JPH05216235A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To provide the chemically amplified-type photosensitive composition small in film shrinkage due to baking after exposure and capable of forming a pattern good in profile and high in resolution. CONSTITUTION:The cheically amplified positive-type photosensitive composition comprises a dissolution inhibitor of formulae I or II or the like and an alkali- soluble resin and an acid-photogenerating agent. In formulae I and II, each of R01 to R03 are H or alkylene having 0 or S; each of R2, R3, R10, R11, and R12, is H or OH or alkyl or the like; and each of a-j is an integer of 0-5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a chemically amplified positive type photosensitive material used in semiconductor manufacturing processes such as lithographic printing plates and ICs, circuit substrates such as liquid crystals and thermal heads, and other photo application processes. It relates to a composition.

[0002]

2. Description of the Related Art As a positive photoresist composition, a composition containing an alkali-soluble resin and a naphthoquinonediazide compound as a photosensitive material is generally used. For example, U.S. Pat. No. 3,666,473 as "Novolak type phenolic resin / naphthoquinone diazide substituted compound",
U.S. Pat. No. 4,115,128 and U.S. Pat. No. 4,173,4
70, etc., and the most typical composition of "novolak resin / trihydroxybenzophenone-1,2-naphthoquinone diazide sulfonate composed of cresol-formaldehyde" is Thompson "Introduction to Microlithography" (LFTho).
mpson "Introduction to Microlithography") (ACS
Publication, No. 219, p112-121).

In such a positive photoresist, which basically consists of a novolac resin and a quinonediazide compound,
The novolac resin provides high resistance to plasma etching, and the naphthoquinonediazide compound acts as a dissolution inhibitor. When naphthoquinonediazide is irradiated with light, naphthoquinonediazide has a property of generating a carboxylic acid, losing its dissolution inhibiting ability, and increasing the alkali solubility of the novolak resin.

From this point of view, many positive type photoresists containing novolac resin and naphthoquinonediazide type photosensitive material have been developed and put to practical use from the viewpoint of 0.8 μm-2.
We have achieved sufficient results in line width processing up to about 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 resolution, 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 a novolac and a naphthoquinonediazide compound is used for pattern formation of lithography using far ultraviolet light or excimer laser light,
The strong absorption of novolak and naphthoquinonediazide in the far-ultraviolet region makes it difficult for light to reach the bottom of the resist, and only a tapered pattern with low sensitivity can be obtained.

One of means for solving such a problem is
U.S. Pat. No. 4,491,628, U.S. Pat. No. 4,996,13
No. 6, etc. are chemically amplified resist compositions. A chemically amplified positive resist composition produces 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 developer. It is a pattern-forming material that changes properties and forms a pattern on a substrate.

The positive type chemically amplified resist is a three-component system consisting of an alkali-soluble resin, a compound (photoacid generator) which generates an acid upon exposure to radiation and a dissolution inhibiting compound,
It can be roughly classified into a two-component system consisting of a resin having a group that becomes alkali-soluble upon reaction with an acid and a photoacid generator. Conventional chemically amplified resists (U.S. Pat. No. 4,491,628, U.S. Pat. No. 4,996,136, U.S. Pat. No. 4,101,323, etc.) have insufficient dissolution inhibiting properties, and therefore film The decrease is large and the resist profile is significantly deteriorated. In addition, since the thermal stability is poor, there is a problem that the resist film shrinks due to baking after exposure, and neither of these has reached a practical level.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a chemically amplified photosensitive composition which has a small profile of film shrinkage due to baking after exposure and has a good profile and high resolution.

[0009]

Means for Solving the Problems As a result of intensive studies made by the present inventors while paying attention to the above points, the object of the present invention is represented by at least one of the following general formulas [I] to [XI]. A chemically amplified positive photosensitive composition comprising a compound, an alkali-soluble resin, and a photoacid generator.

[0010]

[Chemical 9]

[0011]

[Chemical 10]

[0012]

[Chemical 11]

[0013]

[Chemical 12]

[0014]

[Chemical 13] The symbols in the above formula have the following meanings. R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ ; hydrogen atom or R ₀₅ -X-R ₀₆
-Group (provided that R ₀₅ is an alkyl group, R ₀₆ is an alkylene group,
X represents an oxygen atom or a sulfur atom, and in each molecule of [I] to [XI], at least one of R _{01 to} R ₀₄ is R ₀₅ -X-R _06.
-Group. ), R ₁ ; -CO-, -COO-, -NHCONH-, -N
HCOO -, - O -, - S -, - SO -, - SO 2 -,
-SO ₃ -or

[0015]

