KR100313319B1 - Positive photosensitive composition - Google Patents

Abstract

The present invention relates to a scientific amplification-type positive-tone stiffness composition which is less in film shrinkage due to exposure to light and less in film thickness after development, and provides excellent profiles and high resolution without standing waves. The novel positive photosensitive composition according to the present invention,

(a) a resin having an acid-decomposable group whose solubility is increased in an alkali developer by reaction with acid;

(b) a compound which generates an acid upon irradiation with an actinic ray or radiation;

(c) a non-polymeric acid-decomposable dissolution inhibitor having a molecular weight of 3,000 or less and containing acid-decomposable bubbles whose solubility increases in an alkaline developer under reaction with acid,

The non-polymeric acid-decomposable dissolution inhibiting agent is composed of at least three structural units each having one acid-decomposable group on one benzene ring per molecule, and at least nine bond atoms located between the two acid- (Excluding acid-decomposable groups).

Description

[Title of the Invention]

[0001] The present invention relates to a positive working light-sensitive composition,

DETAILED DESCRIPTION OF THE INVENTION [

The present invention relates to a positive photosensitive composition for use in a semiconductor manufacturing process such as a planar printing plate or an integrated circuit (IC), the manufacture of a circuit substrate such as a liquid crystal, a sural mullhead, and other photolithographic processes.

Known positive photoresist compositions generally consist of an alkali soluble resin and a naphthoquinone diazide compound as a sensitizer.

Examples of such compositions include the novolak phenol resin / naphthoquinone diazide substituted compounds disclosed in U.S. Patent Nos. 3,666,473, 4,115,128 and 4,173,470.

Representative examples of such compositions include L.F. Incorporated novolac resins made from cresol formaldehyde / trihydroxybenzophenone-1,2-naphthoquinone diazide sulfonic acid ester as described in Thompson's "Microlithography Primer" ACS, Vol. 219, pages 112-121 do.

Thus, in positive photoresists comprising basically novolac resins and quinone diazide compounds, the novolak resins provide high resistance to plasma etching and the naphthoquinone diazide compounds as solubility inhibitors. Moreover, when light is irradiated, the naphthoquinone diazide compounds generate a carboxylic acid and thus lose their ability to inhibit dissolution and increase the alkali solubility of the novolak resin.

From the above viewpoint, a large number of positive photoresists containing novolac resins and naphthoquinone diazide sensitized products have been developed and put to practical use. These positive photoresists have a fine line having a small line width of about 0.8 μm to 2 μm Providing satisfactory results in manufacturing.

However, the degree of integration of the integrated circuit gradually increases. In the production of semiconductor substrates such as super large scale integration (SLSI), processing of ultrafine patterns consisting of lines having widths less than half microns is required.

In order to obtain the required resolution, the exposure wavelength used in the photolithography exposure apparatus is shifted to a shorter wavelength.

(Such as XeCl, KrF, and ArF), X rays, and the like have been studied.

When a conventional resist composed of a novolac resin and a naphthoquinone diazide compound is used for forming a lithography pattern using external light or excimer laser light, since novolak and naphthoquinone diazide compounds exhibit strong absorption in the region outside the atom It is difficult for light to reach the bottom of the resist. This strong absorption leads to a low sensitivity and tapered pattern.

One of the means for solving such a problem is a chemically amplified resist composition disclosed in U.S. Patent No. 4,491,628 and European Patent No. 249,139. A chemically amplified resist composition is a pattern forming material that generates an acid in an exposed region when irradiated with radiation such as an external light beam.

The acid is then provided as a catalyst for a reaction that increases the solubility of the area irradiated by the actinic radiation into the developer to form a pattern on the substrate.

Examples of such a chemically amplified resist composition include a combination of a compound capable of generating an acid by photolysis and an acetal or an O, N-acetal compound (JP-A-48-89003: "JP-A" (Japanese Patent Application Laid-Open No. 51-120714), a combination of a compound that generates an acid by photolysis with an orthoester or an amide acetal compound (JP-A-51-120714) (JP-A-53-133429), a combination of a compound capable of generating an acid by photolysis and an enol ether compound (Patent Document JP-A- 55-12995), a combination of a compound that generates an acid by photolysis and an N-acyliminocarboxylic acid compound (JP-A-55-126236), a compound that generates an acid by photodecomposition, Ester group-containing polymer (JP-A- A-56-17345), a combination of a compound which generates an acid by photolysis and a tertiary alkyl ester compound (JP-A-60-3625), a compound which generates an acid by photolysis, a silyl ester compound (JP-A-60 10247), and a combination of a compound generating an acid by photolysis and a silyl ether compound (JP-A-60 37549 and JP-A-60 121446) . Such a chemically amplified resist composition principally exhibits a high photosensitivity because its quantum yield exceeds 1.

Examples of the system which is stable at room temperature but which is decomposed by heating in the presence of an acid and is alkali-soluble are disclosed in JP-A-59-45439, JP-A-60-3625, JP-A-62-229242, JP-A -63-27829, JP-A-63-36240, JP-A-63-250642, Polym. Eng. Sce. 23, p. 1012 (1983), ACS. Sym. (1982), pp. 242, 11 (1984), Semiconductor World, 1987, vol. 11, p. 91, Macromolecules, vol. 21, p. 1475 And a combination of a compound with an ester or carboxyl ester compound of a secondary or tertiary carboxylic acid.

Such a system has high photosensitivity, and the system mentioned above is effective in shortening the light source wavelength because the absorption is small in the strong ultraviolet ray region as compared with the naphthoquinonediazide / novolak resin.

The above-mentioned amphoteric chemical amplification resist composition includes a three-component system composed of an alkali-soluble resin, a compound generating an acid by radiation exposure, and a compound having an acid-decomposable group inhibiting the dissolution of an alkali-soluble resin, And a two-component system composed of a resin having a group and a photo acid generating agent.

Since the content of acid-decomposable groups in the resin is large in the two-component system, there is a problem that the resist film is shrunk by baking after exposure.

On the other hand, the three-component system has a problem that the alkali-soluble resin has a poor ability to inhibit dissolution, so that the reduction of the film thickness due to development is large and the resist profile is remarkably deteriorated.

JP-A-4-158363 discloses a tertiary pattern forming material which protects several alkali-soluble groups in an alkali-soluble resin against insufficient dissolution inhibiting ability of an acid-decomposable dissolution inhibitor.

However, the dissolution inhibiting ability of the acid-decomposable dissolution inhibitor exemplified in the above-mentioned patent does not satisfy the requirement. In such a system, film reduction due to development can not be completely prevented.

German Patent No. 4,214,363 also discloses a multifunctional acid-decomposable dissolution inhibiting agent represented by the following structural formula (A). However, the three-component type patterning material composed of such a compound is disadvantageous because it exhibits a remarkable standing wave pattern.

Nevertheless, the three-component system is a promising system because of the very wide choice of materials. However, development of acid-decomposable compounds having excellent dissolution inhibiting ability for use in this system is desired.

An object of the present invention is to provide a positive photosensitive composition which does not exhibit a standing wave but has a small film shrinkage due to post-exposure bake and has a small decrease in film thickness due to development, in order to obtain a good profile and a high resolution.

The above-mentioned objects of the present invention will become more apparent from the following detailed description and examples.

The present inventors have extensively studied the performance of the resist system described above. As a result, the object of the present invention is to provide a resin composition comprising a resin having an acid-decomposable (acid labile) group whose solubility increases in an alkali developing solution by reaction with acid, a photoacid generator and a dissolution inhibiting compound having an acid- And an acid-decomposable dissolution inhibitor having a low molecular weight.

