JPH08220762A - Positive type photosensitive composition - Google Patents

Abstract

PURPOSE: To provide a photosensntive compsn. capable of preventing the deterioration of profile due to post exposure time delay(PED), having high resolution and stability of sensitivity, well in the prevention of film shrinkage at the time of post exposure baking(PEB) and without causing defective development. CONSTITUTION: This photosensitive compsn. contains a resin (A), a simple acid- decomposable dissolution inhibiting compd. (B) having a specified acid- decomposable group, increasing its solubility in an alkali developer by the action of an acid and having a mol.wt. of <=3,000, a compd. (C) which generates an acid by the irradiation of active light or radiation, an org. basic compd. (D) and >=5wt.% surfactant (E).

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 semiconductor manufacturing processes such as lithographic printing plates and ICs, manufacturing of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes. It is about.

[0002]

2. Description of the Related Art As a positive photoresist composition,
Generally, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is used. For example, as "novolac type phenolic resin / naphthoquinonediazide-substituted compound" in US Pat. No. 3,666,473, US Pat. No. 4,115,128 and US Pat. No. 4,173,470, etc.,
As the most typical composition, "Novolak resin consisting of cresol-formaldehyde / trihydroxybenzophenone-1,2-naphthoquinonediazide sulfonate" is an example of Thompson "Introduction to Microlithography" (LFThompson "Intr.
oduction to Microlithography ") (ACS Publishing, N
o. 2,19, p112-121). In such a positive photoresist basically consisting of a novolac resin and a quinonediazide compound, the novolac resin provides high resistance to plasma etching, and the naphthoquinonediazide compound acts as a dissolution inhibitor. When naphthoquinonediazide is irradiated with light, naphthoquinone diazide forms a carboxylic acid and loses its dissolution inhibiting ability, thereby increasing the alkali solubility of the novolak resin.

From this point of view, many positive photoresists containing novolac resin and naphthoquinonediazide type photosensitive material have been developed and put into practical use from the viewpoint of 0.8 μm.
We have achieved sufficient results in line width processing up to about 2 μm. However, the degree of integration of integrated circuits is increasing more and more, and in the manufacture of semiconductor substrates such as VLSI, it has become necessary to process ultrafine patterns having line widths of half micron or less. In order to achieve this required resolving power, the wavelength of the exposure apparatus used for photolithography has become shorter and shorter, and now far-ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) are being studied. ing. When a conventional resist composed of novolak and naphthoquinonediazide compound is used for pattern formation of lithography using far-ultraviolet light or excimer laser light, novolak and naphthoquinonediazide are strongly absorbed in the far-ultraviolet region, so that light reaches the bottom of the resist. It is hard to reach, and only a pattern with low sensitivity and taper can be obtained.

One of the means for solving such a problem is as follows.
It is a chemically amplified resist composition described in US Pat. No. 4,491,628 and European Patent 249,139. A chemically amplified positive resist composition generates an acid in the exposed area by irradiation with radiation such as far-ultraviolet light, and the acid-catalyzed reaction dissolves the active radiation irradiation area and non-irradiation area in the developing solution. It is a pattern-forming material that changes properties and forms a pattern on a substrate.

As such an example, a combination of a compound capable of generating an acid by photolysis with an acetal or O, N-acetal compound (JP-A-48-89003), or a combination of an orthoester or amide acetal compound ( JP-A-51-120714), 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), and a combination with an N-acyliminocarbonate compound (JP-A-55-126236).
No.), 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 silyl ester compound (JP-A-60-102)
47) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-121446).
Etc. can be mentioned. Since these have a quantum yield of more than 1 in principle, they exhibit high photosensitivity.

Similarly, a system which is stable at room temperature over time but decomposes by heating in the presence of an acid to solubilize with an alkali is disclosed in, for example, JP-A-59-45439 and JP-A-60-3625. JP-A-62-229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250642, Polym.Eng.Sce., 23, 101
2 (1983); ACS.Sym.242, 11 (1984); Semicond
uctor World 1987, November issue, p. 91; Macromolecules, 2
Vol. 1, p. 1475 (1988); SPIE, vol. 920, p. 42 (1988), etc.
Mention may be made of systems of secondary or primary carbon (eg t-butyl, 2-cyclohexenyl) in combination with ester or carbonate compounds. These systems also have high sensitivity and, compared to the naphthoquinone diazide / novolak resin system, Deep-UV
Since the absorption in the region is small, it can be an effective system for shortening the wavelength of the light source.

The positive chemically amplified resist is a three-component composition comprising an alkali-soluble resin, a compound (photoacid generator) which generates an acid upon exposure to radiation, and a dissolution inhibiting compound for the alkali-soluble resin having an acid-decomposable group. The system can be roughly classified into a two-component system comprising a resin having a group which is decomposed by a reaction with an acid to be alkali-soluble and a photo-acid generator.

In the case of a two-component system, since the content of acid-decomposable groups in the resin increases, the resist film shrinks due to baking after exposure, or the wettability with a developing solution deteriorates, resulting in poor development. there were. On the other hand, in the case of the three-component system, since the dissolution inhibiting property of the low molecular weight acid-decomposable dissolution inhibitor is insufficient, there is a problem that the film loss during development is large and the resist profile is significantly deteriorated. Further, if the amount of addition is increased in order to obtain dissolution inhibiting properties, the content of acid-decomposable groups in the system will increase, and the same problem as in the two-component system will occur. In addition, a chemically amplified resist generally has high sensitivity but has a problem in stability. For example, there is a problem that the profile becomes a T-top shape or the sensitivity is significantly lowered with the passage of time from the exposure to the baking after the exposure.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to elapse the time after exposure until baking [PED (Post E
By providing a positive photosensitive composition which is free from development defects, it is possible to prevent profile deterioration due to x-posure Time Delay), high resolution, stability of sensitivity, and prevention of film shrinkage during post-exposure bake (PEB). is there.

