JPH06130670A - Positive photosensitive composition - Google Patents

Abstract

PURPOSE:To provide a positive photosensitive compsn. of ternary chemical sensitization type having high sensitivity, high resolution and good profile without producing precipitation when the compsn. is stored for a long time. CONSTITUTION:The positive photosensitive compsn. contains (a) novolac resin, (b) compd. which produces acid by irradiation of active ray or radiation, and (c) low mol.wt. compd. having a single structure of <3000mol.wt. and tertiary alkylester groups, the solubility of which is increased by the effect of acid in an alkali developer. The compd. (c) is a compd. having at least two tertiary alkylester groups in which the distance between the two farest ester groups includes >=10 bonded atoms except for ester groups, or at least three tertiary alkylester groups in which the distance between the two farest ester groups includes >=9 bonded atoms except for ester groups.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive type 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. 219, 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, light is strong in the far ultraviolet region of novolak and naphthoquinonediazide, and 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 means for solving such a problem is
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 above positive type chemically amplified resist is composed of an alkali-soluble resin, a compound which generates an acid upon exposure to radiation (photoacid generator), and a dissolution-inhibiting compound (acid which becomes alkali-soluble by a catalytic reaction with an acid). It can be roughly classified into a three-component system consisting of a decomposable dissolution inhibitor) and a two-component system consisting of a resin having a group which becomes alkali-soluble by reaction with an acid and a photo-acid generator. Two-component chemically amplified positive resist (US Pat. No. 4
No. 491628) mainly reduces the alkali solubility of the binder by crushing the alkali-soluble group of the alkali-soluble binder with an acid-decomposable group. The acid-decomposable dissolution inhibitor of the three-component chemically amplified positive resist (European Patent No. 249139, JP-A No. 2-248953, etc.) is itself alkali-insoluble, and is a binder by interacting with the binder resin. It functions to reduce the alkali solubility of the resin. In this way, it is considered that the two-component system and the three-component system have different mechanisms of expressing alkali dissolution inhibiting ability.

In the case of a two-component system, the content of acid-decomposable groups in the resin is large, so 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 to the alkali-soluble resin is insufficient, the film loss during development is large and the resist profile is remarkably deteriorated. However, the three-component system is a promising system due to the wide range of material selection,
It has been desired to develop an acid-decomposable compound that is used in this system and has excellent dissolution inhibiting properties.

For example, the alkali dissolution inhibiting ability of the acid-decomposable dissolution inhibitor of the three-component chemically amplified positive resist is more effectively exhibited as the proportion of the alkali-soluble group protected by the acid-decomposable group increases. JP-A-2-248593 discloses an acid-decomposable dissolution inhibitor in which an alkali-soluble group (phenolic OH group) is left in the molecule, but the dissolution inhibition is weak and the resolution and the resist profile are sufficient. Not a thing. On the other hand, depending on the type of the acid-decomposable group, as the amount of the acid-decomposable group introduced is increased, there arises a problem that the solubility in a solvent is significantly reduced when a resist solution is prepared. Further, JP-A-63-27829 and JP-A-3-198059 disclose a dissolution inhibitor having naphthalene, biphenyl and diphenylcycloalkane as a skeleton compound. It was insufficient in terms of aisle and resolution.

[0010]

Therefore, the present invention provides a three-component chemical amplification type positive-working photosensitive composition having high sensitivity, high resolution, and good profile, and which does not precipitate with the passage of time. The purpose is to do.

[0011]

Means for Solving the Problems As a result of intensive studies made by the present inventors while paying attention to the above-mentioned various characteristics, the object of the present invention is to find out that an alkali-soluble resin, a photoacid generator, and a dissolution inhibitor having an acid-decomposable group. Found to be achieved by using a positive photosensitive composition containing a compound and satisfying the following requirements,
The present invention has been reached. That is, the present invention includes (a) a novolak resin, (b) a compound that generates an acid upon irradiation with actinic rays or radiation, and (c) a tertiary alkyl ester group, and has a solubility in an alkaline aqueous solution of an acid. Molecular weight increased by the action of 30
In the positive-type photosensitive composition containing a low molecular weight acid-decomposable dissolution-inhibiting compound of 00 or less, the compound (c) is
(I) a compound having at least two tertiary alkyl ester groups, wherein the distance between the ester groups is 10 or more via bond atoms excluding the ester group at the furthest position, and (ii) the third It is at least one selected from the group consisting of a compound having at least three primary alkyl ester groups and having 9 or more bond atoms excluding the ester group at the position where the distance between the ester groups is the longest. The present invention provides a positive-type photosensitive composition characterized by the above.

