JP3194645B2 - Positive photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive composition used in a process for producing semiconductors such as lithographic printing plates and ICs, a circuit substrate for liquid crystals and thermal heads, and other photofabrication processes. It is about.

[0002]

2. Description of the Related Art Positive photoresist compositions include:
In general, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is used. For example, US Pat. No. 3,666,473, US Pat. No. 4,115,128 and US Pat. No. 4,173,470 as “Novolak-type phenol resin / naphthoquinonediazide-substituted compound”
As the most typical composition, "Novolak resin composed of cresol-formaldehyde / trihydroxybenzophenone-1,2-naphthoquinonediazidesulfonic acid ester" is exemplified by Thompson "Introduction to Microlithography" (LFThompson "Intr
oduction to Microlithography ") (ACS Publishing, N
o. 219, pp. 112-121). In such a positive photoresist consisting essentially of a novolak resin and a quinonediazide compound, the novolak resin gives high resistance to plasma etching, and the naphthoquinonediazide compound acts as a dissolution inhibitor. Then, naphthoquinonediazide has the property of losing its dissolution inhibiting ability by generating carboxylic acid upon irradiation with light, and increasing the alkali solubility of the novolak resin.

[0003] From this point of view, many positive photoresists containing a novolak resin and a naphthoquinonediazide-based photosensitive material have been developed and put into practical use.
Sufficient results have been achieved in line width processing down to about 2 μm. However, the degree of integration of integrated circuits has been increasing more and more, and in the manufacture of semiconductor substrates such as VLSIs, processing of ultrafine patterns having a line width of half a micron or less has been required. In order to achieve the required resolution, the wavelength of an exposure apparatus used for photolithography is becoming shorter and shorter, and now far ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) have been studied. ing. When a conventional resist consisting of novolak and naphthoquinonediazide compound is used for lithographic pattern formation using far ultraviolet light or excimer laser light, light is strongly absorbed in the far ultraviolet region of novolak and naphthoquinonediazide. It is difficult to reach, 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 generates an acid in the exposed area by irradiation with radiation such as deep ultraviolet light, and the reaction using the acid as a catalyst dissolves the active radiation irradiated area and the non-irradiated area in the developing solution. This is a pattern forming material that changes the properties and forms a pattern on a substrate.

Examples of such a combination include a combination of a compound that generates an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Laid-Open No. 48-89003), 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 (Japanese Patent Application Laid-Open No. 55-12959), a combination with an N-acyliminocarbonate compound (Japanese Patent Application Laid-Open No. 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),
Combination with a silyl ester compound (JP-A-60-102)
No. 47) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-12446).
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); Semicond
uctor World 1987, November, p. 91; Macromolecules, 2
Vol. 1, p. 1475 (1988); 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-mentioned positive chemically amplified resist comprises three components comprising 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 two-component system comprising a resin having a group which is decomposed by the reaction with an acid and becomes alkali-soluble and a photoacid generator. In the case of the two-component system, the content of the acid-decomposable group in the resin is increased, so that there is a problem that the resist film shrinks due to baking after exposure. On the other hand, in the case of the three-component system, there is a problem that since the dissolution inhibiting property with respect to the alkali-soluble resin is insufficient, the film loss at the time of development is large and the resist profile is significantly deteriorated. However, the three-component system is a promising system because of a wide range of choices of materials, and the development of an acid-decomposable compound having excellent dissolution inhibiting properties used in this system has been desired. Both the two-component system and the three-component system are particularly stable at room temperature in the presence of an acid. However, in the case of a compound system having a group that decomposes upon heating, the compound is exposed to the heat treatment (Post Expos).
If the standing time until the ure bake (PEB) treatment is long, the developability of the resist surface portion is reduced even in the exposed portion, and a so-called T-shaped top shape is exhibited. As a result, there is a problem that the sensitivity is reduced.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive type photosensitive film having a good profile and a high resolution with little change in sensitivity, change in profile shape and film loss during development due to standing from exposure to baking. The present invention is to provide an acidic composition.

[0009]

Means for Solving the Problems The present inventors have made the above-mentioned various features.
As a result of intensive studies with attention paid to
70 ° C or less in the presence of a re-soluble resin, photoacid generator, and acid
Dissolution inhibition with a group that decomposes when heated on top
In a positive chemical amplification system consisting of
A low molecular acid decomposable dissolution inhibitor that meets the following requirements
Uses a blocking compound and further reacts at 50 ° C or less by the action of an acid.
In addition, add a compound that increases alkali solubility or hydrophilicity.
To achieve the present invention
did. That is, the present invention provides: (a) a resin which is insoluble in water and is soluble in an aqueous alkaline solution;
Compound, (c) having a group decomposable by an acid, and in an alkaline developer
Is more than 70 ° C. in the presence of the acid according to (b)
Increased by heating, low molecular weight of 3000 or less
Acid-decomposable dissolution inhibiting compound,as well as (d) Due to the action of the acid according to (b), for 1 hour or less at 50 ° C or less.
Reacts in the alkali developer solubility or hydrophilic
To the positive photosensitive composition containing the compound
And the compound (c) is-COO-A ⁰ Group or -O-
B ⁰ A group decomposable by an acid represented by the group
⁰ Is -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ) Represents a group; ⁰ Is
A ⁰ Or -COO-A ⁰ Represents a group. R ⁰¹ , R ⁰² And R
⁰³ May be the same or different.
, An alkyl group, a cycloalkyl group, an alkenyl group or
Represents an aryl group. Where R ⁰¹ ~ R ⁰³ At least
Two are groups other than a hydrogen atom, and R ⁰¹ ~ R ⁰³ Within
Two groups may combine to form a ring);
One (I) having at least two groups decomposable with an acid,
When the distance between decomposable groups is farthest away, acid-decomposable
A compound having 10 or more bonding atoms excluding a group, and (ii) having at least three groups decomposable with an acid,
At the position where the distance between decomposable groups is the farthest, acid-decomposable
Selected from compounds with 9 or more bonding atoms excluding the group
At least oneWherein the compound (d) is
The general formula (d-1 ) To (d-12).
At least one kindPositive photosensitive composition characterized by having
To provide things.