[0010]

The object of the present invention can be achieved by the following constitutions (1) to (6). (1) (A) resin, (B) (i) having at least two groups capable of being decomposed by an acid,
The distance between the acid-decomposable groups is at the farthest position, at least three bond atoms other than the acid-decomposable group are passed through, or (ii) at least three groups capable of being decomposed by an acid are contained, and the acid At a position where the distance between decomposable groups is the longest, the solubility in an alkali developer is increased by the action of an acid via 9 or more bond atoms excluding the acid-decomposable group, and a molecular weight of 3,000.
The following simple acid-decomposable dissolution-inhibiting compound, (C) a compound that generates an acid upon irradiation with actinic rays or radiation, (D) an organic basic compound, and (E) a surfactant, and (E) The positive photosensitive composition is characterized in that the content of 5 is 5% by weight or more in the composition. (2) The positive photosensitive composition as described in (1) above, wherein (a) is an alkali-soluble resin (preferably polyhydroxystyrene, novolac resin, or derivative thereof). (3) (a) is an alkali-soluble resin containing a p-hydroxystyrene unit [preferably poly (p-hydroxystyrene), poly (p / m-hydroxystyrene), poly (p / o-hydroxystyrene), p -Hydroxystyrene-styrene copolymer, 4-hydroxy-
3-Methylstyrene resin, alkyl-substituted hydroxy resin such as 4-hydroxy-3,5-dimethylstyrene resin], and an alkylated product or acetylated product of the OH part of the above resin, as described in (1) above. Positive photosensitive composition of. (4) The positive as described in (1) above, wherein (a) is a resin having one or more acid-decomposable groups, and preferably the number of acid-decomposable groups is 30 mol% or less of the monomer unit of the resin. -Type photosensitive composition. (5) The positive photosensitive composition as described in (1) above, wherein (c) is an onium salt, disulfone, 4-position naphthoquinonediazide (DNQ) sulfonate, or triazine compound. (6) The positive photosensitive composition as described in (1) above, wherein (d) is a compound having two or more nitrogen atoms in one molecule having different chemical environments in one molecule.

In the present invention, the simple acid-decomposable dissolution-inhibiting compound means a compound which can be distinguished from a structure whose structure cannot be specified and which can be specified because it has a distribution in the number of repeating units as in a polymer. . Hereinafter, the compounds used in the present invention will be described in detail.

(B) Non-polymeric acid decomposable dissolution inhibiting compound (compound of the invention (B)) The non-polymeric acid decomposable dissolution inhibiting compound (hereinafter referred to as an acid decomposable dissolution inhibitor) used in the invention (B). ) Has at least two acid-decomposable groups in its structure, and at the position where the distance between the acid-decomposable groups is the longest, at least 10 bond atoms excluding the acid-decomposable group, preferably At least 1
1, more preferably at least 12 compounds, or at least 3 acid-decomposable groups, and at least the bond atom excluding the acid-decomposable group at the position where the distance between the acid-decomposable groups is the longest. 9, preferably at least 1
It is a compound that passes through 0, more preferably at least 11. The acid-decomposable dissolution inhibitor suppresses the solubility of the alkali-soluble resin in alkali, the acid-decomposable group is deprotected by the acid generated when exposed to light, and conversely promotes the solubility of the resin in alkali. Have an effect. JP-A-63-27829 and JP-A-3-198059 disclose dissolution-inhibiting compounds having naphthalene, biphenyl and diphenylcycloalkane as a skeletal compound, but have a small dissolution inhibitory property against an alkali-soluble resin and have a profile and a resolution. Is insufficient in terms of. In the present invention, the preferred acid-decomposable dissolution inhibiting compound is 1/2 of the alkali-soluble group of the non-polymer type compound having three or more alkali-soluble groups in one molecule.
A compound obtained by protecting the above with an acid-decomposable group can be mentioned. The use of such a dissolution inhibitor leaving an alkali-soluble group is preferable in terms of reducing the effect of PED in addition to solvent solubility. Further, in the present invention, the preferable upper limit of the number of bonding atoms is 50, and more preferably 30. In the present invention, when the acid-decomposable dissolution-inhibiting compound has three or more acid-decomposable groups, preferably four or more, and even when it has two acid-decomposable groups, the acid-decomposable groups have each other. When they are separated by a certain distance or more, the dissolution inhibiting property for the alkali-soluble resin is significantly improved. The distance between acid-decomposable groups in the present invention is indicated by the number of via bond atoms excluding acid-decomposable groups. For example, in the following compounds (1) and (2), the distance between acid-decomposable groups is 4 bonding atoms each, and in compound (3), the bonding atom is 12
Individual.

[0013]

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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 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.
It is 0, more preferably 1,000 to 2,500. When the molecular weight of the acid-decomposable dissolution inhibiting compound of the present invention is in the above range, it is preferable in terms of high resolution.

