JPH06266107A - Positive photosensitive composition - Google Patents

Abstract

PURPOSE:To provide a positive photosensitive composition which realizes reduced shrinkage of the film at the time of performing the postexposure-baking, reduced wear of the film at the time of performing the development, good profiles and high resolving power. CONSTITUTION:The positive photosensitive composition contains (a) a resin that is insoluble in water but soluble in alkali aqueous solutions, (b) a compound that generates acid by irradiating it with an actinic or radioactive ray and (c) a low molecular weight, acid-decomposable, dissolution-inhibitory compound which has a <=3000 molecular weight and contains acid-decomposable groups, and the solubility of which in the alkali developer is increased by the action of acid. The compound (c) features in that it contains at least three acid- decomposable groups per molecule and between each of adjacent two of the acid-decomposable groups at least nine bonding atoms other than the acid- decomposable groups are container when the distance between the adjacent two acid decomposable groups is the longest and further at least three groups including the acid-decomposable groups are branched from the same one of the saturated carbon atoms.

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.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a positive type photosensitive composition having a good profile and a high resolution with less film shrinkage due to baking after exposure and film loss during development. That is.

[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 find out that an alkali-soluble resin, a photo-acid generator, and a dissolution inhibitor having an acid-decomposable group. In a positive chemical amplification system comprising a compound, the inventors have found that this can be achieved by using a low molecular weight acid-decomposable dissolution inhibiting compound that satisfies the following requirements as a dissolution inhibiting compound, and arrived at 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, In a positive photosensitive composition containing a low molecular weight acid-decomposable dissolution-inhibiting compound having a molecular weight of 3,000 or less, the solubility of which in an alkaline developer is increased by the action of an acid, the compound (c) is an acid. A compound having at least 3 groups capable of decomposing and having 9 or more bond atoms excluding the acid decomposable group at a position where the distance between the acid decomposable groups is the longest. A positive-working photosensitive composition is characterized in that at least three containing groups are branched based on the same saturated carbon atom.

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
Has at least three acid-decomposable groups in its structure,
A compound having at least 9, preferably at least 10 and more preferably at least 11 bonding atoms excluding the acid-decomposable group at the position where the distance between the acid-decomposable groups is the longest. Also, the preferable upper limit of the number of bonding atoms is 50, and more preferably 30. In the present invention, when the acid-decomposable dissolution inhibiting compound has 3 or more, preferably 4 or more acid-decomposable groups, if the acid-decomposable groups are separated from each other by a certain distance or more, the alkali-soluble resin The dissolution inhibiting property is remarkably improved. Incidentally, the distance between the acid-decomposable groups in the present invention, excluding the acid-decomposable group,
Indicated by the number of via-bonded atoms. 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.

[0012]

[Chemical 1]

The acid-decomposable dissolution-inhibiting compound of the present invention is a compound composed of a skeleton having one acid-decomposable group on one benzene ring, and has at least 3 groups containing the acid-decomposable group. Each is a compound that branches based on the same saturated carbon (carbon having a so-called SP ₃ hybrid orbital). In this case, the structure of the decomposable dissolution-inhibiting compound spreads spatially greatly, and the dissolution-inhibiting property with respect to the alkali-soluble resin is greatly improved. 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 ), -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—O—A ⁰ group.
R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R ^{05, which} may be the same or different, each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group,
⁰⁶ represents an alkyl group or an aryl group. However, R ⁰¹
At least two of R ⁰³ are groups other than hydrogen atom,
Further, two groups of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ may combine to form a ring. R ⁰ represents a divalent or higher aliphatic or aromatic hydrocarbon group which may have a substituent, and —Ar— represents a divalent or higher divalent aromatic group which may have a monocyclic or polycyclic substituent. Indicates an aromatic group.

Here, the alkyl group is preferably one having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, and cycloalkyl group. Is preferably a group having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and the alkenyl group is 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Four aryl groups are preferable, and the aryl group has 6 to 1 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthracenyl group.
Four is preferable. Further, a hydroxyl group as a substituent,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl groups, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group or a t-butoxy group,
Acyl such as methoxycarbonyl group, ethoxycarbonyl group and other alkoxycarbonyl groups, benzyl group, phenethyl group, cumyl group and other aralkyl groups, aralkyloxy group, 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.

