JPS61219951A - Positive type radiation sensitive composition - Google Patents

Abstract

PURPOSE:To obtain a resist superior in radiation sensitivity and high in dry etching resistance by obtaining a positive type radiation sensitive compsn. composed of a quinonediazide compd. and a deriv. of oxazine, benzothiazine, or the like. CONSTITUTION:The positive type radiation sensitive compsn. to be used as a resist high in radiation sensitivity and high in residual film retentivity can be obtained by incorporating (A) a quinonediazide compd., such as benzoquinonediazide sulfonate or naphthoquinonediazide sulfonate, and (B) at least one of a deriv. of 2H-pyrido[3,2-b]-1,4-oxazin-3[4H]-one, 10H-pyrido[3,2- b]-1,4-benzothiazine, urazole, hydantoin, barbituric acid, glycine anhydride, 1-hydroxybenzotriazole, alloxan, and maleimide.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a positive radiation-sensitive composition that is sensitive to radiation such as visible light, ultraviolet rays, electron beams, and X-rays. The present invention relates to a positive radiation-sensitive composition suitable as a resist with excellent dry etching properties and film retention rate.

Conventional technology In recent years, advances in semiconductor integrated circuit manufacturing technology have been remarkable, and the resists used for manufacturing highly integrated semiconductor integrated circuits are
There is a shift from negative-tone resists based on cyclized isoprene, which suffers from a large drop in resolution due to swelling, to positive-tone resists based on a combination of alkali-soluble resins and quinone diazide compounds, which exhibit less swelling.

Problems to be Solved by the Invention However, positive resists containing quinonediazide compounds require, for example, ultraviolet irradiation for a relatively long period of time, and have problems with their radiation sensitivity.

An object of the present invention is to improve the drawbacks of the above-mentioned conventional techniques and to provide a positive-working radiation-sensitive composition suitable as a resist that has excellent radiation sensitivity, good dry etching resistance, and a high residual film rate. be.

Means for Solving the Problems As a result of intensive research, the present inventors have found that a positive radiation-sensitive composition containing a quinone diazide compound and a specific compound has excellent radiation sensitivity and good dry etching resistance. The present invention was achieved by discovering that it has an even higher residual film rate.

That is, the present invention provides (a) a quinonediazide compound and (a) a quinonediazide compound;
b) 2H-pyrido(3,2-b)-1゜4-oxazin-3[4H]ones, 10H-pyrido(3,2-b)(
1,4]-benzothiazines, urazoles, hydantoins, barbylic acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, and maleimides. The present invention provides a positive radiation-sensitive composition that is sensitive to radiation such as visible light, ultraviolet rays, deep ultraviolet rays, electron beams, X-rays, ion beams, and molecular beams.

The quinonediazide compound (a) used in the present invention is, for example, benzoquinonediazide sulfonic acid ester, naphthoquinonediazide sulfonic acid ester, benzoquinonediazide sulfonic acid amide, naphthoquinonediazide sulfonic acid amide, etc., and known quinonediazide compounds may be used as they are. I can do it. More specifically, J, K
Written by osar'Light-5ensistive Sys
tems"339-3352. (1965), J
ohnWiley & 5ons (New Y
ork) and “Pho” by W. S. De Forest.
to-resist'50. (1975), McG.
RawHill, Inc., (New York), 4-quinonediazide compounds are included.

That is, 1,2-benzoquinonediazide-4-sulfonic acid phenyl ester, di(1',2'-benzoquinonediazide-4#-sulfonyl)-4°4'-dihydroxybiphenyl, 1,2-benzoquinonediazide-4- (N
-ethyl-N-β-naphthyl)-sulfonamide, 1.
2-naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1-(1',2'-naphthoquinonediazide-5'-sulfonyl)-3,5-dimethylpyrazole, 1,2-naphthoquinonediazide-5-sulfonic acid-4
'-Hydroxydiphenyl-4#-azo-β-naphthol ester, N, N-di(1°2-naphthoquinonediazide-5-sulfonyl)-aniline, 2-(1',2
'-naphthoquinonediazide-5'-sulfonyloxy)
-1-Hydroxy-anthraquinone, 2 moles of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4,4
Condensate with 1 mol of '-diaminobenzophenone, 1.2
- Condensate of 2 moles of naphthoquinonediazide-5-sulfonic acid chloride and 1 mole of 4,4'-dihydroxy-1゜1'-diphenylsulfone, 1 mole of 1,2-naphthoquinonediazide-5-sulfonic acid chloride and Puru 105971
Condensation product with mole, 1,2-naphthoquinonediazide-5-
(N-dihydroabiethyl)-sulfonamide and the like can be exemplified.