In a preferred embodiment of the present invention, the acid-decomposable group is a -COO-A ⁰ , -O-B ⁰ group. More preferably the acid decomposable group -R ⁰ -COO-
This is the case where the compound is bonded to the compound with a structure represented by A ⁰ or —Ar—O—B ⁰ . Here, A ⁰ is -C (R ⁰¹ )
^{(R 02) (R 03)} , - showing the ^{Si (R 01) (R 02} ) (R 0 3) or ^{-C (R 04) (R 05} ) -O-R 06 group. B ⁰
Represents an A ⁰ or -CO-O-A ⁰ group. R ⁰¹ , R ⁰² , R
⁰³ , R ⁰⁴ and R ^{05, which} may be the same or different, each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ⁰⁶ represents an alkyl group or an aryl group. Provided that at least two of R ⁰¹ to R ⁰³ is a group other than a hydrogen atom, and, R ⁰¹ ~
Two groups of R ⁰³ and R ^{04 to} R ⁰⁶ 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 aromatic group which may have a monocyclic or polycyclic substituent.

Here, the alkyl group is preferably one 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, and a cycloalkyl group. Is preferably a group having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and the alkenyl group is 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Four aryl groups are preferable, and the aryl group has 6 to 1 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthracenyl group.
Four is preferable. Further, a hydroxyl group as a substituent,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl groups, 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 or a t-butoxy group,
Alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group, cumyl group, aralkyloxy group, acyl such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, valeryl group, etc. Groups, acyloxy groups such as butyryloxy groups, the above alkenyl groups, vinyloxy groups.
Examples thereof include alkenyloxy groups such as propenyloxy group, allyloxy group and butenyloxy group, the above aryl groups, aryloxy groups such as phenoxy group, and aryloxycarbonyl groups such as benzoyloxy group.

Particularly preferred acid-decomposable groups are silyl ether group, cumyl ester group, acetal group, tetrahydropyranyl ether group, enol ether group, enol ester group, tertiary alkyl ether group and tertiary alkyl ester group, It is a tertiary alkyl carbonate group or the like. More preferably, a tertiary alkyl ester group, a tertiary
A primary alkyl carbonate group, a cumyl ester group, a tetrahydropyranyl ether group, and an acetal group.

A preferred acid-decomposable dissolution inhibitor is described in JP-A-1.
-289946, JP-A 1-289947, JP-A-2-2560, JP-A-3-128959, JP-A-3.
No. 158855, JP-A-3-179353, JP-A-3-191351, JP-A-3-200251, JP-A-3-200252, JP-A-3-200253, JP-A-3-200254, JP-A-3-200254. No. 200255,
JP-A-3-259149, JP-A-3-279958
JP-A-3-279959, JP-A4-1650
No. 4-1651, JP-A-4-11260,
JP-A-4-12356, JP-A-4-12357, Japanese Patent Application No. 3-33229, Japanese Patent Application No. 3-230790, Japanese Patent Application No. 3-320438, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-25157. No. 52732, Japanese Patent Application No. 4-103215, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-107885,
A group in which a part or all of the phenolic OH group of the polyhydroxy compound described in the specifications of Japanese Patent Application Nos. 4-107889, 4-152195, etc. is shown above, -R ^0-.
Included are compounds that are protected by a COO-A ⁰ or B ⁰ group.

More preferably, JP-A-1-289946.
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, and JP-A-3-2002.
51, JP-A-3-200252, and JP-A-3-200.
255, JP-A-3-259149, and JP-A-3-27.
No. 9958, JP-A-4-1650, and 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
5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219.
Those using the polyhydroxy compound described in the specification of No. 5 are mentioned.

More specifically, general formulas [I] to [XV
I] can be mentioned.

[0021]

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[0022]

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[0023]

[Chemical 4]

[0024]

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Here, R ¹ , R ² , R ³ , and R ⁴ may be the same or different and each is a hydrogen atom, —R ⁰ —COO—A ⁰ or B ⁰ group, R ₁ : —CO—, —. COO-, -NHCONH-, -N
HCOO -, - O -, - S -, - SO -, - SO 2 -,
-SO _3- , or

[0026]

[Chemical 6]

[0027] 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, halogen atom, -R ₆ -COOR ₇ or -R _8,
-OH, R _6, R _8: an alkylene group, R _7: a hydrogen atom, an alkyl group, an aryl group or an aralkyl _{group,, R 2, R 3,} R 9 ~R 12, R 15, R 17 ~
R ₂₁ , R _{25 to} R ₂₇ , R _{30 to} R ₃₂ , R _{37 to} R ₄₂ , R _{46 to} R
₄₉ and R ₅₁ : may be the same or different, hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, halogen atom, nitro group, carboxyl group, a cyano group or a _{-N, (R 13) (R} 14) (R 13, R 14: H, alkyl or aryl group,), R _16: a single bond, an alkylene group or,

[0028]

[Chemical 7]

R ₂₂ and R ₂₄ may be the same or different and each is 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, acyloxy group, aryl group, nitro group, hydroxyl group, cyano group, or carboxyl group, provided that hydrogen of the hydroxyl group may be substituted with t-butoxycarbonyl group, R ₂₈ , R ₂₉ : the same or different Also, a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, provided that the lower alkyl group in the present application 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, which may be the same or different, are a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or an alkyl group. Siloxy group, R ₅₀ : hydrogen atom, t-butoxycarbonyl group, or

[0030]

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R ₅₂ and R ₅₃ may be the same or different, and may be a hydrogen atom, a lower alkyl group, a lower haloalkyl group or an aryl group, and 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 each of the four substituents having the same symbol does not have to be the same group, Y: -CO-, Alternatively, —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: when more than one, the groups in () 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 from 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: 3 to 8 is an integer, (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 + v
1), (x1 + w1) ≦ 4, but in the case of general formula [V], (w + z), (x + a
1) ≦ 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.

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

[0035]

[Chemical 12]

Specific examples of preferable compound skeletons are shown below.

