JPH1078659A - Photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure high sensitivity and high resolution and to prevent the deterioration of the sensitivity and resolution with the lapse of time from exposure to post-exposure by incorporating a compd. having at least one kind of specified group decomposable by the action of an acid and increasing its solubility in an aq. alkali soln. by the action of the acid. SOLUTION: This photosensitive compsn. contains a compd. having at least one kind of group decomposable by the action of an acid and increasing its solubility in an aq. alkali soln. by the action of the acid. The group is represented by the formula, wherein R is alkylene which may have a substituent, the alkylene is, e.g. methylene, ethylene, propylene or butylene, each of X and Y is O or S, X and Y are not simultaneously 0, R1 is alkyl, alkenyl, aralkyl, aryl or cycloalkyl, each of these groups may have a substituent and (n) is an integer of 0-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive composition, and more particularly to a semiconductor integrated circuit device, a mask for manufacturing an integrated circuit,
The present invention relates to a chemically amplified positive resist composition used for manufacturing printed wiring boards, liquid crystal panels, and the like.

[0002]

2. Description of the Related Art When a conventional resist comprising a novolak and a naphthoquinonediazide compound is used for lithographic pattern formation using far ultraviolet light or excimer laser light, novolak and naphthoquinonediazide have a strong absorption in the far ultraviolet region. Light hardly reaches the bottom of the resist, and only a low-sensitivity, tapered pattern can be obtained.

One of the means for solving such a problem is as follows.
It is a chemically amplified resist composition described in U.S. Pat. No. 4,491,628 and European Patent No. 249,139. The chemically amplified positive resist composition produces an acid in the exposed area by irradiation with radiation such as deep ultraviolet light, and the acid-catalyzed reaction causes the active and non-irradiated parts of the active radiation to dissolve in the developing solution. Is a pattern forming material for forming a pattern on a substrate by changing the pattern.

[0004] Examples of such a combination include a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (JP-A-48-90303), a combination of an orthoester or an amide acetal compound ( JP-A-5120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-1)
No. 33429), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236), a combination with a polymer having an orthoester group in the main chain. (JP-A-56-17345), a combination with a tertiary alkyl ester compound (JP-A-60-3625), and a combination with a silyl ester compound (JP-A-60-10247).
No.) and a combination with a silyl ether compound (Japanese Unexamined Patent Publication No.
0-37549, JP-A-60-112446) and the like. These have high photosensitivity because the quantum yield exceeds 1 in principle.

Similarly, systems which are stable under aging at room temperature, but are decomposed by heating in the presence of an acid and solubilized in alkali are disclosed in, for example, JP-A-59-45439, JP-A-60-3625, JP-A-62-2229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250542, Polym.Eng.Sce., Vol. 23, 101
2 (1983); ACS.Sym. 242, 11 (1984); Semicon
ductor World 1987, November, p. 91; Macromolecules,
Vol.21, p.1475 (1988); a compound capable of generating an acid upon exposure described in SPIE, vol.920, p.42 (1988);
Combination systems with esters or carbonate compounds of primary or secondary carbons (eg t-butyl, 2-cyclohexenyl). These systems also have high sensitivity and have a deep-UV compared to the naphthoquinonediazide / novolak resin system.
Since the absorption in the region is small, it can be an effective system for shortening the wavelength of the light source.

The above chemically amplified positive resist composition comprises an alkali-soluble resin, a compound capable of generating an acid upon exposure to radiation (photoacid generator), and a compound inhibiting dissolution of the alkali-soluble resin having an acid-decomposable group. It can be roughly classified into a three-component system and a two-component system composed of a resin having a group which is decomposed by the reaction with an acid and becomes alkali-soluble, and a photoacid generator.

[0007]

In the above resist composition, t-BOC group, t-butylcarbonyl ester group and the like are used as acid-decomposable groups used in resins or low molecular weight compounds. There is a carbonate type. This carbonate-type acid-decomposable group has a low acid-decomposability, so that the time between exposure and post-exposure bake (PED)
In this case, there was a problem such as T-top formation. On the other hand, an acid-decomposable group includes an acetal group which is easily decomposed by an acid. Although this acetal group can solve problems such as T-top formation by PED, it has a problem in storage stability that it is decomposed during storage.

Accordingly, an object of the present invention is to provide a high sensitivity and a high resolution and have no problems such as formation of a T-top due to lapse of time from exposure to post-exposure bake (PEB) and a decrease in sensitivity and resolution. An object of the present invention is to provide an excellent photosensitive composition that forms a good resist pattern.

[0009]

Means for Solving the Problems The present inventors have made intensive studies on this point, and as a result, have found that a photosensitive composition containing a compound containing a specific acid-decomposable group has a high resolution and the above-mentioned problems. The inventors have obtained the knowledge that the points can be solved, and reached the present invention. The object of the present invention is achieved by the following configurations. (1) It is characterized by containing a compound having at least one group represented by the following general formula (I) which can be decomposed by the action of an acid and whose solubility in an aqueous alkaline solution is increased by the action of an acid. Photosensitive composition.

[0010]

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In the formula (I), R represents an alkylene group which may have a substituent, X and Y may be the same or different and represent an oxygen atom or a sulfur atom, provided that X and Y are They do not represent oxygen atoms at the same time. R ₁ represents an optionally substituted alkyl group, alkenyl group, aralkyl group, aryl group or cycloalkyl group. n is 0
Represents an integer of 3.