In the three-component positive-working photosensitive composition of the present invention, as an acid-decomposable dissolution inhibitor, when the acid-decomposable groups in the structure are separated by a certain value or more, the dissolution-inhibiting property is I have found that it will increase significantly. Furthermore, it has been found that when a novolak resin is used as the alkali-soluble resin to be combined, the interaction with the dissolution inhibitor is increased and the dissolution inhibitory property is improved. When combined with a novolak resin, the thermal decomposition temperature thereof is significantly lowered depending on the type of acid-decomposable group of the dissolution inhibitor. However, when a tertiary alkyl ester group is used as the acid-decomposable group, the thermal decomposition temperature is maintained at a high position (for example, about 150 ° C. for t-butyl ester form). Further, the dissolution inhibitor having a t-butyl ester group has good solubility in the resist solvent even if the amount of the t-butyl ester group introduced is increased. Hereinafter, the compound used in the present invention will be described in detail.

(A) Acid-decomposable dissolution inhibiting compound (Compound of the invention (c)) The acid-decomposable dissolution inhibiting compound used in the invention (c) is
At least two tertiary alkyl ester groups are included in the structure.
A compound having at least 10, more preferably at least 14 and more preferably at least 15 bond atoms excluding the ester group at the position where the distance between the ester groups is farthest, or a tertiary alkyl ester A compound having at least 3 groups and having at least 9 bond atoms other than the ester group, preferably at least 13 and more preferably at least 14 at the position where the distance between the ester groups is the longest. In the present invention, when the acid-decomposable dissolution inhibiting compound has three or more tertiary alkyl ester groups, preferably four or more tertiary alkyl ester groups, and when it has two tertiary alkyl ester groups, the ester groups are When they are separated from each other by a certain distance or more, the ability to suppress dissolution in the alkali-soluble resin is significantly improved. The distance between the ester groups in the present invention is indicated by the number of via bond atoms excluding the ester groups. For example, in the following compound (1), the distance between ester groups is 8 bonding atoms, and in compound (2), the bonding atom is 4
And 16 in the compound (3).

[0014]

[Chemical 1]

Furthermore, the present invention provides at least 10 mol%, preferably 30 mol% of the total content of the compound of the present invention (c).
It is preferable that mol%, more preferably 50 mol%, is a compound in which an alkali-soluble group is intentionally left. The content of alkali-soluble groups is the average number N of alkali-soluble groups in the tertiary alkyl ester group-containing dissolution inhibitor.
It can be represented by N _S / (N _B + N _S ), which is represented by _S and the average number of tertiary alkyl ester groups N _B. The amount of the alkali-soluble group is 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 in one molecule of the dissolution inhibitor (N _1S ) to the tertiary alkyl ester group (N _1B ) is 0.1 ≦ N _1S / (N _1B + N
_1S ) ≤ 0.5, the content of the dissolution inhibitor is 5
This is the case where the content is 0% by weight or more.

Since the alkali-soluble group functions in the developing solution described later, the alkali-soluble group protected by the acid-decomposable bond and the alkali-soluble group to be left preferably have a pK _a of 10 or less. . As a preferred alkali-soluble group, a phenolic hydroxyl group, a carboxylic acid group,
Examples include groups having an imide group, an N-hydroxyimide group, an N-sulfonylamide group, a sulfonamide group, an N-sulfonylurethane group, an N-sulfonylureido group, an active methylene group, and the like, more specifically. ,
The following examples can be given.

[0017]

[Chemical 2]

These groups may be introduced as a mixture in one molecule. However, the preferred alkali-soluble group is not limited to these specific examples. Further, the tertiary alkyl ester group-containing dissolution inhibiting compound of the present invention may have a plurality of tertiary alkyl ester groups on one benzene ring, but is preferably on one benzene ring. It is a compound composed of a skeleton having one tertiary alkyl ester group. Furthermore, the molecular weight of the tertiary alkyl ester group-containing dissolution inhibiting compound of the present invention is 3000 or less, preferably 500 to 3000, and more preferably 1000 to 2500.

