

W-2: Megafac F176 (product of Dainippon Ink Industries, Ltd.)

W-3: Megafac R08 (product of Dainippon Ink Corporation)

W-4: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

W-5: Surflon S-382 (Asahi Glass Co., Ltd.)

From the results in Tables 5 to 8, it can be seen that the positive resist composition of the present invention not only provides a highly sensitive, high resolution, rectangular profile, but also has excellent PCD and PED stability.

This effect is obtained by adding (c) cation polymerizable or (c ') vinyl compound, cycloalkane compound, cyclic ether compound, lactone compound, aldehyde compound and organic basic compound. Moreover, further excellent performance is shown by using the compound represented by general formula (I)-(III) and the compound represented by general formula (A-1) as an acid generator.

In Examples 1, 8, 9, 18, 19, 20, 31, 38, 39, 48, 49 and 50, in the organic basic compound B-1, respectively, B-2, B-3, B-4, B- When changed to 5, the same performance was obtained.

Further, in Examples 1, 8, 9, 18, 19, 20, 31, 38, 39, 48, 49 and 50, W-2, W-3, W-4 and W- in the surfactant W-1, respectively When changed to 5, the same performance was obtained.

In Examples 1, 8, 10, 12, 17, 18, 19, and 20, the same performance was obtained by changing PHS-2 to PHS-4, and the same performance was obtained.

In Examples 31, 38, 40, 42, 47, 48, 49, 50, 51, 58, 60, 62, 67, 68, 69, and 70, PHS-1 was changed to PHS-3. In addition, the same performance was obtained.

In Examples 1, 8, 9, 18, 19, 20, 31, 38, 39, 48, 49, and 50, the solvent was propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 80/20 (weight ratio). The same effect was obtained when it changed to and performed similarly.

In addition, the components shown in Table 1 were dissolved in the solvent, and the composition liquids of Examples 1 to 21 were filtered through a polyethylene filter of 0.1 mu m to prepare a resist solution. About each such resist solution, in-plane uniformity was evaluated as follows.                     

(In-plane uniformity)

Each resist liquid was applied onto an 8-inch silicon wafer, the above-described resist layer was applied, and the same treatment was performed to obtain a resist coating film for in-plane uniformity measurement. This was measured at 36 points evenly so that the coating film thickness was equally cross | crossed along the wafer diameter direction in LambdaA by Dainippon Screen Co., Ltd. product. The standard deviation of each measured value was calculated | required, and the thing which was 50 or more and evaluated that X of 50 times that 3 times of it did not satisfy 50 was evaluated. As a result, those using propylene glycol monomethyl ether acetate (PGMEA) as the resist coating solvent (Examples 1 to 20) had in-plane uniformity. In contrast, the use of ethyl lactate (EL) as the resist coating solvent (Example 21) had an in-plane uniformity x. Therefore, in the present invention, it can be seen that it is preferable to use PAGMEA as the resist coating solvent.

(6) Patterning by equal magnification X-ray irradiation

Using the two resist compositions of the said Example 20 and the comparative example 1, the resist film of 0.40 micrometer in film thickness was obtained by the method similar to said (1). Subsequently, except for using an equal magnification X-ray irradiation apparatus (gap value; 20 nm), it patterned similarly to said (2), and evaluated resist performance (sensitivity, resolution, and pattern shape) by the method similar to said (3). The evaluation results are shown in Table 9.

 Resist composition  Sensitivity (mJ / ㎠)  Resolution (μm)  Pattern shape  Example 20    75   0.10 Rectangle  Comparative Example 1    185   0.18  Taper shape, film peeling  Comparative Example 2    240   0.17  Taper shape

From the above Table 9, it can be clearly seen that the resist composition of the present invention shows very excellent performance even in X-ray irradiation.

Example (1) -2 [Example, Comparative Example]

(1) Resist drawing

The components shown in the following Tables 10-13 were dissolved in 8.2 g of propylene glycol monomethyl ether acetate, and this was filtered through a 0.1 micrometer Teflon filter to prepare a resist solution. In the composition of Example 121, 8.2 g of ethyl lactate was used as the solvent.

Each sample solution was coated on a glass substrate (6025 substrate) coated with chromium oxide using a spin coater, dried at 100 ° C. for 10 minutes in a vacuum suction hot plate to obtain a resist film having a thickness of 0.5 μm.

(2) Preparation of resist pattern

This resist film was irradiated using an electron beam drawing apparatus (pressurized voltage 50 KV).

After irradiation, each was heated with a vacuum suction hot plate (600 seconds at 100 ° C.), immersed in a 2.38% aqueous tetramethylammonium hydroxide (TMAH) solution for 60 seconds, washed with water for 30 seconds, and dried.

The cross-sectional shape of the obtained contact hole pattern and the line and space pattern was observed with a scanning electron microscope.

(3) evaluation of sensitivity and resolution

The limit resolution (minimum diameter of the hole) in the contact hole pattern was defined as the resolution, and the minimum dose that could resolve the limit resolution was defined as the sensitivity.                     