[0037]

[Chemical 13]

[0038]

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[0039]

[Chemical 15]

[0040]

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[0041]

[Chemical 17]

[0042]

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[0043]

[Chemical 19]

[0044]

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[0045]

[Chemical 21]

[0046]

[Chemical formula 22]

[0047]

[Chemical formula 23]

[0048]

[Chemical formula 24]

[0049]

[Chemical 25]

[0050]

[Chemical formula 26]

[0051]

[Chemical 27]

[0052]

[Chemical 28]

[0053]

[Chemical 29]

[0054]

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[0055]

[Chemical 31]

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

[0057]

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Represents However, at least two, or three depending on the structure, are groups other than hydrogen atom, and each substituent R
Do not have to be the same group.

The amount of the compound used in the present invention (B) added 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. When the amount of the compound used in the present invention (B) added is less than 3% by weight, high resolution cannot be obtained, and 50
If it exceeds 5% by weight, the storage stability deteriorates, the film shrinks, and the heat resistance of the resist deteriorates.

(A) Soluble Resin (Compound of the Present Invention (A)) The resin (A) used in the present invention is an alkali-soluble resin (preferably polyhydroxystyrene, novolac resin, or derivative thereof), Alkali-soluble resin containing a p-hydroxystyrene unit (preferably poly (p-hydroxystyrene, p / m-hydroxystyrene, p / o-hydroxystyrene, p-hydroxystyrene-styrene copolymer), 4-hydroxy- Three
An alkyl-substituted hydroxy resin such as methylstyrene resin, 4-hydroxy-3,5-dimethylstyrene resin, an alkylated or acetylated OH moiety of the above resin, a resin having one or more acid-decomposable groups, It is preferable that the number of acid-decomposable groups is 30 mol% or less of the monomer unit of the resin. Furthermore, when a part of the phenol nuclei of the above resin (30 mol% or less of the total phenol nuclei) is hydrogenated, the transparency of the resin is improved, and it is preferable in terms of sensitivity, resolution and short profile formation. Examples of the alkali-soluble resin used in the present invention include novolac resin, hydrogenated novolak resin, acetone-pyrogallol resin, polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, and polyhydroxy. Partial O-alkylated or O-acylated styrene, styrene-maleic anhydride copolymer, carboxyl group-containing methacrylic resin and its derivatives, styrene-polyhydroxystyrene copolymer, hydrogenated polyhydroxystyrene However, the present invention is not limited to these. Particularly preferred alkali-soluble resin used in the present invention is a novolac resin, 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-3,5-
Alkyl-substituted hydroxy resin such as dimethyl styrene resin, alkylated or acetylated OH part of the above resin, partially hydrogenated novolac resin, partially hydrogenated polyhydroxystyrene resin, and the phenolic hydroxyl group is substituted with the acid decomposing group described above. Novolak resins, polyhydroxystyrene resins, partially hydrogenated novolac resins, and partially hydrogenated polyhydroxystyrene resins. In the present invention, polyhydroxystyrene means p-hydroxystyrene monomer, m-
A polymer obtained by polymerizing at least one kind of a monomer selected from a hydroxystyrene monomer, an o-hydroxystyrene monomer, or an alkyl-substituted hydroxystyrene monomer having an ortho position of 1 to 4 carbon atoms is shown. . The novolak resin is obtained by addition-condensing an aldehyde with a predetermined monomer as a main component in the presence of an acidic catalyst.

As the predetermined monomer, phenol, m
-Cresol, p-cresol, o-cresol and other cresols, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,3-xylenol and other xylenols, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2 -Methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, alkoxyphenols such as p-butoxyphenol, 2-methyl-4-isopropyl Feno Bis-alkylphenols etc., m
-Hydroxy aromatic compounds such as chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or in combination of two or more, but are not limited thereto. It is not something that will be done.

Examples of 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 acetals thereof such as chloroacetaldehyde diethyl acetal can be used, and of these, formaldehyde is preferably used. These aldehydes are
They may be used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or the like can be used.

The resin having an acid-decomposable group of the present invention is a resin having an acid-decomposable group in the main chain or side chain of the base resin or in both the main chain and the side chain. Of these, a resin having a side chain having an acid-decomposable group is more preferable.

The group decomposable by an acid is --COO--A ⁰ ,
It is -O-B ⁰ group. More preferably the acid decomposable group -R ⁰ -
In this case, the compound has a structure represented by COO-A ⁰ or -Ar-O-B ⁰ . Where A ⁰ is −C
( ^R01 ) ( ^R02 ) ( ^R03 ), -Si ( ^R01 ) ( ^R02 )
(R ^{0 3} ) or —C (R ⁰⁴ ) (R ⁰⁵ ) —O—R ⁰⁶ group is shown. B ⁰ represents A ⁰ or a —CO—O—A ⁰ group.
R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^{05, which} may be the same or different, each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group,
⁰⁶ represents an alkyl group or an aryl group. However, R ⁰¹
At least two of R ⁰³ are groups other than hydrogen atom,
Further, two groups of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ may combine to form a ring. R ⁰ represents a divalent or higher aliphatic or aromatic hydrocarbon group which may have a substituent, and —Ar— represents a divalent or higher divalent aromatic group which may have a monocyclic or polycyclic substituent. Indicates an aromatic group.