(2) a compound which generates an acid upon irradiation with actinic rays or radiation, a resin which is insoluble in water and soluble in an aqueous alkaline solution, and a group represented by the general formula (I) described in the above (1) A photosensitive composition comprising at least one non-polymeric dissolution inhibiting compound whose solubility in an aqueous alkaline solution is increased by the action of an acid.

(3) A compound which generates an acid upon irradiation with actinic rays or radiation, and has at least one group represented by the general formula (I) described in (1) above, and has a solubility in an aqueous alkaline solution. A polymer type dissolution inhibiting compound which is increased by the action of an acid.

(4) A compound capable of generating an acid upon irradiation with actinic rays or radiation, having at least one kind of the group represented by the general formula (I) described in the above (1), and having a solubility in an aqueous alkaline solution. A non-polymeric dissolution inhibiting compound which increases by the action of an acid, and which has at least one group represented by the general formula (I) described in the above (1), and whose solubility in an aqueous alkaline solution is increased by the action of an acid A photosensitive composition comprising a polymer-type dissolution inhibiting compound.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a non-polymeric dissolution inhibiting compound is a compound having a constant molecular weight of 3000 or less and having a single structure and an acid-decomposable compound represented by the above general formula (I). A compound having a structure in which a group is introduced, and which becomes alkali-soluble by the action of an acid. The polymer-type dissolution inhibiting compound refers to a compound having a molecular weight distribution obtained by polymerizing a monomer, which is represented by the above general formula (I)
Is a compound having a structure into which an acid-decomposable group is introduced, and which becomes alkali-soluble by the action of an acid. Examples of the alkylene group represented by R in the general formula (I) include a methylene group, an ethylene group, a propylene group, and a butylene group, and these may further have a substituent.

The alkyl group represented by R ₁ is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Examples of the alkenyl group include a vinyl group, a propenyl group,
Those having 2 to 4 carbon atoms such as an allyl group and a butenyl group are preferred. The aralkyl group preferably has 7 to 10 carbon atoms, such as a benzyl group, a phenethyl group and a cumyl group.
As the cycloalkyl group, those having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclohexyl group and an adamantyl group are preferred. The aryl group is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a xylyl group, a toluyl group, a cumenyl group, a naphthyl group and an anthracenyl group. Each of these substituents may further have a substituent.

Further substituents in the above include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above-mentioned alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, and a propoxy group. -Hydroxypropoxy group-n-butoxy group-isobutoxy group-sec-butoxy group-alkoxy group such as t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group-ethoxycarbonyl group, benzyl group-phenethyl group-
Aralkyl groups such as cumyl group, aralkyloxy groups, acyl groups such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, valeryl group, acyloxy groups such as butyryloxy group, the above alkenyl group, vinyloxy group and propenyloxy group Examples thereof include alkenyloxy groups such as a group, allyloxy group, and butenyloxy group, aryloxy groups such as the above-mentioned aryl group and phenoxy group, and aryloxycarbonyl groups such as a benzoyloxy group. Hereinafter, specific examples of the acid-decomposable group represented by the general formula (I) are shown, but the present invention is not limited thereto.

[0018]

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[0019]

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Hereinafter, the compounds used in the present invention will be described in detail. In the non-polymeric dissolution inhibiting compound having a group represented by the above general formula (I) used in the present invention, the acid-decomposable group represented by the general formula (I) has At least two, and at the position where the distance between the acid-decomposable groups is farthest away, at least 10, preferably at least 11, bonding atoms excluding the acid-decomposable group.
, More preferably at least 12 compounds,
Or at least three acid-decomposable groups, and at the position where the distance between the acid-decomposable groups is farthest away, at least nine, preferably at least ten, bonding atoms excluding the acid-decomposable groups.
It is advantageous to use compounds via more than one, more preferably at least eleven.

The non-polymeric dissolution inhibiting compound suppresses the solubility of the alkali-soluble resin itself in alkali, and the acid generated upon exposure to light causes the acid-decomposable group to be deprotected. Has the effect of promoting solubility. JP-A-63-27829 and JP-A-3-198059 disclose a dissolution inhibiting compound having a skeleton compound of naphthalene, biphenyl and diphenylcycloalkane, but have a small dissolution inhibiting property for an alkali-soluble resin, and have a high profile and resolution. Is not enough.

In the present invention, a preferred non-polymeric dissolution inhibiting compound is a compound having a single structure having a molecular weight of 3,000 or less and having three or more alkali-soluble groups in one molecule, wherein 70% or more of the alkali-soluble group is represented by the above formula (I). It is a compound protected by the acid-decomposable group of I).

In the present invention, the upper limit of the number of bonding atoms is preferably 50, more preferably 40. In the present invention, when the non-polymer type dissolution inhibiting compound has three or more, preferably four or more acid-decomposable groups of the general formula (I), and even if it has two acid-decomposable groups,
When the acid-decomposable groups are separated from each other by a certain distance or more, the dissolution inhibiting property with respect to an alkali-soluble resin is significantly improved.

The distance between the acid-decomposable groups in the present invention is indicated by the number of via-bond atoms excluding the acid-decomposable groups. For example, in the case of the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonding atoms, and in the compound (3), the bonding atom is 12 bonding atoms.