In addition, the dose of resolving 0.2 μm in a design dimension of 1: 1 in line and space patterns was regarded as sensitivity, and the minimum resolvable size in the dose was set to resolution.

(4) Evaluation of the PCD

The resist film obtained by the method of (1) was left to stand for 120 minutes under high vacuum in the electron beam drawing apparatus, and then the resist pattern was formed by the method of (2).

The minimum contact hole size (diameter) or line and space that can be resolved at the same irradiation dose as the sensitivity obtained in the method of (3) (in this case, not immediately left for 120 minutes under high vacuum after formation of the resist film) was obtained. The PCD stability is better as this magnitude and the marginal resolution obtained in (3) show a proximity value.

(5) Evaluation of PED

When forming a resist pattern, it carried out by the method similar to (2) except adding the process of leaving to stand for 120 minutes under high vacuum in an electron beam drawing apparatus after irradiation. The minimum contact hole size (diameter) or the line and space that can be resolved at the same dose as the sensitivity obtained in the method (3) (in this case, there is no process left for 120 minutes under high vacuum after irradiation, but is heated immediately) was obtained. . As the magnitude and the marginal resolution obtained in (3) show a proximal value, the PED stability is better.                     

Acid generator PAG-1 is as follows.

The composition and physical properties of the binder resin used are as follows.

(c-3): p-hydroxy styrene / p-t-butoxycarboxy styrene copolymer (molar ratio: 80/20), weight average molecular weight (Mw) 13000, molecular weight distribution (Mw / Mn) 1.4

(c-3) ': Mw 8000

(c-4): p-hydroxy styrene / p- (1-ethoxyethoxy) styrene copolymer (molar ratio: 70/30), weight average molecular weight (Mw) 12000, molecular weight distribution (Mw / Mn) 1.3

(c-4) ': Mw 7000

(c-21): p-hydroxy styrene / t-butyl methacrylate copolymer (molar ratio: 70/30), Mw 16000, molecular weight distribution (Mw / Mn) 2.0

(c-21) ': Mw 9500

(c-22): p-hydroxystyrene / p- (1-t-butoxyethoxy) styrene copolymer (molar ratio: 85/15), Mw 12000, molecular weight distribution (Mw / Mn) 1.1

(C-22) ': Mw 7000

(c-28): p-hydroxystyrene / p- (1-phenethyloxyethoxy) styrene copolymer (molar ratio: 85/15), Mw 12000, molecular weight distribution (Mw / Mn) 1.2

(c-28) ': Mw 7000

(c-30): p-hydroxystyrene / p- (1-phenoxy ethoxy ethoxy) styrene copolymer (molar ratio: 85/15), Mw 13000, molecular weight distribution (Mw / Mn) 1.2

(c-30) ': Mw 8000

(c-33): p-hydroxystyrene / p- (1-p-cyclohexylphenoxyethoxy) styrene copolymer (molar ratio: 85/15), Mw 13000, molecular weight distribution (Mw / Mn) 1.2

(c-33) ': Mw 8000

(PHS-1): poly (P-hydroxy styrene) (Nippon-Joitachi Co., Ltd., brand name VP-8000)

(PHS-2): poly (P-hydroxy styrene) (Nippon-Joitachi, brand name VP-5000)

(PHS-3): Poly (P-hydroxy styrene) (Toho Chemical Co., Ltd., brand name H-80A)

(PHS-4): Poly (P-hydroxy styrene) (Toho Chemical Co., Ltd., brand name H-60A)

(PHS / St: synthesized in Synthesis Example 1): p-hydroxystyrene / styrene (molar ratio: 80/20), Mw 26000, molecular weight distribution (Mw / Mn) 1.9

(PHS / St2): Mw 15600

About an organic basic compound, it is as follows.                     

B-1: 2,4,5-triphenylimidazole

B-2: 1,5-diazabicyclo [4.3.0] nona-5-ene

B-3: 4-dimethylaminopyridine

B-4: 1,8-diazabicyclo [5.4.0] undec-7-ene

B-5: N-cyclohexyl-N'-morpholinoethylthiourea

About surfactant, it is as follows.

W-1: Troisol S-366 (Troy Chemical Co., Ltd.)

W-2: Megafac F176 (product of Dainippon Ink Industries, Ltd.)

W-3: Megafac R08 (product of Dainippon Ink Corporation)

W-4: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

W-5: Surflon S-382 (Asahi Glass Co., Ltd.)

From the results of Tables 14-17, it can be seen that the positive electron beam resist composition for mask production of the present invention not only provides a pattern profile with high sensitivity and high resolution, but also has excellent PCD and PED stability.

This effect is obtained by adding (c) a cationically polymerizable compound or (c ') vinyl compound, a cycloalkane compound, a cyclic ether compound, a lactone compound, an aldehyde compound and an organic basic compound. Moreover, further excellent performance is shown by using the compound represented by general formula (I)-(III) and the compound represented by general formula (A-1) as an acid generator.

In Examples 101, 108, 109, 118, 119, 120, 131, 138, 139, 148, 149 and 150, the organic basic compound is selected from B-1, B-2, B-3, B-4 and B, respectively. When changed to -5, the same performance was obtained.