According to the present invention,

(a) a resin having an acid-decomposable group whose solubility is increased in an alkali developer when reacted with an acid, (hereinafter referred to as " resin having an acid-decomposable group "

(b) a compound which generates an acid upon irradiation with an actinic ray or radiation;

(c) a non-polymeric acid-decomposable dissolution inhibitor having a molecular weight of 3,000 or less and containing an acid-decomposable group whose solubility increases in an alkali developing solution by reaction with acid, wherein said compound (c)

At least three structural units each having one acid-decomposable group substituted on one benzene ring per molecule, and at least nine bond atoms inserted between two acid-decomposable groups at the farthest position (acid-decomposable Except for the period.

The compounds used in the present invention will be described in detail as follows.

(A) Resin having an acid-decomposable group: (Compound (a) of the present invention)

The resin having an acid-decomposable group of the present invention has an acid-decomposable group in either or both of the main chain and the side chain.

It is more preferable to use a resin having an acid-decomposable group in its side chain.

Preferable examples of such acid-decomposable groups include -COO-A ⁰ and -OB ^O groups. More preferred examples of such acid-decomposable groups include -R ⁰ -COO-A ⁰ and -Ar-OB ⁰ groups

Said general formula, A is ^{O -C (R O1) (R O2} ) (R O3), -Si (R O1) (R O2) (R O3) or ^{-C (R O4) (R O5} ) -0- R ^O6 group and B ^O represents an A ^O or -CO- ^O -A ^O group.

R ^O1 , R ^O2 , R ^O3 , R ^O4 and R ^O5 may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ^O6 represents an alkyl group or an aryl group.

Provided that at least two of R ^O1 to R ^O3 are groups other than a hydrogen atom and two groups of R ^O1 to R ^O3 and R ^O4 to R ^O6 are a particularly preferred ring containing a tetrahydropyran ring and tetrahydrofuran They may be combined with each other to form. R is ^O may be substituted with more than two C ₁ - ₁₂ represents an aliphatic or aromatic hydrocarbon, which may be substituted -Ar- represents a bivalent or higher monocyclic or polycyclic aromatic group.

Preferable examples of the aforementioned alkyl group represented by R ^O1 to R ^O6 are a C _1-4 alkyl group such as a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group.

Preferred examples of the above-described cycloalkyl group represented by R ^O1 ~ ^O5 R is a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, an adamantyl group, such as C ₃ - ₁₀ is a cycloalkyl group.

Preferred examples of the aforementioned alkenyl group represented by R ^O1 to R ^O5 are a C _2-4 alkenyl group such as a vinyl group, a propenyl group, an allyl group, and a butenyl group.

Preferred examples of the aforementioned aryl group represented by R ^O1 ~ ^O6 R is C _6, such as a phenyl group, a silyl group size, Toru group, cumenyl group, naphthyl group, anthracenyl group - a ₁₄ aryl group.

The above-mentioned alkyl group, cycloalkyl group, alkenyl group and aryl group may be substituted.

Examples of the substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, a C _1-4 alkyl group, an alkoxy group such as a methoxy group, an ethoxy group, Butoxy group, t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl group such as benzyl group, phenethyl group and cumyl group, aralkyl group such as aralkyl An acetyl group, a butyryl group, a benzoyl group, an acyloxy group such as a valylyl group and a butyryloxy group, an alkenyloxy group such as a C _2-4 alkenyl group, a vinyloxy group, a propenyl group such as a propenyl An aryloxycarbonyl group such as an allyloxy group and a butenyloxy group, a C _6-14 aryl group, an aryloxy group such as a phenoxy group, and a benzoyloxy group.

Preferable examples of the acid-decomposable group include a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group, a tertiary alkyl ester group, And a higher alkyl carbonate group.

More preferred among these groups are a tertiary alkyl ester group, a tertiary alkylcarbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

Basic resin acid-decomposable group is connected as a side chain is an alkali-soluble resin having at a side chain -0H or -COOH group, and particularly preferably from -R ^o -COOH or -Ar-OH groups preferably,

Examples of such alkali-soluble resins include poly (hydroxystyrene), hydrogenated polyhydroxystyrene, novolac resin, hydrogenated novolak resin, acetone-pyrogallol resin, halogen or alkyl substituted poly (hydroxystyrene) Styrene-N-substituted maleimide copolymers, some O-acylated poly (hydroxystyrene), styrene maleic anhydride copolymers, carboxy containing methacryl based resins and derivatives thereof, but the present invention is not limited thereto It is not.

The alkali dissolution rate of the alkali-soluble resin is preferably 170 Å / sec or more, and particularly, it is 330 Å / sec or more in 0.261 N tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ° C.

The alkali-soluble resin exhibits a high transmittance with respect to external light or excimer laser light, and in particular, has a transmittance of 20 to 80% at 248 nm for a film thickness of 1 m at an exposed wavelength in order to obtain a rectangular profile (i.e., .

In this regard, particularly preferred examples of the alkali-soluble resin include poly (hydroxystyrene), hydrogenated poly (hydroxystyrene), halogen or alkyl substituted poly (hydroxystyrene), partially o-acylated poly (hydroxystyrene) Novolak resin.

The poly (hydroxystyrenes) used in the above may be two or three moieties of poly (P-hydroxystyrene), poly (m-hydroxystyrene), poly (o- hydroxystyrene) and P- (Monomer) copolymer, m-hydroxystyrene, and 0-hydroxystyrene.

The resin having an acid-decomposable group according to the present invention is a resin having an acid-decomposable group according to what is disclosed in European Patent No. 254,853, JP-A-2-25850, JP-A-3-223860 and JP-A- Soluble resin and a precursor of an acid-decomposable group, or by copolymerizing an alkali-soluble resin monomer having an acid-decomposable group bonded to a plurality of monomers.

The general formulas (a) to (f) of the resin having an acid-decomposable group for use in the present invention are given below, but the present invention is not limited thereto.

(a) (e)

(b) (f)

(c) (d)

From here,

^{L -C00A o, -0-B O} , - (0) nR 0 -COO-A 0 or -Ar-OB ⁰

(Contribute standing, Ar, R ^O, A ⁰ and B ⁰ are defined above);

R ₁ : R ₁ groups in the same molecule may be the same or different, and each is a hydrogen atom or a C _1-4 alkyl group;

R ₂ and R ₄ : in the same molecule, R ₂ and R ₄ groups may be the same or different and each is a hydrogen atom or a C _1-4 alkyl group;

R ₃ : a hydrogen atom, a carboxyl group, a cyano group or a substituted or unsubstituted C _6-20 aryl group;

R ₅ : a hydrogen atom, a cyano group or -COOR ₆ ;

R _{6 is a} C _1-10 linear, branched or cyclic alkyl group;

R ₇ to R ₉ hydrogen atom or C _1-4 alkyl group:

A C _6-20 aromatic group which may be substituted or a C _6-20 cycloalkyl group which may be substituted;

k, l, k _l , l ₁ , m: each independently represents a natural number.

k + l = 1, k? =? l = 1, and 0.01 <k?

n: 0, or 1

.

Particularly preferred examples of Ar include a substituted or unsubstituted phenyl group, a naphthyl group, a cyclonaphthyl group, and an adamantyl group. Preferable examples of the substituent for Ar include C _1-4 alkyl group, C _7-11 aralkyl group, C _1-6 acyl group, C _1-4 alkoxy group, C _2-4 alkenyl group, C _2-4 alkenyloxy group, C _6-10 aryl, C _6-10 aryloxy, C _7-11 aralkyl oxy group, C _1-6 acyloxy, C _2-5 alkoxycarbonyl, C _7-11 aryloxycarbonyl group, a halogen atom, A nitro group, a hydroxyl group, a cyano group and a carboxyl group.