[0010] The three-component positive photosensitive composition of the present invention comprises:
Basically, it consists of an acid-decomposable dissolution inhibitor, an alkali-soluble resin and a photoacid generator. The acid-decomposable dissolution inhibitor suppresses the solubility of the alkali-soluble resin in alkali, the acid-decomposable group is deprotected by an acid generated upon exposure, and conversely promotes the solubility of the resin in alkali. Has an action.
Naphthalene in JP-A-63-27829 and JP-A-3-98059,
Although a dissolution inhibiting compound having a skeleton compound of biphenyl and diphenylcycloalkane has been disclosed, the dissolution inhibiting property with respect to an alkali-soluble resin is small and the profile and the resolving power are insufficient. Hereinafter, the compounds used in the present invention will be described in detail.

(A) Acid-decomposable dissolution inhibiting compound (compound of the present invention (c)) The acid-decomposable dissolution-inhibiting compound used in the present invention (c) is
Decomposes on heating above 70 ° C in the presence of acid.
Further, the structure has at least two groups that can be decomposed by an acid, and at a position where the distance between the acid-decomposable groups is the longest, at least 10 bonding atoms excluding the acid-decomposable group, preferably at least 11 or more preferably at least 12 compounds, or at least 3 acid-decomposable groups.
At the position where the distance between the acid-decomposable groups is farthest away, at least 9, preferably at least 10, and more preferably at least 1 bond atom excluding the acid-decomposable group.
It is a compound via one. The preferred upper limit of the number of the bonding atoms is 50, more preferably 30. In the present invention, the acid-decomposable dissolution inhibiting compound has an acid-decomposable group of 3
Or more, preferably 4 or more, and even those having two acid-decomposable groups, when the acid-decomposable groups are separated from each other by a certain distance or more, the dissolution inhibitory property to the alkali-soluble resin is remarkable. improves. In addition, the distance between the acid-decomposable groups in the present invention is represented by the number of via bond atoms excluding the acid-decomposable groups. For example, the following compound (1),
In the case of (2), the distance between the acid-decomposable groups is 4
And in compound (3), 12 bonding atoms.

[0012]

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Still further, the present invention relates to a compound of the present invention (c), which comprises at least 10 mol%, preferably 30 mol%,
It is preferable that mol%, more preferably 50 mol%, is a compound in which an alkali-soluble group is intentionally left. The content of the alkali-soluble group is determined by the average number of alkali-soluble groups N in the tertiary alkyl ester group-containing dissolution inhibitor.
And _S, expressed in the number N _B of the tertiary alkyl ester groups mean, expressed by _{N S / (N B + N} S). The amount of the alkali-soluble _{group, 0.01 ≦ N S / (N} B + N S) ≦ 0.75
Is preferred. More preferably, 0.1 ≦ N _S / (N _B + N
_S ) ≦ 0.5. Particularly preferably, the ratio of the number of alkali-soluble groups (N _1S ) to the tertiary alkyl ester group (N _1B ) in one molecule of the dissolution inhibitor is 0.1 ≦ N _1S / (N _1B + N
_1S ) The component _satisfying ≦ 0.5 is added to 5% of the total weight of the dissolution inhibitor.
In this case, the content is 0% by weight or more.

In order to function Yotsute alkali-soluble group in the developer to be described later, the alkali-soluble group to an alkali-soluble group and the remaining is protected by an acid-decomposable bond is preferably _a pK _a of 10 or less of group . Preferred alkali-soluble groups, phenolic hydroxyl group, carboxylic acid group,
Examples include an imide group, an N-hydroxyimide group, an N-sulfonylamido group, a sulfonamide group, an N-sulfonylurethane group, an N-sulfonyluureide group, and a group having an active methylene group, and more specifically, ,
The following examples can be given.

[0015]

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These groups may be introduced as a mixture in one molecule. However, preferred alkali-soluble groups are not limited to these specific examples.

Further, the acid-decomposable dissolution-inhibiting compound of the present invention may have a plurality of acid-decomposable groups on one benzene ring, but preferably, one compound on one benzene ring. It is a compound composed of a skeleton having an acid-decomposable group. Further, the molecular weight of the acid-decomposable dissolution-inhibiting compound of the present invention is 3,000 or less, preferably 500 to 3,000.
0, more preferably 1,000 to 2,500.

[0018] In a preferred embodiment of the present invention, group -COO-A ⁰ capable of decomposing by an acid, as the group containing a -O-B ⁰ group, -R ⁰ -COO-A ^0, or -Ar-O -B
^And a group represented by ⁰ . Here, A ⁰ is -C (R
⁰¹ ) represents an (R ⁰² ) (R ⁰³ ) group. B ⁰ is A ⁰ or —CO
Shows a -O-A ⁰ group. R ⁰¹ , R ⁰² and R ⁰³ may be the same or different and each represents a hydrogen atom, an alkyl group,
It represents a cycloalkyl group, an alkenyl group or an aryl group. However, at least two of R ^{01 to} R ⁰³ are groups other than a hydrogen atom, and two groups of R ^{01 to} R ⁰³ may combine to form a ring. R ⁰ represents a divalent or higher valent aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- represents a divalent or higher valent which may have a monocyclic or polycyclic substituent. Shows an aromatic group.

The alkyl group preferably has 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. Preferred are those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl groups having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Preferably, the aryl group has 6 to 1 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl and anthracenyl.
Four are preferred. Further, as a substituent, a hydroxyl group,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group and a t-butoxy group,
Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, aralkyloxy groups, and acyl groups such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, and valeryl group. Group, an acyloxy group such as a butyryloxy group, the above alkenyl group, a vinyloxy group.
Examples thereof include an alkenyloxy group such as a propenyloxy group, an allyloxy group, and a butenyloxy group, an aryloxy group such as the above-described aryl group and phenoxy group, and an aryloxycarbonyl group such as a benzoyloxy group.

Preferred are a cumyl ester group, a tertiary alkyl ether group, a tertiary alkyl ester group, a tertiary alkyl carbonate group and the like. More preferred are a tertiary alkyl ester group and a tertiary alkyl carbonate group.