In a preferred embodiment of the present invention, the group containing a tertiary alkyl ester group is -R ⁰ -C.
It is represented by OO-C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ). R ⁰¹ ,
R ⁰² and R ⁰³ may be the same or different,
It represents an alkyl group, a cycloalkyl group or an alkenyl group, preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms. Also, two groups out of R ^{01 to} R ⁰³ may combine to form a ring. R ⁰ represents a divalent or higher aliphatic or aromatic hydrocarbon group which may have a substituent.
Preferred are t-butyl ester group, t-pentyl ester group, t-hexyl ester group, 2-cyclopropyl-2-propyl ester group and the like, and particularly preferred is t.
A butyl ester group.

Further, preferably, JP-A-1-289946.
JP-A 1-289947 and JP-A-2-2560
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, and JP-A-3-1913.
51, JP-A-3-200251, and JP-A-3-200.
No. 252, JP-A-3-200253, and JP-A-3-20.
No. 0254, JP-A-3-200255, JP-A-3-2
59149, JP-A-3-279958, JP-A-3-
No. 279959, JP-A No. 4-1650, and JP-A No. 4-1
No. 651, JP-A-4-11260, and JP-A-4-123.
56, JP-A-4-12357, Japanese Patent Application No. 3-3322
No. 9, Japanese Patent Application No. 3-230790, Japanese Patent Application No. 3-3204
No. 38, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-5273
No. 2, Japanese Patent Application No. 4-103215, Japanese Patent Application No. 4-1045
42, Japanese Patent Application No. 4-107888, Japanese Patent Application No. 4-107
Phenolic OH groups shown above part or all of the groups of the polyhydroxy compounds described in the specification of 889 No. ^{etc., -R 0 -COO-C (R} 01) (R 02) (R 03) group Included are compounds protected by binding at.

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.
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 and Japanese Patent Application No. 4-107889 include those using the polyhydroxy compounds.

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

[0023]

[Chemical 3]

[0024]

[Chemical 4]

[0025]

[Chemical 5]

[0026]

[Chemical 6]

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—C (R
⁰¹ ) (R ⁰² ) (R ⁰³ ), R ₁ : —CO—, —COO—, —NHCONH—, —N
HCOO-, -O-, -S-, -SO-, -SO2-,
-SO3-, or

[0028]

[Chemical 7]

[0029] 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 ~
_{R 27, R 30 ~R 32,} R 37 ~R 42, R 46 ~R 49 and R _51:
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, cyano group, Alternatively, —N (R ₁₃ ) (R ₁₄ ) (R ₁₃ , R ₁₄ : H, alkyl group, or aryl group), R ₁₆ : single bond, alkylene group, or

[0030]

[Chemical 8]

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 the hydroxyl group is t-
R ₂₈ and R ₂₉ , which may be substituted with butoxycarbonyl group, may be the same or different, methylene group, lower alkyl-substituted methylene group, halomethylene group, or haloalkyl group, R _{33 to} R ₃₆ : the same or different Or a hydrogen atom or an alkyl group, R _{43 to} R _45, which may be the same or different, a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or an acyloxy group, R ₅₀ : a hydrogen atom, t-butoxycarbonyl group , Or

[0032]

[Chemical 9]

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,
Acyloxy group, alkenyl group, alkenyloxy group, aryl group, aryloxy group, or aryloxycarbonyl group, Y: —CO—, or —SO ₂ —, Z, B: single bond, or —O—, A: methylene. Group, lower alkyl-substituted methylene group, halomethylene group, or haloalkyl group, E: single bond, or oxymethylene group, a to z, a1 to y1: 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, s1, u1: 0 or an integer of 1 to 5, r, u, w, x, y, z, a1 to f1 , p1, r1, t1, v1 to x1: 0 or 1
4 integers, j1, n1, z1, a2, b2, c2, d2: 0 or integers 1 to 3, z1, a
At least one of 2, 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 + 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.

[0034]

[Chemical 10]

[0035]

[Chemical 11]

[0036]

[Chemical 12]

[0037]

[Chemical 13]

Specific examples of preferable compounds are shown below.