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

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

[0018]

[Chemical 2]

[0019]

[Chemical 3]

Here, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same or different and each is a hydrogen atom, —R ⁰ —COO—A ⁰ or B.
⁰ group, R _{7 to} R ₁₁ , R _{13 to} R ₂₃ : the same or different, hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, aralkyl Oxy group, halogen atom, nitro group, carboxyl group or cyano group, R ₁₂ single bond, alkylene group, or

[0021]

[Chemical 4]

R _{24 to} R _27, which may be the same or different, are a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carbonyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aralkyl group or an aralkyloxy group. , an acyl group, an acyloxy group, an alkenyl group, alkenyloxy group, an aryl group, an aryloxy group or an aryloxycarbonyl group, wherein the substituent groups of each four identical symbols may not be the same group, R ₂₈ , R ₃₀ : may be the same or different, single bond, alkylene group, —O—, —S—, —CO—, or carboxyl group, R ₂₉ : hydrogen atom, alkyl group, alkoxy group, acyl group, 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 is also -R ⁰ -COO-a ⁰ Ku may be substituted by B ⁰ group, Y: -CO-, or -SO ₂ -, to l: 0 or an integer of 1 to 4, provided that groups in the case of 2 or more () is M, n, o, p, q: 0 or an integer of 1 to 3, which may be the same or different, provided that at least one of m, n, p, q represents 1.

[0023]

[Chemical 5]

[0024]

[Chemical 6]

[0025]

[Chemical 7]

Specific examples of preferable compound skeletons are shown below.

[0027]

[Chemical 8]

[0028]

[Chemical 9]

[0029]

[Chemical 10]

[0030]

[Chemical 11]

[0031]

[Chemical 12]

[0032]

[Chemical 13]

[0033]

[Chemical 14]

[0034]

[Chemical 15]

[0035]

[Chemical 16]

[0036]

[Chemical 17]

R in the compounds (1) to (30) is a hydrogen atom,

[0038]

[Chemical 18]

Represents However, at least three are groups other than hydrogen atoms, and the respective substituents R may not 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) 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.

The novolak resin thus obtained preferably has a weight average molecular weight of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed area after development is large, and if it exceeds 30,000, the developing speed becomes small. Particularly preferred is 2,000-20,
The range is 000. Here, the weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography.

Two or more 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.

(C) Compound that Generates Acid upon Irradiation with Actinic Rays or Radiation (Compound of the Invention (b)) Examples of compounds used in the present invention that decompose upon irradiation with actinic rays or radiation to generate an acid , A photo-initiator for photo-cationic polymerization, a photo-initiator for photo-radical polymerization, a photo-decoloring agent for dyes, a photo-discoloring agent, or a compound that generates an acid by known light used for micro resist and the like. The mixture can be appropriately selected and used. SI Schlesinger, Photogr.Sci.Eng., 18,387 (197
4), TSBal et al, Polymer, 21,423 (1980) and other diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,069,056
No., same Re 27,992, ammonium salts described in Japanese Patent Application No. 3-140,140, DC Necker et al, Macromolecules, 17, 24
68 (1984), CSWen et al, Teh, Proc.Conf.Rad.Curing AS
IA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055,
Phosphonium salts described in 4,069,056, JVCrivello
et al, Macromorecules, 10 (6), 1307 (1977), Chem. & Eng. Ne
ws, Nov.28, p31 (1988), European Patent 104,143, U.S. Pat.
llo et al, Polymer J. 17, 73 (1985), JVCrivello eta
lJOrg.Chem., 43, 3055 (1978), WRWatt et al, J. Polym
er Sci., Polymer Chem. Ed., 22, 1789 (1984), JVCrivel
lo etal, Polymer Bull., 14, 279 (1985), JVCrivello e
tal, Macromorecules, 14 (5), 1141 (1981), JVCrivello
et al, J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (197
9), European Patent Nos. 370,693 and 3,902,114, and 233,567.
No. 297,443, 297,442, U.S. Pat.No. 4,933,377
No. 161, 811, No. 410, 201, No. 339, 049, No. 4, 76
0,013, 4,734,444, 2,833,827, Dokoku Patent No.
2,904,626, 3,604,580, 3,604,581, etc., sulfonium salts, JVCrivello et al, Macromorecule
s, 10 (6), 1307 (1977), JVCrivello et al, J. PolymerSc
i., Polymer Chem. Ed., 17, 1047 (1979) and other selenonium salts, CSWen et al, Teh, Proc. Conf. Rad. Curing AS
IA, p478 Tokyo, Oct (1988) and other onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, Japanese Patent Publication No. 46-4605.
JP-A-48-36281, JP-A-55-32070, JP-A-60-2
39736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62-212401, JP 63-70243
No., organic halogen compounds described in JP-A-63-298339, K. Meier et al, J. Rad. Curing, 13 (4), 26 (1986), TP
Gill et al, Inorg. Chem., 19,3007 (1980), D.Astruc, Ac
c. Chem. Res., 19 (12), 377 (1896), and the organic metal / organic halides described in JP-A-2-161445, S. Hayase et al.
J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al, J. Ph
olymer Sci., Polymer Chem. Ed., 23,1 (1985), QQZhu et
al, J. Photochem., 36, 85, 39, 317 (1987), B. Amit et al, Tet
rahedron Lett., (24) 2205 (1973), DHR Barton et al., J.
Chem Soc., 3571 (1965), PMCollins et al, J. Chem. SoC.,
Perkin I, 1695 (1975), M. Rudinstein et al, Tetrahedron
Lett., (17), 1445 (1975), JWWalker et al J.Am.Chem.So
c., 110,7170 (1988), SCBusman et al, J. Imaging Techno
l., 11 (4), 191 (1985), HM Houlihan et al, Macormolecule
s, 21, 2001 (1988), PMCollins et al, J. Chem. Soc., Chem.
Commun., 532 (1972), S. Hayase et al, Macromolecules, 18,
1799 (1985), E. Reichmanis et al, J. Electrochem. Soc., So
lid State Sci.Technol., 130 (6), FMHoulihan etal, Ma
cromolcules, 21, 2001 (1988), European Patent No. 0290,750,
046,083, 156,535, 271,851, 0,388,343
No. 3,901,710, 4,181,531, U.S. Pat.
-198538, JP-A-53-133022, etc., a photo-acid generator having a 0-nitrobenzyl type protecting group, M.TUNOOKA et al.
Polymer Preprints Japan, 35 (8), G. Berner et al, J. Rad.
Curing, 13 (4), WJMijs et al, Coating Technol., 55 (69
7), 45 (1983), Akzo, H. Adachi etal, Polymer Preprints,
Japan, 37 (3), European Patents 0199,672, 84515, 19
No. 9,672, No. 044,115, No. 0101,122, U.S. 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 generate an acid by being decomposed upon irradiation with actinic rays or radiation, those which are particularly effectively used will be 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).