[0025]

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The non-polymeric dissolution-inhibiting compound of the present invention may have a plurality of acid-decomposable groups on one benzene ring, but preferably has one acid-decomposable group on one benzene ring.
It is a compound composed of a skeleton having two acid-decomposable groups. Further, the molecular weight of the non-polymeric dissolution inhibiting compound of the present invention is 3,500 or less, preferably 500 to 3,0.
00, more preferably 1,000 to 2,500.
When the molecular weight of the non-polymeric dissolution inhibiting compound of the present invention is in the above range, it is preferable in terms of high resolution.

Preferred non-polymeric dissolution inhibiting compounds are
JP-A-1-289946, JP-A-1-289947
JP-A-2-2560, JP-A-3-128959
JP-A-3-158855, JP-A-3-17935
No. 3, JP-A-3-191351, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
No. 253, JP-A-3-200254, JP-A-3-20
0255, JP-A-3-259149, JP-A-3-2
No. 79958, JP-A-3-279959, JP-A-4-
1650, JP-A-4-1651, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
No. 7, Japanese Patent Application No. 3-33229, Japanese Patent Application No. 3-23079
No. 0, Japanese Patent Application No. 3-320438, Japanese Patent Application No. 4-2515
7, Japanese Patent Application No. 4-52732, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
Compounds in which some or all of the phenolic OH groups of the polyhydroxy compound described in the specification such as No. 5 are bonded with the group represented by the general formula (I) and protected are included.

More preferably, JP-A-1-289946.
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
255, JP-A-3-259149, JP-A-3-27
9958, JP-A-4-1650, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
7, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
No. 5 using the polyhydroxy compound described in the specification.

More specifically, general formulas [I] to [XV]
The compound represented by I] is mentioned.

[0030]

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[0031]

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[0032]

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[0033]

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Here, R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ and R ¹³⁰ may be the same or different and are a hydrogen atom or a group represented by the general formula (I).

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

[0036]

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[0037] Here, G = 2 to 6, provided that at least one alkyl group of R ^0.99, R ¹⁵¹ when the ^{G = 2, R 150, R} 151: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH,
-CN, halogen atom, -R ¹⁵² -COOR ^{15 3} or ^{-R 154 -OH, R 152, R} 154: an alkylene group, R ^153: a hydrogen atom, an alkyl group, an aryl group or an 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 and include a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a halogen atom, nitro Group, carboxyl group, cyano group, or -N ( ^R155 ) ( ^R156 ) ( ^R155 , ^R156 : H, alkyl group or aryl group) ^R110 : single bond, alkylene group, or

[0038]

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R ¹⁵⁷ and R ¹⁵⁹ may be the same or different, and represent a single bond, an alkylene group, —O—, —S—, —CO
— Or carboxyl group, R ¹⁵⁸ : hydrogen atom, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, nitro group, hydroxyl group, cyano group, or carboxyl group, provided that the hydroxyl group is replaced with an acid-decomposable group. You may.

R ¹¹⁹ and R ^120, which may be the same or different, are a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group; R ^{124 to} R ¹²⁷ may be the same or different and may be a hydrogen atom or an alkyl group; R ^{135 to} R ¹³⁷ may be the same or different and a hydrogen atom;
An alkyl group, an alkoxy group, an acyl group, or an acyloxy group, R ¹⁴² : a hydrogen atom, a group represented by the general formula (I), or

[0041]

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R ¹⁴⁴ and R ¹⁴⁵ may be the same or different and represent a hydrogen atom, a lower alkyl group, a lower haloalkyl group,
Or an aryl group, R ^{146 to} R ¹⁴⁹ : may be the same or different and represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carbonyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aralkyl group, and an aralkyloxy group. A group, an acyl group, an acyloxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group, provided that the four substituents having the same symbol need not be the same group. : —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: at plural times, the groups in () may be the same or different; a to q, s, t, v, g1 to i1, k1 m1, o1, q1, s1, u1: 0 or an integer of 1 to 5, r, u, w, x, y, z, a1~f1, p1, r1, t1, v1~x1: 0 or 1
An integer of 4, j1, n1, z1, a2, b2, c2, d2: an integer of 0 or 1 to 3, at least one of z1, a2, c2, d2 is 1 or more, y1: an integer of 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, provided that (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), (s1 + u1)
≦ 5.

[0043]

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[0044]

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[0045]

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[0046]

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Specific examples of preferred compound skeletons are shown below.

[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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R in the compounds (1) to (63) represents a hydrogen atom or

[0068]

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This is a group selected from However, at least two, or three depending on the structure, are groups other than hydrogen atoms, and each substituent R may not be the same group.

The amount of the non-polymeric dissolution inhibiting compound used in the present invention is 3 to 30% by weight, preferably 3 to 30% by weight, based on the total weight of the photosensitive composition (excluding the solvent).
２８28% by weight. If the amount of the non-polymeric dissolution inhibiting compound used in the present invention is less than 3% by weight, high resolution cannot be obtained, and if it is more than 30% by weight, film shrinkage occurs or the heat resistance of the resist deteriorates.

The polymer-type dissolution inhibiting compound of the present invention includes at least one kind of acid-decomposable group represented by the general formula (I) in the main chain or side chain of the base resin, or in both the main chain and the side chain. It is preferable to use a resin having a group, and among them, a resin having an acid-decomposable group in a side chain is particularly preferable.