Specific examples of the resin include the following compounds (i) to (xxiii):

(i) (ii)

(iii) (iv)

(V) (Vi)

(Vii) (Vii)

(ix) (X)

(xi) (xii)

(xiii)

(xiV)

(xv)

(xvi)

(xvii)

(xviii)

(xix) (xx)

(xxi) (xxii)

(xxiii)

The content of the acid-decomposable group is represented by B / (B + S) represented by the number B of acid-decomposable groups in the resin and the number of alkali-soluble groups S not protected by an acid-decomposable group.

The content of the acid-decomposable group is generally in the range of 0.01 to 0.5, preferably 0.01 to 0.30, and more preferably 0.01 to 0.15. If the content B / (B + S) exceeds 0.5, film shrinkage due to post exposure bake (PEB) treatment, adhesion decrease due to degeneration and scumming of the developed resist pattern are caused.

On the other hand, when the content B / (B + S) is less than 0.01, a standing wave profile can be generated on the sidewall of the developed resist pattern.

The average molecular weight (Mw) of the resin having an acid-decomposable group is preferably in the range of 1,000 to 100,000.

If the molecular weight of the phenymine is less than 1,000, the film thickness in the unexposed area is greatly reduced by the development. On the other hand, when the average molecular weight of the resin exceeds 100,000, the alkali dissolution rate of the alkali-soluble resin itself decreases and the sensitivity decreases. A particularly preferred average molecular weight of the resin is in the range of 2,000 to 50,000.

The average molecular weight is determined by gel permeation chromatography according to THF and polystyrene standards.

Two or more resins having an acid-decomposable group of the present invention may be mixed and used. The resin having an acid-decomposable group of the present invention may be mixed with an alkali-soluble resin having no acid-decomposable group in order to control the alkali solubility of the resin.

The addition amount of the resin of the present invention is 50 to 97% by weight, preferably 60 to 90% by weight based on the total weight (excluding solvent) of the photosensitive composition.

(B) Non-polymeric acid-decomposable dissolution inhibitor (compound (C) of the present invention)

The non-polymeric acid decomposable dissolution inhibiting agent (C) of the present invention is composed of at least three structural units each having only one acid-decomposable group substituted on one benzene ring per molecule. Also, there are at least nine bond atoms, preferably at least 10 bond atoms, more preferably 11 bond atoms, inserted between at least two acid-decomposable groups of the structural units.

In other words, the compound (C) must have the first acid-decomposable group of the first structural unit a certain distance from the second acid-decomposable group of the second structural unit.

The upper limit of the number of bonded atoms is preferably 50, more preferably 30.

In the present invention, if the acid-decomposable dissolution inhibiting compound has three or more, preferably four or more, structural units each having one acid-decomposable group substituted on one benzene ring, then two When the acid-decomposable groups are separated by a certain distance, the dissolution-inhibiting ability to the alkali-soluble resin is remarkably improved.

As used herein, the phrase " distance between acid-decomposable groups " means the number of bonding atoms inserted between acid-decomposable groups excluding the acid-decomposable group itself. For example, in the case of the following compounds (1) and (2), the distance between acid-decomposable groups is 4 bonding atoms.

In the case of the compound (3), the farthest distance between the acid-decomposable groups is 12 bonding atoms.

(One)

(2)

(3)

Acid-decomposable group: -COO-A ⁰ , -OB ⁰

The molecular weight of the non-polymeric acid-decomposable dissolution inhibiting agent of the present invention is 3,000 or less, preferably 500 to 3,000, and more preferably 1,000 to 2,500.

In the present invention, the group containing an acid-decomposable group is preferably a -COO-A ⁰ or -OB ⁰ group, more preferably a group represented by -R ⁰ -COO-A ⁰ or -Ar-OB ⁰ .

In the above general formulas, A ⁰ , B ⁰ and R ⁰ are as defined above for the acid-decomposable group of the compound (a) of the present invention.

Preferable examples of the non-polymeric acid decomposable dissolution inhibiting agent include a polyhydrogenoligomer having at least one hydroxyl group on each benzene ring in the molecule and having ^-O- COO-A ⁰ or B ⁰ group and at least three hydroxyl groups, Protected compounds obtained by partial or total esterification by a phenolic OH group of a hydroxy compound.

Particularly preferred examples of -R ⁰ -COO-A ⁰ or B ⁰ group are the acid-decomposable groups mentioned above for non-polymeric acid decomposable dissolution inhibitors. A method of esterification is disclosed in, for example, J. Frechet et al., Vol. 24, Aug., pp. 995 (1983).

A useful polyhydroxy compound and its preparation method are disclosed in JP-A-1-289946, JP-A-2-2560, JP-A-3-128959, JP- JP-A-3-191351, JP-A-3-200251, JP-A-3-200252, JP-A-3-200253, JP- JP-A-3-259149, JP-A-3-279958, JP-A-4-1650, JP-A-4-1651, JP- JP-A-4-271349, JP-A-5-158233, JP-A-5-224409, JP-A-5-257275, JP- 5-297583, JP-A-5-309197, JP-A-5-303200, and JP-A-341510,

More preferred examples of the polyhydroxy compounds are disclosed in JP-A-1-289946, JP-A-3-128959, JP-A-3-158855, JP-A-3-179353, JP- , JP-A-3-200252, JP-A-3-200255, JP-A-3-259149, JP-A-3-279958, JP-A-4-1650, JP-A-4-11260, JP -A-4-12356, JP-A-4-12357, JP-A-5-224409, JP-A-5-297581, JP-A-5-297583, JP-A- -5-303200 and JP-A-5-341510.

Specific examples of the non-polymeric acid-decomposable dissolution inhibiting agent of the present invention include the compounds represented by the following general formulas (I) to (XII):

[I] [II]

[III] [IV]

[V] [VI]

[VII] [VIII]

here,

R represents a hydroxyl group, -OR ⁰ -COO-A ⁰ or -OB ⁰ group with the proviso that three or more R groups in each molecule are -0-R ⁰ -CO ⁰ -A ⁰ or OB ⁰ group,

_{R 1 ~R 4, R 7,} R 9 ~R 13, R 17 ~R 19, R 22 ~R 29: these groups bonded to each other to the same or different, each represent a hydrogen atom, a hydroxyl group, C _1-4 alkyl group, C _{1 -4} alkoxy group. C _1-6 acyl C _1-6 acyloxy, C _6-10 aryl, C _6-10 aryloxy, C _7-11 aralkyl, C _7-11 aryl kilok time. Halogen atom, nitro group. A carboxyl group, a cyano group or _{-N (R 5) (R 6} ) ( wherein, R ₅ and R ₆ each represents a hydrogen atom C _1-4 represents an alkyl group or C _6-10 aryl);

R _{8 is a} single bond, a C _1-4 alkylene group,

(Wherein R ₁₄ and R ₁₆ may be the same or different and are each a single bond, a C _1-4 alkylene group, -O-, -S-, -C 0 - or a carboxyl group;

R _{15 is a} hydrogen atom, a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _1-6 acyl group, a C _1-6 acyloxy group, a C _6-10 aryl group, a nitro group, a hydroxyl group, a cyano group or a carboxyl group A hydrogen atom in the hydroxyl group may be substituted with -R ⁰ -COO-A ⁰ or -B ⁰ group;

R _20, R _21:: these groups bonded to each other to the same or different, and are each a methylene group, the term lower alkyl-substituted methylene group, a halo-methylene group or a haloalkyl group (the "lower alkyl group" used herein means a C _1-4 alkyl group do);