[0050]

[Chemical 19]

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.

[0052]

[Chemical 20]

[0053]

[Chemical 21]

[0054]

[Chemical formula 22]

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

[0056]

[Chemical formula 23]

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.

Also, 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.

[0062]

[Chemical formula 24]

[0063]

[Chemical 25]

[0064]

[Chemical formula 26]

[0065]

[Chemical 27]

[0066]

[Chemical 28]

[0067]

[Chemical 29]

[0068]

[Chemical 30]

[0069]

[Chemical 31]

[0070]

[Chemical 32]

[0071]

[Chemical 33]

[0072]

[Chemical 34]

[0073]

[Chemical 35]

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).

[0076]

[Chemical 36]

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.

[0078]

[Chemical 37]

[0079]

[Chemical 38]

[0080]

[Chemical Formula 39]

[0081]

[Chemical 40]

[0082]

[Chemical 41]

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

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

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

The photosensitive composition of the present invention is dissolved in a solvent that dissolves each of the above components and 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, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in a mixture.

A surfactant may be added to the above solvent. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as rate, F-top EF301, E 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora - de FC430, FC43
1 (manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC101, SC102,
Fluorine-based surfactants such as SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) polymerization polyflow No. 75, No. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like. The content of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solid content in the composition of the present invention. These surfactants may be added alone or in some combinations.

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

The developer for the photosensitive composition of the present invention is
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and tertiary amines such as triethylamine and methyldiethylamine. Use alkaline aqueous solutions such as 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 1N, preferably 0.01 to 0.5N, and more preferably 0.03 to 0.3 at a specified concentration.
Used in the N range. 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.

[0090]

【Example】

[Synthesis Example-1 of Dissolution Inhibitor Compound] 1,2,3 g of 1,3,3,5-tetrakis (4'-human-oxyphenyl) pentane was dissolved in 400 ml of tetra-human-rofuran. 22.5 g of potassium tert-butoxide was added to this solution under a nitrogen atmosphere.
After stirring for 10 minutes at room temperature, 45.8 g of di-tert-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 give a compound example (27: R is all t-BOC).
25.6 g was obtained.

[Synthesis Example-2 of Dissolution Inhibitor Compound] 1,3,3,
5-Tetrakis (4'-human oxyphenyl) pentane 22.0 g was added to diethyl ether 400 ml.
Dissolved in. To this solution, under nitrogen atmosphere, 3,4-dihydroxy-2H
-Peran 50.5g, catalytic amount of hydrochloric acid was added to
Reacted for hours. After the reaction was completed, 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 to obtain a compound example (27: R are all THP groups).