Next, when the acid-decomposable group is bonded as a side chain, the base resin is -OH or-
COOH, in particular, -R ⁰ -COOH or -AR-O
An alkali-soluble resin having an H group is preferable, for example,
The alkali-soluble resin containing no acid-decomposable group used in the present invention (hereinafter simply referred to as alkali-soluble resin).
(Preferably, polyhydroxystyrene, a novolak resin, a derivative thereof) and an alkali-soluble resin containing a p-hydroxystyrene unit (preferably, poly (p
-Hydroxystyrene, p / m-hydroxystyrene,
p / o-hydroxystyrene, p-hydroxystyrene-styrene copolymer), an alkyl-substituted hydroxy resin such as a 4-hydroxy-3-methylstyrene resin and a 4-hydroxy-3,5-dimethylstyrene resin; It is preferably an alkylated or acetylated OH moiety.

Further, when a part of the phenol nucleus (30 mol% or less of the total phenol nucleus) of the above resin is hydrogenated, the transparency of the resin is improved, which is preferable in terms of sensitivity, resolution, and rectangular formation of profile. . As the alkali-soluble resin used as the base resin, for example, novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, poly Partially O-alkylated or O-acylated hydroxystyrene, styrene-maleic anhydride copolymer, carboxyl group-containing methacrylic resin and derivatives thereof, styrene-polyhydroxystyrene copolymer, hydrogenated polyhydroxystyrene However, the present invention is not limited to these.

The particularly preferred alkali-soluble resin used as the base resin is a novolak resin or an alkali-soluble resin containing a p-hydroxystyrene unit (preferably poly (p-hydroxystyrene, p / m-
Hydroxystyrene, p / o-hydroxystyrene, p
-Hydroxystyrene-styrene copolymer), 4-hydroxy-3-methylstyrene resin, 4-hydroxy-
Alkyl-substituted hydroxy resins such as 3,5-dimethylstyrene resin, alkylated or acetylated OH portion of the resin, partially hydrogenated polyhydroxystyrene resin, polyhydroxystyrene resin, partially hydrogenated novolak resin,
Partially hydrogenated polyhydroxystyrene resin.

Here, polyhydroxystyrene refers to p
-Hydroxystyrene monomer, m-hydroxystyrene monomer, o-hydroxystyrene monomer or at least one or more monomers selected from alkylstyrene-substituted hydroxystyrene monomers having an ortho-position of 1 to 4 carbon atoms. The polymer obtained by the above is shown.

The alkali dissolution rate of the alkali-soluble resin for the base resin was determined by measuring with 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.) to 1
Those at 70 ° / sec or more are preferred. Particularly preferably 33
0Å / sec or more (Å is Angstroms).
From the viewpoint of achieving a rectangular profile, an alkali-soluble resin having a high transmittance to far ultraviolet light or excimer laser light is preferable. Preferably, a 248 nm film having a thickness of 1 μm
Is 20 to 80%.

From these viewpoints, particularly preferred alkali-soluble resins for the base resin are polyhydroxystyrene,
Hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, partially o-acylated polyhydroxystyrene, hydroxystyrene-styrene copolymer and hydrogenated novolak resin.

The resin having an acid-decomposable group of the present invention is described in European Patent No. 2,485,853, JP-A-2-25850, and JP-A-2-25850.
As disclosed in JP-A-223860 and JP-A-4-251259, an alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an alkali-soluble resin monomer having an acid-decomposable group bonded thereto is mixed with various monomers. It can be obtained by copolymerization.

The general formulas of the resin having an acid-decomposable group thus synthesized are shown below in (a) to (e), but the present invention is not limited to these.

[0080]

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[0081]

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Here, L represents an acid-decomposable group represented by the general formula (I). R _10: may be different or R ₁₀ are each the same in the same molecule, a hydrogen atom or alkyl group having 1 to 4 carbon atoms, R _11, R _13: in each group of the same name in the same molecule the same May be different, a hydrogen atom or carbon number 1-4
Alkyl groups, R ₁₂ : hydrogen atom, carboxyl group, cyano group or substituted aryl group, R ₁₄ : hydrogen atom, cyano group or —COOR ₁₅ , R ₁₅ : straight-chain, branched or A cyclic alkyl group, R ₇ : a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Ar: a monocyclic or polycyclic substituent 1
Valent aromatic groups, k, p, k1, p1, m, and n each independently represent a natural number.

More specifically, the following can be mentioned.

[0084]

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In the polymer-type dissolution inhibiting compound of the present invention, the content of the acid-decomposable group is determined by the number of acid-decomposable groups (B) in the resin and the number of alkali-soluble groups not protected by the acid-decomposable group ( S) and is represented by B / (B + S). The content is 0.10 to 0.40, preferably 0.15 to
0.35, more preferably 0.20 to 0.35.
When B / (B + S)> 0.4, the film contraction after PEB and the profile at the time of defocusing become reversely tapered, and the defocusing latitude with the isolated line becomes narrow, which causes poor adhesion to the substrate and scum. Therefore, it is not preferable.
On the other hand, if B / (B + S) <0.10, sufficient process latitude cannot be obtained.

The weight-average molecular weight of the acid-decomposable group-containing resin of the present invention is preferably in the range of 1,000 to 100,000. If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 100,000, the developing speed is reduced. Particularly preferred are 2,000-6
It is in the range of 0000. Here, the weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography.

In the present invention, these resins having an acid-decomposable group may be used as a mixture of two or more kinds. The amount of the acid-decomposable group-containing resin used is 50 to 97% by weight, preferably 6% by weight, based on the total weight of the photosensitive composition (excluding the solvent).
0 to 90% by weight. 50% by weight of this resin
If the amount is smaller, the dry etching resistance is deteriorated.