Further, in Examples 101, 108, 109, 118, 119, 120, 131, 138, 139, 148, 149 and 150, the surfactants in W-1 were W-2, W-3, W-4 and W, respectively. When changed to -5, the same performance was obtained.

In Examples 101, 108, 110, 112, 117, 118, 119 and 120, the same performance was obtained by changing PHS-2 to PHS-4, and the same performance was obtained.

In addition, in Examples 131, 138, 140, 147, 148, 149, 150, 151, 158, 160, 162, 167, 168, 169, and 170, PHS-1 was changed to PHS-3, The same performance was obtained.

Further, in Examples 101, 108, 109, 118, 119, 120, 131, 138, 139, 148, 149 and 150, the solvent was propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 80/20 (weight ratio). The same effect was obtained when it changed to and performed similarly.

In addition, the components shown in Table 10 were dissolved in the solvent, and the composition liquids of Examples 101 to 121 were filtered through a 0.1 µm polyethylene filter to prepare a resist solution. About each such resist solution, in-plane uniformity was evaluated as follows.

(In-plane uniformity)

Each resist solution was applied onto a glass substrate (6025 substrate) coated with chromium oxide, and the above-described resist layer was coated and subjected to the same treatment to obtain a resist coating film for in-plane uniformity measurement. This was measured at 36 points evenly so that the coating film thickness was equally cross | crossed along the wafer diameter direction in LambdaA by Dainippon Screen Co., Ltd. product. The standard deviation of each measured value was calculated | required, and it evaluated that the thing which is three times that 50 does not satisfy 50 and which is 50 or more. As a result, those using propylene glycol monomethyl ether acetate (PGMEA) as the resist coating solvent (Examples 101 to 120) had in-plane uniformity. In contrast, the use of ethyl lactate (EL) as the resist coating solvent (Example 121) had an in-plane uniformity x.

Therefore, in the present invention, it can be seen that it is preferable to use PAGMEA as the resist coating solvent.

(2) negative resist composition

[Synthesis example of component material]

(1-1) alkali-soluble resin

1) 17.6 g of 3-t-butoxystyrene was added to 27 g of dry THF, and then heated to 70 ° C. under a stream of nitrogen. When the reaction temperature was stabilized, azo radical initiator V-601 manufactured by Wako Pure Chemical Industries, Ltd. was added in 2 mol% of the monomer to initiate the reaction. After reacting for 3 hours, 2 mol% of V-601 was added again, and further reacted for 3 hours. The reaction mixture was diluted with THF and poured into a large amount of methanol to precipitate. The obtained polymer was decomposed under an acid solution of hydrochloric acid by a general method, precipitated in hexane, and reprecipitation purification was repeated twice, followed by drying under reduced pressure to obtain (P-1). The molecular weight (Mw: polystyrene conversion) and molecular weight dispersion degree (Mw / Mn) were calculated | required by THF solvent GPC measurement.

2) Except having changed the monomer, it carried out almost similarly and obtained (P-2)-(P-4).

3) Living anion was polymerized with s-butyllithium as an initiator in 17.6 g of 3-t-butoxystyrene in degassed dry THF at -78 ° C. After 3 hours of reaction, the reaction was terminated in degassed methanol. Then, the mixture was thrown into a large amount of methanol, and the precipitated powder was collected by filtration, and reprecipitation purification was repeated twice, followed by drying under reduced pressure to obtain a resin. Under normal hydrochloric acid, t-butoxy group was decomposed to give (P-1 ′).

4) 16.4 g (0.1 mol) of 3,4-dimethoxystyrene and 158.7 g (0.9 mol) of 4-t-butoxystyrene were dissolved in dry THF, heated to 70 DEG C under nitrogen stream, and Wako Pure Chemical Industries, Ltd. Kazo's azo radical initiator V-601 was added at 2 mol% of the total moles of the monomers. After reacting for 8 hours, the reaction solution was diluted with THF, precipitated in hexane, and purified to recover the polymer. (P-5) was obtained by decomposition with acid in the usual manner. It measured by GPC method, and determined the weight average molecular weight (Mw) and molecular weight dispersion degree (Mw / Mn).

Synthesis of (P-5 ') to (P-42) using the same method as described above and cationic polymerization by BF ₃ EtO ₂ using a protected monomer such as 4-benzyloxystyrene It was.

1.64 g (0.01 mol) of 3,4-dimethoxystyrene and 15.9 g (0.09 mol) of 4-t-butoxystyrene were dissolved in dry THF, and 1 mmol of s-butyllithium at -78 ° C was sealed while the tube was sealed. Used to initiate the reaction by removing the free seal. The powder precipitated in a large amount of hexane was recovered and purified. Treatment with acid using the correct method yielded (P-5 "').

(2) acid generators

1) Synthesis of pentafluorobenzenesulfonic acid tetramethylammonium salt

25 g of pentafluorobenzenesulfonyl chloride was dissolved in 100 ml of methanol under ice cooling, and 100 g of 25% aqueous tetramethylammonium hydroxide solution was slowly added thereto. It stirred at room temperature for 3 hours and obtained the solution of the pentafluorobenzene sulfonate tetramethylammonium salt. This solution was used for salt exchange with sulfonium salts and iodonium salts.