Preferably, JP-A-1-289946,
JP-A-1-289947, JP-A-2-2560, JP-A-3-128959, JP-A-3-158855,
JP-A-3-179353, JP-A-3-191351
JP-A-3-200251, JP-A-3-20025
No. 2, JP-A-3-200253, JP-A-3-2002
No. 54, JP-A-3-200255, JP-A-3-259
149, JP-A-3-279958, JP-A-3-27
9959, JP-A-4-1650, JP-A-4-165
No. 1, JP-A-4-11260, JP-A-4-12356
JP-A-4-12357, Japanese Patent Application No. 3-33229
No., Japanese Patent Application No. 3-230790, Japanese Patent Application No. 3-32043
8, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-52732.
No., Japanese Patent Application No. 4-103215, Japanese Patent Application No. 4-104454
No. 2, Japanese Patent Application No. 4-107885, Japanese Patent Application No. 4-1078
89 No., phenolic OH groups shown above part or all of the groups of the polyhydroxy compounds described herein, such as Nos. 4-152195, coupled with -R ⁰ -COO-A ⁰ or B ⁰ groups And protected compounds.

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.

[0024]

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[0025]

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[0026]

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[0027]

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Here, R ¹ , R ² , R ³ , R ⁴ : may be the same or different, a hydrogen atom, a —R ⁰ —COO—A ⁰ or B ⁰ group, R ₁ : —CO—, — COO-, -NHCONH-, -N
HCOO-, -O-, -S-, -SO-, -SO2-,
-SO3-, or

[0029]

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[0030] Here, G = 2 to 6, provided that at least one alkyl group of R _4, R ₅ when the G = 2, R _4, R _5: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH, -C
N, a halogen atom, —R ₆ —COOR ₇ , or —R ₈
—OH, R ₆ , R ₈ : alkylene group, R ₇ : hydrogen atom, alkyl group, aryl group, or aralkyl group, R ₂ , R ₃ , R _{9 to} R ₁₂ , R ₁₅ , R _{17 to} R ₂₁ , R ₂₅ to
_{R 27, R 30 ~R 32,} R 37 ~R 42, R 46 ~R 49 and R _51:
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, a nitro group, a carboxyl group, a cyano group, or _{-N (R 13) (R 14} ) (R 13, R 14: H, alkyl or aryl group,), R _16: a single bond, an alkylene group or,

[0031]

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R ₂₂ and R ₂₄ may be the same or different and are a single bond, an alkylene group, -O-, -S-, -CO- or a carboxyl group; R ₂₃ : a hydrogen atom, an alkyl group, an alkoxy group, acyl group, an acyloxy group, an aryl group, a nitro group, a hydroxyl group, a cyano group or a carboxyl group, with the proviso that the hydrogen of the hydroxyl group may be substituted with -R ⁰ -COO-a ⁰ group or B ⁰ group, R ₂₈ , R _29: may be the same or different, a methylene group, a lower alkyl-substituted methylene group, halomethylene group or a haloalkyl group, with the proviso the lower alkyl group herein refers to an alkyl group having 1 to 4 carbon atoms, R ₃₃ to R _36: may be the same or different, a hydrogen atom or an alkyl group,, R ₄₃ to R _45: the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, an acyl group Or acyloxy group, R _50: a hydrogen atom, -R ⁰ -COO-A ⁰ group, B ⁰ group, or

[0033]

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R ₅₂ and R ₅₃ may be the same or different and are a hydrogen atom, a lower alkyl group, a lower haloalkyl group, or an aryl group; R _{54 to} R ₅₇ may be the same or different and are a hydrogen atom;
Hydroxyl group, halogen atom, nitro group, cyano group, carbonyl group, alkyl group, alkoxy group, alkoxycarbonyl group, aralkyl group, aralkyloxy group, 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 do not have to be the same group; Y: —CO—, Or —SO ₂ —, Z, B: a 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: a plurality of groups in parentheses May be the same or different, a to q, s, t, v, g1 to i1, k1 to m1, o1, q1, s
1, u1: 0 or an integer of 1 to 5, r, u, w, x, y, z, a1 to f1, p
1, r1, t1, v1 to x1: 0 or an integer of 1 to 4, j1, n1, z1, a
2, b2, c2, d2: 0 or an integer of 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 the general formula [V]
In the case of (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 + l
1), (i1 + m1), (o1 + q1), (s1 + u1) ≦ 5.

[0035]

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[0036]

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[0037]

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[0038]

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Specific examples of preferred compound skeletons are shown below.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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

[0060]

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Represents the following. However, at least two or three depending on the structure are groups other than hydrogen atoms, and each substituent R
Need not be the same group.

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

(B) A compound which reacts with an acid at 50 ° C. or lower within 1 hour (compound of the present invention (d)) The compound of the present invention (d) is a compound of the action of the acid photogenerated from the present invention (b). Reacts within 1 hour at 50 ° C or less,
The solubility in an alkaline developer or hydrophilicity increases. As a result, even if the exposure time from the exposure to the PEB is prolonged, the developability is hardly reduced, the T-shaped top shape is improved, and the sensitivity is less reduced. Examples of such a compound include compounds having various acid-decomposable groups. For example, Japanese Patent Publication No. 52-36442,
-10153, 64-57258, JP-A-1-1-1
No. 06040, No. 1-106041, No. 2-2489
Acetal compounds described in No. 53, etc., JP-B-60-20
738, JP-A-63-241540, JP-A-1-1-1
Orthoester compounds described in JP-A-606041, etc., orthocarbonate compounds described in JP-A-63-241540 and JP-A-3-107163, and JP-A-63-236
No. 028, etc .;
No. 549, JP-A-1-106038, etc .; silyl ester compounds described in JP-A-60-10247, etc .; alkenyl ether compounds described in JP-A-55-12959, etc .; -1765
3, α-heterosubstituted cyclic or acyclic methyl ester type compounds described in JP-A Nos.
Carboxylic acid anhydride compounds described in -110445 and the like,
In addition to the N-acylimino carbonate compounds described in JP-A-55-126236, lactone compounds, cyclic sulfonic acid ester compounds and the like are included. Typically, the general formula [d
-1] to [d-12].