[Chemical 14] (G = 2 to 6, but at least one of R ₄ and R ₅ is an alkyl group when G = 2), R ₄ and R ₅ ; hydrogen atom, alkyl group, alkoxy group,-
OH, -COOH, -CN, halogen atom, -R ₆ -C
OOR ₇ or —R ₈ —OH, R ₆ , R ₈ ; alkylene group, R ₇ ; hydrogen atom, alkyl group, aryl group or aralkyl group, R ₂ , R ₃ , R _{9 to} R ₁₂ , R ₁₅ , R ₁₇ ~ R ₂₁ , R ₂₅ ~ R
₂₇ , R _{30 to} R ₃₂ , R _{37 to} R ₄₂ , R _{46 to} R ₄₉ and R ₅₁ ; hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, a halogen atom, a nitro group, a carboxyl group, a cyano group, or -N (R ₁₃₎ (R
₁₄ ) (R ₁₃ , R ₁₄ ; hydrogen atom, alkyl group, aryl group), R ₁₆ ; single bond, alkylene group or

[0016]

[Chemical 15] R _22, R _24; single bond, an alkylene group, -O -, - S-,
-CO- or Karubookishi group, R _23; a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, a nitro group, a hydroxyl group, a cyano group or a carboxyl group (provided that hydroxy group R ₀₅ -X-
It may be substituted with R ₀₆ -group. ), R ₂₈ , R ₂₉ ; methylene group, lower alkyl-substituted methylene group, halomethylene group or haloalkyl group, R _{33 to} R ₃₆ ; hydrogen atom or alkyl group, R _{43 to} R ₄₅ ; hydrogen atom, alkyl group, alkoxy group, Acyl group or acyloxy group, R ₅₀ ; hydrogen atom, R ₀₅ —X—R ₀₆ — group, or

[0017]

[Chemical 16] R ₅₂ , R ₅₃ ; hydrogen atom, lower alkyl group, lower haloalkyl group or aryl group, Y; —CO— or —SO ₂ —, Z, B; single bond or —O—, A; methylene group, lower alkyl substitution Methylene group, halomethylene group or haloalkyl group, E; single bond or oxymethylene group, aq, s, t, v, g1-i1, k1-m1, o1,
q1, s1, u1; an integer of 0 to 5, r, u, y, w, x, y, z, a1 to f1, p1, r
1, t1, v1 to x1; integer of 0 to 4, j1, n1; integer of 0 to 3, y1; integer of 3 to 8 (a to y1; when 2 or more, groups in () may be the same. Or may be different.), (A + b), (e + f + g), (k + l + m), (q + r + s), (w + x + y), (c1 + d
1), (g1 + h1 + i1 + j1), (o1 + p1), (s1 + t1) ≧ 1, (j1 + n1)
≤3, (r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1 + f
1), (p1 + r1), (t1 + v1), (x1 + w1) ≦ 4, (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.

The compounds of the general formulas [I] to [XI] of the present invention can be prepared according to FR van Heerden et al., Tetrahedron Lett., 6
61 (1978) by reacting the polyhydroxy compound of the general formulas [I '] to [XI'] with, for example, methyloxymethyl chloride in the presence of a basic catalyst in dichloromethane. ..

[0019]

[Chemical 17]

[0020]

[Chemical 18]

[0021]

[Chemical 19]

[0022]

[Chemical 20]

[0023]

[Chemical 21] R ₁ ; -CO-, -COO-, -NHCONH-, -N
HCOO -, - O -, - S -, - SO -, - SO 2 -,
-SO ₃ -or

[0024]

[Chemical formula 22] (G = 2 to 6, but at least one of R ₄ and R ₅ is an alkyl group when G = 2), R ₄ and R ₅ ; hydrogen atom, alkyl group, alkoxy group,-
OH, -COOH, -CN, halogen atom, -R ₆ -C
OOR ₇ or —R ₈ —OH, R ₆ , R ₈ ; alkylene group, R ₇ ; hydrogen atom, alkyl group, aryl group or aralkyl group, R ₂ , R ₃ , R _{9 to} R ₁₂ , R ₁₅ , R ₁₇ ~ R ₂₁ , R ₂₅ ~ R
₂₇ , R _{30 to} R ₃₂ , R _{37 to} R ₄₂ , R _{46 to} R ₄₉ and R ₅₁ ; hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, a halogen atom, a nitro group, a carboxyl group, a cyano group, or -N (R ₁₃₎ (R
₁₄ ) (R ₁₃ , R ₁₄ ; hydrogen atom, alkyl group, aryl group), R ₁₆ ; single bond, alkylene group or

[0025]

[Chemical formula 23] R _22, R _24; single bond, an alkylene group, -O -, - S-,
-CO- or Karubookishi group, R _23; a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, a nitro group, a hydroxyl group, a cyano group or a carboxyl group, R _28, R _29; methylene group, a lower alkyl Substituted methylene group, halomethylene group or haloalkyl group, R _{33 to} R ₃₆ ; hydrogen atom or alkyl group, R _{43 to} R ₄₅ ; hydrogen atom, alkyl group, alkoxy group, acyl group or acyloxy group, R ₅₀ ; hydrogen atom or

[0026]

