JPH0695390A - Positive photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain the positive photosensitive composition having high sensitivity, high resolving power and a good profile and excellent in preservation stability in the compd. contg. an alkali-soluble resin, a compd. generating acid when irradiated with radiation and an acid-decomposable dissolution inhibitor by specifying the inhibitor. CONSTITUTION:This positive photosensitive composition contains an alkali- soluble resin A, a compd. B generating acid when iradiated with radiation and an acid-decomposable dissolution inhibitor C. The inhibitor C is the compd. having at least two groups decomposable with an acid (a) and having 10 atoms except the acid-decomposable group at the position where the distance between the groups is maximized or the compd. having at least three groups decomposable with an acid (b), having 9 atoms except the acid-decomposable group at the position where the distance between the groups is maximized and at least 10mol% of which has an alkali-soluble group.

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 phenol 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.,
The most typical composition is "Novolak resin consisting of cresol-formaldehyde / trihydroxybenzophenone-1,2-naphthoquinonediazide sulfonic acid ester", which is an example of Thompson "Introduction to Microlithography" (LF.Thomp).
son “Induction to Microl
itohography ”) (ACS Publishing, No. 2 1
9, No. 9, P112-121).

In such a positive photoresist, which basically consists 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 type photoresists containing novolac resin and naphthoquinonediazide type photosensitive material have been developed and put to 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 becomes necessary to process an ultrafine pattern having a line width of half micron or less. Came. 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,
The strong absorption of novolak and naphthoquinonediazide in the far-ultraviolet region makes it difficult for light to reach the bottom of the resist, and only a tapered pattern with low sensitivity can be obtained.

One of the 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, for example, a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (JP-A-48-89003) or 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-53-13342).
No. 9), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236), a combination with a polymer having an orthoester group in the main chain. (JP-A-56-17345
No.), a combination with a tertiary alkyl ester compound (JP-A-60-3625), a combination with a silyl ester compound (JP-A-60-10247), and a combination with a silyl ether compound (JP-A-60- 37549, JP-A-60-121446
No.) etc. can be mentioned. Since these have a quantum yield of more than 1 in principle, they show 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 / 59
-45439, 60-3625, 62-229242, 63-27829
Issue 63-36240, Issue 63-250642, Polym Eng.Sci. 23
Volume, 1012 (1983), ACS.Sym.242, 11 (1984), Se
miconductor World 1987, November issue, p. 91, Macromolec
ukes, vol. 21, p. 1475 (1988), SPIE, vol. 920, p. 42 (1988),
And the like, a combination system of a compound capable of generating an acid upon exposure to light and an ester or carbonate compound of a tertiary or secondary carbon (for example, t-butyl, 2-cyclohexenyl, etc.). These systems also have high sensitivity and have smaller absorption in the Deep-UV region than the naphthoquinonediazide / novolak resin system, and thus can be effective systems for shortening the wavelength of the light source.

The positive-type chemically amplified resist is an alkali-soluble resin, a compound (photoacid generator) that generates an acid upon exposure to radiation, and a dissolution-inhibiting compound (acid-decomposable dissolution-inhibiting compound) that becomes alkali-soluble by a catalytic reaction with an acid. Agent) and a two-component system consisting of a resin having a group that becomes alkali-soluble by reaction with an acid and a photo-acid generator. Two-component chemically amplified positive resist (US Pat. No. 4,4
No. 91,628) mainly reduces the alkali solubility of the binder by crushing the alkali-soluble group of the alkali-soluble binder with an acid-decomposable group. Three-component chemically amplified positive resist (European Patent No. 249,139,
The acid-decomposable dissolution inhibitor of JP-A-2-248,953) is itself alkali-insoluble, and acts to reduce the alkali solubility of the binder resin by interacting with the binder resin. . As described above, it is considered that the two-component system and the three-component system have different expression mechanisms of the 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. Further, the three-component system has an insufficient dissolution inhibiting property with respect to the alkali-soluble resin, so that there is a problem that the film loss during development is large and the resist profile is significantly deteriorated. However, in the case of a three-component system,
It is a promising system because of the wide range of material selection, and there has been a demand for the development of acid-decomposable compounds having excellent dissolution inhibiting properties for use in this system.

Similar to the resist composed of novolac and naphthoquinonediazide compound, in order to achieve a high resolution and a rectangular profile even in a chemically amplified positive resist, the dissolution rate ratio between the unexposed part and the exposed part (discriminant It is necessary to increase the nation).

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-2-248,953 discloses an acid-decomposable dissolution inhibitor having an alkali-soluble group (phenolic OH group) left in the molecule, but it has a weak dissolution inhibition property and a sufficient resolution and resist profile. It wasn't. On the other hand, as the amount of the acid-decomposable group introduced is increased, the solubility in the resist solvent remarkably decreases.

[0013]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to have high sensitivity, high resolution and good profile,
It is an object of the present invention to provide a three-component chemical amplification type positive photosensitive composition which does not precipitate with time.