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

[0042]

[Chemical 17]

[0043]

[Chemical 18]

[0044]

[Chemical 19]

[0045]

[Chemical 20]

[0046]

[Chemical 21]

[0047]

[Chemical formula 22]

[0048]

[Chemical formula 23]

[0049]

[Chemical formula 24]

[0050]

[Chemical 25]

[0051]

[Chemical formula 26]

[0052]

[Chemical 27]

[0053]

[Chemical 28]

[0054]

[Chemical 29]

[0055]

[Chemical 30]

[0056]

[Chemical 31]

[0057]

[Chemical 32]

R in the compounds (1) to (63) is --CH.
It represents a ₂ -COO-C ₄ H ₉ ^t or a hydrogen atom. However, at least two, or three depending on the structure, are groups other than hydrogen atoms, and the average number of acid-decomposable groups in the dissolution inhibitor is N
_B , where N _S is the average number of alkali-soluble groups,
01 ≦ N _S / (N _B + N _S ) ≦ 0.75.

The amount of the compound used in the present invention (c) 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.

(B) Novolac Resin (Compound of Present Invention (a)) The novolak resin used in the present invention 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 the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde. , O-chlorobenzaldehyde,
m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-
Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural,
Chloroacetaldehyde and 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 novolak resin thus obtained preferably has a weight average molecular weight of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed area after development is large, and if it exceeds 30,000, the developing speed becomes small. Particularly preferred is 2,000-20,
The range is 000. Here, the weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography.

Two or more kinds of these novolak resins may be mixed and used. Still other alkali-soluble resins such as hydrogenated novolac resins, acetone-pyrogallol resins, polyhydroxystyrenes, halogen- or alkyl-substituted polyhydroxystyrenes, hydroxystyrenes.
An N-substituted maleimide copolymer, a partial o-alkylated product or o-acylated product of polyhydroxystyrene, a styrene-maleic anhydride copolymer, a methacrylic resin containing a carboxyl group and the like can be mixed if necessary. . The amount of the novolak resin used in the present invention is 50 to 9 based on the total weight of the photosensitive composition (excluding the solvent).
It is 7% by weight, preferably 60 to 90% by weight.

(C) Compound that Generates Acid upon Irradiation with Actinic Rays or Radiation (Compound of the Invention (b)) Examples of compounds used in the present invention that decompose upon irradiation with actinic rays or radiation to generate an 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. SI Schlesinger, Photogr.Sci.Eng., 18,387 (197
4), TSBal et al, Polymer, 21,423 (1980) and other diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,069,056
No., same Re 27,992, ammonium salts described in Japanese Patent Application No. 3-140,140, DC Necker et al, Macromolecules, 17, 24
68 (1984), CSWen et al, Teh, Proc.Conf.Rad.Curing AS
IA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055,
Phosphonium salts described in 4,069,056, JVCrivello
et al, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng. Ne
ws, Nov.28, p31 (1988), European Patent 104,143, U.S. Pat.
llo et al, 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
et al, J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (197
9), European Patent Nos. 370,693 and 3,902,114, and 233,567.
No. 297,443, 297,442, U.S. Pat.No. 4,933,377
No. 161, 811, No. 410, 201, No. 339, 049, No. 4, 76
0,013, 4,734,444, 2,833,827, Dokoku Patent No.
2,904,626, 3,604,580, 3,604,581, etc., sulfonium salts, JVCrivello et al, Macromorecule
s, 10 (6), 1307 (1977), JVCrivello et al, J. PolymerSc
i., Polymer Chem. Ed., 17, 1047 (1979) and other selenonium salts, CSWen et al, Teh, Proc. Conf. Rad. Curing AS
IA, p478 Tokyo, Oct (1988) and other onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, Japanese Patent Publication No. 46-4605.
JP-A-48-36281, JP-A-55-32070, JP-A-60-2
39736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62-212401, JP 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), and the organic metal / organic halides described in JP-A-2-161445, 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), PMCollins et al, J. Chem. SoC.,
Perkin I, 1695 (1975), M. Rudinstein et al, Tetrahedron
Lett., (17), 1445 (1975), JWWalker et al 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), PMCollins 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), European Patent No. 0290,750,
046,083, 156,535, 271,851, 0,388,343
No. 3,901,710, 4,181,531, U.S. Pat.
-198538, JP-A-53-133022, etc., a photo-acid 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 (69
7), 45 (1983), Akzo, H. Adachi etal, Polymer Preprints,
Japan, 37 (3), European Patents 0199,672, 84515, 19
No. 9,672, No. 044,115, No. 0101,122, U.S. Patent No. 618,
No. 564, No. 4,371,605, No. 4,431,774, JP-A-64-1814
No. 3, JP-A-2-245756, Japanese Patent Application No. 3-140109, and other compounds that generate sulfonic acid by photolysis, represented by iminosulfonates, etc., and JP-A-61-166544, etc. The listed disulfone compounds 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 to generate an acid upon irradiation with actinic rays or radiation, 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).