Here, the alkyl group is preferably one having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, and cycloalkyl group. Is preferably a group having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and the alkenyl group is 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Four aryl groups are preferable, and the aryl group has 6 to 1 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthracenyl group.
Four is preferable. Further, a hydroxyl group as a substituent,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl groups, 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 or a t-butoxy group,
Alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group, cumyl group, aralkyloxy group, acyl such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, valeryl group, etc. Groups, acyloxy groups such as butyryloxy groups, the above alkenyl groups, vinyloxy groups.
Examples thereof include alkenyloxy groups such as propenyloxy group, allyloxy group and butenyloxy group, the above aryl groups, aryloxy groups such as phenoxy group, and aryloxycarbonyl groups such as benzoyloxy group.

Particularly preferred acid-decomposable groups are silyl ether group, cumyl ester group, acetal group, tetrahydropyranyl ether group, enol ether group, enol ester group, tertiary alkyl ether group and tertiary alkyl ester group, It is a tertiary alkyl carbonate group or the like. More preferably, a tertiary alkyl ester group, a tertiary
A primary alkyl carbonate group, a cumyl ester group, a tetrahydropyranyl ether group, and an acetal group.

Next, when the acid-decomposable group is bonded as a side chain, the mother resin is --OH or --COOH, preferably --R ⁰ --COOH or --COOH.
An alkali-soluble resin having an AR-OH group is preferable,
For example, polyhydroxystyrene, hydrogenated polyhydroxystyrene, novolac resin, hydrogenated novolac resin,
Acetone-pyrogallol resin, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-
Examples thereof include, but are not limited to, N-substituted maleimide copolymers, polyhydroxystyrene partially o-acylated products, styrene-maleic anhydride copolymers, carboxyl group-containing methacrylic resins and derivatives thereof. is not.

The alkali dissolution rate of the alkali-soluble resin for the base resin was 1 as measured by 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.).
It is preferably 70 A / sec or more. Especially preferably 33
0 A / sec or more (A is angstrom).
Further, an alkali-soluble resin having a high transmittance for far ultraviolet light or excimer laser light is preferable from the viewpoint of achieving a rectangular profile. Preferably 248 nm with a thickness of 1 μm
Transmittance is 20 to 80%. From this point of view, particularly preferable alkali-soluble resins for the base resin are polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, partially o-acylated polyhydroxystyrene and hydrogenated novolak resin. is there.

The resin having an acid-decomposable group according to the present invention is described in European Patent No. 254853 and JP-A-2-25850.
No. 3,223,860, and No. 4-251259, etc., an alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an acid-decomposable group is bonded. It can be obtained by copolymerizing an alkali-soluble resin monomer with various monomers.

The general formulas of the resins having an acid-decomposable group thus synthesized are shown in the following (a) to (f), but the present invention is not limited thereto.

[0071]

[Chemical 33]

Here, L: -COOA ⁰ , -O-B ⁰ ,-(O) _n -R ⁰ -COO
^{-A 0, -AR-O-B} 0 ( however, AR, A ⁰ and B ⁰ same as Teigi of supra) R _1: R ₁ in the same molecule may be the same as or different from each other, hydrogen atom or an alkyl group of _{C 1 ~C 4, R 2,} R 4: each group of the same name in the same molecule may be the same or different, a hydrogen atom or an alkyl group of C ₁ ~C _4, R _3: hydrogen atom, a carboxyl group, a cyano group or a substituted aryl group, R _5: a hydrogen atom, a cyano group or -COOR _6, R _6: a straight-branched or cyclic alkyl group of _{C 1 ~C 10, R 7 ~R} 9 Is a hydrogen atom or a C ₁ -C ₄ alkyl group, Ar is a monocyclic or polycyclic substituent group 1
A valent aromatic group, k, l, k1, l1, m: each independently represents a natural number, n: 0 or 1. More specifically, the following (i) to (xxiii) can be mentioned.

[0073]

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[0074]

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[0075]

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The content of acid-decomposable groups is determined by the number of acid-decomposable groups in the resin (B) and the number of alkali-soluble groups not protected by acid-decomposable groups (S). B /
It is represented by (B + S). The content is 0.01 to 0.5, preferably 0.01 to 0.30, and more preferably 0.01.
Is about 0.15. PEB when B / (B + S)> 0.5
It is not preferable because it may cause later film shrinkage, poor adhesion to the substrate, and scum. On the other hand, when B / (B + S) <0.01, a standing wave may remain remarkably on the pattern side wall, which is not preferable.

The weight average molecular weight of the resin of the present invention (A) is
It is preferably in the range of 1,000 to 100,000. If it is less than 1,000, the film loss of the unexposed area after development is large, and if it exceeds 100,000, the developing speed becomes small. Particularly preferred is the range of 2,000-60,000. Here, the weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography.

Two or more kinds of these alkali-soluble resins in the present invention may be mixed and used. 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. The amount of alkali-soluble resin used is 5
If it is less than 0% by weight, dry etching resistance is deteriorated.