[0014]

Means for Solving the Problems As a result of intensive studies made by the present inventors while paying attention to the above-mentioned characteristics, the object of the present invention is to find out that an alkali-soluble resin, a compound which generates an acid upon irradiation with radiation, and an acid-decomposable dissolution inhibitor. In a positive photosensitive composition containing an agent, it was found that the acid-decomposable dissolution inhibitor can be achieved by using a low molecular weight compound satisfying the following requirements, and the present invention has been accomplished.

That is, the present invention comprises (A) a resin insoluble in water and soluble in an aqueous alkali solution, (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (C) a group decomposable by an acid. A low-molecular weight positive compound (C) containing a low-molecular weight compound having a molecular weight of 3000 or less whose solubility in an alkaline developer is increased by the action of an acid.
Wherein (a) has at least two groups capable of decomposing with an acid, and the distance between the acid decomposable groups is at the farthest position, and a compound having 10 or more bond atoms excluding the acid decomposable group is passed through, , (B) a compound having at least three groups capable of decomposing with an acid and having 9 or more bond atoms excluding the acid decomposable group at a position where the distance between the acid decomposable groups is the longest,
The present invention provides a positive-type photosensitive composition, wherein at least 10 mol% is at least one selected from compounds having an alkali-soluble group.

The three-component positive-working photosensitive composition of the present invention comprises
Basically, it comprises an acid-decomposable dissolution inhibitor composed of a low molecular weight compound (C), an alkali-soluble resin and a photo-acid generator.
The acid-decomposable dissolution inhibitor has a function of suppressing the solubility of the alkali-soluble resin in alkali, and deprotecting the acid-decomposable group by the acid generated when exposed to light, and conversely promoting the action of promoting solubility in alkali. Have. JP 63-27,829 and JP 3-19
No. 8,059 discloses a dissolution-inhibiting compound having naphthalene, biphenyl and phenylcycloalkane as a skeletal compound, but its dissolution-inhibiting property to an alkali-soluble resin is small and it is insufficient in terms of profile and resolution.

The compounds used in the present invention will be described in detail below. First, the acid-decomposable dissolution inhibitor will be described. The acid-decomposable dissolution inhibitor has at least two groups capable of decomposing with an acid in its structure, and has at least 10 bond atoms excluding the acid-decomposable group at the position where the distance between the acid-decomposable groups is the longest. , Preferably at least 11, more preferably at least 12 compounds, or at least 3 acid-decomposable groups, and at the position where the distance between the acid-decomposable groups is the longest, It is a compound having at least 9, preferably at least 10 and more preferably 11 bond atoms to be eliminated.

In the present invention, the acid-decomposable dissolution inhibitor is
When it has 3 or more, preferably 4 or more acid-decomposable groups, and also in the case of having 2 acid-decomposable groups, when the acid-decomposable groups are separated from each other by a certain distance or more,
It has been found that the dissolution inhibiting property for an alkali-soluble resin is remarkably improved. The distance between acid-decomposable groups in the present invention is represented 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 distance is 12 bonding atoms.

[0019]

[Chemical 1]

[0020] In the above ^{formula, -O-B 0, -COO-} A 0 is an acid-decomposable group. Furthermore, the present invention is a compound in which at least 10 mol%, preferably 30 mol%, and more preferably 50 mol% of the total content of the acid-decomposable dissolution inhibitor is intentionally left with an alkali-soluble group. Is a major feature. If the amount of the compound in which the alkali-soluble group remains is 10 mol% or less, the dissolution inhibitor may not be dissolved in the resist solvent or may be deposited over time, which is not preferable.

The content of alkali-soluble groups is represented by the average number N _S of alkali-soluble groups in the acid-decomposable dissolution inhibitor and the average number N _B of acid-decomposable groups N _s / (N It can be expressed as _B + N _S ). The amount of the alkali-soluble group is 0.01 ≦ N _s /
It is preferable that (N _B + N _S ) ≦ 0.75. More preferably, 0.1 ≦ N _S / (N _B + N _S ) ≦ 0.5. Particularly preferably, the ratio of the number of alkali-soluble groups (N _1S ) and the number of acid-decomposable groups (N _1B ) in one molecule of the acid-decomposable dissolution inhibitor is 0.1 ≦ N _1S / (N _1B + N _1S). ) .Ltoreq.0.5 is a case where the content of the acid-decomposable dissolution inhibitor is 50% by weight or more based on the total weight.

Since the alkali-soluble group functions by the developing solution described later, the alkali-soluble group protected by an acid-decomposable bond and the alkali-soluble group to be left have a pK _a of 1.
It is preferably 2 or less. Preferable alkali-soluble groups are phenolic hydroxyl group, carboxylic acid group, sulfonic acid group, imide group, N-hydroxyimide group, N-sulfonylamide group, sulfonamide group, N-sulfonylurethane group, N-sulfonylureido group or A group having an active methylene group, and more specifically,

[0023]

[Chemical 2]

(R represents an alkyl group or an aryl group) is mentioned as an example. These groups may be introduced as a mixture in one molecule. Further, the preferable alkali-soluble group is not limited to these specific examples.