[0064]

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In the formula, R ₁ ′, R ₂ ′, R ₅ ′ and R ₆ ′ may be the same or different, and each represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group or aralkyl group. Is shown. R ₃ ', R ₄ ', R ₇ ', R ₈ ', R ₉ ', R
₁₀ ′ may be the same or different and each represents a hydrogen atom, a substituted or unsubstituted alkyl / aryl group or an aralkyl group. In addition, at least one of R ₇ ′ to R ₁₀ ′ is a group other than a hydrogen atom, and [d-1] to
Two of the groups R ₁ ′ to R ₆ ′ represented by [d-3] may combine to form a 5- to 8-membered ring that may contain a hetero atom.

R ₁₁ ′, R ₁₅ ′, R ₁₆ ′ and R ₃₃ ′ each represent a substituted or unsubstituted n-valent alkyl group, alkenyl group, cycloalkyl group or aryl group which may be the same or different. , R ₁₂ ′, R ₁₃ ′ and R ₁₄ ′ represent a substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group or aryloxy group.

R ₁₇ ′, R ₁₈ ′, R ₁₉ ′, R ₂₁ ′ and R ₂₂ ′ may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, cycloalkyl group or aryl group. Alternatively, R ₂₀ ′ and R ₃₁ ′ represent a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group or aralkyl group. In addition, R ₁₇ ′ to R
₁₉ ', and R _20' 2 atoms are bonded of the group to R ₂₂ ', may form a ring also may 5- to 8-membered ring which contains a hetero atom.

X ′ is O, S, SO ₂ or —C
( _R34 ', _R35 ')-.

R ₂₃ ′, R ₂₄ ′, R ₂₅ ′, R ₂₆ ′, R ₂₇ ′, R
_{28 ', R 29', R} 30 ', R 34' and R ₃₅ 'may be the same or different, each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an aryl group, an aralkyl group, an alkoxy R ₃₂ ′
Represents a substituted or unsubstituted alkyl group or aryl group. R ₂₄ ′ and R ₂₆ ′ may be combined to form a single bond, and R ₂₃ ′ to R ₂₆ ′ and R ₂₇ ′ to R ₃₀ ′, R ₃₄ ′ and R ₃₅ ′
And two of the above groups may be bonded to form a 5- to 8-membered ring which may contain a hetero atom. n shows the integer of 1-10.

Here, the alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group,
sec-butyl group, n-hexyl group, n-octyl group,
Those having 1 to 8 carbon atoms, such as a 2-ethylhexyl group, are preferred. As the cycloalkyl group, a cyclopropyl group,
3 carbon atoms such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl
Preferably, the alkenyl group is a group having 2 to 4 carbon atoms such as a vinyl group, a propenyl group and a butenyl group, and the aryl group is a phenyl group, a xylyl group, a toluyl group, a cumenyl group, Those having 6 to 14 carbon atoms such as naphthyl group and anthracenyl group are preferable, and aralkyl groups such as benzyl group, phenethyl group,
Those having 7 to 15 carbon atoms such as 4-methylbenzyl group and 1-naphthylmethyl group are preferable, and the alkoxy group is preferably 1 to 1 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group and octoxy group. Preferably, the aryloxy group has 6 to 10 carbon atoms such as a phenoxy group, a 4-methylphenoxy group and a naphthoxy group.

Examples of the substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above-mentioned alkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, and acetyl group. Acyl groups such as a group, propanoyl group, butanoyl group, and benzoyl group; acyloxy groups such as acetoxy group / propanoyloxy group / butanoyloxy group / benzoyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group / ethoxycarbonyl group; and methyl Sulfonyl groups such as sulfonyl group, ethylsulfonyl group, phenylsulfonyl group, sulfonyloxy groups such as methanesulfonate group, ethanesulfonate group, benzenesulfonate group, tosylate group, mesitylenesulfonate group, methoxysulfonyl group, ethoxysulfonyl group And the groups-phenoxy sulfonyl group, 4-methylphenoxy sulfonyl alkoxysulfonyl and aryloxy sulfonyl group such as.

The addition of such a compound is described in JP-A-63-236028 (addition of an epoxy compound to a silyl ether compound / photoacid generator system) and JP-A-4-2485.
No. 54 (addition of a compound which reacts with water or anionoid compound at a temperature up to 120 ° C. to an alkali-soluble resin / compound system having an acid-decomposable group and a photoacid generating group in the same molecule) and EP 520654 (photoacid And an acetal compound added to a two-component system of a generator / a film-forming polymer having an acid-decomposable group), and describes the effect of suppressing fluctuations in developability and the like due to standing after exposure to PEB.
However, in JP-A-63-236028, there is a problem in stability (shelf life) due to storage aging.
No. 248554 has a problem that the unexposed portion is not sufficiently dissolved in an alkali developing solution and the resolution and profile are reduced. In addition, European Patent 52065
No. 4 had a problem in the two-component chemical amplification system.

Specific examples of the compound of the present invention (d) are shown below, but the present invention is not limited to these.

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[0078]

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(C) Alkali-Soluble Resin (Compound of the Present Invention (a)) Examples of the alkali-soluble resin used in the present invention include novolak resins, hydrogenated novolak resins, and acetone-soluble resins.
Pyrogallol resin, polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, partially O-alkylated or O-acylated polyhydroxystyrene, styrene-maleic anhydride copolymer And a carboxyl group-containing methacrylic resin and a derivative thereof, but are not limited thereto. Particularly preferred alkali-soluble resins are novolak resins and polyhydroxystyrene. The novolak resin is obtained by subjecting a given 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.

The aldehydes include, for example, 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
They 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. Further, alkali-soluble group of these alkali-soluble resins, such as OH groups, the acid decomposable group and a part of the hydrogen atoms of the -COOH group -R ⁰ -COO-
A ⁰ or those substituted with an A ⁰ group are also preferable in terms of improving the dissolution inhibiting property in a developer. In this case, the substitution rate is 1 to 50 mol%, preferably 1 to 30 mol%, more preferably 1 to 15 mol%, based on all the alkali-soluble groups.