(C) Compound that Generates Acid by Irradiation with Actinic Rays or Radiation (Compound of the Invention (C)) The compound used in the present invention to decompose by irradiation with actinic ray or radiation to generate acid , A photo-initiator for photo-cationic polymerization, a photo-initiator for photo-radical polymerization, a photo-decoloring agent for dyes, a photo-discoloring agent, or a compound that generates an acid by known light used for micro resist and the like. The mixture can be appropriately selected and used. In addition, examples of other compounds that generate an acid upon irradiation with actinic rays or radiation (compounds of the present invention (C)) used in the present invention include SI Schlesinger, Photogr.
i.Eng., 18,387 (1974), TSBal etal, Polymer, 21,423 (1
980) and the like, diazonium salts, U.S. Pat.No. 4,069,055
No. 4,069,056, Re 27,992, Japanese Patent Application No. 3-140,140
Ammonium salt, DC Necker et al, Macrom
olecules, 17,2468 (1984), CSWen et al, Teh, Proc.Con
f.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Patent No.
Phosphonium salts described in 4,069,055, 4,069,056, etc., JV Crivello et al, Macromorecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 10
4,143, U.S. Pat.No. 339,049, No. 410,201, JP-A-2-150,848, iodonium salts described in JP-A-2-296,514, JVCrivello et al, Polymer J. 17,73 (1985),
JVCrivello et al. J. Org. Chem., 43, 3055 (1978), WR
Watt et al, J. Polymer Sci., Polymer Chem. Ed., 22,1789
(1984), JVCrivello et al, Polymer Bull., 14,279 (198
5), JVCrivello et al, Macromorecules, 14 (5), 1141 (19
81), JVCrivello et al., J. Polymer Sci., Polymer Chem.
Ed., 17, 2877 (1979), European Patent No. 370,693, and 3,902, 11
4, 233,567, 297,443, 297,442, U.S. Patents 4,933,377, 161,811, 410,201, 339,049.
No., No. 4,760,013, No. 4,734,444, No. 2,833,827,
Dokoku Patent Nos. 2,904,626, 3,604,580 and 3,604,581
Sulfonium salts, JVCrivello et al, Macr
omorecules, 10 (6), 1307 (1977), JVCrivello et al, JP
olymer Sci., Polymer Chem. Ed., 17, 1047 (1979) selenonium salt, CSWen et al, Teh, Proc.Conf.Rad.C
uring ASIA, p478 Tokyo, Oct (1988) onium salts such as arsonium salts described in, U.S. Pat.
JP-A-60-239736, JP-A-61-169835, JP-A-61-169
837, JP 62-58241, JP 62-212401, JP
63-70243, organic halogen compounds described in JP-A-63-298339, K. Meier et al, J. Rad. Curing, 13 (4), 26 (198
6), TPGill et al, Inorg. Chem., 19,3007 (1980), DA
struc, Acc.Chem.Res., 19 (12), 377 (1896), JP-A-2-1614
Organic metal / organic halides described in No. 45, S. Hayase
et al, J. Polymer Sci., 25, 753 (1987), E. Reichmanis eta
l, J.Pholymer Sci., Polymer Chem. Ed., 23,1 (1985), QQ
Zhu et al, J. Photochem., 36, 85, 39, 317 (1987), B. Amit et
al, Tetrahedron Lett., (24) 2205 (1973), DHR Barton e
tal, J.Chem Soc., 3571 (1965), PMCollins et al, J.Che
m.SoC., Perkin I, 1695 (1975), M. Rudinstein et al, Tetrah
edron Lett., (17), 1445 (1975), JWWalker etalJ.Am.Ch
em.Soc., 110,7170 (1988), SCBusman et al, J.Imaging T
echnol., 11 (4), 191 (1985), HM Houlihan et al, Macormol
ecules, 21, 2001 (1988), PMCollins 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), FM Houlihaneta
L, Macromolcules, 21, 2001 (1988), European Patent 0290,750
No. 0, No. 046,083, No. 156,535, No. 271,851, No. 0,38
8,343, U.S. Pat. Nos. 3,901,710, 4,181,531, JP-A-60-198538, JP-A-53-133022, and the like, and a photoacid generator having a 0-nitrobenzyl type protecting group, M.TUNOOKA.
et al, Polymer Preprints Japan, 35 (8), G. Berner et al,
J.Rad.Curing, 13 (4), WJMijs et al, Coating Technol.,
55 (697), 45 (1983), Akzo, H. Adachi etal, Polymer Prepr
ints, Japan, 37 (3), European Patent Nos. 0199,672, 84515,
No. 199,672, No. 044,115, No. 0101,122, U.S. Patent No.
618,564, 4,371,605, 4,431,774, JP-A-64-
No. 18143, JP-A-2-245756, Japanese Patent Application No. 3-140109, etc., compounds which generate sulfonic acid by photolysis represented by iminosulfonates, etc., described in JP-A-61-166544, etc. The disulfone compound can be mentioned.

Further, a group generating an acid by these light,
Alternatively, a compound in which a compound is introduced into the main chain or side chain of a polymer, for example, ME Woodhouse et al., J. Am. Chem.
Soc., 104,5586 (1982), SPPappas et al, J. Imaging Sc
i., 30 (5), 218 (1986), S.Kondoetal, Makromol.Chem., Rap
id Commun., 9,625 (1988), Y.Yamada et al, Makromol.Che
m., 152,153,163 (1972), JVCrivello et al, J. PolymerS
ci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
9,137, Japan 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-
The compounds described in 146029 and the like can be used.

Further, VNR Villai, Synthesis, (1), 1 (198
0), A. Abad et al, Tetrahedron Lett., (47) 4555 (1971),
DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, European Patent 126,712 and the like which generate an acid by light can also be used.

Among the compounds which decompose when exposed to 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
1) or an oxazole derivative represented by the general formula (PA
An S-triazine derivative represented by G2).

[0083]

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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. The following compounds can be specifically mentioned, but the compounds are not limited to these.

[0085]

[Chemical 38]

[0086]

[Chemical Formula 39]

[0087]

[Chemical 40]

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

[0089]

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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. Of these, an aryl group having 6 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms, and a substituted derivative thereof are preferable. 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,
The alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group or an alkoxycarbonyl group.

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 thereof include, but are not limited to:

Two of R ³ , R ⁴ and R ⁵ and A
r ¹ and Ar ² may be bonded to each other via a single bond or a substituent.