2) Synthesis of triphenylsulfonium pentafluorobenzenesulfonate

50 g of diphenyl sulfoxide was dissolved in 800 ml of benzene, and 200 g of aluminum chloride was added thereto, and the mixture was refluxed for 24 hours. The reaction solution was slowly poured into 2 l of ice, and 400 ml of concentrated hydrochloric acid was added thereto, followed by heating at 70 ° C for 10 minutes. This aqueous solution was washed with 500 ml of ethyl acetate, and after filtering, 200 g of ammonium iodide dissolved in 400 ml of water was added. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate and dried to obtain 70 g of triphenylsulfonium iodide.

30.5 g of triphenylsulfonium iodide was dissolved in 1000 ml of methanol, 19.1 g of silver oxide was added to this solution, and the mixture was stirred at room temperature for 4 hours. The solution was filtered and an excess solution of pentafluorobenzenesulfonic acid tetramethylammonium salt was added thereto. The reaction solution was concentrated and dissolved in 500 ml of dichloromethane, and the solution was washed with 5% aqueous tetramethylammonium hydroxide solution and water. The organic phase was dried over anhydrous sodium sulfate and then concentrated to give triphenylsulfonium pentafluorobenzenesulfonate (I-1).

3) Synthesis of Di (4-t-amylphenyl) iodoniumpentafluorobenzenesulfonate

60 g of t-amylbenzene, 39.5 g of potassium iodide, 81 g of acetic anhydride, and 170 ml of dichloromethane were mixed, and 66.8 g of concentrated sulfuric acid was slowly added dropwise thereto under ice cooling. The mixture was stirred for 2 hours under ice cooling, and then for 10 hours at room temperature. 500 ml of water was added to the reaction liquid with ice cooling, and this was extracted with dichloromethane, and the organic phase was washed with sodium bicarbonate and water, and then concentrated to give di (4-t-amylphenyl) iodonium sulfate. This sulfate was added to the solution of the excess amount of pentafluorobenzenesulfonic acid tetramethylammonium salt. 500 ml of water was added to the solution, which was extracted with dichloromethane, the organic phase was washed with 5% aqueous tetramethylammonium hydroxide solution, and washed with water and concentrated to give (4-t-amylphenyl) iodiumpentafluorobenzenesulfo. Nate (III-1) was obtained.

Other compounds can also be synthesized using the same method as described above.

(3) crosslinking agent

Synthesis of Crosslinking Agent [HM-1]

20 g of 1- [α-methyl-α- (4-hydroxyphenyl) ethyl] -4- [α, α-bis (4-hydroxyphenyl) ethyl] benzene (Honshu Kagyo Kogyo KK) Tris-PA ) Was added to a 10% aqueous potassium hydroxide solution, and stirred to dissolve. Then, 60 ml of 37% aqueous formalin aqueous solution was slowly added at room temperature over 1 hour while stirring the solution. After stirring for further 6 hours at room temperature, the solution was poured into a dilute sulfuric acid aqueous solution. The precipitate was filtered, sufficiently washed with water, and then recrystallized with 30 ml of methanol to obtain 20 g of a white powder of phenol derivative [HM-1] having a hydroxymethyl group having the following structure. Purity was 92% (liquid chromatography).

Synthesis of Crosslinking Agent [MM-1]

20 g of a phenol derivative [HM-1] having a hydroxymethyl group obtained in the above synthesis example was added to 1 L of methanol, and stirred by heating to dissolve it. Then, 1 ml of concentrated sulfuric acid was added to this solution, and the mixture was heated to reflux for 12 hours. After the reaction was completed, the reaction solution was cooled and 2 g of potassium carbonate was added. After the mixture was sufficiently concentrated, 300 ml of ethyl acetate was added. The solution was washed with water, concentrated to dryness and solidified to obtain 22 g of a white solid of phenol derivative [MM-1] having a methoxymethyl group having the following structure. Purity was 90% (liquid chromatography).

In the same manner, the phenol derivatives shown below were synthesized.

Example (2) -1 [Example, Comparative Example]

(1) resist drawing

The components shown in Tables 18 to 21 were dissolved in 8.2 g of propylene glycol monomethyl ether acetate, and this was filtered through a 0.1 µm Teflon filter to prepare a resist solution. In the composition of Example (1 '), 8.2 g of ethyl lactate was used as the solvent.

Each sample solution was applied onto a silicon wafer using a spin coater, dried at 120 ° C. for 90 seconds in a vacuum suction hot plate to obtain a resist film having a thickness of 0.5 μm.                     

Each component shown in the said Table 18-21 is shown in detail below.                     