The acid-decomposable dissolution inhibitor of the present invention may have a plurality of acid-decomposable groups on one benzene ring, but preferably one acid-decomposable group on one benzene ring. It is a compound composed of a skeleton having a functional group. Further, the molecular weight of the acid-decomposable dissolution inhibitor of the present invention is 3000 or less, preferably 500 to 3000, more preferably 10
It is 00 to 2500.

In a preferred embodiment of the present invention, the group containing an acid-decomposable --COO--A ⁰ or --O--B ⁰ group is --R ⁰ --COO--A ⁰ or --Ar--O--.
Examples include groups represented by B ⁰ .

Here, A ⁰ is -C (R ⁰¹ ) (R ⁰² ).
( ^R03 ), -Si ( ^R01 ) ( ^R02 ) ( ^R03 ) or -C
(R ⁰⁴ ) (R ⁰⁵ ) -OR ⁰⁶ group is shown. B ⁰ is A ⁰ or −
Shows the 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, cycloalkyl, alkenyl, or aryl group, and R ⁰⁶ is an alkyl or aryl. Indicates a group. However, at least two of R ^{01 to} R ⁰³ are groups other than hydrogen atoms, and two groups of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ are bonded to each other to form a ring. Good. R ⁰ represents a divalent or higher valent aliphatic group or aromatic hydrocarbon group which may have a substituent, and —Ar— represents a divalent group which may have a monocyclic or polycyclic substituent. The above aromatic groups are shown.

Preferably, silyl ether group, cumyl ester group, acetal group, tetrahydropyranyl ether group, enol ether group, enol ester group, third group
Secondary alkyl ether groups, tertiary alkyl ester groups, tertiary alkyl carbonates and groups. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

Preferably, JP-A Nos. 1-289946, 1-289947, 2-2560 and 3-128 are used.
959, 3-158855, 3-179353.
No. 3, No. 3-191351, No. 3-200251, No. 3-200252, No. 3-200253, and No. 3-2.
No. 00254, No. 3-200255, No. 3-2591
No. 49, No. 3-279958, No. 3-279959
No. 4-1650, 4-1651, 4-11
No. 260, No. 4-12356, No. 4-12357,
Japanese Patent Application Nos. 3-33229, 3-230790 and 3
-320438, 4-25157, 4-527.
No. 32, No. 4-103215, No. 4-104542
Nos. 4,107,885, 4,10,889, and the like, a part of or all of the phenolic OH group of the polyhydroxy compound described in the specification is a group -R ⁰ -C shown above.
Included are compounds that are bound and protected by an OO-A ⁰ group or a B ⁰ group.

More preferably, JP-A-1-289946.
No. 3, No. 3-128959, No. 3-158855, No. 3-179353, No. 3-200251, and No. 3-2.
No. 00252, No. 3-200255, No. 3-2591
No. 49, No. 3-279958, No. 4-1650, No. 4-11260, No. 4-12356, No. 4-123.
57, Japanese Patent Application Nos. 4-25157 and 4-103215.
Nos. 4,104,542, 4,107,885, and 4,107,889 may be used.

Preferred are compounds represented by the general formulas (1) to (16).

[0032]

[Chemical 3]

[0033]

[Chemical 4]

[0034]

[Chemical 5]

[0035]

[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-A.
⁰ or B ⁰ group is shown.

R ₁ is --CO--, --COO--, --NHCO
NH-, -NHCOO-, -O-, -S-, -SO-,
-SO ₂ -, - SO ₃ - or

[0038]

[Chemical 7]

Here, G is an integer of 2 to 6, provided that G is 2
When at least one of R ₄ and R ₅ is an alkyl group,
R _4, R ₅ may be the same or different, a hydrogen atom, an alkyl group, an alkoxy group, -OH, -COOH -, - C
N, halogen atom, -R ₆ -COOR ₇ or -R,
_8- OH, R ₆ and R ₈ are alkylene groups, R ₇ is 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 to} R ₃₂ , R _{37 to} R ₄₂ , R _{46 to} R ₄₉ and R ₅₁ may be the same or different, and a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a halogen atom, a nitro group, a carboxyl group, a cyano group or _{-N (R 13) (R 14} ) (R 13, R 14 is a hydrogen atom, an alkyl group or aryl group, ), R ₁₆ is a single bond, an alkylene group, or

[0040]

[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, and R ₂₃ is a hydrogen atom, an alkyl group, an alkoxy group, Acyl group, acyloxy group, aryl group, nitro group, hydroxyl group, cyano group, or carboxyl group,
However, the hydroxyl group may be substituted with a t-butoxycarbonyl group, R ₂₈ and R ₂₉ may be the same or different, and a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, R _{33 to} R _{33. 36} may be the same or different and each represents a hydrogen atom, an alkyl group, R ₄₃ to
R ₄₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, or an acyloxy group,
R ₅₀ is a hydrogen atom, t-butoxycarbonyl group, or