Specific examples include the compounds shown below, but the invention is not limited thereto.

[0095]

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[0096]

[Chemical 43]

[0097]

[Chemical 44]

[0098]

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[0099]

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[0100]

[Chemical 47]

[0101]

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[0102]

[Chemical 49]

[0103]

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[0104]

[Chemical 51]

[0105]

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[0106]

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The onium salts represented by the general formulas (PAG3) and (PAG4) are known, and for example, JWKnapczyk.
et al, 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), HMLeicester, JA
me.Chem.Soc., 51,3587 (1929), JVCrivello et al, J.Po
Lym.Chem.Ed., 18,2677 (1980), U.S. Pat.No. 2,807,648
No. 4,247,473 and JP-A No. 53-101,331, and the like.

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

[0109]

[Chemical 54]

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.

[0111]

[Chemical 55]

[0112]

[Chemical 56]

[0113]

[Chemical 57]

[0114]

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[0115]

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In the present invention, a compound capable of generating an acid upon irradiation with actinic rays or radiation (the compound of the present invention (C))
Is preferably an onium salt, disulfone, 4-position DNQ sulfonate, or triazine compound.

The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.0 based on the total weight of the photosensitive composition (excluding the coating solvent).
It is used in the range of 01 to 40% by weight, preferably 0.0
It is used in the range of 1 to 20% by weight, more preferably 0.1 to 5% by weight. If the amount of the compound that decomposes to generate an acid upon irradiation with actinic rays or radiation is less than 0.001% by weight, the sensitivity will be low, and if it is more than 40% by weight, the light absorption of the resist will be high. Excessive, profile deterioration and narrow process (especially bake) margin are not preferable.

(D) Organic Basic Compound (Compound of the Present Invention (D)) The organic basic compound that can be used in the present invention includes one or more nitrogen atoms having different chemical environments in one molecule. It is a nitrogen basic compound. Examples of preferable chemical environment include the structures of the following formulas (24) to (28).

[0119]

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Further preferred compounds are compounds having both a substituted or unsubstituted amino group and a ring structure containing 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 indazole, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine,
Substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, etc. . Preferred substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group. Is. Particularly preferred compounds include 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, 2-pyrazoline, 3-pyrazolin,
Examples thereof include N-aminomorpholine and N- (2-aminoethyl) morpholine, but are not limited thereto.

These nitrogen-containing basic compounds may be used alone or in combination of two or more. The amount of the nitrogen-containing basic compound used is usually 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the resin (A) or the resin (B). If it is less than 0.001 part by weight, the pattern shape and adhesiveness tend to be deteriorated, while if it exceeds 10 parts by weight, the sensitivity is lowered and the developability of the non-exposed portion tends to be deteriorated.

(E) Surfactant (Surfactant of (E) of the Present Invention) The surfactant used in the present invention is specifically polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene. Polyoxyethylene alkyl ethers such as cetyl ether and polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene alkylallyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan Sorbitan fats such as monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Polyoxyethylene sorbitan such as acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Nonionic surfactants such as fatty acid esters, Ftop EF301, EF3
03, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Fluoro FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-.
382, SC101, SC102, SC103, SC1
04, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants, organosiloxane polymer KP
341 (manufactured by Shin-Etsu Chemical Co., Ltd.) or acrylic acid-based or methacrylic acid-based (co) polymerized polyflow No. 75, N
o. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like. These surfactants may be added alone or in some combinations. The content of the surfactant used in the present invention is 5% by weight or more in the composition, preferably 5% by weight to 20% by weight,
It is more preferably 6% by weight to 10% by weight. Further, in the present invention, the content of the surfactant is preferably 30% by weight or less in the composition. Within this range, the effect of PED is small, the coatability is good, and the development failure is small, which is preferable. That is, when the amount is less than 5% by weight, the influence of PED occurs (sensitivity change, etc.), and when the amount is more than 20% by weight, the film-verification tends to occur.

The photosensitive composition of the present invention may optionally contain
Further, a dye, a pigment, a plasticizer, a photosensitizer, and a compound having two or more phenolic OH groups for promoting solubility in a developer can be contained. Suitable dyes include oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue B.
OS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.), Crystal Violet (CI42555), Methyl Violet (CI42).
535), Rhodamine B (CI45170B), Malachite Green (CI42000), Methylene Blue (C).
I52015) and the like.

Further, the following spectral sensitizers are added to the photosensitive composition of the present invention by sensitizing it to a wavelength region longer than far ultraviolet where the photo-acid generator used has no absorption. Sensitivity can be imparted 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, 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 not limited to these.

The photosensitive composition of the present invention is prepared by dissolving it in a solvent that dissolves each of the above components and coating it on a support.
As the solvent that can be used, ethylene dichloride, cyclohexanone, cyclopentanone, 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, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, Alone or as a mixture thereof used.