R ₃₀ , R ₃₁ : These groups may be the same or different and are each a hydrogen atom, a lower alkyl group, a lower haloalkyl group or a C _6-10 aryl group;

R ₃₂ to R ₃₅ may be the same or different and each represents a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _2-5 alkoxycarbonyl group . C _7-11 aralkyl kilok time, C _1-6 acyl, C _1-6 acyloxy, C _2-4 alkenyl, C _2-4 alkenyloxy group. A C _6-10 aryl group, a C _6-10 aryloxy group, or a C _7-11 aryloxycarbonyl group, with the proviso that the four substituents denoted by the same symbol per molecule may not be the same group;

E is a single bond or an oxymethylene group;

Y: -CO- or -SO ₂ -;

A: a methylene group, a lower alkyl-substituted methylene group, a halomethylene group or a C _1-4 haloalkyl group;

a to g, i to k, p to r: an integer of 0 to 4, and groups in the parentheses () when plural a to j each are plural may be the same or different;

h, l to o, s, t, v to z: integers from 0 to 3, provided that at least one of v, w, y and z is 1 or more;

u: an integer from 3 to 8

(IX)

R ₃₆ .2-valent organic group (e.g., C _1-4 alkylene, C _3-5 alkenylene, C _6-14 arylene group), or a trivalent organic group (for example, C _1-4 alkylene, C _3-5 alkenylene, or C _6-14 arylene. A single bond, -S-, -S0-, or

R _37: a hydrogen atom, a halogen atom, a hydroxyl group, a monovalent organic group (e.g., C _1-4 alkyl, C _1-4 alkoxy C _1-6 acyl, C _1-6 acyloxy, C _6-10 aryl. , C _6-10 aryloxy, C _{7 -11} arylalkyl, C _{7 -11} arylalkyloxy, C _1-4 haloalkyl)

R ₃₈ ~R _42: these groups bonded to each other to the same or different, each represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, -OR ^O -COO-A ^O or -OB ⁰ group (wherein, R ^O , A ⁰ and B ⁰ are as defined above), provided that at least three of R ₃₈ to R ₄₂ are -O-R ⁰ -CO-A ⁰ group or -O-B ⁰ group and 4 To six substituents may not be the same;

X is a single bond or a divalent organic group (e.g., C _1-4 alkylene, C _3-5 alkenylene, C _6-14 arylene);

al: 0 or 1

(X)

here,

R ₄₃ to R ₄₆ : These groups may be the same or different and each represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group or an alkenyl group, with the proviso that 4 to 6 substituents denoted by the same symbols are not the same good;

R ₄₇ to R ₄₈ : each a hydrogen atom. Alkyl group or

R ^5: R, at least three of the ^five groups are -0-R ^O -CO0-A ⁰ group or a -0-B ⁰ group (wherein, A ^0, B ⁰ being as defined above and R ⁰ is a) the remaining R ⁵ group is a hydroxyl group to be;

bl, c1, d1: an integer from 0 to 5, respectively

(XI)

here,

R ₄₉ ~R _55: these groups bonded to each other to the same or different and are each a hydrogen atom, a hydroxyl group, a halogen atom, a C _1-4 alkyl group, C _1-4 alkoxy group, a nitro group, a C _2-4 alkenyl group, C _{6- 10} aryl group, C _7-11 aralkyl, C _2-5 alkoxy group, a C _7-11 aryl group, or a C _1-6 acyloxy, C _1-6 acyl, C _7-1l aralkyl kilok time. Or a C _6-10 aryloxy group. However, the six substituents denoted by the same symbol may not be the same;

At least three of R ⁶ : R ⁶ groups are -O-R ⁰ -CO-A ⁰ group or -O-B ⁰ group, and the remaining R ⁶ groups are hydroxyl groups.

(X1I)

here,

R ₅₆ : a hydrogen atom or a C _1-4 alkyl group, provided that a plurality of R ₅₆ groups may not be represented by the same group (for example, an alkyl group having a different number of carbon atoms);

R ₅₇ to R ₆₀ : each of three substituents denoted by a hydroxyl group, a hydrogen atom, a halogen atom, a C _1-4 alkyl group or a C _1-4 alkoxy group,

-0-R ⁷ R ^O -CO0 ^A-O group (wherein, A ^0, B ^0, and R ^O are as defined above) or ^0-B 0 group, provided that the three R ⁷ groups may need not represent the same group.

Specific examples of preferred compound skeletons for the non-polymeric acid-decomposable dissolution inhibiting agent of the present invention are given below.

(1) (2) (3)

(4) (5) (6)

(7) (8)

(9) (10)

(11) (12)

(13) (14)

(15) (16)

(17) (18)

(19) (20)

(21) (22)

(23) (24)

(25) (26)

(27) (28)

(29) (30)

(31) (32)

(33) (34)

(35) (36)

(37) (38)

(39)

(40) (41)

(42) (43)

In the foregoing general formulas (1) ~ (43), R is a hydrogen _{atom, -CH 2 -CO0-C (CH} 3) 2 C 6 H 5, -CH 2 -CO0-C 4 H 9 t, -CO0- C ₄ H ₉ ^t or,

Provided that at least three of the R groups in each molecule are other than hydrogen atoms and the chirality groups R do not have to be the same group,

The content of the acid-decomposable group in the non-polymeric acid decomposable dissolution inhibitor (C) is determined by the average number N _B of acid-decomposable groups in the dissolution inhibitor (C) and the average number N _S of a part not protected by the acid- N _B / (N _B + N _S ). The content of the acid-decomposable group is preferably 0.025? N _B / (N _B + N _S )? 1, more preferably 0.5? N _B / (N _B + N _S )?

At least 50% by weight of the non-polymeric acid-decomposable dissolution inhibitor is added to the number N _1B of acid-decomposable groups and a part of the acid-decomposable group which is protected by the acid-decomposable group but not by the mole of the non- It is particularly preferable that the structural unit is 0.5? N _1B (N _1B + N _1S )? 1 represented by the number N _1S .

The addition amount of the compound (C) of the present invention is 3 to 50% by weight, preferably 5 to 35% by weight, based on the total weight of the photosensitive composition (excluding the solvent).

(C) a compound which generates an acid upon irradiation with an actinic ray

(Compound (b) of the present invention)

The compound capable of generating an acid by irradiation with an actinic ray used in the present invention is a compound which can be used for a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a light decolorizer for a color tone, a photochromic agent, Is appropriately selected from the group consisting of known compounds which generate an acid.

As used herein, the term " actinic ray " includes electron beams x-rays, molecular beams and r-rays having a wavelength of 150-500 nm.