<Suzy>

P-101: Poly (p-hydroxystyrene) Mw 10,000

       Mw / Mn = 1.4

P-102: Novolak Resin

       m-cresol / p-cresol = 45/55 (molar ratio)

Mw 6,500

(menstruum)

PGME: Propylene Glycol Monomethyl Ether

PGMEA: propylene glycol monomethyl ether acetate

(Organic basic compound)

B-1: 2,4,5-triphenylimidazole

B-2: 1,5-diazabicyclo [4.3.0] -nona-5-ene

B-3: 4-dimethylaminopyridine                     

B-4: 1,8-diazabicyclo [5.4.0] undec-7-ene

B-5: N-cyclohexyl-N'-morpholinoethylthiourea

(Surfactants)

W-1: Troisol S-366 (Troy Chemical Co., Ltd.)

W-2: Megafac F176 (product of Dainippon Ink Industries, Ltd.)

W-3: Megafac R08 (product of Dainippon Ink Corporation)

W-4: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

W-5: Surflon S-382 (Asahi Glass Co., Ltd.)

(2) Preparation of resist pattern

This resist film was irradiated using an electron beam drawing apparatus (pressurized voltage 50 KeV).

After irradiation, each was heated for 60 seconds on a vacuum adsorption hot plate at 110 ° C., and then immersed in a 2.38% by mass aqueous tetramethylammonium hydroxide (TMAH) solution for 60 seconds, washed with water for 30 seconds, and dried. The cross-sectional shape of the obtained pattern was observed with a scanning electron microscope.

(3) Sensitivity was taken as the minimum exposure amount at the time of resolving a 0.20 micrometer line (line: space = 1: 1), and limit resolution (line and space separated resolution) in the irradiation amount was made into resolution. When the 0.20 µm line (line: space = 1: 1) was not resolved, the limit resolution was regarded as resolution, and the irradiation dose at that time was regarded as sensitivity.

PCD and PED stability evaluation was performed as follows.

After the resist film coated by the method of (1) above was allowed to stand for 120 minutes in an electron beam drawing apparatus, a resist pattern was formed by the method of (2). Determine the minimum pattern size that can be resolved at the same dose as the minimum dose obtained in the method (3) (in this case, immediately after formation of the resist film), and the difference between this size and the marginal resolution obtained in (3) is 3%. What was within was made PCD stability pass.

In addition, when forming a resist pattern, it carried out by the method similar to (2) except adding the process of leaving to stand for 120 minutes in an electron beam drawing apparatus after irradiation. Determine the minimum pattern size that can be resolved at the same dose as the minimum dose obtained in the method of (3) (in this case, immediately after forming the resist film), and compare this size with the limit resolution obtained in (3). The difference within 3% was made into PED stability pass.

And the resist which passed both PCD stability and PED stability is (◎)

Only PCD stability and PED stability can pass resists

Resists that failed both PCD stability and PED stability were evaluated with x.

The performance evaluation results of the resists of Tables 18 to 21 are shown in Tables 22 to 25, respectively.                     

[Explanation of Evaluation Results]

From the results of Tables 22 to 25, the resist composition using the nitrogen-containing compound, the alkali-soluble resin, the crosslinking agent and the acid generator according to the present invention is more sensitive, higher resolution, and rectangular than the compositions other than the present invention [Comparative Examples 201 to 203]. It shows that the phosphorus profile, not only improves PCD and PED stability, but also has excellent performance.

In Examples 205, 209, 225, 228, 258, 262, 278, and 281, it can also be seen that the use of monodisperse alkali-soluble resins significantly improves sensitivity.

In Examples 201 and 254, the organic basic compound was changed from B-1 to B-2, B-3, B-4, and B-5, and the same performance was obtained.

In Examples 201 and 254, the surfactant was changed from W-1 to W-2, W-3, W-4, and W-5, respectively, and the same performance was obtained.

And in Examples 201 and 254, the solvent was changed to propylene glycol monomethyl ether and it carried out similarly, and the same result was obtained.

In Examples 201 and 254, the nitrogen-containing compound was evaluated by changing from (Ia-12) to (Ia-1) to (Ia-II), respectively, and the same result was observed.

Example 4

 Each resist solution of Examples 201 and 254 was applied and processed on an 8-inch silicon wafer in the same manner as described above to obtain a resist coating film for in-plane uniformity measurement. This was measured at 36 points | pieces evenly so that the coating film thickness might cross | intersect along the wafer diameter direction in Lambda A by Dainippon Screen. The standard deviation of the standard value was calculated | required, and it evaluated that the thing which is three times that 50 does not satisfy 50 and which is 50 or more.

The result was all 0. On the other hand, in Example 1 ', it was x.

Example 5 Patterning by Equal X-Ray Exposure

Using the resist compositions of Example 201 and Comparative Examples 201 and 202, a resist film having a film thickness of 0.40 mu m was obtained in the same manner as in Example 201. Subsequently, the patterning was carried out in the same manner as in Example 201 except that an equal magnification X-ray exposure apparatus (gap value; 20 nm) was used, and the resist performance (sensitivity, resolution, and pattern shape) was evaluated in the same manner as in Example 201. . The evaluation results are shown in Table 26.