[0069]

[Chemical 33]

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.

[0071]

[Chemical 34]

[0072]

[Chemical 35]

[0073]

[Chemical 36]

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

[0075]

[Chemical 37]

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 a substituted derivative 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 an alkyl group for the alkyl group. An alkoxy group having 1 to 8 carbon atoms, a carboxyl group, and an alkoxycarbonyl group.

Z ⁻ represents a counter anion, for example, BF ₄ ⁻ ,
_{^{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
Perfluoroalkane sulfonate anions such as CF ₃ SO ₃ ⁻ , pentafluorobenzene sulfonate anions, condensed polynuclear aromatic sulfonate anions such as naphthalene-1-sulfonate anions, anthraquinone sulfonate anions, sulfonate group-containing dyes, etc. 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.

[0081]

[Chemical 38]

[0082]

[Chemical Formula 39]

[0083]

[Chemical 40]

[0084]

[Chemical 41]

[0085]

[Chemical 42]

[0086]

[Chemical 43]

[0087]

[Chemical 44]

[0088]

[Chemical formula 45]

[0089]

[Chemical formula 46]

[0090]

[Chemical 47]

[0091]

[Chemical 48]

[0092]

[Chemical 49]

The onium salts represented by the general formulas (PAG3) and (PAG4) are known, and for example, JWKn
apczyk et al, J. Am. Chem. Soc., 91, 145 (1969), ALMayco
k et al, J. Org. Chem., 35, 2532, (1970), E. Goethas et al
, Bull.Soc.Chem.Belg., 73,546, (1964), HMLeiceste
r, J.Ame.Chem.Soc., 51,3587 (1929), JVCrivello eta
l, J.Polym.Chem.Ed., 18,2677 (1980), U.S. Pat.No. 2,80
It can be synthesized by the method described in 7,648 and 4,247,473, JP-A-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).

[0095]

[Chemical 50]

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

[0097]

[Chemical 51]

[0098]

[Chemical 52]

[0099]

[Chemical 53]

[0100]

[Chemical 54]

[0101]

[Chemical 55]

The amount of the compound that 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.

The photosensitive composition of the present invention may optionally contain
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 oil 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 Industry Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170).
B), malachite green (CI42000), methylene blue (CI52015) and the like.

Further, the photosensitive composition of the present invention can be obtained by adding a spectral sensitizer as described below and sensitizing it to a wavelength region longer than deep 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 dissolved in a solvent that dissolves each of the above components and applied onto a support. As the solvent used here, 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, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in a mixture.

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 octylphenol 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 Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as rate, F-top EF301, E 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,
Fluorine-based surfactants such as SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) polymerization polyflow No. 75, No. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like. The content 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 solid content in the composition of the present invention. These surfactants may be added alone or in some combinations.

The photosensitive composition described above is applied onto a substrate (eg, silicon / silicon dioxide coating) used for the production of precision integrated circuit devices by an appropriate 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 developing solution for the photosensitive composition of the present invention includes:
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. Aqueous solutions of triamines, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and alkalis such as cyclic amines such as pyrrole and pyrelidine. Can be used. Further, an appropriate amount of alcohols and surfactants may be added to the above aqueous solution of alkalis for use. Hereinafter, the present invention will be described in more detail with reference to Examples, but the content of the present invention is not limited thereto.

