JPH06273924A - Positive photosensitive composition - Google Patents

Abstract

PURPOSE:To provide the positive composition small in change of sensitivity in a state left as it is from exposure to baking, change of a profile, and decrease of film thickness at the time of development, and good in the profile and high in resolution. CONSTITUTION:The positive photosensitive composition contains (a) a resin insoluble in water but soluble in an aqueous solution of alkali, (b) a compound to be allowed to produce acid by irradiation with active rays car radiation, (c) a low-molecular-weight acid-decomposable dissolution-inhiting compound having a molecular weight <=3000 and a group decomposable by acid and increased in activity by heating to >=70 deg.C in the presence of the acid. and (d) a compound to be allowed to react within 1 hour at a temperature of 50 deg.C by the action of the acid by (b) and increasing in solubility or hydrophilicity in an alkali developer.

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 positive chemically amplified resist is a three-component composition comprising an alkali-soluble resin, a compound (photoacid generator) which generates an acid upon exposure to radiation, and a dissolution inhibiting compound for the alkali-soluble resin having an acid-decomposable group. The system can be roughly classified into a two-component system comprising a resin having a group which is decomposed by a reaction with an acid to be alkali-soluble and a photo-acid generator. In the case of a two-component system, the content of acid-decomposable groups in the resin increases, 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 because the range of selection of raw materials is large, and development of an acid-decomposable compound having excellent dissolution inhibiting properties used in this system has been desired. In addition, both the two-component system and the three-component system are stable especially in the presence of an acid at room temperature, but in the case of a compound system having a group which decomposes by heating, from the exposure to the heat treatment (Post Expos).
When the standing time before the ure Bake (PEB) treatment becomes long, the developability of the resist surface portion is lowered even in the exposed portion, so that a so-called T-shaped top shape is exhibited, and as a result, the sensitivity is lowered.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to reduce the sensitivity change from exposure to baking by leaving it to stand, profile shape change and film loss during development, and to provide a positive type photosensitive material having a good profile and high resolution. To provide a sex composition.

[0009]

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 obtain an alkali-soluble resin, a photo-acid generator and an acid at 70 ° C. or higher. In a positive-type chemical amplification system comprising a dissolution inhibiting compound having a group capable of decomposing upon heating, a low molecular weight acid-decomposable dissolution inhibiting compound satisfying the following requirements is used as a dissolution inhibiting compound, The inventors have found that this can be achieved by adding a compound that reacts at a temperature of not higher than 0 ° C. and has increased alkali solubility or hydrophilicity, and reached the present invention. That is, the present invention has (a) a resin insoluble in water and soluble in an alkaline aqueous solution, (b) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (c) a group decomposable by an acid, Solubility in alkaline developers is increased by heating above 70 ° C. in the presence of acid according to (b),
A low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 3000 or less,
(d) A positive-type photosensitive composition containing a compound which reacts at 50 ° C. or lower within 1 hour to increase solubility or hydrophilicity in an alkali developing solution by the action of an acid according to (d), c) has at least two groups capable of decomposing with (i) an acid, and the distance between the acid decomposable groups is at the farthest position via 10 or more bond atoms excluding the acid decomposable group. A compound and (ii) a compound having at least three groups capable of decomposing with an acid, and having at least nine bond atoms excluding the acid decomposable group at positions where the distance between the acid decomposable groups is the longest. The present invention provides a positive photosensitive composition characterized by being at least one selected from the following.