[0042]

[Chemical 9]

R ₅₂ and R ₅₃ may be the same or different, 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 a hydrogen atom, a 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 An aryloxycarbonyl group, provided that each of the four same symbols does not have to be the same group. Y is -CO- or -SO ₂ -, Z, B is a single bond or -O-, A is a methylene group, a lower alkyl-substituted methylene group, halomethylene group or a haloalkyl group,, E is a single bond or oxymethylene When the groups, a to yl, are plural, the groups in () may be the same or different, a to q, s, t, v,
g _{1 to} i ₁ , k _{1 to} m ₁ , o ₁ , q ₁ , s ₁ and u ₁ are 0.
Specifically, an integer of 1 to 5, r, u, y, w, x, y, z, a
_{1 ~f 1, p 1, r} 1, t 1, v 1 ~x 1 is 0 or an integer of 1 to _{4, j 1, n 1, z} 1, a 2, b 2, c 2,
d ₂ is 0 or an integer of _{1 to} 3, at least one of z ₁ , a ₂ , c ₂ and d ₂ is 1 or more, y ₁ is an integer of 3 to 8, (a + b), (e + f + g), (k + l + m), (q + r + s), (w + x + y), (c
₁ + d ₁ ), (g ₁ + h ₁ + i ₁ + j ₁ ), (o ₁ + p ₁ ), (s ₁ + t ₁ ) ≧ 1, (j ₁ + n ₁ ) ≦ 3, (r + u), (w + z), (x + a ₁ ), (y + b ₁ ), (c ₁ + e ₁ ), (d ₁ + f ₁ ).
, (P ₁ + r ₁ ), (t ₁ + v ₁ ), (x ₁ + w ₁ ) ≦ 4, (a + c), (b + d), (e + h), (f + i) , (G + j), (k + n), (l
+ o), (m + p), (q + t), (s + v), (g ₁ + k ₁ ), (h ₁ + l ₁ ),
It represents (i ₁ + m ₁ ), (o ₁ + q ₁ ), and (s ₁ + u ₁ ) ≦ 5.

[0044]

[Chemical 10]

R ₅₈ is an organic group, a single bond, —S—, —SO—
Alternatively, —SO ₂ —, R ₅₉ is a hydrogen atom, a monovalent organic group, or

[0046]

[Chemical 11]

R _{60 to} R ₆₄ are hydrogen atom, hydroxyl group, halogen atom, alkyl group, alkoxy group, alkenyl group, --O
-R ⁰ -COO-A ⁰ group or -O-B ⁰ group, provided that each 4 or 5 identical symbols do not have to be the same group.

X represents a divalent organic group, and e ₂ represents 0 or 1.

[0049]

[Chemical 12]

Here, R _{65 to} R ₆₈ may be the same or different and each is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group or an alkenyl group, provided that each of them is 4 to 4.
Six identical symbols need not be identical groups.

R _{69 to} R ₇₀ are a hydrogen atom, an alkyl group, or

[0052]

[Chemical 13]

R ⁵ is a hydrogen atom, -R ⁰ -COO-A ⁰ ,
Alternatively, B ⁰ group, f ₂ , h ₂ represent 0 or 1, g ₂ represents 0 or an integer of 1 to 4.

[0054]

[Chemical 14]

R _{71 to} R ₇₇ may be the same or different and each is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, an alkoxy group, a nitro group, an alkenyl group, an aryl group, an aralkyl group, an alkoxycarbonyl group or an arylcarbonyl group. , An acyloxy group, an acyl group, an alloxyl group, or an aralkoxy group, provided that each six identical symbols do not have to be the same group.

R ⁶ is a hydrogen atom, -R ⁰ -COO-A ⁰ ,
Alternatively, it represents a B ⁰ group.

[0057]

[Chemical 15]

R ₇₈ is a hydrogen atom or an alkyl group, provided that they are not all the same.

R _{79 to} R ₈₂ are each a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group or an alkoxy group, provided that the same three symbols are not the same.

R ⁷ is a hydrogen atom, -R ⁰ -COO-A ⁰ ,
Alternatively, it represents a B ⁰ group.

Specific examples of preferable compounds are shown below.