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

The developer for the photosensitive composition of the present invention is
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 tertiary amines such as triethylamine and methyldiethylamine. Use alkaline aqueous solutions of triamines, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and piperidine. be able to. Furthermore, alcohols and surfactants may be added in appropriate amounts to the alkaline aqueous solution before use. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

(Synthesis example) [Synthesis example-1 of dissolution inhibitor compound] 1- [α-methyl-
α- (4′-hydroxyphenyl) ethyl] -4-
42.4 g (0.10 mol) of [α ', α'-bis (4 "-hydroxyphenyl) ethyl] benzene was dissolved in 300 ml of N, N-dimethylacetamide, and 49.5 g (0.35 of potassium carbonate was added thereto. Mol) and 84.8 g (0.33 mol) of bromoacetic acid cumyl ester, and then stirred for 7 hours at 120 ° C. The reaction mixture was poured into 2 l of ion-exchanged water and neutralized with acetic acid. The compound was extracted with ethyl acetate, concentrated, and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 2/8 (volume ratio)). (18: R is all -CH ₂ COOC
70 g of (CH ₃ ) ₂ C ₆ H ₅ group) was obtained. [Synthesis example-2 of dissolution inhibitor compound] α, α, α ', α', α ",
α "-hexakis (4-hydroxyphenyl) -1,3,
5-Triethylbenzene 14.3 g (0.020 mol)
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
The mixture was stirred at 20 ° C for 7 hours. Then, 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 in the same manner as in Synthesis Example [1] to obtain 24 g of a pale yellow powder. NMR
Therefore, this is a compound example (62: R is all -CH ₂ -C
OO—C ₄ H ₉ ^t group).

[0129]

【Example】

Example Resists A to F of the present invention were prepared using the compounds of the present invention shown in Table 1. The prescription at that time is shown in Table 1. Table 2 shows the acid-decomposable dissolution inhibitors used.

Comparative Example Comparative resists G to I were prepared according to the formulations shown in Table 1 as in the example.

[0131]

[Table 1]

In Table 1, the exposure of the resist F is an i-line stepper, the other is an excimer laser super, and the developing solutions for the resists A, G and H are 1.19%.
Tetramethylammonium hydroxide (TMA
H), the resist I is as described in Example 3 of JP-A-5-232706, and 2.38% TM otherwise.
It is AE. The sensitivity change was evaluated as ◯ when the sensitivity change was 5% or less when comparing the results on different evaluation days, and as x when the sensitivity change was more than 5%. The profile deterioration due to the lapse of time (PED) from the exposure to the baking is indicated by ◯ when the pattern of 0.5 μm does not become T-top shape by PED for 60 minutes, and as × when it becomes T-top shape. The compounds used in the examples are shown below. Further, the structures of the acid-decomposable solubilizers b-1 to b-4 in Table 1 above are summarized in Table 2 below.

[0133]

[Chemical formula 61]

[0134]

Embedded image

[0135]

[Table 2]

[Preparation and Evaluation of Photosensitive Composition] Resists A to H were dissolved in propylene monoethyl acetate so that the materials shown in Table 1 had appropriate concentrations, and Resist I was dissolved in methyl 3-methoxypropionate. Dissolve, 0.2 μm
A resist solution was prepared by filtering with a filter. This resist solution is applied on a silicon wafer,
After drying at 60 ° C. for 60 seconds on a vacuum adsorption type hot plate, a resist film having a film thickness of 0.85 μm was obtained. The resist film was exposed using a 248 nm KrF excimer laser stepper. After the exposure, heating was performed for 60 seconds on a vacuum adsorption type hot plate at 90 ° C., and immediately with an aqueous solution of tetramethylammonium hydroxide (TMAH).
It was immersed for 0 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 resist profile. The results are shown in Table 2.

The sensitivity was defined as the reciprocal of the exposure dose for reproducing a 0.40 μm mask pattern, and was shown by the relative value of the sensitivity of Comparative Example 1. The film shrinkage is expressed as a percentage of the ratio of the film thickness before and after exposure and baking in the exposed area. The resolving power represents a limiting resolving power at an exposure amount for reproducing a mask pattern of 0.40 μm. From the results in Table 1, it is understood that the resist of the present invention has less film shrinkage due to baking after exposure, and has a good profile and high resolution.

[0138]

INDUSTRIAL APPLICABILITY The present invention can provide a positive photosensitive composition which is free from profile deterioration due to PED, high resolution, stability of sensitivity, and prevention of film shrinkage during PEB, and is free from development defects. it can.

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[Procedure amendment]

[Submission date] March 28, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0136

[Correction method] Change

[Correction content]

[Preparation and Evaluation of Photosensitive Composition] Resists A to H were dissolved in propylene monoethyl acetate so that the materials shown in Table 1 had appropriate concentrations, and Resist I was dissolved in methyl 3-methoxypropionate. Dissolve, 0.2 μm
A resist solution was prepared by filtering with a filter. This resist solution is applied on a silicon wafer,
After drying at 60 ° C. for 60 seconds on a vacuum adsorption type hot plate, a resist film having a film thickness of 0.85 μm was obtained. The resist film was exposed using a 248 nm KrF excimer laser stepper. After the exposure, heating was performed for 60 seconds on a vacuum adsorption type hot plate at 90 ° C., and immediately with an aqueous solution of tetramethylammonium hydroxide (TMAH).
It was immersed for 0 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 resist profile. The results are shown in Table 1 .

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Claims (1)

[Claims] 1. A resin (A), (B) (i) having at least two groups decomposable by an acid,
The distance between the acid-decomposable groups is at the farthest position, at least three bond atoms other than the acid-decomposable group are passed through, or (ii) at least three groups capable of being decomposed by an acid are contained, and the acid At a position where the distance between decomposable groups is the longest, the solubility in an alkali developer is increased by the action of an acid via 9 or more bond atoms excluding the acid-decomposable group, and a molecular weight of 3,000.
The following simple acid-decomposable dissolution-inhibiting compound, (C) a compound that generates an acid upon irradiation with actinic rays or radiation, (D) an organic basic compound, and (E) a surfactant, and (E) The positive photosensitive composition is characterized in that the content of 5 is 5% by weight or more in the composition.