The three-component positive photosensitive composition of the present invention comprises
Basically, it consists of an acid-decomposable dissolution inhibitor, an alkali-soluble resin and a photo-acid generator. The acid-decomposable dissolution inhibitor suppresses the solubility of the alkali-soluble resin in alkali, the acid-decomposable group is deprotected by the acid generated when exposed to light, and conversely promotes the solubility of the resin in alkali. Have an effect.
Naphthalene in JP-A-63-27829 and JP-A-3-198059,
Dissolution-inhibiting compounds containing biphenyl and diphenylcycloalkane as a skeleton compound have been disclosed, but their solubility-inhibiting properties to alkali-soluble resins are small, and they are insufficient in terms of profile and resolution. 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
Decomposes by heating above 70 ° C in the presence of acid.
Further, it has at least two groups capable of decomposing with an acid in its structure, and at a position where the distance between the acid decomposable groups is the longest, at least 10 bond atoms excluding the acid decomposable group, preferably at least 11 compounds, more preferably at least 12 compounds, or at least 3 acid-decomposable groups
At least 9, and preferably at least 10 and more preferably at least 1 bond atom excluding the acid-decomposable group at the position where the distance between the acid-decomposable groups is the longest.
It is a compound that passes through one. Also, the preferable upper limit of the number of bonding atoms is 50, and more preferably 30. In the present invention, the acid-decomposable dissolution inhibiting compound has an acid-decomposable group of 3
When the number of the acid-decomposable groups is two or more, preferably four or more, or when the number of the acid-decomposable groups is two or more, the acid-decomposable groups are remarkably inhibited from dissolving in an alkali-soluble resin when they are separated from each other by a certain distance or more. improves. The distance between acid-decomposable groups in the present invention is indicated by the number of via bond atoms excluding acid-decomposable groups. For example, the following compound (1),
In the case of (2), the distance between acid-decomposable groups is 4 for each bonding atom.
And the compound (3) has 12 bonding atoms.

[0012]

[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 wt% or more.

Since the alkali-soluble group functions according to the developing solution described later, the alkali-soluble group protected by the acid-decomposable bond and the alkali-soluble group to be left are preferably groups having 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.

[0015]

[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.

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

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

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

Preferred are cumyl ester group, tertiary alkyl ether group, tertiary alkyl ester group, tertiary alkyl carbonate group and the like. More preferably, it is a tertiary alkyl ester group or a tertiary alkyl carbonate group.

Preferably, JP-A-1-289946,
JP-A 1-289947, JP-A-2-2560, JP-A-3-128959, JP-A-3-158855,
JP-A-3-179353, JP-A-3-191351
No. 3, JP-A-3-200251, JP-A-3-2000025
No. 2, JP-A-3-200253, and JP-A-3-2002.
54, JP-A-3-200255, and JP-A-3-259.
149, JP-A-3-279958, and JP-A-3-27
No. 9959, JP-A-4-1650, and JP-A-4-165.
1, JP-A-4-11260, and JP-A-4-12356.
Japanese Patent Application Laid-Open No. 4-12357, Japanese Patent Application No. 3-33229.
Japanese Patent Application No. 3-230790, Japanese Patent Application No. 3-32043
No. 8, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-52732.
Japanese Patent Application No. 4-103215, Japanese Patent Application No. 4-10454
No. 2, Japanese Patent Application No. 4-107885, Japanese Patent Application No. 4-1078
No. 89, No. 4-152195 and the like, a part or all of the phenolic OH group of the polyhydroxy compound described above is bonded with a group shown by the formula, —R ⁰ —COO—A ⁰ or B ⁰ group. And protected compounds are included.

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, Japanese Patent Application Nos. 4-107889 and 4-15219.
Those using the polyhydroxy compound described in the specification of No. 5 are mentioned.

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

[0024]

[Chemical 3]

[0025]

[Chemical 4]

[0026]

[Chemical 5]

[0027]

[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, R ₁ : -CO-,-. COO-, -NHCONH-, -N
HCOO-, -O-, -S-, -SO-, -SO2-,
-SO3-, or

[0029]

[Chemical 7]

[0030] Here, G = 2 to 6, provided that at least one alkyl group of R _4, R ₅ when the G = 2, R _4, R _5: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH, -C
N, 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

[0031]

[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, an acyloxy group, an aryl group, a nitro group, a hydroxyl group, a cyano group or a carboxyl group, with the proviso that the hydrogen of the hydroxyl group may be substituted with -R ⁰ -COO-a ⁰ group or B ⁰ group, R ₂₈ , R _29, which may be the same or different, are a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, provided that the lower alkyl group in the present application refers to an alkyl group having 1 to 4 carbon atoms, R _{33 to} R _36: may be the same or different, a hydrogen atom or an alkyl group,, R ₄₃ to R _45: the same or different and represent a hydrogen atom, an alkyl group, an alkoxy group, an acyl group Or acyloxy group, R _50: a hydrogen atom, -R ⁰ -COO-A ⁰ group, B ⁰ group, or

[0033]

[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,
An acyloxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group, provided that each of the four substituents having the same symbol does not have to be the same group, Y: -CO-, or -SO ₂ -, Z, B: a single bond,
Alternatively, -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 group in () May be the same or different, a to q, s, t, v, g1 to i1, k1 to m1, o1, q1, s
1, u1: 0 or an integer from 1 to 5, r, u, w, x, y, z, a1 to f1, p
1, r1, t1, v1 to x1: 0 or an integer of 1 to 4, j1, n1, z1, a
2, b2, c2, d2: 0 or an integer of 1 to 3, at least one of z1, a2, c2, d2 is 1 or more, y1: an integer of 3 to 8, (a + b), (e + f + g), (k + l + m), (q + r + s), (w
+ x + y), (c1 + d1), (g1 + h1 + i1 + j1), (o1 + p1), (s1 + t1) ≧ 2,
(j1 + n1) ≦ 3, (r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1
+ f1), (p1 + r1), (t1 + v1), (x1 + w1) ≦ 4, but general formula [V]
In the case of, (w + z), (x + a1) ≦ 5, (a + c), (b + d), (e + h), (f + i),
(g + j), (k + n), (l + o), (m + p), (q + t), (s + v), (g1 + k1), (h1 + l
1), (i1 + m1), (o1 + q1), (s1 + u1) ≦ 5.

[0035]

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical 12]

[0038]

[Chemical 13]

Specific examples of preferable compound skeletons are shown below.

[0040]

[Chemical 14]

[0041]

[Chemical 15]

[0042]

[Chemical 16]

[0043]

[Chemical 17]

[0044]

[Chemical 18]

[0045]

[Chemical 19]

[0046]

[Chemical 20]

[0047]

[Chemical 21]

[0048]

[Chemical formula 22]

[0049]

[Chemical formula 23]

[0050]

[Chemical formula 24]

[0051]

[Chemical 25]

[0052]

[Chemical formula 26]

[0053]

[Chemical 27]

[0054]

[Chemical 28]

[0055]

[Chemical 29]

[0056]

[Chemical 30]

[0057]

[Chemical 31]

[0058]

[Chemical 32]

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

[0060]

[Chemical 33]

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

The amount of the compound used in the present invention (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) Compound that reacts with an acid at 50 ° C. or less within 1 hour (Compound of the present invention (d)) The compound of the present invention (d) acts by the acid generated from the present invention (b). Reacts within 1 hour at 50 ° C or below,
The solubility or hydrophilicity in an alkaline developer is increased. As a result, even if the exposure time from exposure to PEB is prolonged, the developability is less likely to decrease, the T-shaped top shape is improved, and the sensitivity is less likely to decrease. Examples of such a compound include compounds having various acid-decomposable groups. For example, Japanese Examined Patent Publication No. 52-36442 and Japanese Patent Laid-Open No. 63-63
-10153, 64-57258, JP-A 1-1
06040, 1-106041, 2-2489.
53, etc., acetal compounds, Japanese Patent Publication No. 60-20
No. 738, JP-A-63-241540, JP-A 1-1
Orthoester compounds described in JP-A-06041, JP-A-63-241540, JP-A-3-107163, and JP-A-63-236.
No. 028, etc., and epoxy compounds described in JP-A-60-37.
549, silyl ether compounds described in JP-A-1-106038 and the like, silyl ester compounds described in JP-A-60-10247, alkenyl ether compounds described in JP-A-55-12995 and JP-A-3. -1765
No. 3, 3-208056 and the like, α-hetero-substituted cyclic or acyclic methyl ester type compounds, JP-A-63-63
Carboxylic acid anhydride compounds described in, for example, No. 110445,
In addition to the N-acyliminocarbonate compounds described in JP-A-55-126236, lactone compounds, cyclic sulfonate compounds and the like are included. Typically, the general formula [d
-1] to [d-12].

[0064]

[Chemical 34]

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

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

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

X'is O, S, SO ₂ or -C
(R ₃₄ ′, R ₃₅ ′) − is shown.

R ₂₃ ', R ₂₄ ', R ₂₅ ', R ₂₆ ', R ₂₇ ', R
₂₈ ′, R ₂₉ ′, R ₃₀ ′, R ₃₄ ′ and R ₃₅ ′ may be the same or different and each is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group / aryl group / aralkyl group / alkoxy. Group or hydroxy group, R ₃₂ '
Represents a substituted or unsubstituted alkyl group or aryl group. R ₂₄ ′ and R ₂₆ ′ may combine to represent a single bond, and R ₂₃ ′ to R ₂₆ ′ and R ₂₇ ′ to R ₃₀ ′, R ₃₄ ′, R ₃₅ ′.
Two of the above groups may combine to form a 5- to 8-membered ring which may contain heteroatoms. n shows the integer of 1-10.

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

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

Regarding the addition of such a compound, JP-A-63-236028 (addition of epoxy compound to silyl ether compound / photo-acid generator system), JP-A-4-2485.
No. 54 (alkali-soluble resin / compound system having acid-decomposable group and photoacid-generating group in the same molecule, compound added to react with water or anionoid compound at temperature up to 120 ° C.) and European Patent 520654 (photoacid The addition of an acetal compound to a two-component system of a film-forming polymer having a generator / acid-decomposable group) and the like, and the effect of suppressing a change in developability due to standing after exposure to PEB is described.
However, in JP-A-63-236028, there is a problem in stability with time of storage (shelf life).
In No. 248554, there was a problem that the dissolution inhibiting property of the unexposed portion in the alkali developing solution was not sufficient and the resolution and the profile were lowered. European patent 52065
No. 4 had a problem in the two-component chemical amplification system.

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

[0074]

[Chemical 35]

[0075]

[Chemical 36]

[0076]

[Chemical 37]

[0077]

[Chemical 38]

[0078]

[Chemical Formula 39]

(C) Alkali-Soluble Resin (Compound of the Present Invention (a)) Examples of the alkali-soluble resin used in the present invention include novolac resins, hydrogenated novolak resins and acetone-
Pyrogallol resin, polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, polyoxystyrene partially O-alkylated or O-acylated, styrene-maleic anhydride copolymer Examples thereof include, but are not limited to, a carboxyl group-containing methacrylic resin and its derivative. 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 -Methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, alkoxyphenols such as p-butoxyphenol, 2-methyl-4-isopropyl Feno Bis-alkylphenols etc., m
-Hydroxy aromatic compounds such as chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or in combination of two or more, but are not limited thereto. It is not something that will be done.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde. , O-chlorobenzaldehyde,
m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-
Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural,
Chloroacetaldehyde and acetals thereof such as chloroacetaldehyde diethyl acetal can be used, and of these, formaldehyde is preferably used. These aldehydes are
They may be used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid or the like can be used. Further, alkali-soluble group of these alkali-soluble resins, such as OH groups, the acid decomposable group and a part of the hydrogen atoms of the -COOH group -R ⁰ -COO-
A ^0, or those substituted with A ⁰ group are also preferred in terms of improving the dissolution inhibiting in a developer. In that case, the substitution rate is 1 to 50 mol%, preferably 1 to 30 mol%, and more preferably 1 to 15 mol% based on all alkali-soluble groups.

The weight average molecular weight of these alkali-soluble resins is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed area after development is large, and if it exceeds 30,000, the developing speed becomes small. Especially preferred is 2,000 to 20,000.
The range is 0. 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.

(D) Compound capable of generating an acid upon irradiation with actinic rays or radiation (Compound of the invention (b)) Examples of the compound capable of decomposing 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 No. 104,143, U.S. Patent No. 339,049, No. 410,201, JP-A-2-150,848, JP-A-2-296,514 and the like iodonium salt described in JVCrive.
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. Pat.
8,564, 4,371,605, 4,431,774, JP-A-64-18
No. 143, JP-A No. 2-245756, Japanese Patent Application No. 3-140109, and the like, compounds which generate sulfonic acid by photolysis, represented by iminosulfonates, etc., and described in JP-A No. 61-166544. 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 when exposed to actinic rays or radiation to generate an acid, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
1) or an oxazole derivative represented by the general formula (PA
An S-triazine derivative represented by G2).

[0088]

[Chemical 40]

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.

[0090]

[Chemical 41]

[0091]

[Chemical 42]

[0092]

[Chemical 43]

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

[0094]

[Chemical 44]

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 -,
CF ₃ SO ₃ ^- perfluoroalkane sulfonate anion such as, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonyl phosphate anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes However, the present invention is not limited to these.

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, but are not limited to, the compounds shown below.

[0100]

[Chemical formula 45]

[0101]

[Chemical formula 46]

[0102]

[Chemical 47]

[0103]

[Chemical 48]

[0104]

[Chemical 49]

[0105]

[Chemical 50]

[0106]

[Chemical 51]

[0107]

[Chemical 52]

[0108]

[Chemical 53]

[0109]

[Chemical 54]

[0110]

[Chemical 55]

[0111]

[Chemical 56]

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).

[0114]

[Chemical 57]

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.

[0116]

[Chemical 58]

[0117]

[Chemical 59]

[0118]

[Chemical 60]

[0119]

[Chemical formula 61]

[0120]

[Chemical formula 62]

The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.0 based on the total weight of the photosensitive composition (excluding the coating solvent).
It is used in the range of 01 to 40% by weight, preferably 0.0
It is used in the range of 1 to 20% by weight, more preferably 0.1 to 5% by weight.

In the photosensitive composition of the present invention, if necessary,
Further, a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, and a compound having two or more phenolic OH groups for promoting solubility in a developer can be contained.
Suitable dyes include 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 following spectral sensitizers are added to the photosensitive composition of the present invention by sensitizing it to a longer wavelength region than far ultraviolet where the photo-acid generator used 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 which 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 ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or as 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 above photosensitive composition is applied onto a substrate (eg, silicon / silicon dioxide coating) used for the production of precision integrated circuit devices by a suitable coating method such as a spinner or coater, and then passed through a predetermined mask. A good resist pattern can be obtained by exposing, baking and developing.

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

[0128]

【Example】

[Synthesis example-1 of dissolution inhibitor compound] α, α ', α''-tris (4
20 g of human hydroxyoxyphenyl) -1,3,5-triisoprophylbenzene was dissolved in 400 ml of tetrahylfurofuran. 14 g of potassium tert-butoxide was added to this solution under a nitrogen atmosphere, and the mixture was stirred at room temperature for 10 minutes,
29.2 g of rt-butyl dicarbonate 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 layer was further washed with water, dried and the solvent was distilled off. The obtained crystalline solid was recrystallized (diethyl ether) and dried to obtain 25.6 g of a compound example (31: R is all t-BOC group).

[Synthesis Example-2 of Dissolution Inhibitor Compound] α,
α ', α "-tris (4-hydroxyphenyl) -1,3,
5-triisopropylbenzene 19.2 g (0.040
21.2 g (0.15 mol) of potassium carbonate and 27.1 g (0.14 mol) of t-butyl bromoacetate were added to a 120 ml solution of N, N-dimethylacetamide (mol. It was stirred. 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. By NMR, this was confirmed to be a compound example (31: R are all —CH ₂ COOC ₄ H ₉ ^t groups).