[Synthesis Example-3 of Dissolution Inhibitor Compound] 1,3,3,
5-tetrakis (4'-human oxyphenyl) pentane 22.0 g (0.050 mol) of N,
To 200 ml of N-dimethylacetamide solution, 33.2 g (0.24 mol) of potassium carbonate and t-bromoacetate were added.
Butyl 42.9 g (0.22 mol) was added, and the temperature was 120 ° C.
The mixture was stirred for 7 hours. Then, the reaction mixture was added to 1.5 l of water and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 3/7 (volume ratio)). White powder 3
9 g was obtained. According to NMR, this is an example compound (27: R
Were all —CH ₂ COOC ₄ H ₉ ^t groups).

[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 (8). : 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. 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. According to NMR, this is an example of a compound (29: R is all --CH ₂ --COO
-C ₄ H ₉ ^t group) was confirmed.

[Synthesis Example-6 of Dissolution Inhibitor Compound] 1,3,3,
22.0 g (0.050 mol) of 5-tetrakis (4'-human oxyphenyl) pentane was dissolved in 400 ml of tetrahydrofuran (THF). 16.8 g of potassium t-butoxide was added to this solution under a nitrogen atmosphere.
(0.15 mol) was added, and after stirring at room temperature for 10 minutes, 32.7 g (0.15 mol) of di-t-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 extract was concentrated and subjected to column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 1/5).
(Volume ratio)) as a result of fractional purification, the compound example (27: 3
18 g of each R is a t-BOC group and one R is a hydrogen atom.

[Synthesis Example-7 of Dissolution Inhibitor Compound] 1,3,3,
4-Tetrakis (4'-human oxyphenyl) pentane 44.1 g (0.10 mol) was dissolved in 250 ml of dimethylacetamide, and potassium carbonate 41.5 g (0.30 mol) and bromoacetic acid t-
58.5 g (0.30 mol) of butyl were 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 purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 1/5 (volume ratio)). As a result, the compound example (27: 3 R is -CH ₂ -COO-
35 g of a C ₄ H ₉ ^t group and one R is a hydrogen atom) were obtained.

[Synthesis Example of Novolac Resin] 40 g of m-cresol, 60 g of p-cresol, 49 g of 37% formalin aqueous solution and 0.13 g of oxalic acid were placed in a three-necked flask and heated to 100 ° C. with stirring for 15 hours. It was made to react. 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 18 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 Examples 1 and 2 t-butoxycarbonyloxystyrene polymer and t-butoxycarbonyloxy-α-methylstyrene polymer were synthesized according to the method described in US Pat. No. 4,491,628 to prepare a two-component positive type composition. A resist was prepared.
The prescription at that time is shown in Table 1.

Comparative Examples 3,4,5 The compound di-t-butyl terephthalate, 4-t-butoxy-p-, described in EP 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.

[0104]

[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) TBAMS t-Butoxycarbonyloxy-α-methylstyrene polymer (number average molecular weight 46,900)

<Dissolution Inhibitor> DTBTP Di-t-butyl terephthalate TBPBP 4-t-butoxy-p-biphenyl TBNC t-butyl-2-naphthyl carbonate

<Acid-decomposable group in dissolution inhibitor>

[0109]

[Chemical 42]

[Preparation and Evaluation of Photosensitive Composition] Each material shown in Table 1 was dissolved in 6 g of diglyme and filtered through a 0.2 μm filter to prepare a resist solution. This resist solution was applied onto a silicon wafer using a spin coater with a rotation speed of 3000 rpm, and dried on a vacuum adsorption type hot plate at 110 ° C. for 60 seconds to give a film thickness of 1.0.
A μm resist film was obtained. 248n on this resist film
mKrF excimer laser stepper (NA = 0.4
2) was used for exposure. After the exposure, it was heated on a vacuum adsorption type hot plate at 90 ° C for 60 seconds, and immediately 2.3
It was immersed in an 8% (1.19% for Examples 14 and 16) tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds and dried. The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist profile. The results are shown in Table 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. 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, and has a good profile and high resolution.

[0112]

[Table 2]

[0113]

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.

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. In a positive photosensitive composition containing a low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less, the solubility of which in a developing solution is increased by the action of an acid, the compound (c) is decomposed by an acid. Which has at least three groups capable of being
A compound having 9 or more bonding atoms excluding an acid-decomposable group, wherein at least three groups containing the acid-decomposable group are branched based on the same saturated carbon atom. -Type photosensitive composition.