[Chemical formula 24] R ₅₂ , R ₅₃ ; hydrogen atom, lower alkyl group, lower haloalkyl group or aryl group, Y; —CO— or —SO ₂ —, Z, B; single bond or —O—, A; methylene group, lower alkyl substitution Methylene group, halomethylene group or haloalkyl group, E; single bond or oxymethylene group, aq, s, t, v, g1-i1, k1-m1, o1,
q1, s1, u1; an integer of 0 to 5, r, u, y, w, x, y, z, a1 to f1, p1, r
1, t1, v1 to x1; integer of 0 to 4, j1, n1; integer of 0 to 3, y1; integer of 3 to 8 (a to y1; when 2 or more, groups in () may be the same. Or may be different.), (A + b), (e + f + g), (k + l + m), (q + r + s), (w + x + y), (c1 + d
1), (g1 + h1 + i1 + j1), (o1 + p1), (s1 + t1) ≧ 1, (j1 + n1)
≤3, (r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1 + f
1), (p1 + r1), (t1 + v1), (x1 + w1) ≦ 4, (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.

The three-component positive-working photosensitive material comprises 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, and the acid generated when exposed to light deprotects the acid-decomposable group, and conversely has the action of promoting solubility in alkali. Have. JP-A-63-27829 and JP-A-3-198059 disclose a dissolution inhibitor having naphthalene, biphenyl and diphenylcycloalkane as a skeletal compound, but they are insufficient in view of film shrinkage after baking, profile and resolution. is there.

The dissolution inhibitor of the present invention has the general formula [I]
Represented by [XI], these specific compounds use a skeleton compound that satisfies any of the following conditions which are not known in the related art, and the purpose of the present invention can be achieved for the first time. You can (1) A structure composed of two or more aromatic rings having a hydrogen-bonding linking group or a substituent. (2) A diphenyl structure having a linear alkylene chain having 2 or more carbon atoms or a branched alkylene chain having 4 or more carbon atoms as a linking group. (3) A structure having three or more aromatic rings and a structure having an indane or flavone skeleton.

Of these, the preferred one is when the skeleton compound satisfies any of the following conditions. (1) -CO -, - SO -, - SO 2 -, - SO 3 -,
A structure having -COO- and -NHCOO- as an aromatic ring linking group. (2) A diphenyl structure having a branched alkylene chain having 4 or more carbon atoms as a linking group. (3) A structure having 3 to 7 aromatic rings and a structure having an indane or flavone skeleton.

Among these, more preferred are those having 3 or more functional groups (the number of R ₀₅ —X—R ₀₆ — groups in one molecule). When the number of functional groups is 2 or less, the solubility in a solvent is lowered, and it is not preferable in terms of profile and resolution. The following compounds can be exemplified as the acid decomposable inhibitor, but the present invention is not limited thereto.

[0031]

[Chemical 25]

[0032]

[Chemical formula 26]

[0033]

[Chemical 27]

[0034]

[Chemical 28]

[0035]

[Chemical 29]

[0036]

[Chemical 30]

[0037]

[Chemical 31]

[0038]

[Chemical 32]

[0039]

[Chemical 33]

[0040]

[Chemical 34]

[0041]

[Chemical 35]

[0042]

[Chemical 36]

[0043]

[Chemical 37]

[0044]

[Chemical 38]

[0045]

[Chemical Formula 39]

[0046]

[Chemical 40]

[0047]

[Chemical 41]

[0048]

[Chemical 42]

[0049]

[Chemical 43]

[0050]

[Chemical 44] In the compounds represented by the general formulas [I] to [XI] used in the present invention, R _{01 to} R ₀₄ are hydrogen atoms or R ₀₅ —X—R ₀₆ — groups (R ₀₅ is an alkyl group, R ₀₆ is an alkylene. Group X is an oxygen atom or a sulfur atom). In the above dehydrochlorination reaction, a polyhydroxy compound of alkyloxy (or thio) alkylene chloride (general formula [I ']
Any number of R ⁵ —X—R ⁶ — groups can be introduced by varying the molar ratio to [XI ′]).

General formulas [I] to [XI] used in the present invention
The content of R ₀₅ —X—R ₀₆ — group in the compound represented by
-100% is preferable, and the range of 50% -100% is more preferable. When the R ₀₅ -X-R ₀₆ -group content is 30% or less, the effect of suppressing the dissolution of the alkali-soluble resin is small, and the film loss is large. Examples of the alkali-soluble resin used in the present invention include novolac resins, acetone-pyrogallol resins, polyhydroxystyrene, styrene-maleic anhydride copolymers, carboxyl group-containing methacrylic resins and derivatives thereof. It is not limited to these.

A particularly preferred alkali-soluble resin is a novolac resin. 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
-Cresols such as cresol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol,
Xylenols such as 2,3-xylenol, m-ethylphenol, p-ethylphenol, o-ethylphenol, pt-butylphenol, alkylphenols such as 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, p-butoxyphenol, etc. Alkoxyphenols, bisalkylphenols such as 2-methyl-4-isopropylphenol, 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 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 weight average molecular weight of the novolak resin thus obtained is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed area after development is large, and if it exceeds 30,000, the developing speed becomes small. Particularly preferred is the range of 2,000 to 20,000.