 Resist composition  Sensitivity (mJ / ㎠)  Resolution (μm)  Pattern shape  Example 201    90   0.09  Rectangle  Comparative Example 201    180   0.20  Taper shape  Comparative Example 202    210   0.18  Taper shape

From Table 26, it can be seen that the resist composition of the present invention shows very excellent performance even in X-ray exposure.

Example (2) -2 [Example, Comparative Example]

(1) Resist drawing

The components shown in the following Tables 27-30 were dissolved in 8.2 g of propylene glycol monomethyl ether acetate, and this was filtered through a 0.1 µm Teflon filter to prepare a resist solution. In the composition of Example 401 ', 8.2 g of ethyl lactate was used as the solvent.

Each sample solution was coated on a glass substrate (6025 substrate) coated with chromium oxide using a spin coater, dried at 100 ° C. for 10 minutes in a vacuum suction hot plate to obtain a resist film having a thickness of 0.5 μm.                     

Each component shown in the said Table 27-30 is the same as that of the said Example (2) -1.

(2) Preparation of resist pattern

This resist film was manufactured in the same manner as in Example (2) -1, and a resist pattern was obtained. The cross-sectional shape of the obtained pattern was observed with a scanning electron microscope.

Sensitivity, resolution, PCD stability and PED stability were evaluated in the same manner as in Example (2) -1.

The resist performance evaluation results of Tables 27-30 were shown in Tables 31-34, respectively.

[Explanation of Evaluation Results]

As for the result of Tables 31-34, the resist composition using the nitrogen-containing compound, alkali-soluble resin, crosslinking agent, and acid generator which concerns on this invention is more sensitive, high resolution, and rectangular than the composition [Comparative Examples 401-403] other than this invention. It shows that the phosphorus profile, not only improves PCD and PED stability, but also has excellent performance.

Further, in Examples 405, 409, 425, 428, 458, 462, 478 and 481, it can also be seen that the sensitivity is remarkably improved when monodisperse alkali-soluble resins are used.

In Examples 401 and 454, the organic basic compound was changed from B-1 to B-2, B-3, B-4, and B-5, and the same performance was obtained.

In Examples 401 and 454, the surfactants were changed from W-1 to W-2, W-3, W-4, and W-5, respectively, whereby the same performance was obtained.

And in Examples 401 and 454, the solvent was changed to propylene glycol monomethyl ether and it carried out similarly, and the same result was obtained.

In Examples 401 and 454, the nitrogen-containing compound was evaluated in (Ia-12) by changing to (Ia-1) to (Ia-II), respectively, and the same result was observed.

Example 4

 Each resist solution of Examples 401 and 454 was applied and treated in the same manner as described above on an organic coating (6025 substrate) coated with chromium oxide to obtain a resist coating film for in-plane uniformity measurement. This was measured at 36 points | pieces evenly so that the coating film thickness might cross | intersect along the wafer diameter direction in Lambda A by Dainippon Screen. The standard deviation of the standard value was calculated | required, and it evaluated that the thing which is three times that 50 does not satisfy 50 and which is 50 or more.

The result was all 0. On the other hand, in Example 401 ', it was x.

 The electron beam or X-ray resist composition of the present invention can provide a highly sensitive, high resolution, rectangular excellent pattern profile, and can provide an electron beam or X-ray resist composition excellent in PCD, PED stability and applicability. .

Furthermore, the positive electron beam resist composition for mask manufacture of the present invention solves the problem of deteriorating the shape of the resist pattern on a film that is highly reactive to an acid catalyst, such as chromium oxide of a photomask, and retains high sensitivity and high resolution. In addition, it is possible to provide a positive electron beam resist composition for mask manufacture that is not only capable of providing an excellent pattern profile that is rectangular, but also excellent in PCD and PED stability, and excellent in coating property (in-plane uniformity).

Claims (30)

(a1) a compound which generates an acid by irradiation with an electron beam or X-ray, and (b) A positive electron beam or X-ray resist composition comprising a nitrogen-containing compound having at least one substructure represented by the following general formula (X) in a molecule.

The positive electron beam or X-ray resist composition according to claim 1, wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (Ia).

In general formula (Ia), Ra represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group which may have a substituent. Rb represents a hydrogen atom, an aryl group which may have a substituent, -C (= O) -Ra, or -N = N-Ra. Ra and Rb may combine with each other to form a ring. The positive electron beam or X-ray resist composition according to claim 1, wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (IIa).

In general formula (IIa), R represents the C1-C20 monovalent organic residue. The positive electron beam or X-ray resist composition according to claim 1, wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (IIb).

[In Formula (IIb), R ₅₀₁ to R ₅₁₀ are the same or different and represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, a hydroxyalkyl group, a cycloalkyl group, or an aryl group.] The positive electron beam or X-ray resist composition according to any one of claims 1 to 4, further comprising (c) a compound having a cationically polymerizable function. The positive electron beam according to any one of claims 1 to 4, which contains at least one compound selected from (c ') vinyl compounds, cycloalkane compounds, cyclic ether compounds, lactone compounds, and aldehyde compounds. Or X-ray resist composition. (a1 ') a compound which generates an acid by irradiation of an electron beam, and (b) A positive electron beam resist composition for manufacturing a mask, comprising a nitrogen-containing compound having at least one substructure represented by the following general formula (X) in a molecule.