A resin insoluble in water and soluble in an aqueous alkali solution used in the present invention (an alkali-soluble resin containing no acid-decomposable group, hereinafter simply referred to as an alkali-soluble resin).
Are alkali-soluble resins (preferably polyhydroxystyrene, novolak resins, derivatives thereof), p-
Alkali-soluble resins containing hydroxystyrene units (preferably poly (p-hydroxystyrene, p /
m-hydroxystyrene, p / o-hydroxystyrene, p-hydroxystyrene-styrene copolymer), 4
Alkyl-substituted hydroxy resins such as -hydroxy-3-methylstyrene resin and 4-hydroxy-3,5-dimethylstyrene resin, and alkylated or acetylated OH moieties of the above resins are preferred.

Further, when a part of the phenol nucleus (30 mol% or less of all phenol nuclei) of the above resin is hydrogenated, the transparency of the resin is improved, which is preferable in terms of sensitivity, resolution, and formation of a rectangular profile. . As the alkali-soluble resin used in the present invention, for example, novolak resin,
Hydrogenated novolak resin, acetone-pyrogallol resin,
Polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-
Substituted maleimide copolymer, partially O-alkylated or O-acylated polyhydroxystyrene, styrene-maleic anhydride copolymer, carboxyl group-containing methacrylic resin and derivatives thereof, styrene-polyhydroxystyrene copolymer, Examples include, but are not limited to, hydrogenated polyhydroxystyrene.

Particularly preferred alkali-soluble resins used in the present invention are novolak resins and alkali-soluble resins containing p-hydroxystyrene units (preferably poly (p-hydroxystyrene, p / m-hydroxystyrene, p / o- Hydroxystyrene, p-hydroxystyrene-styrene copolymer), 4-hydroxy-3-
Alkyl-substituted hydroxy resins such as methylstyrene resin, 4-hydroxy-3,5-dimethylstyrene resin,
An alkylated or acetylated product of the OH portion of the above resin, a partially hydrogenated polyhydroxystyrene resin, a polyhydroxystyrene resin, a partially hydrogenated novolak resin, and a partially hydrogenated polyhydroxystyrene resin.

In the present invention, polyhydroxystyrene refers to a p-hydroxystyrene monomer, an m-hydroxystyrene monomer, an o-hydroxystyrene monomer or a hydroxystyrene monomer having an ortho-substituted alkyl group having 1 to 4 carbon atoms. It shows a polymer obtained by polymerizing at least one kind of monomer selected from the above.

The novolak resin is obtained by subjecting a predetermined monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

As the predetermined monomer, phenol, m
Cresols such as -cresol, p-cresol and o-cresol, xylenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and 2,3-xylenol, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, Alkoxyphenols such as -methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol, 2-methyl-4-isopropyl Fenault Bis-alkylphenols etc., m
Hydroxychloro compounds such as -chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or as a mixture of two or more, but are not limited thereto. It is not something to be done.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde , O-chlorobenzaldehyde,
m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-
Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural,
Chloroacetaldehyde and its acetal form, such as chloroacetaldehyde diethyl acetal, can be used, and among these, formaldehyde is preferably used.

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

The case where the photosensitive composition of the present invention is used for a chemically amplified positive resist composition will be described below as an example. The photoacid generator used in the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation. Compounds that are decomposed by irradiation with actinic rays or radiation to generate an acid used in the present invention include a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes,
Known light used in photochromic agents or micro resists (ultraviolet rays of 400 to 200 nm, far ultraviolet rays,
Particularly preferably, g line, h line, i line, KrF excimer laser beam), ArF excimer laser beam, electron beam, X
A compound that generates an acid by a beam, a molecular beam, or an ion beam and a mixture thereof can be appropriately selected and used.