Here, the weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography. In the present invention, the use ratio of the compounds represented by the general formulas [I] to [XI] and the alkali-soluble resin is 100 parts by weight of the alkali-soluble resin, and the ratio of the general formulas [I] to
The amount of the compound represented by [XI] is 3 to 100 parts by weight, preferably 5 to 60 parts by weight. If the usage ratio is less than 3 parts by weight, the residual film rate is significantly reduced, and if it exceeds 100 parts by weight, the heat resistance and dry etching resistance of the resist are degraded.

As the compound used in the present invention, which decomposes upon irradiation with actinic rays or radiation to generate an acid, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization,
Photobleaching agents, photochromic agents of dyes, or known compounds that generate an acid by light used in micro resists and the like and mixtures thereof can be appropriately selected and used.

For example, SI Schlesinger, Photogr. Sci.
Eng., 18, 387 (1974), TS Bal et al, Polymer, 21,
423 (1980) etc., diazonium salt, U.S. Pat.
No. 9,055, No. 4,069,056, No. Re 27,992, and Japanese Patent Application No. 3-
140140 and other ammonium salts, DC Necker et a
l, Macromolecules, 17, 2468 (1984), CS Wen et al,
Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oc
t (1988), U.S. Pat.Nos. 4,069,055, 4,069,056 and the like, phosphonium salts, JV Crivello et al, Macr.
omorecules, 10 (6), 1307 (1977), Chem. & Eng. New
s, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent Nos. 339,049, 410,201, and Japanese Patent Laid-Open No. 2-150848.
No. 2, iodonium salts described in JP-A-2-296514, JV
Crivelloet al, Polymer J. 17, 73 (1985), JV Criv
ello et al. J. Org. Chem., 43,3055 (1978), WR W
att et al, J. Polymer Sci., Polymer Chem. Ed., 22,
1789 (1984), JV Crivello et al, Polymer Bull.,
14, 279 (1985), JV Crivello et al, Macromorecule
s, 14 (5), 1141 (1981), JV Crivello et al, J. Po.
lymer Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patent Nos. 370,693, 3,902,114, 233,567,
No. 297,443, No. 297,442, U.S. Pat.
, 161,811, 410,201, 339,049, 4,
760,013, 4,734,444, 2,833,827, German Patents 2,904,626, 3,604,580, 3,604,581, etc., sulfonium salts, JV Crivello et al, Macro
morecules, 10 (6), 1307 (1977), JV Crivello et al,
J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (197
9) selenonium salt described in, CS Wen et al, Teh,
Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (198
8) Onium salts such as arsonium salts described in U.S. Pat. No. 3,905,815, JP-B-46-4605, JP-A-48-36281
JP-A-55-32070, JP-A-60-239736, JP-A-61
-169835, JP-A-61-169837, JP-A-62-58241,
JP-A-62-212401, JP-A-63-70243, JP-A-63-298
Organic halogen compounds described in No. 339, K. Meier et a
l, J. Rad. Curing, 13 (4), 26 (1986), TP Gill et
al, Inorg. Chem., 19, 3007 (1980), D.Astruc, Acc.
Chem. Res., 19 (12), 377 (1896), organic metal / organic halides described in JP-A-2-161445, S. Hayase et a
l, J. Polymer Sci., 25, 753 (1987), E. Reichmanis
et al, J. Polymer Sci., Polymer Chem. Ed., 23, 1 (1
985), QQ Zhu et al, J. Photochem., 36, 85, 39, 3
17 (1987), B. Amit et al, Tetrahedron Lett., (24).
2205 (1973), DHR Barton et al, J. Chem Soc., 3
571 (1965), PM Collins et al, J. Chem. Soc., Per.
kin I, 1695 (1975), M. Rudinstein et al, Tetrahedro
n Lett., (17), 1445 (1975), JW Walker et al, J.
Am. Chem. Soc., 110, 7170 (1988), SC Busman et
al, J. Imaging Technol., 11 (4), 191 (1985), HM
Houlihan et al, Macoromolecules, 21, 2001 (1988),
PM Collins et al, J. Chem. Soc., Chem. Commun.,
532 (1972), S. Hayase et al, Macromolecules, 18, 1
799 (1985), E. Reichmaniset al, J. Electrochem. So
c., Solid State Sci. Technol., 130 (6), FM Houlih
an et al, Macromolecules, 21, 2001 (1988), European Patent Nos. 0290,750, 046,083, 156,535 and 271,
851, 0,388,343, U.S. Pat.No. 3,901,710,
4,181,531, JP-A-60-198538, JP-A-53-133022
, A photoacid generator having an o-nitrobenzyl type protecting group, M. TUNOOKA et al, Polymer Preprints Japan,
35 (8), G. Berner et al, J. Rad. Curing, 13 (4), W.
J. Mijset al, Coating Technol., 55 (697), 45 (1983)
, Akzo, H. Adachi et al, Polymer Preprints, Japa
n, 37 (3), European Patents 0199,672, 84515, 19
9,672, 044,115, 0101,122, U.S. Pat.
18,564, 4,371,605, 4,431,774, JP-A-6
4-18143, Japanese Patent Application Laid-Open No. 2-245756, Japanese Patent Application No. 3-140109, and other compounds that generate sulfonic acid by photolysis, represented by iminosulfonates, and JP-A-61-1665.
The disulfone compound described in No. 44 can be mentioned.