The positive electron beam resist composition for manufacturing a mask according to claim 7, wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (Ia).

In general formula (Ia), Ra represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group which may have a substituent. Rb represents a hydrogen atom, an aryl group which may have a substituent, -C (= O) -Ra, or -N = N-Ra. Ra and Rb may combine with each other to form a ring. 8. The positive electron beam resist composition for manufacturing a mask according to claim 7, wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (IIa).

In general formula (IIa), R represents the C1-C20 monovalent organic residue. The positive electron beam resist composition for manufacturing a mask according to claim 7, wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (IIb).

[In Formula (IIb), R ₅₀₁ to R ₅₁₀ are the same or different and represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, a hydroxyalkyl group, a cycloalkyl group, or an aryl group.] The positive electron beam resist composition for mask manufacture according to any one of claims 7 to 10, further comprising (c) a compound having a cationically polymerizable function. The mask manufacturing method according to any one of claims 7 to 10, which contains at least one compound selected from (c ') vinyl compounds, cycloalkane compounds, cyclic ether compounds, lactone compounds, and aldehyde compounds. Positive electron beam resist composition. The mask blank which coat | covered the positive resist composition in any one of Claims 7-10. (a2) a compound which generates an acid by irradiation of an electron beam or X-ray, (b) a nitrogen-containing compound having at least one substructure represented by the following general formula (X) in a molecule, (h) alkali-soluble resins, and (i) A chemical amplification negative resist composition for electron beams or X-rays, comprising a crosslinking agent crosslinked by an acid.

15. The chemically amplified negative resist composition for electron beams or X-rays according to claim 14, wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (Ia).

In general formula (Ia), Ra represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group which may have a substituent. Rb represents a hydrogen atom, an aryl group which may have a substituent, -C (= O) -Ra, or -N = N-Ra. Ra and Rb may combine with each other to form a ring. 15. The chemically amplified negative resist composition for electron beams or X-rays according to claim 14, wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (IIa).

In general formula (IIa), R represents the C1-C20 monovalent organic residue. 15. The chemically amplified negative resist composition for electron beams or X-rays according to claim 14, wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (IIb).

[In Formula (IIb), R ₅₀₁ to R ₅₁₀ are the same or different and represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, a hydroxyalkyl group, a cycloalkyl group, or an aryl group.] The alkali-soluble resin according to any one of claims 14 to 17, wherein the alkali-soluble resin of (h) includes a structural unit represented by the following General Formula (1), and has a weight average molecular weight of more than 3,000 and an alkali of 300,000 or less. An electron beam or X-ray chemically amplified negative resist composition, characterized in that it is a soluble resin.

In formula (1), R <_1a> represents a hydrogen atom or a methyl group. The alkali-soluble resin according to any one of claims 14 to 17, wherein the alkali-soluble resin of (h) has an weight average molecular weight of more than 3,000, 300,000 or less, and an alkali satisfying the following conditions (a1) and (b1). An electron beam or X-ray chemically amplified negative resist composition, characterized in that it is a soluble resin. (a1) Having at least one repeating unit derived from an aromatic ring having 6 to 20 carbon atoms and a monomer having an ethylenically unsaturated group bonded directly or via a linking group to the aromatic ring. (b1) The following relationship holds between the number of electrons of the lone electron pair of the said aromatic ring and the aromatic ring substituent.

(Nπ represents the total number of π electrons, and N _lone is a linear, branched or cyclic alkoxy group, alkenyloxy group, aryloxy group, aralkyloxy group, or hydroxy group having 1 to 12 carbon atoms as the aromatic ring substituent. The total number of electrons of the lone pair of electrons is 2 or more alkoxy groups or hydroxy groups may be bonded to two adjacent to each other to form a 5-membered ring or more ring structure.) 20. The electron beam or X according to claim 19, wherein the alkali-soluble resin of (h) holds at least one of the repeating units represented by the following General Formulas (3) to (7) as a component. Aromatic chemical amplification system negative resist composition.

In General Formulas (3) to (7), R ₁₀₁ represents a hydrogen atom or a methyl group. L represents a divalent linking group. Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, and Rl are each independently a linear, branched, or cyclic alkyl group, alkenyl group, aryl group, aral having 1 to 12 carbon atoms A kill group or a hydrogen atom is represented. In addition, they may be linked to each other to form a 5-membered or more ring having 24 or less carbon atoms. l, m, n, p, q, r, s, t, u, v, w, x represent integers from 0 to 3, l + m + n = 2, 3, p + q + r = 0 , 1, 2, 3, s + t + u = 0, 1, 2, 3, v + w + x = 0, 1, 2, 3. The compound which generate | occur | produces an acid by irradiation of (a2) electron beam or X-ray is 1 type in the compound in any one of Claims 14-17 represented by following General formula (I)-General formula (III). An electron beam or X-ray chemically amplified negative resist composition containing the above.