Further, examples of other compounds used in the present invention that generate an acid upon irradiation with actinic rays or radiation include, for example, SISchlesinger, Photogr. Sci. Eng., 18, 3
87 (1974), TSBetal, Polymer, 21,423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,06
Ammonium salts described in 9,056, Re 27,992, Japanese Patent Application No. 3-140,140, etc., DC Necker et al., Macromolecules, 1
7,2468 (1984), CSWenetal, Teh, Proc.Conf.Rad.Curing
ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055
No. 4,069,056, etc.
vello etal, Macromorecules, 10 (6), 1307 (1977), Chem.
& Eng.News, Nov. 28, p31 (1988), EP 104,143,
U.S. Patent Nos. 339,049 and 410,201, JP-A-2-150,84
No. 8, iodonium salts described in JP-A-2-296,514 etc.,
JVCrivello etal, Polymer J. 17, 73 (1985), JVCrive
llo etal. J. Org. Chem., 43, 3055 (1978), WRWatt eta
l, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984),
JVCrivello etal, Polymer Bull., 14,279 (1985), JV
Crivello etal, Macromorecules, 14 (5), 1141 (1981), J.
V. Crivello etal, J. PolymerSci., Polymer Chem. Ed., 17,
2877 (1979), European Patent Nos. 370,693 and 3,902,114
233,567, 297,443, 297,442, U.S. Pat.
No. 33,377, No. 161,811, No. 410,201, No. 339,049,
No. 4,760,013, No. 4,734,444, No. 2,833,827, Dokoku Patent No. 2,904,626, No. 3,604,580, No. 3,604,581, etc.
ecules, 10 (6), 1307 (1977), JVCrivello etal, J. Polym
erSci., Polymer Chem. Ed., 17, 1047 (1979), etc., selenonium salts, CSWen et al., Teh, Proc. Conf. Rad.
g Onium salts such as arsonium salts described in ASIA, p478 Tokyo, Oct (1988) and the like, U.S. Pat.No. 3,905,815, JP-B-46
No. 4605, JP-A-48-36281, JP-A-55-32070, JP-A
No. 60-239736, JP-A-61-169835, JP-A-61-169837
No., JP-A-62-58241, JP-A-62-212401, JP-A-63-58241
No. 70243, organic halogen compounds described in JP-A-63-298339, etc., K. Meier et al, J. Rad.Curing, 13 (4), 26 (1986),
TPGill et al, Inorg.Chem., 19,3007 (1980), D. Astru
c, Acc. Chem. Res., 19 (12), 377 (1896), organometallic / organic halides described in JP-A-2-14145, etc., S. Hayase et.
al, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al.
J.Pholymer Sci., Polymer Chem.Ed., 23, 1 (1985), QQZh
u etal, J. Photochem., 36, 85, 39, 317 (1987), B. Amit eta
l, Tetrahedron Lett., (24) 2205 (1973), DHR Barton eta
l, J. Chem Soc., 3571 (1965), PM Collins et al., J. Chem.
SoC., Perkin I, 1695 (1975), M. Rudinstein et al, Tetrahe
dron Lett., (17), 1445 (1975), JWWalker etal J. Am. Che
m.Soc., 110, 7170 (1988), SCBusman et al., J. Imaging Te
chnol., 11 (4), 191 (1985), HMHoulihan et al, Macormole
cules, 21, 2001 (1988), PM Collins et al., J. Chem. Soc.,
Chem. Commun., 532 (1972), S. Hayase et al, Macromolecule
s, 18, 1799 (1985), E. Reichmanis et al., J. Electrochem. So
c., Solid State Sci. Technol., 130 (6), FMHoulihan et.
al, Macromolcules, 21, 2001 (1988), EP 0290,750
Nos. 046,083, 156,535, 271,851, 0,38
No. 3,343, U.S. Pat.
etal, Polymer Preprints Japan, 35 (8), G. Berner etal,
J.Rad.Curing, 13 (4), WJMijs etal, Coating Techno
l., 55 (697), 45 (1983), Akzo, H. Adachi et al, Polymer Pr
eprints, Japan, 37 (3), European Patent Nos. 0199,672 and 84515
No. 199,672, No. 044,115, No. 0101,122, U.S. Pat.Nos. 618,564, 4,371,605, 4,431,774, JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No. 3- Compounds which generate sulfonic acid upon photolysis, such as the iminosulfonates described in 140109 and the like, and disulfone compounds described in JP-A-61-166544 and the like can be mentioned.

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
Soc., 104, 5586 (1982), SPPappas etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Rap
id Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Che
m., 152, 153, 163 (1972), JVCrivello etal, J. PolymerS
ci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
49,137, Dokoku Patent 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038
JP-A-63-163452, JP-A-62-153853, JP-A-63-163452
Compounds described in JP-A-146029 can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
Compounds that generate an acid by light described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PA)
An S-triazine derivative represented by G2).

[0101]

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In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0103]

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[0104]

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[0105]

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(2) An iodonium salt represented by the following formula (PAG3) or a sulfonium salt represented by the following formula (PAG4).

[0107]

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

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, an aryl group having 6 to 14 carbon atoms, 1 to 8 carbon atoms
And substituted derivatives thereof. Preferred substituents are those having 1 to 8 carbon atoms for the aryl group.
And an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom. The alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group or an alkoxycarbonyl group. is there.

[0110] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

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

Specific examples include the following compounds, but are not limited thereto.

[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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The onium salts represented by the general formulas (PAG3) and (PAG4) are known, and include, for example, JWKnapczyk
etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok eta
l, J. Org. Chem., 35, 2532, (1970), E. Goethas et al., Bul
l.Soc.Chem.Belg., 73,546, (1964), HM Leicester, JA
me.Chem.Soc., 51,3587 (1929), JVCrivello etal, J.Po
Chem. Ed., 18,2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

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

[0126]

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In the formula, Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
Indicates an unsubstituted alkyl group or aryl group. A is a substitution
Or unsubstituted alkylene, alkenylene, arylene
Shows a substituent group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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In the present invention, the compound that generates an acid upon irradiation with actinic rays or radiation is preferably an onium salt, disulfone, imidosulfonate, 4-position DNQ sulfonic acid ester, or a triazine compound.

The amount of the compound capable of decomposing upon irradiation with actinic rays or radiation to generate an acid is usually 0.03% based on the total weight of the photosensitive composition (excluding the coating solvent).
It is used in the range of 0.01 to 40% by weight, preferably 0.0
It is used in an amount of 1 to 20% by weight, more preferably 0.1 to 5% by weight. If the amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid is less than 0.001% by weight, the sensitivity is low, and if the amount is more than 40% by weight, the light absorption of the resist is high. This is not preferable because the profile is deteriorated and the process (especially baking) margin is narrowed.

In the photosensitive composition of the present invention, an organic basic compound can be used. Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound is preferable. Preferred chemical environments include the following formulas (A) to (A).
(E) Structure can be mentioned.