[0109]

【Example】

[Synthesis example-1 of dissolution inhibitor compound] α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene 19.2 g (0.040 mol) of N, N −
To a solution of 120 ml of dimethylacetamide, 21.2 g (0.15 mol) of potassium carbonate and 27.1 g (0.14 mol) of t-butyl bromoacetate were added, and the mixture was stirred at 120 ° C for 7 hours. Then, the reaction mixture was added to 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)), which was a pale yellow viscous solid. 30 g was obtained. According to NMR, this is an example compound (31:
It was confirmed that all R were —CH ₂ —COO—C ₄ H ₉ ^t groups) (dissolution inhibitor (a)).

[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) of N, N-dimethylacetamide 120 m
1 solution, 21.2 g (0.15 mol) of potassium carbonate,
Further, 27.1 g (0.14 mol) of t-butyl bromoacetate
Was added and stirred at 120 ° 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 by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 2/8 (volume ratio)), which was a pale yellow powder. 24 g was obtained. By NMR, this compound Example (62: R are all -CH ₂ -COO
-C ₄ H ₉ ^t group) was confirmed to be (dissolution inhibitor (b)).

[Synthesis Example-3 of Dissolution Inhibitor Compound] α,
α ', α "-tris (4-hydroxyphenyl) -1,3,
4-Isotripropylbenzene 48.1 g (0.10 mol) was dissolved in dimethylacetamide 300 ml, and potassium carbonate 22.1 g (0.16 mol) and t-butyl bromoacetate 42.9 g (0.22) were dissolved therein. Mol) 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 then extracted with ethyl acetate. The ethyl acetate extract was concentrated and subjected to column chromatography (carrier: silica gel, developing solvent:
Purification with ethyl acetate / n-hexane = 1/5 (volume ratio)) gave a dissolution inhibitor (c) having the following structure.

[0112]

[Chemical 56]

[Synthesis Examples of Dissolution Inhibitor Compounds-4 to 11]
Similarly, dissolution inhibitors (d) to (k) having an acid-decomposable group —CH ₂ —COO—C ₄ H ₉ ^t group were synthesized. The structures of these dissolution inhibitors and the N _S / (N _B + N _S ) values are shown in Table 1.

[0114]

[Table 1]

Here, N _S represents a residual phenolic OH group, and N _B represents a —CH ₂ —COO—C ₄ H ₉ ^t group. Also,
The structure indicates the number of the structural example in the specification.

[Synthesis of Dissolution Inhibitor (l) for Comparative Example] α,
α ', α "-tris (4-hydroxyphenyl) -1,3,
20 g (0.042 mol) of 5-triisopropylbenzene was dissolved in 400 ml of tetrahydrofuran (THF). 14 g (0.125 mol) of potassium t-butoxide was added to this solution under a nitrogen atmosphere, and after stirring at room temperature for 10 minutes, 29.2 g of di-t-butyl dicarbonate (0.
13 mol) was added. The reaction was carried out 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 was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 1/5 (volume ratio)). As a result, a dissolution inhibitor (l) having the following structure Got

[0117]

[Chemical 57]

[Synthesis of Dissolution Inhibitor (m) for Comparative Example] A dissolution inhibitor (m) having the following structure was synthesized according to the method described in JP-A-2-248593.

[0119]

[Chemical 58]

[Synthesis of Dissolution Inhibitor (n) for Comparative Example] A dissolution inhibitor (n) having the following structure was synthesized according to the method described in European Patent 249139.

[0121]

[Chemical 59]

[Synthesis Example of Novolac Resin] 40 g of m-cresol, 60 g of p-cresol, 49 g of 37% aqueous formalin solution and 0.13 g of oxalic acid were placed in a three-necked flask and heated to 100 ° C. with stirring for 15 hours. It was made to react. After that, the temperature is raised to 200 ° C and gradually increased to 5 mm.
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 recovered. The obtained novolak resin (NOV.3) had a weight average molecular weight of 7100 (converted to polystyrene).

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

85 g of m-cresol, 1 of p-cresol
5 g, 53 g of 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 with stirring for 5 hours. Next, 100 g of the same cresol mixture and 47 g of a formalin aqueous solution were continuously charged into the same flask, and the mixture was further heated and stirred 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 kept at 110 ° C., and the reaction was carried out under reflux for 15 hours. Then, the content was poured into water containing 1% hydrochloric acid and the reaction product was extracted with ethyl cellosolve acetate. Then, this was transferred to a vacuum still, the temperature was raised to 200 ° C. and dehydrated, and further 2 to 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 target novolak resin (NOV.7, Mw = 7,500).