[0062]

[Chemical 16]

[0063]

[Chemical 17]

[0064]

[Chemical 18]

[0065]

[Chemical 19]

[0066]

[Chemical 20]

[0067]

[Chemical 21]

[0068]

[Chemical formula 22]

[0069]

[Chemical formula 23]

[0070]

[Chemical formula 24]

[0071]

[Chemical 25]

[0072]

[Chemical formula 26]

[0073]

[Chemical 27]

[0074]

[Chemical 28]

[0075]

[Chemical 29]

[0076]

[Chemical 30]

[0077]

[Chemical 31]

[0078]

[Chemical 32]

[0079]

[Chemical 33]

[0080]

[Chemical 34]

[0081]

[Chemical 35]

R in the compounds (1) to (63) is a hydrogen atom, --COO--C ₄ H ₉ ^t ,

[0083]

[Chemical 36]

[0084] represents a _{-CH 2 -COO-C 4 H 9} t, or _{-CH 2 -COO-C (CH 3} ) 2 C 6 H 5 group. However, at least 2 or more, or 3 depending on the structure
Is a group other than a hydrogen atom, the average number of acid-decomposable groups in the dissolution inhibitor is N _B , and the average number of alkali-soluble groups is N.
_{When S} , 0.01 ≦ N _S / (N _B + N _S ) ≦ 0.
75.

The amount of the acid-decomposable dissolution inhibitor 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).

Examples of the alkali-soluble resin [compound of the present invention (A)] used in the present invention include novolac resin, hydrogenated novolac resin, acetone-pyrogallol resin, polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, and hydroxy. Styrene-N
-Substituted maleimide copolymer, partial O-alkyl compound or O-acyl compound of polyhydroxystyrene, styrene-maleic anhydride copolymer, methacrylic resin containing a carboxyl group and derivatives thereof can be mentioned. It is not limited.

Particularly preferred alkali-soluble resins are novolac resins and polyhydroxystyrenes. 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- Alkoxyphenols such as methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, p-butoxyphenol and the like, 2-methyl-4-isopropylphenol. 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 applied, 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 2,000-2
It is in the range of 10,000. 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).
Is about 90% by weight.

Next, the compound [the compound of the present invention (B)] which generates an acid upon irradiation with actinic rays or radiation according to the present invention will be described. Examples of the compound used in the present invention that decomposes upon irradiation with actinic rays or radiation to generate an acid include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photobleaching agents for dyes, and photochromic A known compound used for an agent or a micro resist, which generates an acid by light, and a mixture thereof can be appropriately selected and used.

For example, SISchlesinger, Photogr.Sci.En
g., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) the diazonium salts described in U.S. Pat. No. 4,069,055
No. 4,069,056, Re 27,992, Japanese Patent Application No. 3-140,14
Ammonium salts described in No. 0, DC Necker et al, Macr
omolecules, 17,2468 (1984), CSWen et al, Teh, Proc.Co
nf.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, 4,069,056 and other phosphonium salts, JVCrivello et al., Macromorecules, 10 (6), 1307.
(1977), Chem. &. Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent No. 339,049, and No. 410,201.
JP-A-2-150,848, JP-A-2-296,514, etc., iodonium salts, JVCrivello et al, Polymer J. 17,7
3 (1985), JVCrivello et al. J. Org. Chem., 43, 3055 (19
78), WRWatt et al, J. Polymer Sci., Polymer Chem.E
d., 22,1789 (1984), JVCrivello et al, Polymer Bul
l., 14,279 (1985), JVCrivello et al, Macromorecules,
14 (5), 1141 (1981), JVCrivello et al, J. Polymer Sc
i., Polymer Chem. Ed., 17, 2877 (1979), European Patent 370,
693, 3,902,114, 233,567, 297,443
No. 297,442, U.S. Pat.Nos. 4,933,377, 161,81.
No. 1, No. 410,201, No. 339,049, No. 4,734,444,
No. 2,833,872, Dokoku Patent No. 2,904,6260, No. 3,604,58
No. 0, No. 3,604,581, etc., sulfonium salts, J.
V.Crivello et al, Macromorecules, 10 (6), 1307 (1977),
JVCrivello et al, J. Polymer Sci. Polymer Chem. Ed., 1
7,1047 (1979) and other selenonium salts, CSWen eta
l, Teh, Proc.Conf.Rad.Curing ASIA, p478, Toky, Oct (198
8) and other onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, Japanese Patent Publication No. 46-4605, and Japanese Patent Laid-Open No. 48-36281.
JP-A-55-32070, JP-A-60-239736, JP-A-61-16
9835, JP 61-169837, JP 62-58241, JP 62-212401, JP 63-70243, JP 63-29833
Organic halogen compounds described in No. 9, etc., K. Meier et al, JR
ad.Curing, 13 (4), 26 (1986), TPGill et al, Inorg.Che
m., 19,3007 (1980), D.Astruc, Acc.Chem.Res., 19 (12), 3
77 (1896), organic metal / organic halides described in JP-A-2-61445, S. Hayase et al, J. Polymer Sci., 25, 75
3 (1987), E. Reichmanis et al., J. Pholymer Sci., Polyme.
r Chem. Ed., 23, 1 (1985), QQZhu et al, J. Photochem., 3
6,85,39,317 (1987), B. Amit et al, Tetrahedron Lett., (2
4) 2205 (1973), DHR Barton et al, J. Chem Soc., 3571 (1
965), PMCollins et al, J. Chem. SoC., Perkin I, 1695 (1
975), M. Rudinstein et al, Tetrahedron Lett., (17) 1455.
(1975), JWWalker et al J. Am. Chem. Soc., 110, 7170 (19
88), SCBusman et al J. Imaging Technol., 11 (4), 191
(1985), HM Houlihan et al, Macormolecules, 21, 2001 (1
988), PMCollins et al, J. Chem. Soc., Chem. Commun. 532
(1972), S. Hayase et al, Macromolecules 18,1799 (198
5), E. Reichmanis et al, J. Electrochem. Soc., Solid Sta.
te Sci.Technol., 130 (6), FMHoulihan etal, Macromol
cules, 21, 2001 (1988), European Patent No. 0290,750, 046,
083, 156,535, 271,851, 0,388,343
U.S. Pat.Nos. 3,901,710 and 4,181,531.
60-198538, JP-A-53-133022, and other photoacid generators 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., 5
5 (697), 45 (1983), Akzo, H. Adachi etal, Polymer Prepri
nts, Japan, 37 (3), European Patent 0199,672, 84515
No. 199,672, No. 044,115, No. 0101,122, U.S. Pat.No. 618,564, No. 4,371,605, No. 4,431,774,
JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No. 3-140109
Compounds which generate sulfonic acid by photolysis represented by iminosulfonates described in JP-A-61-166544
And the disulfone compounds described in JP-A No. 1994-242242.