[0136]

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Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol,
Substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted imidazole, substituted or unsubstituted pyrazoline, substituted Alternatively, unsubstituted piperazine, substituted or unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is. As particularly preferred compounds, guanidine, 1,1-dimethylguanidine, 1,1,3,
3, -tetramethylguanidine, 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) piperidine, 4- Amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-
Aminoethyl) pyrrolidine, pyrazole, 3-amino-
5-methylpyrazole, 5-amino-3-methyl-1-
p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, imidazole, 2,4,5-triphenylimidazole,
Examples include, but are not limited to, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001-10 parts by weight, preferably 0.01-5 parts by weight, per 100 parts by weight of the photosensitive resin composition (excluding the solvent). If the amount is less than 0.001 part by weight, the effects of the present invention cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the unexposed part tends to deteriorate.

If necessary, the chemically amplified positive resist composition of the present invention may further contain a phenolic OH group which promotes solubility in a surfactant, a dye, a pigment, a plasticizer, a photosensitizer and a developer. A compound having two or more compounds can be contained.

Suitable surfactants include, specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate ,
Sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate and other sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxy Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as ethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; EFTOP EF301, EF303;
EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), MegaFac F1
71, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora
Do FC430, FC431 (Sumitomo 3M Limited)
Made), Asahi Guard AG710, Surflon S-38
2, SC101, SC102, SC103, SC10
Fluorinated surfactants such as 4, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP3
No. 41 (manufactured by Shin-Etsu Chemical Co., Ltd.) or acrylic acid-based or methacrylic acid-based (co) polymerized polyflow No. 41 75, N
o. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like.

[0141] These surfactants may be added alone or in some combination. A preferable addition amount is 100 parts of the composition (excluding the solvent).
0.0005 to 0.01 parts by weight with respect to parts by weight. Suitable dyes include oily dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green B
G, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B (CI45)
170B), malachite green (CI42000),
Methylene blue (CI52015) and the like can be mentioned.

Further, the following spectral sensitizers are added to sensitize the photoacid generator to be used in the wavelength region longer than the deep ultraviolet where the photoacid generator used has no absorption, thereby obtaining the chemically amplified positive resist of the present invention. Can be made sensitive to the i or g line. Examples of suitable spectral sensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, and pyrene. , Perylene,
Phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 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 are not limited thereto.

Examples of the compound having two or more phenolic OH groups that promote solubility in a developing solution include polyhydroxy compounds. Preferably, the polyhydroxy compound includes phenols, resorcin, phloroglucin, phloroglucid, 3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene,
Tris (4-hydroxyphenyl) methane, Tris (4
-Hydroxyphenyl) ethane, 1,1′-bis (4-
(Hydroxyphenyl) cyclohexane.

The chemically amplified positive resist composition of the present invention is prepared by dissolving the above components in a solvent capable of dissolving and coating the solution on a support. Examples of usable solvents include ethylene dichloride, cyclohexanone and cyclohexanone. Pentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, Ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate,
Propyl pyruvate, N, N-dimethylformamide,
Dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

The above-mentioned chemically amplified positive resist composition is applied onto a substrate (eg, silicon / silicon dioxide coating) to be used in the manufacture of precision integrated circuit devices by an appropriate application method such as a spinner or a coater, and then applied to a predetermined position. A good resist pattern can be obtained by exposing through a mask, baking and developing.

Examples of the developer for the chemically amplified positive resist composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium phosphate, sodium metasilicate, and aqueous ammonia. Primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine,
Alcoholamines such as triethanolamine, amides such as formamide and acetamide, tetramethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tributylmethylammonium hydroxide, and tetraethanolammonium hydroxide , Methyltriethanol ammonium hydroxide,
Quaternary ammonium salts such as benzylmethyldiethanolammonium hydroxide, benzyldimethylethanolammonium hydroxide, benzyltriethanolammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide, and alkalis such as cyclic amines such as pyrrole and piperidine And the like.

[0147]

(Synthesis example of non-polymer type compound of the present invention)

(Synthesis of bromothioacetic acid-t-butyl ester) 25 g of bromoacetic acid-t-butyl ester was dissolved in 100 g of toluene, and the system was placed under an argon atmosphere. There, Lawe
13 g of the sson reagent was added, and the mixture was heated under reflux for 5 hours. The reaction solution was passed through silica gel column chromatography
The residue of the sson reagent was removed, and toluene was removed.
23 g of the desired product was obtained.

(Synthesis of Compound 60; Route 1)
88 g of 3,5-tetrakis (4-hydroxyphenyl) pentane was added to DMAc (N, N-dimethylacetamide).
Dissolved in 600 g of bromothioacetic acid-
147 g of t-butyl ester and 114 potassium carbonate
g was added and stirred. The reaction solution was heated to 120 ° C., stirred for 4 hours and allowed to cool to room temperature. The reaction solution was poured into water, and the precipitate was collected by filtration and dried to obtain 160 g of the desired product. The desired product is a compound 60 described above, all of the acid-decomposable group (R) is -CH ₂
—C (＝ S) —O—C ₄ H ₉ (t).

(Synthesis of Compound 60; Route 2)
50 g of 3,5-tetrakis (4-t-butylcarbonyloxymethyloxyphenyl) pentane was added to toluene 20
Dissolve in 0 g (Kendaku) and put Lawesson reagent 31 g there
Was added and heated under reflux for 4 hours. The reaction solution was passed through silica gel column chromatography, and toluene was distilled off to obtain 65 g of the desired product. The desired product is a compound 60 described above, all of the acid-decomposable group (R) is _{-CH 2 -C (= S) -O} -C 4
H ₉ (t). In the same manner as above, the non-polymer type compound used in this example was synthesized.