Examples of such compounds include, but are not limited to, the compounds described in S. I Schlesinger, Photogr. Sci. Eng., 18387 (1974), T. Diazonium salts described in S. Poll, Polymer, 21423 (1980) and others, US Pat. Nos. 4069055, 4069056, 27992, and JP-A-3-140140. city. Necker and his colleagues, Macromolecules, 172468 (1984), U.S. Wen and his colleague Proc. Conf. Rad. Curing ASIA, 478, Tokyo, Oct (1988), U.S. Patent Nos. 4069055 and 4069056, and the like. V. Macromolecules, 10 (6), 1307 (1977), Chem. and Eng. News, Nov. 28, 31 (1988) European Patent No. 104143, JP-A-2-150848, JP-A-2-296514 and the like. V. Creebello et al., Polymer J. 17, 73 (1985), J.V. Crivelo and his colleagues J.Org. Chem., 43, 3055 (1978), W. Al Watts and colleagues J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), J. V. Cribello and his colleagues Polymer Bull., 14, 279 (1985), J. V. Cribello and his colleagues Macromolecules, 14 (5), 1141 1981), J. V. Cribello and colleagues J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patents 370694, 3902114, 233567, 297443, 297442, 4933377, 4760013, 4734444, 2833872, The sulfonium salts described in German Patent Nos. 2904626, 3604580 and 3604581, and the like, Macromolecules, 10 (6), 1307 (1977), J. V. Cribelo and his colleagues J. Polymer Sci, Polymer Chem. Ed., 17, 1047 (1979) and the like, Si, S, Wen and colleagues Teh, Proc. Conf. Rad. Curing ASIA, 478, Tokyo, Oct (1988), and the like. US Patent No. 3905815, Patent Publication JP-B-46-4605 (here, " JP-B " means a published Japanese patent application after examination), Patent Publication JP-A-48-36281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-62-58241, JP- Organic halogen compounds described in JP-A-212401, JP-A-63-70243, JP-A-63-298339, Meyer and his colleagues J. Rad. Curing, 13 (4), 26 (1986), T. P. Gill and his associate Inorg. Chem., 19, 3007 (1980), Acc.Chem.Res., 19 (12), 377 (1896), and JP-A-2-161445 , s. Hayase and his colleagues, J. Polymer Sci., 25, 753 (1987), Lake Manis and his colleagues, J. Polymer Sci., Polymer Chem. Ed., 23, 1 (1985), Q.Quest and his colleagues, J. Photochem., 36, 85, 39, 317 (1987) Amit and his colleagues Tetrahedron Lett., (24) 2205 (1973), D. Echler, Barton and colleagues J. Chem. Soc., 3571 (1985), P. M. Collins and his colleagues J. Chem., Soc., Perkim I, 1695 (1975), M. Rudinstein and colleagues Tetrahedron Lett., (17) 1445 (1975), J. W. Walker and his colleagues J. Am. Chem. Soc., 110, 7170 (1988), S. Boothmann and his colleagues, J. Imaging Technol., 11 (4), 191 (1985), H. Hoelly and his colleagues Macromolecules, 21 , 2001 (1988), P. M. Collins and colleagues J. Chem. Soc., Chem. Commun. 532 (1972). s. Hayase and his colleagues Macromolecules 18, 1799 (1985), J. Rakmanis and colleagues J. Electrochem Soc., Solid State Sci. Technol., 130 (6), EF, M., Hoyolan et al., Macromolcules, 21, 2001 (1988), EP 0290750, EP 046083, EP 156535, EP 271851, EP 0388343, Nitrobenzyl type protecting groups described in U.S. Patent Nos. 3901710, 4181531, JP-A-60-198538, JP-A-53-133022, Fellow Polymer Preprints Japan, 35 (8), J. Burner and his colleagues, J. Rad. Coating Technol., 55 (697), 45 (1983), Akzo, Ezeki, Adachi and colleagues, Polymer Preprints, Japan, 37 (3) European Patent No. 0199672, No. 84515, No. 199672, No. 044115, No. 0101122, No. 4,618,564, No. 4371605, No. 4431774, No. JP-A-64-18143, A-2-245756, JP-A-3-140109 and the like, imino sulfonates, and the like, compounds which generate sulfonic acid by photolysis, compounds disclosed in JP-A-61-166544 Sulfone compounds can be listed.

Further, a polymer compound having one or more groups or compounds which generate an acid upon irradiation with light in the main chain or side chain may be used.

Examples of such polymeric compounds include those described by M. I. Woodhouse and colleagues in J. Am. Chem. Soc., 104, 5586 (1982), S.P.Papas and colleagues J. Imaging Sci., 30 (5), 218 (1986), S. Kondo and his colleagues Markromol. Chem., Rapid Commun., 9, 625 (1988), Wai, Yamada and colleagues Markromol. Chem., 152, 153, 163 (1972), J. Am. V. Polymer Chem., Ed., 17, 3845 (1979), U.S. Patent No. 3849137, German Patent No. 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP- 153853, JP-A-63-146029 and the like.

In addition, Synthesis, (1), 1 (1980), A. Abad and his colleagues Tetrahedron Lett., (47) 4555 (1971), D. Echoes, Barton and his colleagues J. Chem. Soc., (C), 329 (1970), US Pat. No. 3,779,777, European Patent No. 126712, and the like.

Among the above-mentioned compounds which are decomposed by irradiation of an actinic ray to generate an acid, those which are particularly effective are described as follows.

(1) a trihalomethyl-substituted oxazole derivative represented by the following general formula (PAG1) or a trimethyl-substituted s-triazine derivative represented by the following general formula (PAG2)

(PAG1) (PAG2)

here,

R ¹ represents a substituted or unsubstituted C _6-10 aryl group or a C _2-4 alkenyl group;

R ² is a substituted or a substituted C _6-10 aryl group. C _2-4 alkenyl group. A C _1-4 alkyl group or -CY ₃ ;

Y represents a chlorine atom or a bromine atom.

Specific examples of these compounds are given below, but the present invention is not limited thereto.

(PAG-1) (PAG-2)

(PAG-3) (PAG-4)

(PAG-5) (PAG-6)

(PAG-7) (PAG-8)

(PAG2-1) (PAG2-2) (PAG2-3) (PAG2-4)

(PAG2-5) (PAG2-6) (PAG2-7)

(PAG2-8) (PAG2-9) (PAG2-10)

(2) an iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the following general formula (PAG4)

(PAG3) (PAG4)

In the above general formula, Ar ¹ and Ar ² each independently represent a C _6-10 substituted or unsubstituted aryl group. In the case of an aryl group, preferred examples of the substituent include a C _1-4 alkyl group, a C _1-4 haloalkyl group, a C _3-10 cycloalkyl group, a C _6-10 aryl group, a C _1-4 alkoxy group, a nitro group, a carboxyl group, a C _{2 -5} alkoxycarbonyl group, a hydroxyl group, a mercapto group and a halogen atom.

R ³ , R ⁴ and R ⁵ each independently represents a substituted or unsubstituted alkyl group or an aryl group, preferably a C _6-14 aryl group, a C _1-8 alkyl group or a substituted derivative thereof

Preferable examples of substituents for these groups. An aryl group, a C _1-8 alkoxy group, a C _1-8 alkyl group, a nitro group, a carboxyl group, a hydroxyl group and a halogen atom; The alkyl group includes a C _1-8 alkoxy group, and a carboxyl group C _2-5 alkoxycarbonyl group.

Z ^- represents anion. Examples of such anions include perfluoroalkanesulfonic acid anions such as BF ₄ ^- , AsF ₆ ^- , PF ₆ ^- , SbF ₆ ^- , SiF ₆ ^2- , C 10 ₄ ^- , CF ₃ SO ₃ ^- , pentafluorobenzene Sulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinonesulfonic acid anion and sulfonic acid group-containing dyes, and the like.

^{Two of} R ³ , R ⁴ and R ⁵ , or Ar ¹ and Ar ² may be bonded to each other through a single bond or a divalent substituent, and preferred examples thereof include a C _1-4 alkylene group. A C _3-5 alkenyl group, and a C _6-14 arylene group, each of which is a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _1-6 acyl group, C _1-6 acyloxy, C _6-l0 aryl group, C _6-10 aryloxy, C _7-11 aralkyl group. C _7-11 alral kilok group, C _1-4 haloalkyl group, may be chiwan by a halogen atom, a hydroxyl group or a cyano group.