The weight average molecular weight of these alkali-soluble resins is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred are 2,000 to 20,000
It is in the range of 0. Here, the weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography.

In the present invention, two or more of these alkali-soluble resins may be used as a mixture. The amount of the alkali-soluble resin used is 50 to 97% by weight, preferably 60%, based on the total weight of the photosensitive composition (excluding the solvent).
~ 90% by weight.

(D) Compound capable of generating an acid upon irradiation with actinic rays or radiation (compound of the present invention (b)) The compound used in the present invention which decomposes upon irradiation with actinic rays or radiation to generate an acid includes: , A photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photodecolorant for dyes, a photochromic agent, or a compound capable of generating an acid by known light used in a microresist or the like, and The mixture can be appropriately selected and used. For example, SISchlesinger, Photogr.Sci.Eng., 18,387 (197
4), TSBal et al., Polymer, 21,423 (1980) and the like diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,069,056
Ammonium salt, DC Necker et al., Macromolecules, 17, 24 described in Japanese Patent Application No. 3-140,140.
68 (1984), CSwen et al., Teh, Proc. Conf. Rad. Curing AS
IA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055,
4,069,056, etc., phosphonium salts, JVCrivello
etal, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng.Ne
ws, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent No. 339,049, No. 410,201, JP-A-2-150,848, JP-A-2-296,514 Iodonium salts described in JP-A-2-296,514 and the like, JVCrive
llo etal, Polymer J. 17, 73 (1985), JVCrivello eta
lJOrg.Chem., 43, 3055 (1978), WRWatt et al., J. Polym
er Sci., Polymer Chem. Ed., 22, 1789 (1984), JVCrivel
lo etal, Polymer Bull., 14,279 (1985), JVCrivello e
tal, Macromorecules, 14 (5), 1141 (1981), JVCrivello
etal, J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (197
9), European Patent Nos. 370,693, 3,902,114 and 233,567
Nos. 297,443 and 297,442; U.S. Pat.No.4,933,377
Nos. 161,811, 410,201, 339,049, 4,76
No. 0,013, 4,734,444, 2,833,827, Dokoku Patent No.
2,904,626, 3,604,580, 3,604,581, etc., sulfonium salts, JVCrivello etal, Macromorecule
s, 10 (6), 1307 (1977), JVCrivello etal, J. PolymerSc
Selenonium salts described in i., Polymer Chem.Ed., 17, 1047 (1979), etc., CSWen et al., Teh, Proc. Conf. Rad. Curing AS
Onium salts such as arsonium salts described in IA, p478 Tokyo, Oct (1988), U.S. Pat.No. 3,905,815, JP-B-46-4605
No., JP-A-48-36281, JP-A-55-32070, JP-A-60-2
39736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401, JP-A-63-70243
No., organic halogen compounds described in JP-A-63-298339, K. Meier et al., J. Rad.Curing, 13 (4), 26 (1986), TP
Gill et al., Inorg.Chem., 19,3007 (1980), D. Astruc, Ac
c. Chem. Res., 19 (12), 377 (1896), organometallics / organic halides described in JP-A-2-14145, etc., S. Hayase et al.
J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al., J. Ph
olymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQZhu et.
al, J. Photochem., 36, 85, 39, 317 (1987), B. Amit et al, Tet
rahedron Lett., (24) 2205 (1973), DHR Barton et al., J.
Chem Soc., 3571 (1965), PM Collins et al., J. Chem. SoC.,
Perkin I, 1695 (1975), M. Rudinstein et al, Tetrahedron
Lett., (17), 1445 (1975), JWWalker etal J. Am. Chem. So
c., 110,7170 (1988), SCBusman et al, J.Imaging Techno
l., 11 (4), 191 (1985), HM Houlihan et al, Macormolecule
s, 21, 2001 (1988), PM Collins et al., J. Chem. Soc., Chem.
Commun., 532 (1972), S. Hayase et al, Macromolecules, 18,
1799 (1985), E. Reichmanis et al., J. Electrochem. Soc., So
lid State Sci.Technol., 130 (6), FMHoulihan etal, Ma
cromolcules, 21, 2001 (1988), EP 0290,750,
046,083, 156,535, 271,851, 0,388,343
No. 3,901,710, 4,181,531, U.S. Pat.
-198538, a photoacid generator having a 0-nitrobenzyl-type protecting group described in JP-A-53-133022, M. TUNOOKA et al.
Polymer Preprints Japan, 35 (8), G. Berner et al., J. Rad.
Curing, 13 (4), WJMijs et al, Coating Technol., 55 (69
7), 45 (1983), Akzo, H. Adachi et al, Polymer Preprints,
Japan, 37 (3), European Patent Nos. 0199,672, 84515, 19
No. 9,672, No. 044,115, No. 0101,122, U.S. Pat.
No. 8,564, 4,371,605, 4,431,774, JP-A-64-18
No. 143, JP-A-2-245756, and compounds that generate sulfonic acid by photolysis, such as iminosulfonate described in Japanese Patent Application No. 3-140109, and JP-A-61-166544. The disulfone compound described above can be mentioned.

Further, a group capable of generating 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.
No. 9,137, Dokoku Patent No. 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 No. 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).

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In the formula, R ¹ represents a substituted or unsubstituted aryl group or alkenyl group, and R ² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group or —CY ₃ . Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

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

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Here, 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 ³ , R ⁴ and R ⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferred are an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and substituted derivatives thereof. Preferred substituents are an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom for the aryl group, and a substituent for the alkyl group. It is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, or an alkoxycarbonyl group.

[0097] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^- perfluoroalkane sulfonate anion such as, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonyl phosphate anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes However, the present invention is not limited to these.

Also, two of R ³ , R ⁴ and R ⁵ and A
r ¹ and Ar ² may be bonded via a single bond or a substituent.