A compound in which an acid-generating group or a compound is introduced into the main chain or side chain of a polymer, for example, ME Woodhouse et al, J. Am. Chem. S.
oc., 104, 5586 (1982), SP Pappas et al, J. Imagi.
ng Sci., 30 (5), 218 (1986), S. Kondo et al, Makromo
l. Chem., Rapid Commun., 9,625 (1988), Y. Yamadaet
al, Makromol. Chem., 152, 153, 163 (1972), JV C
rivello et al, J. Polymer Sci., Polymer Chem. Ed.,
17, 3845 (1979), U.S. Patent No. 3,849,137, German Patent No. 3,914,407, JP-A-63-26653, JP-A-55-164824.
JP-A-62-69263, JP-A-63-1460387, JP-A-63-1
The compounds described in JP 63452, JP-A-62-153853, JP-A-63-146029 and the like can be used.

Further, VNR Pillai, Synthesis, (1), 1
(1980), A. Abad et al, Tetrahedron Lett., (47) 4555.
(1971), DHR Barton et al, J. Chem. Soc., (C), 3
29 (1970), U.S. Pat.No. 3,779,778, European Patent 126,71
Compounds which generate an acid by light described in No. 2 and the like can also be used. Among the compounds which decompose to generate an acid upon irradiation with actinic rays or radiation, those which are particularly effectively used are described below.

(1) An oxazole derivative represented by the following general formula (XII) substituted with a trihalomethyl group or an S-triazine derivative represented by the general formula (XIII). Where R ¹
Is a substituted or unsubstituted aryl group, alkenyl group, R
² is a substituted or unsubstituted aryl group, alkenyl group,
It represents an alkyl group or -CY ₃ . Y represents a chlorine atom or a bromine atom.

Specifically, the following compounds XII-1 to 8 and
Examples thereof include, but are not limited to, XIII-1 to XIII-1.

[0062]

[Chemical 45]

[0063]

[Chemical 46]

[0064]

[Chemical 47]

[0065]

[Chemical 48]

[0066]

[Chemical 49] (2) an iodonium salt represented by the following general formula (XIV),
Alternatively, a sulfonium salt represented by the general formula (XV). In the formula,
Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents are alkyl groups,
Examples thereof include haloalkyl group, cycloalkyl group, aryl group, alkoxy group, nitro group, carboxyl group, alkoxycarbonyl group, hydroxy group, mercapto group and 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 a carbon atom for the alkyl group. They are an alkoxy group, a carboxyl group, and an alkoxycarbonyl group of the numbers 1 to 8. Z ⁻ represents a counter anion, for example, BF ₄ ⁻ , As F ₆ ⁻ , P
F ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ⁻ , ClO ₄ ⁻ , CF ₃
Examples include, but are not limited to, condensed polynuclear aromatic sulfonate anions such as SO ₃ ⁻ , BPh ₄ ⁻ (Ph = phenyl), naphthalene-1-sulfonate anion, anthraquinone sulfonate anion, and sulfonate group-containing dye. It is not something that will be done.

Two of R ³ , R ⁴ and R ⁵ and Ar ¹ and Ar ² may be bonded to each other via a single bond or a substituent. The onium salts represented by the general formulas (XIV) and (XV) are known, and for example, JW Knapczyk et a
l, J. Am. Chem. Soc., 91, 145 (1969), AL Maycok
et al, J. Org. Chem., 35,2532 (1970), E. Goethas e
tal, Bull. Soc. Chem. Belg., 73,546, (1964), HM
Leicester, J. Ame. Chem. Soc., 51, 3587 (1929), J.
B. Crivello et al, J. Polym. Chem. Ed., 18, 2677 (1
980), U.S. Pat.Nos. 2,807,648 and 4,247,473,
It can be synthesized by the method described in JP-A-53-101,331.

As specific examples, the compounds XIV-1 to
20 and XV-1 to 34, but are not limited thereto.

[0070]

[Chemical 50]

[0071]

[Chemical 51]

[0072]

[Chemical 52]

[0073]

[Chemical 53]

[0074]

[Chemical 54]

[0075]

[Chemical 55]

[0076]

[Chemical 56]

[0077]

[Chemical 57]

[0078]

[Chemical 58]

[0079]

[Chemical 59]

[0080]

[Chemical 60]

[0081]

[Chemical formula 61]

[0082]

[Chemical formula 62]

[0083]

[Chemical 63]

[0084]

[Chemical 64] (3) A disulfone derivative represented by the following general formula (XVI) or an iminosulfonate derivative represented by the general formula (XVII). In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenyl group, or arylene group.