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. So.
c., 104,5586 (1982), SPPappas et al, J. Imaging Sci.,
30 (5), 218 (1986), S.Kondo et al, Makromol.Chem., Rapid.
Commun., 9,625 (1988), Y.Yamada et al, Makromol.Che
m., 152,153,163 (1972), JVCrivello et al, J. Polymer
Sci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
849,137, United States Patent No. 3914407, JP-A-63-26653,
JP-A-55-164824, JP-A-62-69263, JP-A-63-146
The compounds described in JP-A No. 038, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029 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) An oxazole derivative represented by the general formula (PAG1) or an S-triazine derivative represented by the general formula (PAG2) in which a trihalomethyl group is substituted.

[0098]

[Chemical 37]

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 not limited to these.

[0101]

[Chemical 38]

[0102]

[Chemical Formula 39]

[0103]

[Chemical 40]

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

[0105]

[Chemical 41]

Here, 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 -, CF 3
Examples include condensed polynuclear aromatic sulfonate anions such as perfluoroalkane sulfonate anions such as SO ₃ ⁻ , pentafluorobenzene sulfonate anions, naphthalene-1-sulfonate anions, anthraquinone sulfonate anions, and sulfonate group-containing dyes. However, the present invention is not limited to these. Also R ³ , R ⁴ and R ⁵
Two of them and Ar 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.

[0109]

[Chemical 42]

[0110]

[Chemical 43]

[0111]

[Chemical 44]

[0112]

[Chemical formula 45]

[0113]

[Chemical formula 46]

[0114]

[Chemical 47]

[0115]

[Chemical 48]

[0116]

[Chemical 49]

[0117]

[Chemical 50]

[0118]

[Chemical 51]

[0119]

[Chemical 52]

[0120]

[Chemical 53]

The onium salts represented by the general formulas (PAG3) and (PAG4) are known, and for example, JWKnapcz.
yk et al, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok e
tal, J.Org.Chem., 35,2532 (1970), E.Goethas et al, Bul
l.Soc.Chem.Belg., 73,546, (1964), HMLeicester, J.
Ame.Chem.Soc., 51,3587 (1929), JVCrivello et al., J.
Polym. Chem. Ed., 18, 2677 (1980), U.S. Pat.No. 2,807,648.
Nos. 4,247,473 and 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).

[0123]

[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, alkenyl group, or arylene group. Specific examples thereof include the compounds shown below, but the invention is not limited thereto.

[0125]

[Chemical 55]

[0126]

[Chemical 56]

[0127]

[Chemical 57]

[0128]

[Chemical 58]

[0129]

[Chemical 59]

The amount of the compound that decomposes to generate an acid upon irradiation with actinic rays or radiation 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.

In the photosensitive composition of the present invention, if necessary,
Further, a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, a compound having two or more phenolic OH groups for promoting solubility in a developing solution, and the like can be contained.

Suitable dyes include oily dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 60.
3, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.), Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B.
(CI45170B), Malachite Green (CI42
000), methylene blue (CI52015) and the like.

Furthermore, the photosensitive composition of the present invention is obtained by adding a spectral sensitizer as described below and sensitizing the photoacid generator to be used in the long wavelength region beyond the deep ultraviolet which does not have 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 coated on 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 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 as a mixture. To use.

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, etc. Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, F-top EF301, E 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431
(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 is coated on a substrate (eg, silicon / silicon dioxide coating) used in the production of precision integrated circuit devices by a suitable coating method such as a spinner or coater, and then exposed through a predetermined mask, A good resist pattern can be obtained by 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, triethylamine, methyldiethylamine and the like. Of tertiary amines, 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. Aqueous solutions 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.