Specific examples of the iodonium salt and the sulfonium salt are given below, but the present invention is not limited thereto,

(PAG3-1) (PAG3-2) (PAG3-3)

(PAG3-4) (PAG3-5)

(PAG3-6) (PAG3-7)

(PAG3-8) (PAG3-9)

(PAG3-10) (PAG3-11)

(PAG3-12) (PAG3-13)

(PAG3-14) (PAG3-15)

(PAG3-16) (PAG3-17)

(PAG3-18) (PAG3-19)

(PAG3-20) (PAG3-21)

(PAG3-22) (PAG3-23)

(PAG3-24) (PAG3-25)

(PAG3-26) (PAG3-27)

(PAG4-1) (PAG4-2) (PAG4-3)

(PAG4-4) (PAG4-5) (PAG4-6)

(PAG4-7) (PAG4-8)

(PAG4-9) (PAG4-10)

(PAG4-11) (PAG4-12)

(PAG4-13) (PAG4-14)

(PAG4-15) (PAG4-16)

(PAG4-17) (PAG4-18) (PAG4-19)

(PAG4-20) (PAG4-21)

(PAG4-22) (PAG4-23)

(PAG4-24) (PAG4-25)

(PAG4-26) (PAG4-27)

(PAG4-28) (PAG4-29)

(PAG4-30) (PAG4-31)

(PAG4-32) (PAG4-33)

(PAG4-34)

The onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, Nafczig and his colleagues J. Am. Chem. Soc., 91, 145 (1969), A. L. Meocock and colleagues J.0rg. Chem., 35, 2532 (1970). Lee Gothas and his colleague Bull.Soc. Chem. Belg. 73, 546 (1964), et al., J. Ray. Chem. Soc., 51, 3587 (1929), J. V. Cribello and his colleague J. Polym. Chem. Ed., 18, 2677 (1980), U.S. Patent Nos. 2807648 and 4247473, and JP-A-53-101331.

(3) Disulfone derivatives represented by the following formula (PAG5) and iminosulfonate derivatives represented by the following formula (PAG6).

(PAG5) (PAG6)

Wherein Ar ³ and Ar ⁴ each independently represent a C _6-10 substituted or unsubstituted aryl group,

R ⁶ represents a substituted or unsubstituted C _1-4 alkyl group or a C _6-10 aryl group;

A represents a substituted or unsubstituted C _1-4 alkylene group, a C _3-5 alkenylene group or a C _6-14 arylene group.

Disulfone derivatives are described in, for example, Rat, City, Danger. Can be prepared by the method described in Jr. and colleagues, "Organic Chemistry Journal," vol. 31, pp. 3418-3419 (1966), and J.P. Hildy's "Journal of Chemical Society" Vol. 93, pp. 1524-1527 have.

Specific examples of these compounds are given below, but the present invention is not limited to these.

(PAG5-1) (PAG5-2)

(PAG5-3) (PAG5-4)

(PAG5-5) (PAG5-6)

(PAG5-7) (PAG5-8)

(PAG5-9) (PAG5-10)

(PAG5-11) (PAG5-12)

(PAG5-13)

(PAG6-1) (PAG6-2)

(PAG6-3) (PAG6-4)

(PAG6-5) (PAG6-6)

(PAG6-7) (PAG6-8) (PAG6-9)

(PAG6-10) (PAG6-11)

(PAG6-12) (PAG6-13)

(PAG6-14) (PAG6-15)

The amount of the compound capable of decomposing by irradiation with an actinic ray to generate an acid is in the range of 0.001 to 40 wt%, preferably 0.01 to 20 wt%, more preferably 0.01 to 10 wt%, based on the total weight of the photosensitive composition (excluding the coating solvent) By weight is 0.1 to 5% by weight.

The photosensitive composition according to the present invention may further contain compounds having two or more phenolic OH groups which promote solubility in dyes, pigments, plasticizers, surfactants, photosensitizers and developing solutions.

Preferred examples of the dyes include oil dyes and basic dyes. Specific examples thereof include oil yellow # 101, oil yellow # 103, oil mink # 312, oil green BG, oil blue B0S, oil blue # 603, oil black BY, oil black BS and oil black T-505 (manufactured by Orient Chemical Industries, ), Crystal violet (CI42555), methyl violet (CI42535), rotamin B (CI45170B), maragit green (CI42000), methylene blue (CI52015) and the like.

Furthermore, a spectral sensitizer may be added to the photosensitive composition of the present invention so as to increase or decrease to a longer wavelength region than an atomic region. Since the photoacid generator does not have absorption in this long wavelength region, the photosensitive composition is not photosensitive to the i or g line. Examples of preferred spectral sensitizers are benzophenone, P, P'-tetramethyldiaminobenzophenone, P, P'-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxy Benzene, acridine orange, benzofurabin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2- N-acetyl-P-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, N-acetyl-N-nitroaniline, N-acetyl- 2-benzanthraquinone, 1, 2-benzanthraquinone, 3-methyl-1,3-diaza-1, 9-benzanthrone, dibenzalacetone , 1, 2-naphthoquinone, 3,3'-carbonyl-bis (5, 7-dimethoxycarbonylcoumarin) and coronene, but the present invention is not limited thereto .

The thus-prepared photosensitive composition of the present invention is applied on a support in a form dissolved in a solvent capable of dissolving each component described above.

Preferable examples of the solvent include ethylene-dichloride, cyclohexanone, cyclopentanone, 2-heptanone, (Gamma) -butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , Ethyl acetate, ethyl lactate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, pyruvate, N, N-dimethylformamide, dimethyl sulfoxide , N-methylpyrrolidone, tetrahydrofuran and the like, and these solvents may be used alone or in combination.

A surfactant may be added to the solvent. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether and Polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene nonylphenol ether and the like, polyoxyethylene-polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan imum palmitate, sorbitan monostearate, Sorbitan fatty acid esters such as sorbitan trioleate, sorbitan trioleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monostearate, Ethylene sorbitan trioleate, polyoxyethyl And FO Top EF301, EF303, and EF352 (manufactured by Shin-Etsu Chemical Co., Ltd.), Megafac F171, and F173 (manufactured by Nippon Ink K.K.), and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan fatty acid esters Fluorine surfactants such as Prolide FC430 and FC431 (manufactured by Joo 3M Co., Ltd.), Asahi Guide AG710, Chaplon S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (Manufactured by Shin-Etsu Chemical Co., Ltd.) and acrylic acid-based or methacrylic acid-based (co) polymerization Polyflow N0.75, N0.95 (manufactured by Kokusa Seiyaku Kagaku Kogyo Co., Ltd.).

The amount of these surfactants to be added is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solid content of the photosensitive composition of the present invention.

These surfactants may be added singly or in combination of several.

The photosensitive composition thus prepared is coated on a substrate (for example, a substrate coated with silicon / silicon dioxide) for use in the production of precision integrated circuit devices by a suitable application means such as a spin coater, and then exposed through a mask , Baked and then developed to obtain an excellent resist pattern.

Examples of the developing solution for developing the photosensitive composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, primary amines such as ethylamine and n-propylamine, , Tert-amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium Quaternary ammonium salts such as hydroxides, and cyclic amines such as pyrrole and piperidine.

The alkalinity of the alkaline aqueous solution (developing solution) is in the range of 0.001 to 1 N, preferably 0.01 to 0.5 N, particularly 0.05 to 0.3 N.

Further, an appropriate amount of alcohol, a surfactant or the like may be mixed with the alkaline aqueous solution.

The present invention can be explained in more detail by way of the following examples, but the present invention is not limited thereto.

[Synthesis Example 1]

[Synthesis of resin having an acid-decomposable group: Compound (i)]

(1) A catalytic amount of 2,2'-azobisisobutyronitrile was added to 17.6 g of P-tert-butoxystyrene. The reaction product is polymerized in a toluene solvent at 80 DEG C for 6 hours under a nitrogen atmosphere. The reaction solution was cooled and then injected into methanol to precipitate crystals. The precipitated crystals were collected by filtration, washed with methanol, and dried under reduced pressure to obtain 15.5 g of poly (P-tert-butoxystyrene) in the form of a white powder. The product had a weight average molecular weight of 12,400.