[Synthesis Example of Polymer Type Compound of the Present Invention] 21 g of poly-p-hydroxystyrene was added to DMAc (N, N
-Dimethylacetamide), 50 g of bromothioacetic acid-t-butyl ester of the above synthesis and 32 g of potassium carbonate were added thereto, and the mixture was stirred. Reaction solution
C., stirred for 4 hours and allowed to cool to room temperature. The reaction solution was poured into water, and the precipitate was collected by filtration and dried to obtain 28 g of the desired product. This is p-hydroxystyrene / TBTE-PH
S copolymer (70/30) with a weight average molecular weight of 13.0
00. TBTE-PHS: pt-butoxythiocarbonyloxymethyloxystyrene Same as above,
The polymer compound used in this example was synthesized.

Examples 1 to 12 and Comparative Examples 1 to 3 [Preparation and Evaluation of Photosensitive Composition]
It was dissolved in 8 g of MEA (propylene glycol monoethyl ether acetate) and filtered through a 0.2 μm filter to prepare a resist solution. This resist solution was applied on a silicon wafer using a spin coater, and dried on a vacuum suction type hot plate at 120 ° C. for 60 seconds to obtain a resist film having a thickness of 0.8 μm.

[0152]

[Table 1]

The abbreviations used in Table 1 represent the following contents. <Polymer> (): molar ratio PHS / St: p-hydroxystyrene / styrene copolymer (85/25) (weight-average molecular weight: 25,000) PHS: poly-p-hydroxystyrene (weight-average molecular weight: 12,000) PHS / TBTE -PHS: p-hydroxystyrene / pt-butoxythiocarbonyloxymethyloxystyrene copolymer (70/30) (weight average molecular weight 13,000) PHS / St / TBTE-PHS: p-hydroxystyrene / styrene / Pt-butoxythiocarbonyloxymethyloxystyrene copolymer (60/15/25) (weight average molecular weight 12000) PHS / TBE-PHS: p-hydroxystyrene / pt-butoxycarbonyloxy methyloxystyrene copolymer Coalescing (70/30) (weight Average molecular weight 13,000) <acid-decomposable group of the resin or dissolution _{inhibitor> TBE: -O-CH 2 -COO} -C 4 H 9 (t) TBOC: -O-COO-C 4 H 9 (t) TBTE _{: -CH 2 -C (= S)} -O-C 4 H 9 (t) TBTTE: -CH 2 -C (= S) -S-C 4 H 9 (t)

This resist film was exposed using a 248 nm KrF excimer laser stepper (NA = 0.45). After the exposure, the film was heated on a hot plate at 100 ° C. for 60 seconds, immediately immersed in a 0.26 N aqueous solution of 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 to evaluate the performance of the resist. Table 2 shows the results.

The sensitivity was defined as an exposure amount for reproducing a 0.40 μm mask pattern. 0.40μ resolution
It represents the critical resolution at the exposure dose for reproducing the m mask pattern. The profile of the resist pattern was evaluated by observing the pattern on the silicon wafer obtained as described above with a scanning electron microscope. When heating each of the above evaluations immediately after exposure,
And one hour after exposure.

[0156]

[Table 2]

From the results shown in Table 2, it can be seen that the resist of the present invention has high sensitivity and high resolution, and there is no decrease in sensitivity or resolution over time between exposure and post-exposure baking. It can be seen that it has a good resist pattern having no tapered shape.

[0158]

According to the present invention, a good resist pattern which has high sensitivity and high resolution and has no problems such as a decrease in sensitivity or resolution due to lapse of time between exposures (PEB) and formation of a T-top can be obtained. It can provide a photosensitive composition that can be formed.

Claims (4)

[Claims] 1. A compound having at least one group represented by the following general formula (I) which can be decomposed by the action of an acid and whose solubility in an aqueous alkaline solution is increased by the action of an acid. Photosensitive composition. Embedded image In the formula (I), R represents an alkylene group which may have a substituent, and X and Y may be the same or different and represent an oxygen atom or a sulfur atom, provided that X and Y are simultaneously an oxygen atom Is not represented. R ₁ represents an optionally substituted alkyl group, alkenyl group, aralkyl group, aryl group or cycloalkyl group. n represents the integer of 0-3. 2. A compound capable of generating an acid upon irradiation with actinic rays or radiation, a resin insoluble in water and soluble in an aqueous alkali solution, and at least one group represented by the general formula (I) according to claim 1. A photosensitive composition comprising a non-polymeric dissolution inhibiting compound having a species and having an increased solubility in an aqueous alkali solution due to the action of an acid. 3. A compound capable of generating an acid upon irradiation with actinic rays or radiation, and having at least one kind of the group represented by the general formula (I) according to claim 1 and having a solubility in an alkaline aqueous solution of an acid. A photosensitive composition comprising a polymer-type dissolution inhibiting compound which is increased by the action of the compound. 4. A compound capable of generating an acid upon irradiation with actinic rays or radiation, having at least one group represented by the general formula (I) according to claim 1, and having a solubility in an aqueous alkaline solution of the acid. A non-polymeric dissolution inhibiting compound which increases by an action; and a polymer type which has at least one group represented by the general formula (I) according to claim 1 and whose solubility in an aqueous alkaline solution is increased by the action of an acid. A photosensitive composition comprising a dissolution inhibiting compound.