Specific examples include the compounds XVI-1 to
12 and XVII-1 to 12, but are not limited thereto.

[0086]

[Chemical 65]

[0087]

[Chemical 66]

[0088]

[Chemical 67]

[0089]

[Chemical 68]

[0090]

[Chemical 69]

[0091]

[Chemical 70]

[0092]

[Chemical 71]

[0093]

[Chemical 72] The amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.001 to 40% by weight based on the total weight of the photosensitive composition (excluding coating solvent). And preferably used in the range of 0.1 to 20% by weight. The photosensitive composition of the present invention may further contain a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, etc., if necessary.

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

Further, a spectral sensitizer as described below is added to the photosensitive composition of the present invention by sensitizing it to a wavelength region longer than deep ultraviolet where the photo-acid generator used has no absorption. It can have sensitivity to i or g rays. Specific examples of suitable spectral sensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene and 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 (5,5
7-dimethoxycarbonylcoumarin), coronene, and the like, but are not limited thereto.

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, 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, toluene, ethyl acetate, methyl lactate, ethyl lactate, N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran and the like are preferable, and these solvents are used alone or as a mixture.

Further, 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 nonylphenol ether, etc. Sorbitans such as polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Nonionic surfactants such as tate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, and other polyoxyethylene sorbitan fatty acid esters, Ftop EF301, EF303, EF352 (new Akita Kasei Co., Ltd., Megafac F171, F173 (Dainippon Ink Co., Ltd.), Florard 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 (Kyoeisha Oil and Fat Chemical Co., Ltd.)
Manufactured) 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 combination of several kinds. The photosensitive composition is coated on 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 a coater, and then exposed through a predetermined mask, A good resist pattern can be obtained by baking and developing.

The developer for the photosensitive composition of the present invention is as follows:
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate, and ammonia water, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and tertiary amines such as triethylamine and methyldiethylamine. Aqueous solutions of triamines, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and alkalis such as cyclic amines such as pyrrole and pyrelidine. Can be used.

Furthermore, alcohols and surfactants may be added to the aqueous solution of the above alkalis in appropriate amounts.

[0101]

EFFECT OF THE INVENTION The positive photosensitive composition of the present invention has little film shrinkage due to baking after exposure and has a good profile and high resolution.

[0102]

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

[0103]

[Examples 1 to 10] Each of the materials shown in Table 1 was made into diglyme 6
g, and filtered through a 0.2 μm filter to prepare a resist solution. This resist solution is 3000r.pm
Was coated on a silicone wafer by using a spin coater having a rotation speed of, and dried at 90 ° C. for 60 seconds on a vacuum adsorption type hot plate to obtain a resist film having a thickness of 1.0 μm.

[0104]

Comparative Examples 1 and 2 According to the method described in US Pat. No. 4,491,628, t-butoxycarbonyloxystyrene polymer and t-butoxycarbonyloxy-polymer were prepared.
[alpha] -Methylstyrene polymer was synthesized and Examples 1-10
A two-component positive type resist film was obtained by the same operation as described above.
The composition ratio at that time is shown in Table 1.

[0105]

[Comparative Examples 3 to 5] Compound di-t-butyl terephthalate, 4 described in European Patent 249,139
Examples 1 to 10 using -t-butoxy-p-biphenyl and t-butyl-2-naphthyl carbonate as dissolution inhibitors.
A three-component positive resist film was obtained by the same operation as described above.
The composition ratio at that time is shown in Table 1.