(2) 15.0 g of the above poly (P-tert-butoxystyrene) in the form of a white powder was dissolved in 1,4-dioxane. Then, 10 ml of concentrated hydrochloric acid was added to the solution. The mixture is then heated under reflux for 2.5 hours. After cooling the reaction solution, it is injected into water to precipitate crystals. The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 9 g of poly (P-tert-butoxystyrene-P-hydroxystyrene) in the form of a white powder. The thus obtained polymer was confirmed by ¹ H-NMR to have a ratio of P-tert-butoxystyrene unit and P-hydroxystyrene unit of 1: 3. The weight average molecular weight of the polymer was 9,800.

[Synthesis Example 2]

[Synthesis of resin having an acid-decomposable group: compound (ii)]

9 g of poly (hydroxystyrene) (weight average molecular weight: 9,600) was dissolved in 100 ml of dimethoxyethane. Then 2.6 g of 3, 4-dihydro-2H-pyran and 0.5 ml of sulfuric acid were added to the solution. Then, the mixture was stirred at 30 to 40 DEG C for 15 hours. After completion of the reaction, the reaction solution is concentrated under reduced pressure. The residue is neutralized with sodium carbonate and then poured into water to precipitate crystals. The precipitated crystals were collected by filtration, washed with water, and dried under reduced pressure to obtain 11.0 g of poly (P-tetrahydropyranyloxystyrene-P-hydroxystyrene) in the form of a white powder. The thus obtained polymer was confirmed by ¹ H-NMR that the P-tetrahydropyranyloxystyrene unit and the P-hydroxystyrene unit were constituted by a ratio of 3 · 7 (by number).

[Synthesis Example 3]

[Synthesis of resin having an acid-decomposable group: compound (iii)]

22 g of Pt-butoxycarbonyloxystyrene obtained by the method described in U.S. Patent No. 4,491, 628 was dissolved in toluene in the presence of 2,2'-azobis (2,4-dimethylvaleronitrile) At 90 DEG C for 5 hours. Subsequently, the reaction solution was treated in the same manner as in Synthesis Example 1 (1) to obtain 15 g of poly (P-tert-butoxycarbonyloxystyrene) in the form of a white powder. Then, 7 g of the powder was subjected to the same reaction and post-treatment conditions as in the synthesis example ((2)) to obtain 4 g of poly (P-tert-butoxycarbonyloxystyrene-P-hydroxystyrene) in the form of a white powder . The thus obtained polymer was confirmed by ¹ H-NMR that the ratio of P-tert-butoxycarbonyloxystyrene unit and P-hydroxystyrene unit was 1: 9 (by number).

[Synthesis Example 4]

[Synthesis of resin having an acid-decomposable group: Compound (xvi)]

28 g of P-tert-butoxystyrene and 3.1 g of fumaronitrile were polymerized in toluene in the presence of 2,2'-azobis (methyl 2-methylpropionate) in a nitrogen atmosphere at 90 DEG C for 2 hours. After the reaction is completed, the reaction solution is poured into methanol to precipitate crystals. The precipitated crystals were collected by filtration, washed and dried to obtain 20 g of poly (P-tert-butoxystyrene-fumaronitrile) in the form of a white powder. Next, 15 g of poly (P-tert-butoxystyrene-P-hydroxystyrene-pumaronitrile) in the form of a white powder was added to 20 g of the powder under the same conditions as in Synthesis Example 1 (2) . The thus obtained polymer was confirmed by ¹ H-NMR that the ratio of P-tert-butoxystyrene unit to P-hydroxystyrene unit was 1: 4 (by number).

[Synthesis Examples 5 to 7]

[Synthesis of resin having an acid-decomposable group: Compound (i)]

The polymer obtained in Synthesis Example l (1) was treated in the same manner as in Synthesis Example 1 (2) except that the time of heating under stirring reflux was changed, and P-tert-butoxystyrene unit and P-hydroxystyrene (By the number) of 1: 1 (Synthesis Example 5), 1: 1.5 (Synthesis Example 6) and 1: 9 (Synthesis Example 7), respectively.

[Synthesis Example 8]

[Synthesis of resin having an acid-decomposable group: Compound (xix)]

5.8 g of N- (P-tert-butoxycarbonyloxyphenyl) -maleimide obtained by the method described in European Patent No. 254, 853 and 2 g of styrene were dissolved in 2, 2'-azobisisobutyronitrile In a nitrogen atmosphere at 80 ° C for 6 hours. Then, the reaction solution was treated in the same manner as in Synthesis Example 1 (1) to give 5 g of styrene-N- (4-tert-butoxycarbonyloxyphenyl) -maleimide copolymer. The thus obtained polymer was confirmed by ¹ H NMR, in which the styrene unit and the N- (4-tert-butoxycarbonyloxyphenyl) -maleimide unit consisted of a ratio of 1: 9 (by number).

[Synthesis Example 9]

[Synthesis of resin having an acid-decomposable group: Compound (v)]

12 g of poly (P-hydroxystyrene) (weight average molecular weight: 9,600) was dissolved in 120 ml of N, N-dimethylacetamide. To the solution was then added 7 g of potassium carbonate and 9 g of t-butyl bromoacetate. Then, the reaction mixture was stirred at 120 ° C for 7 hours, and then the reaction solution was treated in the same manner as in Synthesis Example 1 (1) to obtain a resin represented by the general formula (V) It was confirmed by ¹ H NMR that the units consisted of hydroxystyrene units in a ratio of 1: 6 (by number).

[Synthesis Example 10]

[Synthesis of dissolution inhibiting compound (1)

, ', -Tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene was dissolved in 400 ml of tetrahydrofuran. To this solution was then added 14 g of tert-butoxy potassium in a nitrogen atmosphere Tert-butyl dicarbonate (29.2 g) was added to the solution. After the reaction was allowed to proceed at room temperature for 3 hours, the reaction solution was poured into ice water, and the product was dissolved in ethyl The resulting crystalline solid material was recrystallized from diethyl ether and dried to give the title compound 16 (a), which was purified by column chromatography (Here, all R groups were t-BOC groups).

[Synthesis Example 11]

[Synthesis of dissolution inhibiting compound (2)

, ', -Tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene was dissolved in 400 ml of diethyl ether. To this solution, 3, 4-dihydro-2H-pyran After the reaction was completed, a small amount of sodium hydroxide was added and the mixture was filtered. Then, the solvent was removed from the filtrate The resulting product was purified by column chromatography and then dried to give a typical compound 16, wherein all R groups are THP groups.

[Synthesis 12]

[Synthesis of dissolution inhibiting compound (3)] [

, ', 21.2 g (0.15 mol) of potassium carbonate was added to a solution of 19.2 g (0.04 mol) of tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene in 120 ml of N, N- dimethylacetamide, After addition of 27.1 g (0.14 mol) of butyl bromoacetate, the mixture was stirred for 7 hours at 120 DEG C. The reaction mixture was then poured into 1.5 liters of water and then extracted with ethyl acetate. , And the extract was concentrated and distilled off by column chromatography (carrier: silica gel; developing solvent: ethyl acetate and n-hexane 3: 7 (volume ratio)) to obtain 30 g of a pale yellowish solid. And all of the groups are -CH ₂ COOC ₄ H ₉ ^t groups).