[0138]

【Example】

(Synthesis of dissolution inhibitor (a)) Trisphenol-T
C (Mitsui Petrochemical Co., Ltd.) 20g (0.042mo
1) was dissolved in 400 ml of tetrahydronolane (THF). 9.3 g (0.083 mol) of tert-butoxypotassium was added to this solution under a nitrogen atmosphere, and after stirring at room temperature for 10 minutes, 19.5 g (0.087 mol) of di-tert-butyl dicarbonate was added. At room temperature, 3
After reacting for a time, 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 (filler: silica gel, developing solution: ethyl acetate / hexane = 1/5) to obtain a dissolution inhibitor (a) having the following structure.

[0140]

[Chemical 60]

(Synthesis of Dissolution Inhibitor (b)) Trisph
48.1 g (0.10 mol) of enol-TC was dissolved in 300 ml of dimethylacetamide, and 22.1 g (0.16 mol) of potassium carbonate and t of bromoacetic acid were added.
-Butyl 42.9 g (0.22 mol) was added. Then, it stirred at 120 degreeC for 5 hours. The reaction mixture was poured into 2 liters of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate.

The ethyl acetate extract was concentrated and purified by column chromatography (filler: silica gel, developing solution: ethyl acetate / hexane = 1/5) to obtain a dissolution inhibitor (b) having the following structure.

[0143]

[Chemical formula 61]

(Synthesis of Dissolution Inhibitors (c) to (k)) Bis (3,5-dimethyl-4-hydroxyphenyl) -3,
36.4 g of 4-dihydroxyphenylmethane (0.1 m
was dissolved in 200 ml of THF, and 31.9 g (0.38 mol) of 3,4-dihydro-2H-pyran was added thereto. Further, 0.2 g of trifluoroborane diethyl ether complex was added as a catalyst, and the mixture was stirred at 50 ° C. for 7 hours.

The reaction mixture was concentrated under reduced pressure and purified by column chromatography (filler: silica gel, developing solution: ethyl acetate / hexane = 1/5) to obtain a dissolution inhibitor (c) having the following structure. .

[0146]

[Chemical formula 62]

Similarly, dissolution inhibitors (d) to dissolution inhibitor (k) were synthesized. Table 1 shows the structures, acid-decomposable groups, residual alkali-soluble groups, and N _S / (N _B + N _S ) values of these dissolution inhibitors.

[0148]

[Table 1]

* 1 Structure represents the number of a specific structural example in the specification. * 2 acid-decomposable groups of the type: tBOC are, -O-CO-O-C (CH 3) 3 group tBuE _{is, -O-CH 2 -CO-O} -C (CH 3) 3
Group CuE _{is, -O-CH 2 -CO-O} -C (CH 3) 2 C
₆ H ₅ group Pyra is a pyranyl ether group [Synthesis of dissolution inhibitor for comparative example] (Synthesis of dissolution inhibitor (l)) Trisphenol-T
C (Mitsui Petrochemical Co., Ltd.) 20g (0.042mo
l) was dissolved in 400 ml of THF. 14 g (0.12) of potassium tert-butoxide was added to this solution under a nitrogen atmosphere.
5 mol) was added, and the mixture was stirred at room temperature for 10 minutes, and then di-te.
29.2 g of rt-butyl dicarbonate (0.13 mo
l) 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 (filler: silica gel, developing solution: ethyl acetate / hexane = 1/5) to obtain a dissolution inhibitor (l) having the following structure. .

[0151]

[Chemical formula 63]

(Synthesis of Dissolution Inhibitor (m)) Trisph
48.1 g (0.10 mol) of enol-TC was dissolved in 300 ml of dimethylacetamide, and 33.2 g (0.24 mol) of potassium carbonate and 64.4 g (0.33 mol) of t-butyl bromoacetate were added thereto.
Then, it stirred at 120 degreeC for 5 hours. The reaction mixture was added to 2 liters of ion-exchanged water and neutralized with acetic acid,
It was extracted with ethyl acetate.

The ethyl acetate extract was concentrated and purified by column chromatography (filler: silica gel, developing solution: ethyl acetate / hexane = 1/5) to obtain a dissolution inhibitor (m) having the following structure. .

[0154]

[Chemical 64]

(Synthesis of Dissolution Inhibitor (n)) Trisp-
PA (manufactured by Honshu Kagaku Co., Ltd.) (compound (18) in which all R's are hydroxyl groups)
Dissolve in 200 ml of F and add to it 3,4-dihydro-2
27.7 g (0.33 mol) of H-pyran was added. Further, 0.20 g of trifluoroborane diethyl ether complex was added as a catalyst, and the mixture was stirred at 50 ° C. for 7 hours.

The reaction mixture was concentrated under reduced pressure and purified by column chromatography (filler: silica gel, developing solution: ethyl acetate / hexane = 1/5). As a result, all phenyl hydroxyl groups were protected with pyranyl groups. A colorless viscous solid of the tritetrahydropyratyl ether compound (dissolution inhibitor (n)) was obtained.