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

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The onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKn
apczyk etal, J. Am. Chem. Soc., 91, 145 (1969), ALMayco
k etal, J. Org. Chem., 35, 2532, (1970), E. Goethas etal
, Bull.Soc.Chem.Belg., 73,546, (1964), HM Leiceste
r, J. Ame. Chem. Soc., 51, 3587 (1929), JVCrivello eta
1, J. Polym. Chem. Ed., 18, 2677 (1980), U.S. Pat.
No. 7,648 and 4,247,473 and JP-A-53-101,331 can be synthesized.

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

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples include the following compounds, but are not limited thereto.

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The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.02% 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.

In the photosensitive composition of the present invention, if necessary,
Further, a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, and a compound having two or more phenolic OH groups for promoting solubility in a developer can be contained.
Suitable dyes include oily dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 1
03, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-5
05 (all manufactured by Orient Chemical Industries, Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170)
B), malachite green (CI42000), methylene blue (CI52015) and the like.

Further, a spectral sensitizer as described below is added to sensitize the photosensitive composition of the present invention to a longer wavelength region than the far ultraviolet where the photoacid generator used has no absorption. Sensitivity can be given to the i or g line. Suitable spectral sensitizers include, specifically, benzophenone,
p, p'-tetramethyldiaminobenzophenone, p,
p'-tetraethylethylaminobenzophenone, 2-
Chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, setoflavin-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.

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving each of the above components, and coated on a support. Examples of the solvent used herein include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, and 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, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

A surfactant may be added to the above solvent. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants such as polyoxyethylene sorbitan fatty acid esters such as acrylates, etc .; 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora - de FC430, FC43
1 (manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC101, SC102,
Fluorinated surfactants such as SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic (co) polymerized polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. These surfactants may be added alone or in some combination.

The above-mentioned photosensitive composition is applied on a substrate (eg, silicon / silicon dioxide coating) to be used in the production of precision integrated circuit devices by a suitable application method such as a spinner or a coater, and then passed through a predetermined mask. By exposing, baking and developing, a good resist pattern can be obtained.

As the developer for the photosensitive composition of the present invention,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and triethylamine and methyldiethylamine Use alkaline aqueous solutions such as triamines, alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pichelidine. be able to. The concentration of these alkalis is 0.001 to 1 N, preferably 0.01 to 0.50 N, more preferably 0.03 to 0.
Used in the range of 30N. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[0128]

【Example】

[Synthesis Example 1 of Dissolution Inhibitor Compound] α, α ′, α ″ -Tris (4
20 g of (human peroxyphenyl) -1,3,5-triisopropylbenzene were dissolved in 400 ml of tetrahydrofuran. 14 g of potassium tert-butoxide was added to this solution under a nitrogen atmosphere, and the mixture was stirred at room temperature for 10 minutes.
29.2 g of rt-butyl carbonate were added. The reaction was allowed to proceed at room temperature for 3 hours, the reaction solution was poured into ice water, and the product was extracted with ethyl acetate. The ethyl acetate layer was further washed with water and dried, after which the solvent was distilled off. The obtained crystalline solid was recrystallized (diethyl ether) and dried to obtain 25.6 g of a compound example (31: R are all t-BOC groups).

[Synthesis Example 2 of Dissolution Inhibitor Compound] α,
α ', α "-tris (4-hydroxyphenyl) -1,3,
19.2 g of 5-triisopropylbenzene (0.040
21.2 g (0.15 mol) of potassium carbonate and 27.1 g (0.14 mol) of t-butyl bromoacetate were added to a 120 ml solution of N, N-dimethylacetamide of Stirred. Thereafter, the reaction mixture was poured into 1.5 l of water, and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 3/7 (volume ratio)). As a result, a pale yellow viscous solid was obtained. 30 g were obtained. By NMR, this compound Example (31: R are all -CH ₂ COOC ₄ H ₉ ^t group) was confirmed to be.

[Synthesis Example 3 of Dissolution Inhibitor Compound] 1-
42.4 g (0.10 mol) of [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene was added to N, N -Dissolved in 300 ml of dimethylacetamide, added with 49.5 g (0.35 mol) of potassium carbonate and 84.8 g (0.33 mol) of cumyl bromoacetate, and then stirred at 120 ° C for 7 hours. The reaction mixture was poured into 2 liters of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate.The ethyl acetate extract was concentrated and purified in the same manner as in Synthesis Example [3] to give Compound Example (18). : R
Got all _{-CH 2 COOC (CH 3) 2} C 6 H 5 group) 70 g.

[Synthesis Example 4 of Dissolution Inhibitor Compound] α, α,
α ′, α ′, α ″, α ″ -Hexakis (4-hydroxyphenyl) -1,3,5-triethylbenzene 14.3 g (0.
020 mol) N, N-dimethylacetamide 120m
1 solution contains 21.2 g (0.15 mol) of potassium carbonate,
Furthermore, t-butyl bromoacetate 27.1 g (0.14 mol)
Was added and stirred at 120 ° C. for 7 hours. Thereafter, the reaction mixture was poured into 1.5 l of water and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 2/8 (volume ratio)), resulting in a pale yellow powder 24 g were obtained. According to NMR, this is a compound example (62: R is all —CH ₂ —COO).
—C ₄ H ₉ ^t group).

[Synthesis Example 5 of Dissolution Inhibitor Compound] α,
α ', α "-tris (4-hydroxyphenyl) -1,3,
20 g (0.042 mol) of 5-triisopropylbenzene was dissolved in 400 ml of tetrahydrofuran (THF). To this solution, 9.3 g (0.083 mol) of potassium t-butoxide was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 10 minutes, and then 19.5 g of di-t-butyl dicarbonate was added.
(0.087 mol) was added. The reaction was allowed to proceed at room temperature for 3 hours, the reaction solution was poured into ice water, and the product was extracted with ethyl acetate. The ethyl acetate extract is concentrated and subjected to column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-
As a result of fractional purification with hexane = 1/5 (volume ratio), 7 g of a compound example (31: 2 Rs are a t-BOC group, 1 R is a hydrogen atom) was obtained.