[Synthesis Example 13]

[Synthesis of dissolution inhibiting compound (4)] [

One- [ -methyl- - (4'-hydroxyphenyl) ethyl] -4- [ ', (0.010 mole) of bis (4 "-hydroxyphenyl) ethyl] benzene was dissolved in 300 ml of N, N-dimethylacetamide. To this solution were added 49.5 g (0.35 mol) of potassium carbonate, The reaction mixture was then poured into 2 liters of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate. To the residue was added ethyl acetate The acetate extract was concentrated and purified in the same manner as in Synthesis Example (3) to obtain 70 g of a typical compound 8 (all R groups being -CH ₂ COOC (CH ₃ ) ₂ C ₆ H ₅ groups).

[Synthesis Example 14]

[Synthesis of dissolution inhibiting compound (5)] [

, , ', ', ", (0.15 mol) of potassium carbonate and a mixture of t (t-butylphenoxy) -1,3,5-triethylbenzene (0.033 mol) in N, N-dimethylacetamide (0.14 mol) of butyl bromoacetate were added and the mixture was stirred for 7 hours at 120 DEG C. The reaction mixture was then poured into 1.5 liters of water and then extracted with ethyl acetate, dried over magnesium sulfate The extract was concentrated and purified by column chromatography (carrier: silica gel; developing solvent: ethyl acetate and n-hexane 2: 8 (by volume)) to give 24 g of pale yellow powder. And all of the groups are -CH ₂ -CO-C ₄ H ₉ ^t groups).

[Synthesis Example 15]

[Synthesis of dissolution inhibiting compound (6)] [

, , ', ', ", 10.6 g (0.14 mol) of potassium carbonate was added to a solution of 14.3 g (0.020 mol) of hexasuccine (4-hydroxyphenyl) -1,3,5-triethylbenzene in 120 ml of N, N- dimethylacetamide, After adding 13.6 g (0.07 mol) of butyl bromoacetate, the mixture was stirred for 7 hours at 120 ° C. The reaction mixture was then poured into 1.5 L of water and extracted with ethyl acetate. , concentrated extract was purified by column chromatography (carrier: silica gel: developing solvent: ethyl acetate and n- hexane 1: 5 (volume ratio)), R 3 in the typical compound 40 (where the molecule by a group -CH ₂ -CO0- C ₄ H ₉ ^t group, and the remaining R groups are hydrogen atoms).

[Examples 1 to 22]

The compounds according to the present invention described in the above Synthesis Examples were used for preparing resists having the formulations described in Table 1. [

[Comparative Examples 1 and 2]

According to the method described in U.S. Patent No. 4,491,628, t-butoxycarbonyloxystyrene polymer and t-butoxycarbonyloxy- -Methylstyrene polymer was synthesized. These polymers were used to prepare two-component positive resist. The prescriptions (formulas) of these resists are described in Table 1.

[Comparative Examples 3, 4, 5]

Compounds having the following general formula described in German Patent No. 4,214,363 and di-t-butyl terephthalate described in JP-A-4-158363 and tri-t-butoxyfluoroglycitricarbonate are shown in Table 1 Was used as a dissolution inhibitor to prepare a three component positive resist having the prescribed recipe.

[Comparative Example 6]

Poly (P-hydroxystyrene) was used as a resin not having the acid-decomposable group and the dissolution inhibitor compound (42) of the present invention by preparing a three-component positive resist. The prescription of the resist is described in Table 1.

[Table 1: Prescription of Photosensitive Composition]

The abbreviations used in Table 1 are as follows.

(Suzy)

TBOCS: t-butoxycarbonyloxystyrene polymer

(Number average molecular weight: 21,600)

TBAMS: t-Butoxycarbonyloxy- - methylstyrene polymer

(Weight average molecular weight: 46,900)

PVP: P-hydroxystyrene polymer

(Weight average molecular weight: 9,600)

(Dissolution inhibiting agent)

DTBTP: di-t-butyl terephthalate

TBFTC: Tri-t-butoxy fluoroglycidyl tricarbonate

TBE6SI:

(Acid-decomposable group in dissolution inhibiting agent)

[Preparation and evaluation of photosensitive composition]

Each of the materials shown in Table 1 is dissolved in 6 g of diglyme. Thereafter, the solution was filtered through a 0.2 mu m filter to prepare a resist solution. The resist solution was applied onto a silicon wafer using a spin coater at a rotation speed of 3,000 rpm, and then vacuum-adsorbed at 110 DEG C And dried on a hot plate for 60 seconds to obtain a resist film having a film thickness of 1.0 mu m.

This resist film was exposed with an excimer laser stepper (NA = 0.42) of 248 nm KrF. After the exposure, the substrate was heated at 100 캜 on a vacuum adsorption type hot plate for 60 seconds, immediately immersed in an aqueous solution of 1.19 wt% tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope (SEM) to evaluate the profile of the resist (sidewall angle). The results are shown in Table 2.

Here, the sensitivity was defined as a reciprocal of the exposure required to reproduce a mask pattern of 0.50 mu m, and expressed as a relative value of the sensitivity of Comparative Example 1 evaluated at 1.0. Film shrinkage was expressed by the item of film thickness ratio before and after exposure and baking. In Table 2, the resolution means a marginal resolution expressed by the reproduced minimum mask pattern size depending on the exposure required to completely reproduce the mask pattern size of 0.5 mu m. P indicates a worse state than the reference, and G indicates a state that is better than or equal to the reference.

From the results shown in Table 2, it can be seen that the resist according to the present invention is not sensitive to the influence of the standing wave and provides a good profile and a high resolution since the film shrinkage after exposure is low.

[Table 2: Results of evaluation]

The chemically amplified positive photosensitive composition of the present invention provides a good profile and high resolution without generation of a standing wave since film shrinkage due to post-exposure bake is small and film reduction after development (in unexposed areas) is small.

Although the present invention has been described in detail with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications may be made therein without departing from the spirit and scope of the invention.

Claims (4)

(a) a resin having an acid-decomposable group whose solubility increases in an alkaline developer by reaction with acid. (b) a compound which generates an acid upon irradiation with an actinic ray or radiation; (c) at least three structural units each having a molecular weight of 3,000 or less including an acid-decomposable group whose solubility is increased in an alkali developing solution by reaction with acid and each having one acid-decomposable group substituted on one benzene ring per molecule And a non-polymeric acid-decomposable dissolution inhibitor having at least 9 bond atoms (excluding an acid-decomposable group) interposed between two acid-decomposable groups at the farthest position, Wherein the resin (a) is a resin obtained by protecting an alkali-soluble group of an alkali-soluble resin having an acid-decomposable group and the alkali dissolution rate of the alkali-soluble resin (a) is 0.261N in an aqueous solution of tetramethylammonium hydroxide (TMAH) Lt; RTI ID = 0.0 &gt; A / sec &lt; / RTI &gt; (a) a resin having an acid-decomposable group whose solubility is increased in an alkali developer by reaction with an acid, (b) a compound which generates an acid upon irradiation with an actinic ray or radiation: (c) at least three structural units each having a molecular weight of 3,000 or less including an acid-decomposable group whose solubility is increased in an alkali developing solution by reaction with acid and each having one acid-decomposable group substituted on one benzene ring per molecule And a non-polymeric acid-decomposable dissolution inhibitor having at least 9 bond atoms (excluding an acid-decomposable group) interposed between two acid-decomposable groups at the farthest position, Wherein the resin (a) has a fungus molecular weight of 1,000 to 100,000. The positive photosensitive composition according to claim 1 or 2, wherein the acid-decomposable dissolution inhibiting compound (c) has a molecular weight of 500 to 3,000. 3. The positive photosensitive composition according to claim 1 or 2, wherein the non-polymeric acid-decomposable dissolution inhibiting agent (c) has a molecular weight of 1,000 to 2,500.