[In the general formula (I) ~ the general formula _{(III), R 1 ~ R} 37 is a group represented by a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, or -SR _38. R ₃₈ in -SR ₃₈ represents an alkyl group or an aryl group. R ₁ to R ₃₈ may be the same or different. In the case of R ₁ to R ₁₅ , two or more selected from them may be bonded directly to each other or through an element selected from oxygen, sulfur and nitrogen to form a ring structure. In the case of R ₁₆ to R ₂₇ , a ring structure may be similarly formed. In the case of R ₂₈ to R ₃₇ , a ring structure may be similarly formed. X ⁻ is an anion of sulfonic acid.] (a2 ') A compound which generates an acid by irradiation of an electron beam, (b) a nitrogen-containing compound having at least one substructure represented by the following general formula (X) in a molecule, (h) alkali-soluble resins, and (i) The electron beam negative resist composition for mask manufacture containing the crosslinking agent bridge | crosslinked by an acid.

The electron beam negative resist composition according to claim 22, wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (Ia).

In general formula (Ia), Ra represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group which may have a substituent. Rb represents a hydrogen atom, an aryl group which may have a substituent, -C (= O) -Ra, or -N = N-Ra. Ra and Rb may combine with each other to form a ring. 23. The electron beam negative resist composition according to claim 22, wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (IIa).

In general formula (IIa), R represents the C1-C20 monovalent organic residue. 23. The electron beam negative resist composition according to claim 22, wherein the nitrogen-containing compound of (b) is a compound represented by the following general formula (IIb).

[In Formula (IIb), R ₅₀₁ to R ₅₁₀ are the same or different and represent a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, a hydroxyalkyl group, a cycloalkyl group, or an aryl group.] The alkali-soluble resin according to any one of claims 22 to 25, wherein the alkali-soluble resin of (h) includes a structural unit represented by the following general formula (1), and has a weight average molecular weight of more than 3,000 and an alkali of 300,000 or less. It is a soluble resin, The electron beam negative resist composition for mask manufacture.

In formula (1), R <_1a> represents a hydrogen atom or a methyl group. The alkali-soluble resin according to any one of claims 22 to 25, wherein the alkali-soluble resin of (h) has an weight average molecular weight of more than 3,000, 300,000 or less, and an alkali that satisfies the following conditions (a1) and (b1). It is a soluble resin, The electron beam negative resist composition for mask manufacture. (a1) Having at least one repeating unit derived from an aromatic ring having 6 to 20 carbon atoms and a monomer having an ethylenically unsaturated group bonded directly or via a linking group to the aromatic ring. (b1) The following relationship holds between the number of electrons of the lone electron pair of the said aromatic ring and the aromatic ring substituent.

(Nπ represents the total number of π electrons, and N _lone is a linear, branched or cyclic alkoxy group, alkenyloxy group, aryloxy group, aralkyloxy group, or hydroxy group having 1 to 12 carbon atoms as the aromatic ring substituent. Represents the total number of unshared electron pairs of two or more alkoxy groups or hydroxy groups, and two neighboring two may combine with each other to form a 5-membered ring or more ring structure.) The electron beam negative for mask manufacture according to claim 27, wherein the alkali-soluble resin of (h) has at least one of repeating units represented by the following general formulas (3) to (7) as a component. Resist composition.

In General Formulas (3) to (7), R ₁₀₁ represents a hydrogen atom or a methyl group. L represents a divalent linking group. Ra, Rb, and Rc each independently represent a linear, branched or cyclic alkyl group, alkenyl group, aryl group, or aralkyl group having 1 to 12 carbon atoms. Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, and Rl each independently represent a linear, branched, or cyclic alkyl, alkenyl, aryl, aralkyl, or hydrogen atom having 1 to 12 carbon atoms. Indicates. In addition, they may be linked to each other to form a 5-membered or more ring having 24 or less carbon atoms. l, m, n, p, q, r, s, t, u, v, w, x represent integers from 0 to 3, l + m + n = 2, 3, p + q + r = 0 , 1, 2, 3, s + t + u = 0, 1, 2, 3, v + w + x = 0, 1, 2, 3. The compound which generate | occur | produces an acid by irradiation of the (a2 ') electron beam is 1 or more types of the compound represented by the following general formula (I)-general formula (III) in any one of Claims 22-25. The electron beam negative resist composition for mask manufacture containing the above-mentioned.

[In the general formula (I) ~ the general formula _{(III), R 1 ~ R} 37 is a group represented by a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a halogen atom, or -SR _38. R ₃₈ in -SR ₃₈ represents an alkyl group or an aryl group. R ₁ to R ₃₈ may be the same or different. In the case of R ₁ to R ₁₅ , two or more selected from them may be bonded to each other directly or through an element selected from oxygen, sulfur and nitrogen to form a ring structure. In the case of R ₁₆ to R ₂₇ , a ring structure may be similarly formed. In the case of R ₂₈ to R ₃₇ , a ring structure may be similarly formed. X ⁻ is an anion of sulfonic acid.] The mask blank which coat | covered the electron beam negative resist composition for mask manufacture of any one of Claims 22-25.