[Synthesis Example 6 of Dissolution Inhibitor Compound] α,
α ', α "-tris (4-hydroxyphenyl) -1,3,
48.1 g (0.10 mol) of 5-triisopropylbenzene was dissolved in 300 ml of dimethylacetamide, and 22.1 g (0.16 mol) of potassium carbonate and 42.9 g (0.22 mol) of t-butyl bromoacetate were added thereto. ) Was added. Then, it stirred at 120 degreeC for 5 hours. The reaction mixture was poured into 2 l of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate. The ethyl acetate extract is concentrated and subjected to column chromatography (carrier: silica gel, developing solvent:
As a result of fractionation and purification with ethyl acetate / n-hexane = 1/5 (volume ratio), the compound example (31: 2 Rs are -CH _2-)
COO-C ₄ H ₉ ^t group, one R is to obtain a hydrogen atom) 10 g.

[Synthesis Example of Novolak Resin] 40 g of m-cresol, 60 g of p-cresol, 49 g of 37% formalin aqueous solution and 0.13 g of oxalic acid were charged into a three-necked flask, and the temperature was raised to 100 ° C. with stirring for 15 hours. Reacted. Then, raise the temperature to 200 ° C and gradually
The pressure was reduced to Hg to remove water, unreacted monomers, formaldehyde, oxalic acid and the like. Next, the molten alkali-soluble novolak resin (NOV.3) was returned to room temperature and collected. The obtained novolak resin (NOV.3) had a weight average molecular weight of 7,100 (in terms of polystyrene).

In the same manner, the following novolak resins having different monomer compositions were synthesized. NOV. 1 m-cresol / p-cresol = 60/40, Mw = 12,000 NOV. 2 m-cresol / p-cresol = 50/50, Mw = 8,700 NOV. 4 m-cresol / p-cresol / 3,5-xylenol = 25/50/28, Mw = 5,200 NOV. 5 m-cresol / 2,3,5-trimethylphenol = 55/57, Mw = 5,800

The novolak resin obtained above (NOV.
3) After completely dissolving 20 g in 60 g of methanol, 30 g of water was gradually added thereto with stirring to precipitate a resin component. The upper layer was removed by decantation to collect the precipitated resin, which was heated to 40 ° C. and dried under reduced pressure for 24 hours to obtain an alkali-soluble novolak resin (NOV.
6) was obtained. The weight average molecular weight was 8000 (in terms of polystyrene).

85 g of m-cresol, p-cresol 1
5 g and 53 g of a 37% formalin aqueous solution were charged into a three-necked flask and stirred well while heating in an oil bath at 110 ° C.
2.4 g of zinc acetate dihydrate was added, and the mixture was heated and stirred for 5 hours. Next, 100 g of the same cresol mixture and 47 g of formalin aqueous solution were continuously charged into the same flask, and heating and stirring were continued for 1 hour. Then, the temperature was lowered to 80 ° C., and 0.2 g of oxalic acid was added. Again, the temperature of the oil bath was maintained at 110 ° C., and the reaction was carried out under reflux for 15 hours. Thereafter, the content was poured into water containing 1% hydrochloric acid, and the reaction product was extracted with ethyl cellosolve acetate. This was then transferred to a vacuum still, the temperature was raised to 200 ° C. and dewatered, and a further 2-3 mmHg
Distillation was performed for 2 hours under reduced pressure to remove residual monomers.
The molten polymer was recovered from the flask to obtain the desired novolak resin (NOV.7, Mw = 7,500).

Examples 1 to 22 Resists were prepared using the compounds of the present invention shown in the above Synthesis Examples. Table 1 shows the prescription at that time.

Comparative Example 1 A t-butoxycarbonyloxystyrene polymer was synthesized according to the method described in US Pat. No. 4,491,628 to prepare a two-component positive resist. Table 1 shows the prescription at that time.

Comparative Example 2 Tris (4-t) described in JP-A-4-248554
-Butoxycarbonyloxyphenyl) sulfonium trifluoromethanesulfonate was synthesized to prepare a two-component positive resist. The prescription is shown in Table 1.

Comparative Examples 3,4,5 Compounds described in EP 249,139 di-tert-butyl terephthalate, 4-tert-butoxy-p-
A three-component positive resist was prepared using biphenyl, t-butyl-2-naphthyl carbonate as a dissolution inhibitor.
Table 1 shows the prescription at that time.

Comparative Example 6 A resist was prepared by removing only the compound (d) of the present invention from the composition of the present invention. Table 1 shows the prescription at that time.

[0143]

[Table 1]

The abbreviations used in Table 1 represent the following contents.

<Polymer> NOV.1-7 Novolak resin PVP p-human peroxystyrene polymer (weight average molecular weight 9,600) TBOCS t-hydroxycarboxy oxystyrene polymer (number average molecular weight 2)
1,600)

<Dissolution inhibitor> TBCPS Tris (4-t-butoxycarbonyloxyphenyl) sulfonium trifluoromethanesulfonate DTBTP di-t-butyl terephthalate TBPBP 4-t-butyl-p-diphenyl TBNC t-butyl- 2-naphthyl carbonate

<Acid-decomposable group in dissolution inhibitor>

[0148]

Embedded image

[Preparation and Evaluation of Photosensitive Composition] Each material shown in Table 1 was dissolved in 6 g of propylene glycol monomethyl ether acetate / diglyme (7/3), and 0.2 μm
The resultant was filtered through a filter of m to prepare a resist solution. This resist solution was applied on a silicon wafer using a spin coater with a rotation speed of 3000 rpm, and 11
Dry on a vacuum adsorption type hot plate at 0 ° C for 60 seconds,
A resist film having a thickness of 1.0 μm was obtained. A 248 nm KrF excimer laser stepper (N
(A = 0.42). After the exposure, heating is performed for 60 seconds on a 90 ° C. vacuum adsorption hot plate, and immediately immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds (for a system using polyhydroxystyrene as a polymer, heating 1 hour).
00 ° C, 60 seconds, development 1.60% with 1.19% TMAH aqueous solution
Second), rinsed with water for 30 seconds and dried. The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope, and the profile of the resist was evaluated.
Table 2 shows the results.