Examples 1 to 11 Resists were prepared using the compounds of the present invention shown in the above synthesis examples. The prescription at that time is shown in Table 2.

Comparative Examples 1 to 3 Three component resists were prepared using the above dissolution inhibitors (1) to (n). The prescription at that time is shown in Table 2.

Comparative Example 4 According to the method described in US Pat. No. 4,491,628, t-butoxycarbonyloxystyrene polymer was synthesized to prepare a two-component positive resist.
The prescription at that time is shown in Table 2.

[0129]

[Table 2]

The abbreviations used in Table 2 have the following meanings.

<Polymer> NOV.1-7 Novolac resin PVP p-Human ethoxystyrene polymer (weight average molecular weight 9,600) TBOCS t-Butoxycarbonyloxystyrene polymer (number average molecular weight 2
1,600)

[Preparation and Evaluation of Photosensitive Composition] Each material shown in Table 2 was dissolved in 6 g of diglyme and filtered through a 0.2 μm filter to prepare a resist solution. This resist solution was applied onto a silicon wafer using a spin coater with a rotation speed of 3000 rpm, and dried on a vacuum adsorption type hot plate at 110 ° C. for 60 seconds to give a film thickness of 1.0.
A μm resist film was obtained. 248n on this resist film
mKrF excimer laser stepper (NA = 0.4
2) was used for exposure. After the exposure, it was heated on a vacuum adsorption type hot plate at 90 ° C for 60 seconds, and immediately 2.3
8% tetramethylammonium hydroxide (T
MAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds and dried. The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist profile. The results are shown in Table 3.

The sensitivity was defined as the reciprocal of the exposure dose for reproducing a 0.70 μm mask pattern, and was shown by the relative value of the sensitivity of Comparative Example 4. The resolving power represents a limiting resolving power at an exposure amount that reproduces a 0.70 μm mask pattern. The solubility (storage stability) in the coating solvent was determined by adding an acid-decomposable dissolution inhibitor to ECA, EL (ethyl lactate), PEGMEA (propylene glycol monoethyl ether acetate) and MMP (methyl methoxypropionate) each of 6 g. A solution having 1 g dissolved therein was prepared and stored under forced conditions at 40 ° C. for 20 days to evaluate precipitation. The evaluation results are represented by ○ when there was no precipitation, and by X when there was precipitation.
The results are shown in Table 3. From the results of Table 3, the resist of the present invention is
It can be seen that it has high sensitivity, high resolution, a good profile and excellent storage stability.

[0134]

[Table 3]

Example 12 Using resist films having the compositions of Examples 1 and 3 (invention) of Table 2 and Comparative Example 1, by differential thermal analysis and thermogravimetric analysis,
The decomposition temperature of each dissolution inhibitor in the resist film was measured. As a result, the decomposition temperature of the dissolution inhibitor (l) of Comparative Example was 125.
, The dissolution inhibitor of the present invention (a),
The decomposition temperature of (c) was as high as 154 ° C., and it was found that the thermal stability in the resist film containing the novolak resin was excellent.

[0136]

Industrial Applicability The chemically amplified positive photosensitive composition of the present invention has high sensitivity, high resolution and good profile,
Moreover, the storage stability and heat stability of the resist solution are also excellent.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication location H01L 21/027 (72) Inventor Tadaka Kokubo 4000 Kawasakiri, Yoshida-cho, Hara-gun, Shizuoka Prefecture Fujisha Shin Film Co., Ltd. In the company

Claims (1)

[Claims] 1. A compound of (a) novolak resin, (b) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (c) a tertiary alkyl ester group, and having a solubility in an alkaline aqueous solution of an acid. Increased molecular weight of 30
In the positive-type photosensitive composition containing a low molecular weight acid-decomposable dissolution-inhibiting compound of 00 or less, the compound (c) is
(I) a compound having at least two tertiary alkyl ester groups, wherein the distance between the ester groups is at the farthest position, and 10 or more bond atoms other than the ester group are present, and (ii) the third It is at least one selected from the group consisting of a compound having at least three primary alkyl ester groups, and a compound having 9 or more bond atoms excluding the ester group at the position where the distance between the ester groups is the longest. A positive photosensitive composition, comprising: