JPH09211865A - Positive type photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve sensitivity, resolving power, etc., by incorporating a resin insoluble in water but soluble in an aq. alkali soln., a compd. which generates an acid when irradiated with active light or radiation and a specified low molecular acid-degradable dissolution inhibiting compd. SOLUTION: This compsn. contains a resin insoluble in water but soluble in an aq. alkali soln., a compd. which generates an acid when irradiated with active light or radiation and a low molecular acid-degradable dissolution inhibiting compd. having basic nitrogen and a group degradable by the generated acid. The solubility of the dissolution inhibiting compd. in an alkali developer is increased by the action of the acid and the mol.wt. of the compd. is <=3,000. Since the amt. of basic nitrogen in a resist can be delicately regulated by regulating the amt. of basic nitrogen in the compd. or the amt. of the compd. added to the resist, the diffusion of the acid and the deactivation of the acid in the surface part of the resist with the lapse of time after the end of exposure to heating can be easily and properly prevented and the dissolution inhibiting effect of the dissolution inhibiting compd. can be maintained.

Description

Detailed Description of the Invention

[0001]

[0001] The present invention relates to a lithographic printing plate or an IC.
The present invention relates to a positive photosensitive composition used in a semiconductor manufacturing process such as the above, a circuit substrate such as a liquid crystal and a thermal head, and other photofabrication processes.

[0002]

2. Description of the Related Art Positive photoresist compositions include:
In general, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is used. For example, 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 composed of cresol-formaldehyde / trihydroxybenzophenone-1,2-naphthoquinonediazidesulfonic acid ester" is exemplified by Thompson "Introduction to Microlithography" (LFThompson "Intr
oduction to Microlithography ") (ACS Publishing, N
o. 2, 19, p112-121). In such a positive photoresist consisting essentially of a novolak resin and a quinonediazide compound, the novolak resin gives high resistance to plasma etching, and the naphthoquinonediazide compound acts as a dissolution inhibitor. Then, naphthoquinonediazide has the property of losing its dissolution inhibiting ability by generating carboxylic acid upon irradiation with light, and increasing the alkali solubility of the novolak resin.

[0003] From this point of view, many positive photoresists containing a novolak resin and a naphthoquinonediazide-based photosensitive material have been developed and put into practical use.
Sufficient results have been achieved in line width processing down to about 2 μm. However, the degree of integration of integrated circuits has been increasing more and more, and in the manufacture of semiconductor substrates such as VLSIs, processing of ultrafine patterns having a line width of half a micron or less has been required. In order to achieve the required resolution, the wavelength of an exposure apparatus used for photolithography is becoming shorter and shorter, and now far ultraviolet light and excimer laser light (XeCl, KrF, ArF, etc.) have been studied. ing. When a conventional resist consisting of novolak and naphthoquinonediazide compound is used for lithographic pattern formation using far ultraviolet light or excimer laser light, light is strongly absorbed in the far ultraviolet region of novolak and naphthoquinonediazide. It is difficult to reach, and only a low-sensitivity, tapered pattern can be obtained.

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

Examples of such a combination include a combination of a compound that generates an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Laid-Open No. 48-89003), a combination of an orthoester or an amide acetal compound ( JP-A-5120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-1)
No. 33429), a combination with an enol ether compound (JP-A-55-12995), and 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), a combination with a tertiary alkyl ester compound (JP-A-60-3625),
Combination with a silyl ester compound (JP-A-60-102)
No. 47) and a combination with a silyl ether compound (JP-A-60-37549, JP-A-60-12446).
And the like. These have high photosensitivity because the quantum yield exceeds 1 in principle.

Similarly, systems which are stable under aging at room temperature but are decomposed by heating in the presence of an acid and solubilized in alkali are disclosed in, for example, JP-A-59-45439, JP-A-60-3625, JP-A-62-2229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250542, Polym.Eng.Sce., Vol. 23, 101
2 (1983); ACS.Sym. 242, 11 (1984); Semicond
uctor World 1987, November, p. 91; Macromolecules, 2
Vol. 1, p. 1475 (1988); SPIE, vol. 920, p. 42 (1988);
Combination systems with esters or carbonate compounds of primary or secondary carbons (eg t-butyl, 2-cyclohexenyl). These systems also have high sensitivity and have a deep-UV compared to the naphthoquinonediazide / novolak resin system.
Since the absorption in the region is small, it can be an effective system for shortening the wavelength of the light source.

The positive chemically amplified resist comprises an alkali-soluble resin, a compound that generates an acid upon exposure to radiation or the like (photoacid generator), and a compound that inhibits dissolution of the alkali-soluble resin having an acid-decomposable group. A three-component system,
A two-component system consisting of a resin having a group that becomes alkali-soluble by decomposition with an acid and a photoacid generator, or a resin having a group that becomes alkali-soluble by decomposition by reaction with an acid, a dissolution inhibiting compound and light It can be roughly divided into 2.5 component systems consisting of acid generators. In these two-component, 2.5-component or three-component positive chemically amplified resists, an acid from a photoacid generator is interposed by exposure, and after heat treatment and development, a resist pattern is obtained. Here, as the standing time from the exposure to the heat treatment (PEB treatment) becomes longer, the generated acid diffuses and the basic impurities in the atmosphere deactivate the acid on the resist surface portion, resulting in sensitivity,
Further, there is a problem that the profile and line width of the resist pattern after development are changed.

As a means for solving these problems, a technique of adding a low molecular weight amine to a chemical amplification system is disclosed in JP-A-63-14.
9640, JP-A-5-232706, and JP-A 5-2
49662, JP-A-5-127369, W
O-94 / 1805 and the like. In these techniques, the low-molecular amine easily moves in the resist film, and the resist solution is applied, dried, and exposed to PE.
Since the low molecular weight amine volatilizes and diffuses during the process such as B treatment, the effect of adding the amine is insufficient. On the other hand, in Japanese Patent Laid-Open No. 4-75062,
It has been reported that the inclusion of a tertiary amine in the base polymer can prevent the acid generated by exposure from diffusing and improve the dimensional accuracy of the resist pattern.
However, the amount of the tertiary amine needs to be finely adjusted according to the amount of acid generated. When the tertiary amine is introduced into the base polymer as in the above technique, it is practically difficult to finely adjust the amount of amine in the polymer corresponding to the amount of acid generated. Further, when the above-mentioned base polymer containing a tertiary amine is used, the effect of the base polymer itself becomes insufficient, and a part of the non-image area is eluted during development, or it may be a cause of development residue (scum) in the image area. There was something to do.

[0009]

Therefore, the object of the present invention is to easily and appropriately prevent the diffusion or deactivation of the acid with the passage of time from the exposure to the heat treatment, and improve the dissolution inhibiting effect and the developability. And to provide a positive photosensitive composition having a good profile and high resolution.

[0010]

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 solve the following dissolution inhibiting compounds containing a basic nitrogen in a positive chemical amplification system. The inventors have reached the present invention by finding out what can be achieved by using it. That is, it has been found that the object of the present invention is achieved by the following constitutions. (1) Solubility in an alkaline developer having a resin that is insoluble in water and soluble in an alkaline aqueous solution, a compound that generates an acid upon irradiation with actinic rays or radiation, basic nitrogen, and a group that can be decomposed by an acid. A low-molecular acid-decomposable, dissolution-inhibiting compound having a molecular weight of 3,000 or less, which is increased by the action of an acid.

(2) By a resin having a group that decomposes by the action of an acid to increase the solubility in an alkali developing solution, a compound that generates an acid upon irradiation with actinic rays or radiation, and basic nitrogen and an acid. A positive photosensitive composition containing a low molecular weight acid-decomposable dissolution-inhibiting compound having a molecular weight of 3,000 or less, which has a decomposable group and whose solubility in an alkaline developer is increased by the action of an acid. Stuff.

(3) A resin that is insoluble in water and soluble in an aqueous alkali solution, a compound that generates an acid upon irradiation with actinic rays or radiation, a group that can be decomposed by an acid, and has a solubility in an alkali developing solution of that of an acid. Molecular weight increased by action 3,0
A low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 00 or less, basic nitrogen, and a group capable of being decomposed by an acid, and the solubility in an alkali developing solution is increased by the action of an acid.
000 or less low molecular weight acid decomposable dissolution inhibiting compound is contained, The positive photosensitive composition characterized by the above-mentioned.

(4) A resin having a group that decomposes by the action of an acid to increase the solubility in an alkaline developer, a compound that generates an acid upon irradiation with actinic rays or radiation, and a group that can be decomposed by an acid. However, it has a low molecular weight acid-decomposable dissolution-inhibiting compound having a molecular weight of 3,000 or less whose solubility in an alkali developing solution is increased by the action of an acid, and basic nitrogen, and a group capable of being decomposed by an acid. A positive photosensitive composition comprising a low molecular weight acid-decomposable dissolution-inhibiting compound having a molecular weight of 3,000 or less whose solubility in a liquid is increased by the action of an acid.

As described above, in the chemically amplified resist, by using the low molecular weight acid-decomposable dissolution inhibiting compound containing basic nitrogen, the amount of basic nitrogen in the compound can be appropriately adjusted, or the compound can be appropriately adjusted. The amount of basic nitrogen in the resist can be finely adjusted by adjusting the amount added to the resist, making it easy to add basic nitrogen that corresponds to the amount of acid generated during exposure. And it becomes possible to do it appropriately. Further, since the base component has a structure larger than that of a simple basic compound such as a dissolution inhibiting compound, volatilization of the base component is suppressed and a more stable system can be constructed. Moreover, since the base component has the same structure as the dissolution inhibiting compound, it is not necessary to worry about the compatibility problem. Furthermore, since the base component has a dissolution inhibiting ability, the decrease in sensitivity is suppressed as compared with the case where a simple base component is introduced, and a better resist can be provided. By these, excessive diffusion of acid and deactivation of acid on the resist surface can be prevented, and a positive photosensitive composition having a good profile and resolution can be obtained.

Furthermore, three-component system, 2.5-component system or two-component system
Since basic nitrogen is not introduced into the base polymer, which is the main component of the component system, and basic nitrogen and a low-molecular acid-decomposable dissolution inhibiting compound having an acid-decomposable group are added, the base polymer (alkali-soluble resin ) And the dissolution inhibitor can be favorably carried out, and the dissolution inhibitor effect of the dissolution inhibitor can be maintained in the non-image area during development, and the dissolution of the non-image area can be prevented. On the other hand, it is possible to prevent undeveloped residue in the image area and obtain a positive photosensitive composition having a good profile and high resolution.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention are described in detail below. A low molecular weight acid-decomposable dissolution-inhibiting compound having a basic nitrogen and a group capable of decomposing with an acid, and further having a solubility in an alkali developing solution increased by the action of an acid and having a molecular weight of 3,000 or less. , Also referred to as a basic nitrogen-containing dissolution inhibiting compound). The basic nitrogen-containing dissolution inhibiting compound used in the present invention includes a functional group containing a basic nitrogen in its structure (hereinafter abbreviated as basic group) and an acid-decomposable group (hereinafter abbreviated as acid-decomposable group). Is a compound having a molecular weight of 3,000 or less, the solubility of which in the alkaline developer is increased by the action of an acid. The basic nitrogen-containing dissolution inhibiting compound may contain two or more basic groups and acid-decomposable groups which may be the same or different. The basic nitrogen-containing dissolution inhibiting compound of the present invention has a molecular weight of 3,000 or less, preferably 500 to 3,
000, more preferably 500 to 2,500.

In the present invention, the basic group includes an amino group, an N-alkyl-substituted amino group, an N-aryl-substituted amino group, an N-aralkyl-substituted amino group, an N, N-dialkyl-substituted amino group, and an N, N-group. Aryl-substituted amino group,
N, N-Diaralkyl-substituted amino group, N-alkyl-N
An aryl-substituted amino group and an N-alkyl-N-aralkyl-substituted amino group. The alkyl group bonded to the nitrogen atom is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl. is there. The aryl group bonded to the nitrogen atom is preferably an aryl group having 6 to 12 carbon atoms, more preferably 6 to 12 carbon atoms such as phenyl, tolyl and naphthyl.
It is 10 aryl groups. The aralkyl group bonded to the nitrogen atom is preferably an aralkyl group having 7 to 14 carbon atoms, and more preferably an aralkyl group having 7 to 10 carbon atoms such as benzyl and 4-methylbenzyl. Further, these alkyl groups, aryl groups and aralkyl groups are further alkoxy groups such as methoxy and ethoxy,
It may contain a substituent such as a halogen atom such as chloro and bromo, a cyano group, a carboxyl group, an alkoxycarbonyl group such as methoxycarbonyl and ethoxycarbonyl, a hydroxy group, a tetraalkylammonium group and a nitro group.

Specific examples of such a basic group include amino group, N-methylamino group, N-ethylamino group and N-group.
-Propylamino group, N- (2-methoxyethyl) amino group, N-butylamino group, N-phenylamino group, N
-Benzylamino group, N- (4-methoxyphenyl) amino group, N- (4-chlorophenyl) amino group, N, N
-Dimethylamino group, N, N-diethylamino group, N,
N-dipropylamino group, N, N-dibutylamino group,
N, N-diphenylamino group, N, N-dibenzylamino group, N-methyl-N-phenylamino group, N-methyl-N-benzylamino group, N-ethyl-N-phenylamino group, N-ethyl Examples thereof include -N-benzylamino group and N-ethyl-N- (2-hydroxyethyl) amino group, but are not limited thereto. Further, as the other basic group, a piperidyl group, a piperazinyl group, a morpholinyl group, a quinuclidinyl group, a pyridyl group, a pyrazinyl group, a pyrimidinyl group, a quinolyl group, an isoquinolyl group,
Nitrogen-containing 6-membered ring heterocyclic group such as naphthyridinyl group, quinoxalinyl group, quinazolinyl group, purinyl group, acridinyl group, phenothiazinyl group, and pyrrolidinyl group, pyrrolinyl group, pyrrolyl group, imidazolidinyl group,
It includes a nitrogen-containing 5-membered heterocyclic group such as an imidazolinyl group, an imidazolyl group, a pyrazolyl group, an indolinyl group, an indolyl group, an isoindonilyl group, an isoindolyl group, a carbazolyl group, an oxazolyl group and a thiazolyl group. Substituents such as the above alkyl group, aryl group, aralkyl group, alkoxy group, halogen atom, carboxyl group, alkoxycarbonyl group, hydroxy group and mercapto group may be further bonded to these heterocyclic groups.

In the present invention, the acid-decomposable group is preferably an acid-decomposable group, namely --COO--A ⁰ ,-.
Examples of the group containing an O-B ⁰ group, include groups represented by -R ⁰ -COO-A ^0, or -Ar-O-B ^0. Here, A ⁰ is -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), -Si
(R ⁰¹ ) (R ⁰² ) (R ^{0 3} ) or -C (R ⁰⁴ ).
It represents a (R ⁰⁵ ) -O-R ⁰⁶ group. B ⁰ is A ⁰ or -CO-
It represents an ^OA group. R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R
⁰⁵ are the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ⁰⁶ represents an alkyl group or an aryl group. However, at least two of R ^{01 to} R ⁰³ are groups other than hydrogen atom, and R ^{01 to} R ⁰³ and R ⁰⁴ to
Two groups in R ⁰⁶ may combine to form a ring. R
⁰ represents a divalent or higher valent aliphatic or aromatic hydrocarbon group which may have a substituent, and —Ar— represents a divalent or higher valent aromatic which may have a monocyclic or polycyclic substituent. Indicates a group. As the divalent or higher aliphatic group, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group,
Divalent such as isobutylene group and t-butylene group, trivalent and tetravalent such as methine group and ethyne group, and having 1 to 4 carbon atoms
The number is preferably one, and these may be further substituted with a substituent. Further, as the divalent or higher aromatic group, 1,4-phenylene, 1,3-phenylene, 1,2
-Monocyclic such as phenylene, 1,2-naphthylene, 1,3-naphthylene, 1,4-naphthylene, 1,5
-Naphthylene, 1,6-naphthylene, 1,7-naphthylene, 1,8-naphthylene, 2,3-naphthylene, 2,4
-Two-ring ones such as naphthylene, 2,5-naphthylene, 2,6-naphthylene, 2,7-naphthylene and 2,8-naphthylene, and three-ring ones such as anthracene, and the like, and more The ring may be condensed and may have a substituent.

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 are preferred. Further, as a substituent, a hydroxyl group,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group and a t-butoxy group,
Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, aralkyloxy groups, and acyl groups such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, and valeryl group. Group, an acyloxy group such as a butyryloxy group, the above alkenyl group, a vinyloxy group.
Examples thereof include 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.

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a ketal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group, and a third group. And a tertiary alkyl carbonate group and the like. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, a tetrahydropyranyl ether group, and an acetal group.

The acid-decomposable group in the basic nitrogen-containing dissolution inhibiting compound used in the present invention has at least eight bond atoms excluding the acid-decomposable group at the position where the distance between the acid-decomposable groups is the longest. The compound is preferably. In the present invention, more preferably, the basic nitrogen-containing dissolution inhibiting compound has at least two groups capable of decomposing with an acid in its structure, and the acid-decomposable group has the largest distance between
At least 10, preferably at least 11 and more preferably at least 12 bond atoms excluding acid-decomposable groups.
Or a compound having at least three acid-decomposable groups, and at a 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 at least 11 bond atoms excluding the acid-decomposable group. The preferred upper limit of the number of the bonding atoms is 50, more preferably 30. In the present invention, when the basic nitrogen-containing dissolution inhibiting compound has three or more acid-decomposable groups, preferably four or more, even when it has two acid-decomposable groups, the acid-decomposable groups are mutually When they are separated by a certain distance or more, the dissolution inhibiting property with respect to the alkali-soluble resin is remarkably improved. In addition, the distance between the acid-decomposable groups in the present invention is represented by the number of via bond atoms excluding the acid-decomposable groups. For example, in the following compounds (1) and (2), the distance between acid-decomposable groups is 4 bonding atoms each, and in compound (3), 12 bonding atoms.

[0023]

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The basic nitrogen-containing dissolution inhibiting compound of the present invention may have a plurality of acid-decomposable groups on one benzene ring, but preferably one benzene ring each has one acid-decomposable group. It is a compound composed of a skeleton having an acid-decomposable group. Further, in the basic nitrogen-containing dissolution inhibiting compound of the present invention, the basic group is not limited in the number of via bond atoms and the substitution position, and can be bonded to any position.

The basic nitrogen-containing dissolution-inhibiting compound of the present invention is preferably a polyhydroxy compound as shown below into which a basic group and an acid-decomposable group are introduced.
Such polyhydroxy compounds are preferably JP-A-1-289946 and JP-A-1-28994.
7, JP-A-2-2560, JP-A-3-128959.
No. 3, JP-A-3-158855, JP-A-3-17935.
3, JP-A-3-191351, and JP-A-3-2002.
No. 51, JP-A-3-200252, JP-A-3-200
No. 253, JP-A-3-200254, JP-A-3-20
No. 0255, JP-A-3-259149, JP-A-3-2
79958, JP-A-3-279959, JP-A-4-
1650, JP-A-4-1651, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
No. 7, Japanese Patent Application No. 3-33229, Japanese Patent Application No. 3-23079
No. 0, Japanese Patent Application No. 3-320438, Japanese Patent Application No. 4-2515
7, Japanese Patent Application No. 4-52732, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
And polyhydroxy compounds described in the specification such as No. 5, etc., and some or all of the phenolic OH groups of these polyhydroxy compounds are shown above, -R ⁰ -C.
A compound bonded and protected by an OO-A ⁰ or B ⁰ group,
Further, those into which a basic group has been introduced can be mentioned.

The above polyhydroxy compound is more preferably JP-A-1-289946 and JP-A-3-12.
8959, JP-A-3-158855, JP-A-3-1
79353, JP-A-3-200251, JP-A-3-20051
JP-A-200252, JP-A-3-200255, JP-A-3-3205
-259149, JP-A-3-279958, JP-A-4-1650, JP-A-4-11260, JP-A-4-1992
No. 12356, JP-A-4-12357, Japanese Patent Application No. 4-2
No. 5157, Japanese Patent Application No. 4-103215, Japanese Patent Application No. 4-1
04542, Japanese Patent Application No. 4-107885, Japanese Patent Application No. 4-
And those using the polyhydroxy compound described in the specifications of Japanese Patent No. 107889 and No. 4-152195.

More specifically, the basic nitrogen-containing dissolution inhibiting compound of the present invention is a compound represented by the general formulas [I] to [XVI] or the following preferred compound skeletons (1) to (63).
In which one or more of the above basic groups are introduced.

[0028]

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[0029]

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[0030]

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[0031]

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

[0033]

[Chemical 6]

[0034] 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

[0035]

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R ₂₂ and R _24, which may be the same or different, are a single bond, an alkylene group, —O—, —S—, —CO—, or a carboxyl group, R ₂₃ : a hydrogen atom, an alkyl group, an alkoxy group, Acyl group, acyloxy group, aryl group, nitro group, hydroxyl group, cyano group, or carboxyl group, provided that hydrogen of the hydroxyl group may be substituted with t-butoxycarbonyl group, R ₂₈ and R ₂₉ : the same or different And a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, wherein 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, Siloxy group, R _50: a hydrogen atom, t-butoxycarbonyl group or,

[0037]

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R ₅₂ and R ₅₃ may be the same or different, and may be a hydrogen atom, a lower alkyl group, a lower haloalkyl group or an aryl group, and R _{54 to} R ₅₇ may be the same or different and are a hydrogen atom,
Hydroxyl group, halogen atom, nitro group, cyano group, carbonyl group, alkyl group, alkoxy group, alkoxycarbonyl group, aralkyl group, aralkyloxy group, acyl group,
An acyloxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group, provided that each of the four substituents having the same symbol does not have to be the same group, Y: -CO-, Alternatively, —SO ₂ —, Z, B: single bond, or —O—, A: methylene group, lower alkyl-substituted methylene group, halomethylene group, or haloalkyl group, E: single bond, or oxymethylene group, a to z, a1 to y1: when more than one, the groups in () may be the same or different, a to q, s, t, v, g1 to i1, k1 to m1, o1, q1, s1, u1: 0 or An integer of 1 to 5, r, u, w, x, y, z, a1 to f1, p1, r1, t1, v1 to x1: 0 or 1
An integer of 4, j1, n1, z1, a2, b2, c2, d2: an integer of 0 or 1 to 3, z1, a
2, at least one of 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, except for the general formula [V], where (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 + l1), (i1 + m1), (o1 + q1), (s1 + u1)
≦ 5.

[0039]

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[0040]

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[0041]

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[0042]

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Specific examples of preferable compound skeletons are shown below.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

[Chemical 21]

[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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

[0064]

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Represents the following. However, at least two or three depending on the structure are groups other than hydrogen atoms, and each substituent R
Need not be the same group. Further, the R part in the compound may be substituted. However, not all R are substituted with a basic group. The above general formulas [I] to [XVI]
In the compounds represented by and the compound skeletons (1) to (63), the basic group may be bonded to any substitution position of these compounds. Specific examples of these basic nitrogen-containing dissolution inhibiting compounds are shown below, but the present invention is not limited thereto.

[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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The basic nitrogen-containing dissolution inhibiting compound used in the present invention can be synthesized, for example, by reacting the above-mentioned phenolic compound with a secondary amine compound and an aldehyde or ketone compound to introduce a basic group. The compound can be obtained by subsequently protecting the phenolic hydroxyl group with an acid-decomposable protecting group. As a method for introducing a basic group into the above phenolic compound, Japanese Patent Application No. 7-136 can be used.
A method similar to the method for synthesizing an aminomethylated product in which a secondary amine compound is introduced into a phenol compound described in No. 535 can be mentioned. Moreover, when substituting a basic group with a phenolic hydroxyl group, it can synthesize | combine using various condensation methods. In addition to this, if it is a method capable of introducing a basic group,
The method is not limited to this. The amount of the basic nitrogen-containing dissolution inhibiting compound added to the photosensitive composition (excluding the coating solvent) can be appropriately set depending on the amount of the acid generating compound described below, and preferably the acid generating compound and the dissolution inhibiting compound. The content molar ratio of basic nitrogen therein is set to 1/2 to 100/1, more preferably 1/2 to 50/1, further preferably 1/1 to 20/1, and particularly preferably 2/1. Set to 10/1.

Resin which is insoluble in water and soluble in an aqueous alkali solution (hereinafter, also referred to as alkali-soluble resin) As the alkali-soluble resin used in the present invention, for example, novolac resin,
Hydrogenated novolak resin, acetone-pyrogallol resin,
o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-Hydroxystyrene Copolymer, Partial O-Alkyl Compound to Polyhydroxystyrene Hydroxyl Group (for example, 5 to 30 mol% O-
Methylated product, O- (1-methoxy) ethylated product, O-
(1-Ethoxy) ethylated product, O-2-tetrahydropyranylated product, O- (t-butoxycarbonyl) methylated product, etc. or O-acylated product (for example, 5 to 30 mol% of o-acetylated product, O-). (T-butoxy) carbonyl compound, etc., styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing methacrylic resin and derivatives thereof. However, the present invention is not limited to these. Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partial O-alkylation of polyhydroxystyrene, Or an O-acylated product, a styrene-hydroxystyrene copolymer, or an α-methylstyrene-hydroxystyrene copolymer. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

As the predetermined monomer, phenol, m
Cresols such as -cresol, p-cresol and o-cresol, xylenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and 2,3-xylenol, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, Alkoxyphenols such as -methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol, 2-methyl-4-isopropyl Fenault Bis-alkylphenols etc., m
Hydroxychloro compounds such as -chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or as a mixture of two or more, but are not limited thereto. It is not something to be done.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, 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 their acetal compounds, such as chloroacetaldehyde diethyl acetal, among which formaldehyde is used Is preferred. These aldehydes are used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

The novolak resin thus obtained preferably has a weight average molecular weight in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred are 2,000-20,
000. The weight average molecular weight of the polyhydroxystyrene other than the novolac resin, its derivative, and the copolymer is 2000 or more, preferably 5000.
~ 200,000, more preferably 10,000-1000
00. Further, from the viewpoint of improving the heat resistance of the resist film, 25000 or more is preferable. here,
The weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography. In the present invention, these alkali-soluble resins may be used as a mixture of two or more kinds. The amount of alkali-soluble resin used is
5 based on the total weight of the photosensitive composition (excluding the solvent)
It is 0 to 97% by weight, preferably 60 to 90% by weight.

Compounds Generating Acid upon Irradiation with Actinic Rays or Radiation Compounds used in the present invention to decompose to generate an acid upon irradiation with actinic rays or radiation include photoinitiators for photocationic polymerization and photoradical polymerization. The photo-initiator, photo-decoloring agent of dyes, photo-color-changing agent, or known light-generating compound used for micro resist or the like and a mixture thereof can be appropriately selected and used. .

For example, SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) etc., U.S. Pat.No.4,069,055
No. 4,069,056, Re 27,992, Japanese Patent Application No. 3-140,140
Salt, DCNecker etal, Macrom
olecules, 17, 2468 (1984), CSwen et al, Teh, Proc. Con
f.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Patent No.
Nos. 4,069,055 and 4,069,056, and phosphonium salts described in JVCrivello et al., Macromorecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 10
No. 4,143, U.S. Pat.Nos. 339,049, 410,201, JP-A-2-150,848, Iodonium salts described in JP-A-2-296,514, etc., JVCrivello et al.
JVCrivello et al. J. Org. Chem., 43, 3055 (1978), WRW
att etal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1
984), JVCrivello etal, Polymer Bull., 14,279 (198
5), JVCrivello etal, Macromorecules, 14 (5), 1141 (19
81), JVCrivello etal, J. PolymerSci., Polymer Chem.
Ed., 17,2877 (1979), European Patent Nos. 370,693, 3,902,1
No. 14, 233,567, 297,443, 297,442, U.S. Patent Nos. 4,933,377, 161,811, 410,201, 33
9,049, 4,760,013, 4,734,444, 2,833,827
No. 2,904,626, 3,604,580, 3,604,
No. 581 etc., sulfonium salt, JVCrivello etal, M
acromorecules, 10 (6), 1307 (1977), JVCrivello etal,
J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), etc., selenonium salts, CSwen et al., Teh, Proc. Conf.R
onium salts such as arsonium salts described in ad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 3,905,815,
JP-B-46-4605, JP-A-48-36281, JP-A-55-32070
No., JP-A-60-239736, JP-A-61-169835, JP-A-61-169835
1-169837, JP-A-62-58241, JP-A-62-212401,
JP-A-63-70243, organic halogen compounds described in JP-A-63-298339, etc., K. Meier et al., J. Rad.Curing, 13 (4), 26
(1986), TPGill et al., Inorg.Chem., 19, 3007 (198
0), D. Astruc, Acc.Chem.Res., 19 (12), 377 (1896), organometallics / organic halides described in JP-A-2-14145 and the like,
S. Hayase et al., J. Polymer Sci., 25, 753 (1987), E. Reich
manis etal, J.Pholymer Sci., Polymer Chem.Ed., 23,1 (1
985), QQZhu et al., J. Photochem., 36, 85, 39, 317 (1987),
B. Amit etal, Tetrahedron Lett., (24) 2205 (1973), DH
R. Barton et al., J. Chem Soc., 3571 (1965), PMCollins
et al, J. Chem. SoC., Perkin I, 1695 (1975), M. Rudinstein
etal, Tetrahedron Lett., (17), 1445 (1975), JWWalker
etal. J. Am. Chem. Soc., 110, 7170 (1988), SCBusman et al.
J. Imaging Technol., 11 (4), 191 (1985), HM Houlihan et.
al, Macormolecules, 21, 2001 (1988), PMCollins etal,
J. Chem. Soc., Chem. Commun., 532 (1972), S. Hayase et al., M
acromolecules, 18, 1799 (1985), E. Reichmanis et al., J. El.
ectrochem.Soc., Solid State Sci.Technol., 130 (6), F.
M. Houlihan et al., Macromolcules, 21, 2001 (1988), European Patent Nos. 0290,750, 046,083, 156,535, 271,85
1, 0,388,343, U.S. Pat.Nos. 3,901,710, 4,18
No. 1,531, JP-A-60-198538, photoacid generator having an o-nitrobenzyl-type protecting group described in JP-A-53-133022, M.TUNOOKAetal, Polymer Preprints Japan, 35 (8), G .
Berner et al, J. Rad. Curing, 13 (4), WJMijs et al, Coati
ng Technol., 55 (697), 45 (1983), Akzo, H. Adachi et al, P
olymer Preprints, Japan, 37 (3), European Patent 0199,672
No. 84515, No. 199,672, No. 044,115, No. 0101,12
No. 2, U.S. Pat.Nos. 618,564, 4,371,605, 4,431,7
No. 74, JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No. 3
Compounds which generate sulfonic acid upon photolysis, such as iminosulfonate described in JP-A-140109, etc.
-166544 and the like.

Further, a group capable of generating an acid by these lights,
Alternatively, a compound having a compound introduced into a main chain or a side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Rap
id Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Che
m., 152,153,163 (1972), JVCrivello et al, J. Polymer
Sci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
49,137, United States Patent No. 3914407, JP-A-63-26653,
JP-A-55-164824, JP-A-62-69263, JP-A-63-1460
No. 38, JP-A-63-163452, JP-A-62-153853, JP-A-63-146029 and the like can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
Compounds that generate an acid by light described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PA)
An S-triazine derivative represented by G2).

[0088]

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

[0090]

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[0091]

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[0092]

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

[0094]

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In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Here, preferable substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group and a halogen atom.

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

[0097] Z ^- represents a counter anion, for example BF ₄ ^{-,
_{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

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

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

[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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The onium salts represented by the general formulas (PAG3) and (PAG4) are known, and for example, JWKnap.
czyk etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok
etal, J. Org. Chem., 35, 2532, (1970), E. Goethas etal,
Bull.Soc.Chem.Belg., 73,546, (1964), HM Leicester,
J. Ame. Chem. Soc., 51, 3587 (1929), JVCrivello etal,
J. Polym. Chem. Ed., 18,2677 (1980), U.S. Pat.
It can be synthesized by the methods described in JP-A Nos. 8 and 4,247,473 and JP-A-53-101,331.

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

[0114]

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

[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.0 based on the total weight of the photosensitive composition (excluding the coating solvent).
It is used in the range of 0.01 to 40% by weight, preferably 0.0
It is used in an amount of 1 to 20% by weight, more preferably 0.1 to 5% by weight.

In the present invention, it is preferable to use the following acid-decomposable dissolution inhibiting compound together with the above basic nitrogen-containing dissolution inhibiting compound. This is preferable in that the discrimination is further improved and the resolution is improved. The acid-decomposable dissolution inhibiting compound used in the present invention has at least two groups capable of decomposing with an acid in its structure, and the acid-decomposable group is present at a position where the distance between the acid-decomposable groups is the longest. It is a compound having at least eight bond atoms other than. In the present invention, the acid-decomposable dissolution-inhibiting compound preferably has at least two groups capable of being decomposed by an acid in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, the acid-decomposable group A compound having at least 10, preferably at least 11, and more preferably at least 12 bonding atoms excluding the above, or a position where the distance between the acid-decomposable groups is the longest, having at least three acid-decomposable groups Is a compound having at least 9, preferably at least 10, and more preferably at least 11 bonding atoms excluding an acid-decomposable group. The preferred upper limit of the number of the bonding atoms is 50, more preferably 30. In the present invention, the acid-decomposable dissolution inhibiting compound is
Alkali-soluble resin having three or more acid-decomposable groups, preferably four or more, or two acid-decomposable groups, provided that the acid-decomposable groups are separated from each other by a certain distance or more. The dissolution inhibiting property against is significantly improved.

The distance between acid-decomposable groups in the present invention is represented by the number of via-bond atoms excluding acid-decomposable groups. The specific description of the distance between the acid-decomposable groups is the same as described above. 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 a group. Furthermore,
The acid-decomposable dissolution inhibiting compound of the present invention has a molecular weight of 3,000.
It is the following, preferably 500 to 3,000, and more preferably 500 to 2,500.

In a preferred embodiment of the present invention, groups capable of being decomposed by an acid, namely --COO--A ⁰ and --O--B ^0.
The group containing a group, -R ⁰ -COO-A ^0, or -Ar
Examples thereof include a group represented by —O—B ⁰ . Where A ⁰ is −
C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), -Si (R ⁰¹ ) (R ⁰² ).
(R ^{0 3} ) or —C (R ⁰⁴ ) (R ⁰⁵ ) —O—R ⁰⁶ group is shown. B ⁰ represents A ⁰ or a —CO—OA ⁰ group. Here, R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ , R ⁰⁵ , R ⁰ , and Ar have the same meanings as described above.

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a ketal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group or a tertiary group. And an alkyl ester group, a tertiary alkyl carbonate group, and the like. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, a tetrahydropyranyl ether group, and an acetal group.

The acid-decomposable dissolution inhibiting compound is preferably JP-A-1-289946 or JP-A-1-2899.
No. 47, JP-A-2-2560, JP-A-3-12895
9, JP-A-3-158855, JP-A-3-1793
No. 53, JP-A-3-191351, JP-A-3-200
No. 251, JP-A-3-200252, JP-A-3-20
0253, JP-A-3-200254, JP-A-3-2
0255, JP-A-3-259149, JP-A-3-259
279958, JP-A-3-279959, JP-A-4
JP-A-1650, JP-A-4-1651, JP-A-4-11
No. 260, JP-A-4-12356, JP-A-4-123
No. 57, Japanese Patent Application No. 3-33229, Japanese Patent Application No. 3-2307
No. 90, Japanese Patent Application No. 3-320438, Japanese Patent Application No. 4-251
No. 57, Japanese Patent Application No. 4-52732, Japanese Patent Application No. 4-1032
No. 15, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-107
No. 885, Japanese Patent Application No. 4-107889 and No. 4-1521
Compounds protected by bonding some or all of the phenolic OH groups of the polyhydroxy compound described in the specification such as No. 95 with the group shown above, —R ⁰ —COO—A ⁰ or B ⁰ group, included.

More preferably, JP-A-1-289946.
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
255, JP-A-3-259149, JP-A-3-27
9958, JP-A-4-1650, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
7, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
No. 5 using the polyhydroxy compound described in the specification.

In the present invention, preferred acid-decomposable dissolution-inhibiting compounds are compounds represented by the above general formulas [I] to [XVI], and preferred compound skeletons (1) to
Examples of (63) include compounds containing no basic group.

The amount of the acid-decomposable dissolution inhibiting compound used in the present invention is 3 to 50% by weight, preferably 5 to 35% by weight based on the total weight of the photosensitive composition (excluding the solvent).
% By weight.

In the present invention, a two-component system or 2.5
The same compounds as described above can be used as the compound that generates an acid by actinic rays or radiation used in the component-type chemically amplified resist. Further, as a resin having a group that decomposes with an acid used in a two-component or 2.5-component chemically amplified resist to increase the solubility in an alkali developing solution, the main chain or side chain of the resin, Alternatively, it is a resin having an acid-decomposable group in both the main chain and the side chain. Among them, a resin having a group which can be decomposed by an acid in a side chain is more preferable. Preferred group capable of decomposing by an acid, the -COOA ^0, a -O-B ⁰ group, more preferably, -R ⁰ -COOA ^0, or -A _r -
A group represented by O-B ^0. Where A ⁰ is −C
( ^R01 ) ( ^R02 ) ( ^R03 ), -Si ( ^R01 ) ( ^R02 )
(R ^{0 3} ) or —C (R ⁰⁴ ) (R ⁰⁵ ) —O—R ⁰⁶ group is shown. B ⁰ represents A ⁰ or a —CO—O—A ⁰ group (R ⁰ , R ^{01 to} R ⁰⁶ , and Ar are as defined above).

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group or a tertiary alkyl ester. Group, a tertiary alkyl carbonate group, and the like. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

[0132] Next, as the matrix resin in the case where the group capable of decomposing by an acid is bonded as a side chain, -OH or -COOH in the side chain, preferably -R ⁰ -COOH or -A _r -OH group It is an alkali-soluble resin that has. For example, the alkali-soluble resin can be used.

The alkali dissolution rate of these alkali-soluble resins was 170 measured by 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.).
A / sec or more is preferable. Especially preferably 330A
/ Sec or more (A is angstroms). Further, an alkali-soluble resin having a high transmittance for far ultraviolet light or excimer laser light is preferable from the viewpoint of achieving a rectangular profile. Preferably, the transmittance at 248 nm of a 1 μm film thickness is 20 to 80%. From this perspective,
Particularly preferred alkali-soluble resins are o-, m-, p-
Polyhydroxystyrene and copolymers thereof, hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, part of polyhydroxystyrene, O-alkylated or O-acylated product, styrene-hydroxystyrene copolymer, α -Methylstyrene-hydroxystyrene copolymer and hydrogenated novolak resin.

The resin having an acid-decomposable group used in the present invention is described in European Patent No. 254853 and JP-A No. 2-25.
No. 850, No. 3-223860, No. 4-251259.
As disclosed in US Pat. No. 6,086,098, an alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an alkali-soluble resin monomer having an acid-decomposable group bonded thereto is copolymerized with various monomers. Can be obtained.

Specific examples of the resin having an acid-decomposable group used in the present invention are shown below, but the present invention is not limited thereto.

[0136]

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[0137]

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[0138]

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The content of acid-decomposable groups is determined by the number of acid-decomposable groups in the resin (B) and the number of alkali-soluble groups not protected by acid-decomposable groups (S). B /
It is represented by (B + S). The content is preferably 0.01 to
0.5, more preferably 0.05 to 0.40, and still more preferably 0.05 to 0.30. B / (B + S)>
A value of 0.5 is not preferred because it causes film shrinkage after PEB, poor adhesion to the substrate and scum. On the other hand, B / (B + S) <
A value of 0.01 is not preferable because standing waves may be remarkably left on the pattern side wall.

The weight average molecular weight (Mw) of the resin having an acid-decomposable group is preferably in the range of 2,000 to 200,000. If the molecular weight is less than 2,000, the film loss is large due to the development of the unexposed portion. If the molecular weight exceeds 200,000, the dissolution rate of the alkali-soluble resin itself in alkali becomes slow and the sensitivity is lowered. More preferably, 5,
The range is from 000 to 100,000, and more preferably from 8,000 to 50,000. Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.

Two or more kinds of the resins having an acid-decomposable group in the invention may be mixed and used. The amount of these resins used in the present invention is 40 to 99% by weight, preferably 60 to 95% by weight, based on the total weight of the photosensitive composition (excluding the solvent). Further, in order to adjust the alkali solubility, an alkali-soluble resin having no acid-decomposable group may be mixed.

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

Further, a spectral sensitizer as described below is added to sensitize the photosensitive composition of the present invention to a longer wavelength region than the deep ultraviolet where the photoacid generator used has no absorption. Sensitivity can be given to the i or g line. Suitable spectral sensitizers include, specifically, benzophenone,
p, p'-tetramethyldiaminobenzophenone, p,
p'-tetraethylethylaminobenzophenone, 2-
Chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, setoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline,
N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,
9-benzanthrone, dibenzalacetone, 1,2-
Naphthoquinone, 3,3′-carbonyl-bis (5,7-
Dimethoxycarbonylcoumarin) and coronene, but are not limited thereto.

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving each of the above components and applied 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 in combination.

A surfactant may be added to the above solvents. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants such as polyoxyethylene sorbitan fatty acid esters such as acrylates and the like, 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,
Fluorinated surfactants such as SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic (co) polymerized polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. These surfactants may be added alone or in some combination.

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

As the developer for the photosensitive composition of the present invention,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and triethylamine and methyldiethylamine Use alkaline aqueous solutions such as triamines, alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pichelidine. be able to. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0148]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the contents of the present invention are not limited thereto.

Synthesis Example 1: Nitrogen-containing dissolution inhibiting compound (I-
1) 20 g of the following compound (1), 79 g of 50% dimethylamine aqueous solution, and 69 g of 37% formalin aqueous solution were added to ethanol 1
It was dissolved in 50 ml and heated under reflux for 5 hours. The reaction solution is water 2
The mixture was poured into a liter and the obtained viscous material was washed with water to obtain 27.6 g of the following compound (2). Compound (2) obtained
To DMAc (N, N-dimethylacetamide) 100 m
1 g, potassium carbonate 24.3 g, bromoacetic acid-t
-Butyl 34.3 g was added, and the mixture was heated with stirring at 120 ° C. for 4 hours. The reaction liquid was slowly added to 3 liters of water, and the obtained powder was filtered under reduced pressure to obtain 41 g of the target product (I-1). The structure was confirmed by NMR and HPLC.

[0150]

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Synthesis Example 2: Nitrogen-containing dissolution inhibiting compound (I-
5) 15 g of the following compound (4) and 26 g of 50% dimethylamine aqueous solution were dissolved in 50 ml of ethanol. To this solution, 23 g of 37% formalin aqueous solution was added dropwise over 30 minutes,
The mixture was heated under reflux for 5 hours. Pour the reaction solution into 1 liter of water,
The crystals obtained were washed with water and dried to obtain 16.1 g of the following compound (5). The obtained compound (5) was used as DMAc1.
This was dissolved in 00 ml, 12.1 g of potassium carbonate and 17.1 g of tert-butyl bromoacetate were added, and the mixture was heated with stirring at 120 ° C. for 4 hours. The reaction solution was slowly poured into 2 liters of water, and the obtained powder was filtered under reduced pressure to obtain the target product (I-5) in 2
Obtained in 2 g. The structure was confirmed by NMR and HPLC, and the product was a mixture of 3-substituted product, 2-substituted product and 1-substituted product.

[0152]

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

[Synthesis Example-2 of Dissolution Inhibitor Compound] α,
α ′, α ″ -tris (4-hydroxyphenyl) -1,3,
20 g of 5-triisopropylbenzene in diethyl ether
Dissolved in 400 ml. 3,4-
31.6 g of dihydro-2H-pyran and a catalytic amount of hydrochloric acid were added, and the mixture was reacted under reflux for 24 hours. After completion of the reaction, a small amount of sodium hydroxide was added and the mixture was filtered. The solvent of the filtrate was distilled off, and the obtained product was purified by column chromatography and dried, and the compound example (31: R was all TH)
P group).

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

[Synthesis Example-4 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-5 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. Thereafter, the reaction mixture was poured into 1.5 l of water and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 2/8 (volume ratio)), 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).

[Synthesis Example-6 of Dissolution Inhibitor Compound] α,
α ', α "-tris (4-hydroxyphenyl) -1,3,
20 g (0.042 mol) of 5-triisopropylbenzene was dissolved in 400 ml of tetrahydrofuran (THF). To this solution, 9.3 g (0.083 mol) of potassium t-butoxide was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 10 minutes, and then 19.5 g of di-t-butyl dicarbonate was added.
(0.087 mol) was added. The reaction was allowed to proceed at room temperature for 3 hours, the reaction solution was poured into ice water, and the product was extracted with ethyl acetate. The ethyl acetate extract is concentrated and subjected to column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-
As a result of fractional purification with hexane = 1/5 (volume ratio), 7 g of a compound example (31: 2 Rs are t-BOC groups, 1 R is a hydrogen atom) was obtained.

[Synthesis Example-7 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 placed in a three-necked flask and heated to 100 ° C. with stirring for 15 hours. It was made to react. Thereafter, the temperature was raised to 200 ° C., and the pressure was gradually reduced to 5 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 collected. The obtained novolak resin (NOV.3) had a weight average molecular weight of 7,100 (in terms of 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 thereto with stirring to precipitate a resin component. The upper layer was removed by decantation to collect the precipitated resin, which was heated to 40 ° C. and dried under reduced pressure for 24 hours to obtain an alkali-soluble novolak resin (NOV.
6) was obtained. The weight average molecular weight was 8000 (in terms of polystyrene).

85 g of m-cresol, 15 g of p-cresol, and 53 g of 37% aqueous formalin solution were placed in a three-necked flask, and well stirred while heating in an oil bath at 110 ° C., and 2.4 g of zinc acetate dihydrate was added. 5
Heating and stirring were performed for hours. Next, 100 g of the same cresol mixture and 47 g of formalin aqueous solution were successively charged into the same flask, and further heated and stirred for 1 hour.
The temperature was lowered to 0 ° C., and 0.2 g of oxalic acid was added. Again, the temperature of the oil bath was maintained at 110 ° C., and the reaction was carried out under reflux for 15 hours. Thereafter, the content was poured into water containing 1% hydrochloric acid, and the reaction product was extracted with ethyl cellosolve acetate. This was then transferred to a vacuum still, the temperature was raised to 200 ° C. and dewatered,
Further, distillation was performed under reduced pressure of 2 to 3 mmHg for 2 hours to remove residual monomers. The molten polymer was recovered from the flask, and the desired novolak resin (NOV.7, Mw = 7.5)
00).

Examples 1 to 22 and Comparative Examples 1 to 5 Resists were prepared using the compounds of the present invention shown in the above synthetic examples. Table 1 shows the prescription at that time.

[0165]

[Table 1]

The abbreviations used in Table 1 have the following meanings. <Polymer> () shows the molar ratio NOV.1-7 Novolac resin PHS / St p-hydroxystyrene / styrene copolymer (85/15) (weight average molecular weight 25,000) PHS / TBOCS p-hydroxystyrene / t-butoxy Carbonyloxystyrene copolymer (70/30) (weight average molecular weight 21,000) PHS / TBOMS p-hydroxystyrene / t-butoxycarbonylmethyloxystyrene copolymer (80/20) (weight average molecular weight 35,000) PHS / VP p-Hydroxystyrene / 4-vinylpyridine copolymer (97/3) (weight average molecular weight 18,000) PHS / AcST p-Hydroxystyrene / p-acetoxystyrene (80/20) (weight average molecular weight 12,000) PHS / OHS p -Hydroxystyrene / o-hydroxystyrene (80/20) (weight average molecular weight 32,000)

<Dissolution Inhibitor> BTBPP 2,2-bis (t-butoxycarbonyloxyphenyl) propane

<Acid-decomposable group in dissolution inhibitor>

[0169]

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<Comparison Amine Compound> Im Imidazole ANA Anthranilic Acid BAPM Bis (4-aminophenylmethane) 4VPy / VP 4-Vinylpyridine / Vinylphenol Copolymer (70/30) (Weight Average Molecular Weight 20,000) [Photosensitivity] Preparation and Evaluation of Composition] Each material shown in Table 1 was used as propylene glycol monomethyl ether acetate 9.5.
g, and filtered through a 0.2 μm filter to prepare a resist solution. This resist solution is applied on a silicon wafer using a spin coater, and the temperature is 120 ° C.
It was dried for 60 seconds on a vacuum adsorption type hot plate to obtain a resist film having a film thickness of 1.0 μm. 2 on this resist film
48nm KrF excimer laser stepper (NA =
0.45) was used for exposure. Immediately after the exposure and 1 hour after the exposure, heating was performed for 60 seconds on a vacuum adsorption type hot plate at 100 ° C., immediately, immersed in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and rinsed with water for 30 seconds. And dried. The profiles, sensitivities and resolving powers of the patterns thus obtained on the silicon wafer, which were subjected to heat treatment immediately after exposure and after 1 hour after exposure, were evaluated and compared as follows. Table 2 shows the results.

[Profile] The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist profile. [Sensitivity] Sensitivity was defined as an exposure amount for reproducing a 0.50 μm mask pattern. [Resolving power] The resolving power indicates a limit resolving power at an exposure amount for reproducing a 0.50 μm mask pattern.

[0172]

[Table 2]

From the results shown in Table 2, the resist of the present invention is capable of preventing acid diffusion and acid deactivation on the resist surface portion with the passage of time from the exposure to the heat treatment, and the dissolution inhibiting effect of the dissolution inhibiting compound. It can be seen that the positive photosensitive composition has a good profile, high sensitivity, and high resolution. On the other hand, in Comparative Examples 1 to 5, as shown in Table 2, it can be seen that the resolution and profile over time are poor as compared with the present invention.

[0174]

EFFECTS OF THE INVENTION The chemically amplified positive photosensitive composition of the present invention can easily and appropriately prevent the diffusion of acid and the deactivation of acid on the resist surface over time from exposure to heat treatment. In addition, the dissolution inhibiting effect of the dissolution inhibiting compound is maintained, and a positive photosensitive composition having a good profile, high sensitivity, and high resolution can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kazuya Uenishi 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd.

Claims (4)

[Claims] 1. A resin which is insoluble in water and soluble in an aqueous alkali solution,
A compound that generates an acid upon irradiation with actinic rays or radiation, and basic nitrogen, and a group that can be decomposed by an acid, and the solubility in an alkaline developer is increased by the action of the acid.
A positive photosensitive composition comprising a low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less. 2. A resin having a group that decomposes by the action of an acid to increase the solubility in an alkali developing solution, a compound that generates an acid upon irradiation with actinic rays or radiation, and basic nitrogen and an acid that decomposes Having a possible group, the solubility in an alkaline developer is increased by the action of an acid,
A positive photosensitive composition comprising a low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less. 3. A resin which is insoluble in water and soluble in an aqueous alkali solution,
A compound having a group capable of generating an acid upon irradiation with actinic rays or radiation, having a group decomposable by an acid, and having a solubility in an alkali developing solution increased by the action of the acid, a molecular weight of 3,000.
The following low-molecular-weight acid-decomposable dissolution-inhibiting compound, and basic nitrogen, and a group that can be decomposed by an acid, and the solubility in an alkaline developer is increased by the action of an acid,
A positive photosensitive composition comprising a low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less. 4. A resin having a group capable of decomposing by the action of an acid to increase the solubility in an alkali developing solution, a compound capable of generating an acid upon irradiation with actinic rays or radiation, and a group capable of decomposing by an acid. , A low molecular weight acid-decomposable dissolution-inhibiting compound having a molecular weight of 3,000 or less, whose solubility in an alkali developing solution is increased by the action of an acid, and basic nitrogen, and a group capable of decomposing by an acid, The solubility in it is increased by the action of acid,
A positive photosensitive composition comprising a low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less.