The abbreviations shown in Table 1 are as follows. <Polymer> NOV m / p = 45/55 Novolac (weight average molecular weight 6,000) PVP p-hydroxystyrene polymer (weight average molecular weight 9,600) TBOCS t-butoxycarbonyloxystyrene polymer
(Number average molecular weight 21,600) TBAMS t-Butoxycarbonyloxy-α-methylstyrene polymer (Number average molecular weight 46,900) TBNC t-Butyl-2-naphthyl carbonate <Photo acid generator> TPSFA (XV in the examples of photo acid generators) -3) TPSFS 〃 (XV-5) DPIFP 〃 (XIV-2) IPPS 〃 (XVI-12) PIMS 〃 (XVII-1) <Dissolution inhibitor> DTBTP Di-t-butyl terephthalate TBPBP 4-t-butoxy- p-Biphenyl TBNC t-Butyl-2-naphthylcarbonate 25 on this resist film through a test pattern mask.
Exposure was performed with 4 nm far-ultraviolet light. 110 ° C after exposure
Was heated for 60 seconds on the vacuum adsorption type hot plate, and immediately immersed in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed for 30 seconds and dried. The pattern on the silicone wafer thus obtained is observed with a scanning electron microscope,
The resist profile was evaluated. 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 shown as a relative value to the sensitivity of Comparative Example 1. The film shrinkage was expressed as a percentage of the ratio of the film thickness of the exposed part before and after the exposure. The resolving power represents a limiting resolving power at an exposure amount that reproduces a 0.70 μm mask pattern. Second
From the results in the table, 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. Table 1 Alkali-soluble resin Photo acid generator Dissolution inhibitor 1 NOV 1.5g TPSFA 0.1g Compound (2) 0.8g 2 NOV 1.5g TPSFS 0.1g Compound (7) 0.8g Actual 3 NOV 1.5g DPIFP 0.1g Compound (11) 0.8g 4 NOV 1.5g IPPS 0.1g Compound (17) 0.8g Application 5 NOV 1.5g PIMS 0.1g Compound (25) 0.8g 6 NOV 1.5g TPSFA 0.1g Compound (29) 0.8g Example 7 NOV 1.5g DPIFP 0.1g Compound ( 33) 0.8g 8 NOV 1.5g DPIFP 0.1g Compound (42) 0.8g 9 PVP 1.5g IPPS 0.1g Compound (13) 0.8g 10 PVP 1.5g TPSFS 0.1g Compound (33) 0.8g Ratio 1 TBOCS 1.0g TPSFA 0.2 g ─── 2 TBAMS 1.0g TPSFA 0.2g ─── Comparison 3 NOV 1.5g TPSFA 0.1g DTBTP 0.8g 4 NOV 1.5g TPSFA 0.1g TBPBP 0.8g Example 5 NOV 1.5g TPSFA 0.1g TBNC 0.8g Table 2 Resist pattern relative sensitivity Film shrinkage (%) Resolution (μm) profile 1 1.3 2 0.45 Good 2 1.5 3 0.42 Good Actual 3 1.5 2 0.40 Good 4 1.3 1 0.37 Good 51.4 2 0.37 Good 6 1.5 2 0.40 Good Example 7 1.6 1 0.35 Very good (vertical) 8 1.4 2 0.40 Good 9 1.5 2 0.42 Good 10 1.8 1 0.38 Very good (vertical) ratio 1 1.0 10 0.52 Taper 2 0.9 11 0.50 Taper comparison 3 1.1 8 0.50 Taper 4 1.1 7 0.50 Taper Example 5 1.1 9 0.52 Tapered NOV m / p = 45/55 Novolac (weight average molecular weight 6,000) PVP p-hydroxystyrene polymer (weight average molecular weight 9,600) TBOCS t-butoxycarbonyloxystyrene polymer
(Number average molecular weight 21,600) TBAMS t-Butoxycarbonyloxy-α-methylstyrene polymer (Number average molecular weight 46,900) TBNC t-Butyl-2-naphthyl carbonate <Photo acid generator> TPSFA (XV in the examples of photo acid generators) -3) TPSFS 〃 (XV-5) DPIFP 〃 (XIV-2) IPPS 〃 (XVI-12) PIMS 〃 (XVII-1) <Dissolution inhibitor> DTBTP Di-t-butyl terephthalate TBPBP 4-t-butoxy- p-Biphenyl TBNC t-Butyl-2-naphthylcarbonate 25 on this resist film through a test pattern mask.
Exposure was performed with 4 nm far-ultraviolet light. 110 ° C after exposure
Was heated for 60 seconds on the vacuum adsorption type hot plate, and immediately immersed in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed for 30 seconds and dried. The pattern on the silicone wafer thus obtained is observed with a scanning electron microscope,
The resist profile was evaluated. 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 as a relative value to the sensitivity of Comparative Example 1. The film shrinkage was expressed as a percentage of the ratio of the film thickness of the exposed part before and after the exposure. The resolving power represents a limiting resolving power at an exposure amount that reproduces a 0.70 μm mask pattern. Second
From the results in the table, 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. Table 1 Alkali-soluble resin Photo acid generator Dissolution inhibitor 1 NOV 1.5g TPSFA 0.1g Compound (2) 0.8g 2 NOV 1.5g TPSFS 0.1g Compound (7) 0.8g Actual 3 NOV 1.5g DPIFP 0.1g Compound (11) 0.8g 4 NOV 1.5g IPPS 0.1g Compound (17) 0.8g Application 5 NOV 1.5g PIMS 0.1g Compound (25) 0.8g 6 NOV 1.5g TPSFA 0.1g Compound (29) 0.8g Example 7 NOV 1.5g DPIFP 0.1g Compound ( 33) 0.8g 8 NOV 1.5g DPIFP 0.1g Compound (42) 0.8g 9 PVP 1.5g IPPS 0.1g Compound (13) 0.8g 10 PVP 1.5g TPSFS 0.1g Compound (33) 0.8g Ratio 1 TBOCS 1.0g TPSFA 0.2 g ─── 2 TBAMS 1.0g TPSFA 0.2g ─── Comparison 3 NOV 1.5g TPSFA 0.1g DTBTP 0.8g 4 NOV 1.5g TPSFA 0.1g TBPBP 0.8g Example 5 NOV 1.5g TPSFA 0.1g TBNC 0.8g Table 2 Resist pattern relative sensitivity Film shrinkage (%) Resolution (μm) profile 1 1.3 2 0.45 Good 2 1.5 3 0.42 Good Actual 3 1.5 2 0.40 Good 4 1.3 1 0.37 Good 51.4 2 0.37 Good 6 1.5 2 0.40 Good Example 7 1.6 1 0.35 Very good (vertical) 8 1.4 2 0.40 Good 9 1.5 2 0.42 Good 10 1.8 1 0.38 Very good (vertical) ratio 1 1.0 10 0.52 Taper 2 0.9 11 0.50 Taper comparison 3 1.1 8 0.50 Taper 4 1.1 7 0.50 Taper Example 5 1.1 9 0.52 Taper