[0157]

[Chemical 65]

(Synthesis of Dissolution Inhibitor (o)) JP-A-2-2
According to the method described in No. 48,953, a dissolution inhibitor (o) having the following structure was synthesized.

[0159]

[Chemical formula 66]

(Synthesis of Dissolution Inhibitor (p)) European Patent No. 2
According to the method described in No. 49,139, a dissolution inhibitor (p) having the following structure was synthesized.

[0161]

[Chemical formula 67]

(Synthesis Example of Novolac Resin) 40 g of m-cresol, 60 g of p-cresol, 49 g of 37% formalin aqueous solution and 0.13 g of oxalic acid were placed in a three-necked flask and heated to 100 ° C. with stirring for 15 hours. It was made to react.

Thereafter, the temperature is raised to 200 ° C. and gradually increased to 5
The pressure was reduced to mmHg 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 = 45/55 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 20 g of the novolak resin (NOV.3) obtained above was completely dissolved in 70 g of methanol, and water 30 was added thereto. The mixture was gradually added with stirring to precipitate the 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). The weight average molecular weight was 9000 (converted to polystyrene).

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 heating and stirring were continued for further 1 hour. Then, the temperature was lowered to 80 ° C. and 0.2 g of oxalic acid was added. Again, change the temperature of the oil bath to 11
The mixture was kept at 0 ° C. and reacted at 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 distiller, the temperature was raised to 200 ° C., and further distilled under a reduced pressure of 2 to 3 mmHg for 2 hours to remove residual monomers. The molten polymer was recovered from the flask, and the target novolak resin (NOV.7, Mw = 7.5
00) was obtained.

(Examples 1 to 14) Resists were prepared using the compounds of the present invention shown in the above synthesis examples. The composition ratio at that time is shown in Table 2.

Comparative Examples 1 to 3 Three component positive resists were prepared using the melting inhibitors (l) to (n) having no residual alkali-soluble group. The composition ratio at that time is shown in Table 2.

(Comparative Example 4) Using the melting inhibitor (o) described in JP-A-2-248,953, 3
A component type positive resist was prepared. The composition ratio at that time is shown in Table 2.

(Comparative Example 5) Using the melting inhibitor (p) described in European Patent 249,139, 3
A component type positive resist was prepared. The composition ratio at that time is shown in Table 2.

Comparative Example 6 US Pat. No. 4,491,62
According to the method described in the specification of No. 8, t-butoxycarbonyloxstyrene polymer was synthesized to prepare a two-component positive resist. The composition ratio at that time is shown in Table 2.

The abbreviations used in Table 2 have the following meanings. (Polymer) NOV. 1-7 Novolac resin PVP p-hydroxystyrene polymer (weight average molecular weight 9,600) TBOCS t-butoxycarbonyloxystyrene polymer (number average molecular weight 21,600)

[0174]

[Table 2]

[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 μm.
m resist film was obtained.

The resist film was exposed using a 248 nm KrF excimer laser stepper (NA = 0.42). After the exposure, the film was heated on a vacuum adsorption type hot plate at 90 ° C. for 60 seconds, immediately immersed in a 2.38% tetramethylammonium hydroxide (TMAH) 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 6. The resolving power represents a limiting resolving power at an exposure amount that reproduces a 0.70 μm mask pattern.

Solubility in coating solvent (storage stability)
Is an acid-decomposable dissolution inhibitor 1 for 6 g each of ECA (ethyl cellosolve acetate), EL (ethyl lactate), PEGMEA (propylene glycol monoethyl acetate) and MMP (methyl methoxypropionate).
A solution in which g was dissolved was prepared and stored under forced conditions at 40 ° C. for 20 days to evaluate precipitation. The evaluation results are shown in Table 3, in which no precipitation is indicated by ◯ and precipitation is indicated by x. From the results shown in Table 3, it can be seen that the resist of the present invention has high sensitivity, high resolution, good profile, and excellent storage stability.

[0179]

[Table 3]

[0180]

The positive photosensitive composition of the present invention has high sensitivity, high resolution and good profile and is excellent in storage stability.

─────────────────────────────────────────────────── ─── 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. Alkali development having (A) a resin insoluble in water and soluble in an aqueous alkali solution, (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (C) a group decomposable by an acid. In a positive photosensitive composition containing a low molecular weight compound having a molecular weight of 3000 or less, the solubility of which in a liquid is increased by the action of an acid, the low molecular weight compound (C) contains at least a group capable of decomposing with an acid (a). A compound having two and at least the distance between the acid-decomposable groups and having 10 or more bond atoms excluding the acid-decomposable group and (b) a group capable of decomposing with an acid. A compound having three and having 9 or more bond atoms excluding the acid-decomposable group at a position where the distance between the acid-decomposable groups is the longest, and at least 1
A positive photosensitive composition, characterized in that 0 mol% is at least one selected from compounds having an alkali-soluble group.