The sensitivity was defined as the reciprocal of the exposure amount for reproducing a mask pattern of 0.70 μm, and was represented by the relative value of the sensitivity of Comparative Example 1. The film shrinkage was expressed as a percentage of the ratio of the film thickness before and after exposure of the exposed portion and baking. The resolving power indicates a limit resolving power at an exposure amount for reproducing a mask pattern of 0.70 μm. After exposure of the resist film, the resist film was allowed to stand at room temperature for 1 hour, and then subjected to heat treatment, development, rinsing, and drying in the same manner. Table 2 shows the sensitivity ratios (exposure ratios) of those processed after standing for 1 hour and those processed without standing as described above. From the results shown in Table 2, it can be seen that the resist of the present invention has a small film shrinkage due to baking after exposure, has a good profile and a high resolution, and has a small decrease in sensitivity even after being subjected to heat treatment after exposure.

[0151]

[Table 2]

[0152]

As described above, the chemically amplified positive photosensitive composition of the present invention has a good profile and a high resolution with little film shrinkage due to baking after exposure and film loss after development. Further, even after the aging until the heat treatment (PEB) after exposure, the decrease in sensitivity is small.

Continuation of the front page (56) References JP-A-64-6946 (JP, A) JP-A-5-45883 (JP, A) JP-A-5-297576 (JP, A) JP-A-6-11835 (JP) JP-A-6-194834 (JP, A) JP-A-5-158242 (JP, A) JP-A-2-19849 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) G03F 7/00-7/42

Claims (1)

(57) [Claims] 1. A (a) a resin soluble in an alkali aqueous solution with water insoluble, (b) an actinic ray or a compound which generates an acid when exposed to radiation having a group decomposable by (c) an acid, an alkali developer A low-molecular acid-decomposable dissolution inhibiting compound having a molecular weight of 3000 or less, whose solubility in a liquid is increased by heating to 70 ° C. or more in the presence of the acid according to (b) , and (d) the action of the acid according to (b) A compound which reacts within 1 hour at 50 ° C. or lower to increase the solubility or hydrophilicity in an alkali developing solution .
The group which can be decomposed by an acid in (c) is -COO-A
⁰ group or —O—B ⁰ group (where A ⁰ is —C (R ⁰¹ )
(R ⁰² ) represents an (R ⁰³ ) group, and B ⁰ represents A ⁰ or —COO—
A ⁰ group is shown. R ⁰¹ , R ⁰² and R ⁰³ are each the same
May be different from each other, and may include a hydrogen atom, an alkyl group,
It represents an alkyl group, an alkenyl group or an aryl group. However
And at least two of R ^{01 to} R ⁰³ are groups other than a hydrogen atom
And two groups out of R ^{01 to} R ⁰³ are bonded to form a ring
And (i) the compound (c) has at least two groups that can be decomposed by an acid, and the distance between the acid-decomposable groups is (I) a compound having at least three groups decomposable with an acid via at least 10 bonding atoms excluding an acid-decomposable group, and At least one compound selected from the group consisting of nine or more bonding atoms excluding a decomposable group , and the compound (d) further comprises:
Compounds represented by the following general formulas (d-1) to (d-12)
A positive photosensitive composition, characterized by being at least one of the following. Embedded image Wherein R ¹ ′, R ² ′, R ⁵ ′ and R ⁶ ′ are the same
May be substituted or unsubstituted, alkyl
Group, cycloalkyl group, aryl group or aralkyl group
Show. R ³ ', R ⁴ ', R ⁷ ', R ⁸ ', R ⁹ 'and R ¹⁰ '
May be the same or different, and each represents a hydrogen atom,
A substituted or unsubstituted alkyl group, aryl group or aral
Represents a kill group. Note that at least one of R ⁷ ′ to R ¹⁰ ′
One is a group other than a hydrogen atom, and has the formulas [d-1] to [d-
3], two of the groups represented by R ¹ ′ to R ⁶ ′ are bonded to each other.
To form a 5-8 membered ring which may contain heteroatoms
You may . ^{R 11 ', R 15',} R 16 ' and R ^33' is then
Which may be the same or different and are substituted or unsubstituted, n
Divalent alkyl, alkenyl, cycloalkyl or
Represents an aryl group, and R ¹² ′, R ¹³ ′ or R ¹⁴ ′ is
May be the same or different, and may be substituted or unsubstituted
Alkyl, alkenyl, cycloalkyl, aryl
Group, aralkyl group, alkoxy group or aryloxy group
Show. ^{R 17 ', R 18',} R 19 ', R 21' and R ²² 'Waso
Each may be the same or different, and may include a hydrogen atom,
Represents an unsubstituted alkyl group, cycloalkyl group, aryl
R ²⁰ ′ and R ³¹ ′ each represent a group or an aralkyl group.
May be the same or different, and may be substituted or unsubstituted
Alkyl, cycloalkyl, aryl or aralkyl
Represents a hydroxyl group. Note that R ¹⁷ ′ to R ¹⁹ ′ and R ²⁰ ′ to R ²² ′
Two of the groups may be linked to contain a heteroatom
A 5- to 8-membered ring may be formed. X 'is -O-, -S
—, —SO ₂ — or —C (R ³⁴ ′) (R ³⁵ ′) —
You. ^{R 23 ', R 24',} R 25 ', R 26', R 27 ',
^{R 28 ', R 29',} R 30 ', R 34' and R ³⁵ 'are each
Hydrogen atom, halogen atom
, Substituted or unsubstituted alkyl group, aryl group, ara
A alkyl group, an alkoxy group or a hydroxy group,
R ³² ′ is a substituted or unsubstituted alkyl group or aryl group
Is shown. R ²⁴ ′ and R ²⁶ ′ are combined to form a single bond.
R ²³ ′ to R ²⁶ ′ and R ²⁷ ′ to R ³⁰ ′,
Two of the groups R ³⁴ ′ and R ³⁵ ′ are bonded to form a heteroatom
May be formed to form a 5- to 8-membered ring. n is 1 to
Indicates an integer of 10.