Claims (1)

[Claims] 1. At least one of the general formulas [I] to [XI]
A chemically amplified positive photosensitive composition comprising a compound represented by any of the above, an alkali-soluble resin, and a photoacid generator. [Chemical 1] [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] In the formula, R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ ; hydrogen atom or R ₀₅ —X—R ₀₆
-Group (provided that R ₀₅ is an alkyl group, R ₀₆ is an alkylene group,
X represents an oxygen atom or a sulfur atom, and in each molecule of [I] to [XI], at least one of R _{01 to} R ₀₄ is R ₀₅ -X-R _06.
-Group. ), R ₁ ; -CO-, -COO-, -NHCONH-, -N
HCOO -, - O -, - S -, - SO -, - SO 2 -,
—SO ₃ — or embedded image (G = 2 to 6, but when G = 2, at least one of R ₄ and R ₅ is an alkyl group.) R ₄ and R ₅ ; hydrogen atom, alkyl group, alkoxy group,-
OH, -COOH, -CN, halogen atom, -R ₆ -C
OOR ₇ or —R ₈ —OH, R ₆ , R ₈ ; alkylene group, R ₇ ; hydrogen atom, alkyl group, aryl group or aralkyl group, R ₂ , R ₃ , R _{9 to} R ₁₂ , R ₁₅ , R ₁₇ ~ R ₂₁ , R ₂₅ ~ R
₂₇ , R _{30 to} R ₃₂ , R _{37 to} R ₄₂ , R _{46 to} R ₄₉ and R ₅₁ ; hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, a halogen atom, a nitro group, a carboxyl group, a cyano group, or -N (R ₁₃₎ (R
₁₄ ) (R ₁₃ , R ₁₄ ; hydrogen atom, alkyl group, aryl group), R ₁₆ ; single bond, alkylene group or R _22, R _24; single bond, an alkylene group, -O -, - S-,
-CO- or Karubookishi group, R _23; a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, a nitro group, a hydroxyl group, a cyano group or a carboxyl group (provided that hydroxy group R ₀₅ -X-
It may be substituted with R ₀₆ -group. ), R ₂₈ , R ₂₉ ; methylene group, lower alkyl-substituted methylene group, halomethylene group or haloalkyl group, R _{33 to} R ₃₆ ; hydrogen atom or alkyl group, R _{43 to} R ₄₅ ; hydrogen atom, alkyl group, alkoxy group, Acyl group or acyloxy group, R ₅₀ ; hydrogen atom, R ₀₅ —X—R ₀₆ — group or R ₅₂ , R ₅₃ ; hydrogen atom, lower alkyl group, lower haloalkyl group or aryl group, Y; —CO— or —SO ₂ —, Z, B; single bond or —O—, A; methylene group, lower alkyl substitution Methylene group, halomethylene group or haloalkyl group, E; single bond or oxymethylene group, aq, s, t, v, g1-i1, k1-m1, o1,
q1, s1, u1; an integer of 0 to 5, r, u, y, w, x, y, z, a1 to f1, p1, r
1, t1, v1 to x1; integer of 0 to 4, j1, n1; integer of 0 to 3, y1; integer of 3 to 8 (a to y1; when 2 or more, groups in () may be the same. Or they may be different.), (A + b), (e + f + g), (k
+ l + m), (q + r + s), (w + x + y), (c1 + d1), (g1 + h1 + i1 + j1),
(o1 + p1), (s1 + t1) ≧ 1, (j1 + n1) ≦ 3, (r + u), (w + z),
(x + a1), (y + b1), (c1 + e1), (d1 + f1), (p1 + r1), (t1 + v1),
(x1 + w1) ≦ 4, (a + c), (b + d), (e + h), (f + i), (g + j),
(k + n), (l + o), (m + p), (q + t), (s + v), (g1 + k1), (h1 + l
1), (i1 + m1), (o1 + q1), (s1 + u1) ≦ 5.