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

[Synthesis Example-4 of Dissolution Inhibitor Compound] α, α,
α ', α', α ", α" -hexakis (4-hydroxyphenyl) -1,3,5-triethylbenzene 14.3 g (0.
020 mol) 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.

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

[Synthesis Example-6 of Dissolution Inhibitor Compound] α,
α ', α "-tris (4-hydroxyphenyl) -1,3,
4-Triisopropylbenzene 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 mol) were dissolved therein. ) 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:
As a result of fractional purification with ethyl acetate / n-hexane = 1/5 (volume ratio), a compound example (31: 2 R is —CH ₂ —
COO-C ₄ H ₉ ^t group, one R is to obtain a hydrogen atom) 10 g.

[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 charged 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 22 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 1.

Comparative Example 1 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 1.

Comparative Example 2 Tris (4-t described in JP-A-4-248554)
A 2-component positive resist was prepared by synthesizing a trifluoromethanesulfonate of -butoxycarbonyloxyphenyl) sulfonium. The prescription is shown in Table 1.

Comparative Examples 3,4,5 The compound di-t-butyl terephthalate, 4-t-butoxy-p-, described in European Patent 249,139.
A three-component positive resist was prepared using biphenyl, t-butyl-2-naphthyl carbonate as a dissolution inhibitor.
The prescription at that time is shown in Table 1.

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

[0143]

[Table 1]

The abbreviations used in Table 1 have the following meanings.

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

<Dissolution Inhibitor> TBCPS Tris (4-t-butoxycarbenyloxyphenyl) sulfonium trifluoromethanesulfonate DTBTP Di-t-butyl terephthalate TBPBP 4-t-butoxy-p-biphenyl TBNC t-butyl- 2-naphthyl carbonate

<Acid-decomposable group in dissolution inhibitor>

[0148]

[Chemical formula 63]

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

The sensitivity was defined as the reciprocal of the exposure dose for reproducing a 0.70 μm mask pattern, and was shown by the relative value of the sensitivity of Comparative Example 1. The film shrinkage is expressed as a percentage of the ratio of the film thickness before and after exposure and baking in the exposed area. The resolving power represents a limiting resolving power at an exposure amount that reproduces a 0.70 μm mask pattern. Further, after the resist film was exposed, the resist film was left at room temperature for 1 hour, and then similarly heat-treated, developed, rinsed and dried. Table 2 shows the sensitivity ratios (exposure amount ratios) of the samples that were treated after being left for 1 hour and the samples that were directly treated without being left. From the results shown in Table 2, it can be seen that the resist of the present invention has little film shrinkage due to baking after exposure, has a good profile and high resolution, and shows little sensitivity reduction even if it is left to stand after the heat treatment after exposure.

[0151]

[Table 2]

[0152]

The chemical amplification type positive photosensitive composition of the present invention has a good profile and a high resolution with little film shrinkage due to baking after exposure and film loss after development. Further, the sensitivity does not decrease much even after the heat treatment (PEB) after exposure.

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area H01L 21/027

Claims (1)

[Claims] 1. An alkali 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. The action of the acid by (d) and (b), which is a low molecular weight acid-decomposable dissolution-inhibiting compound having a molecular weight of 3000 or less, whose solubility in a developer is increased by heating to 70 ° C. or more in the presence of the acid by (b). According to the above, in a positive-type photosensitive composition containing a compound which reacts at 50 ° C. or lower within 1 hour and whose solubility or hydrophilicity in an alkali developing solution increases, the compound (c) is decomposed by (i) an acid. Has at least two groups capable of being
A compound having 10 or more bond atoms excluding the acid-decomposable group at the furthest position and (ii) at least three groups capable of being decomposed by an acid are included, and the distance between the acid-decomposable groups is the largest. A positive photosensitive composition, which is at least one compound selected from compounds having 9 or more bond atoms excluding an acid-decomposable group at distant positions.