Also, Japanese Patent Publication No. 37-1953, No. 37-3627
Publication No. 37-13109, Publication No. 40-2612
Publication No. 6, Publication No. 40-3801, Publication No. 45-5604
No. 45-27345, No. 51-1301
Publication No. 3, JP-A-48-96575, JP-A-48-96575, JP-A No. 4B-6
Publication No. 3802, Publication No. 4B-63803, Publication No. 58-
Publication No. 75149, Publication No. 58-17112, Publication No. 59
Quinonediazide compounds described in JP-A-165053 and the like can also be used.

Furthermore, the following general formula (I), or the following general formula (II), (wherein a and b are the same or different and an integer of 3 or 4, l and m are the same or different and an integer of 0 to 3,
C is an integer of 1 to 4, n is an integer of 0 to 3, and (a
-1), (b-m) and (c-n) are all integers of 1 or more, R1, Rs and R1 are the same or different,
1.2-naphthoquinonediazide-4-sulfonyl group, 1
．． 2-naphthoquinonediazide-5-sulfonyl group or 1゜2-benzoquinonediazide-4-sulfonyl group, R
t , Rh , Re and Ro are the same or different and are hydrogen atom, halogen atom, alkyl group, aryl group, aralkyl group, alkoxy group, cyano group or nitro group, R
3, R4, R9 and R1° are the same or different and represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and R5 and R4 and R9 and RIG are carbon-
A ring can be formed by a carbon bond or an ether bond) The following general formula (1), (where n' is an integer of 2 to 4, 1 r is an integer of O to 3, m' is an integer of 1 to 4) An integer, k' is an integer from 1 to 4, and k
' +1 '+m' = 5, and R+z is the general formula (
1) It is also the same as R+ SRs and R1 in (U), and Rt3 is Rt, R& in general formula (I) or (II).
, Rs and R11, and Z represents methane or the residue of an aromatic compound. ) The following general formula (IV), or the following general formula (V), (wherein a#, b# and C# are the same or different, and 1
Integers of ~4, l#, m# and n# are the same or different, integers of 0 to 3, (a # Z # ), (b'-m
') and (C'-n#) are integers greater than or equal to 1, R1 and Rt
5 and Rlm are R+ of general formula (1) or (■),
Same as Rs, and R1, and Rt6, R1? and R19 is R2, R6 of general formula (1) or (II),
It is the same as R11 and R11, R2° represents an alkyl group, aryl group or aralkyl group, and Y represents an alkylene group or oxaalkylene group with or without a substituent. ) The following general formula (Vl), (wherein R□, R2t and R13 may be the same or different and represent a hydrogen atom, a halogen atom or an alkyl group, and D is the general formula (1) or (U) R8, R55
It is the same as R11 and R7, and the three Ds may be the same or different. ) and the like can also be used.

The 1,2-quinonediazide compound represented by the above general formula (1) is, for example, di(2,3,4-)lihydroxyphenyl)methane, 1,1-di(2,3°4-trihydroxyphenyl) Propane, 2,2-di(2,3,4-1-lihydroxyphenyl)propane, 1,1-di(2,3,
4-)lihydroxyphenyl)butane, 1,1-di(2
, 3,4-trihydroxy)cyclohexane, 1.1-
Di(2,3,4-lihydroxy)-4-oxacyclohexane, di(2,4,6-1-lihydroxyphenyl)methane, 1,1-di(2,4,6-trihydroxyphenyl) Propane, 2. 2-cy(2,4,6-)lihydroxyphenyl)propane, 1,1-di(2,4,6
-trihydroxyphenyl)butane, 1,1-di(2,
4,6-trihydroxyphenyl)cyclohexane, 1
．． 1-'; (2,4,6-trihydroxyphenyl)
-4-Oxacyclohexane, di(2,3,4-)dihydroxy-5-bromophenyl)methane, 2゜2-di(
2,4,6-dolihydroxy-3-chlorophenyl)propane, di(2,3,4-)dihydroxy-5-methylphenyl)methane, 2,2-(2,4,6-)dihydroxy-3-methyl ) Propane, di(2,3,4-)dihydroxy-5-cyanophenyl)methane, 2,2-di(2,4°6-dolihydroxy-3-nitrophenyl)
Polyhydroxy compounds such as propane, di(1,2,3,4-tetrahydroxyphenyl)methane, 2,2-di(1,2,3,5-tetrahydroxyphenyl)propane and 1,2-naphthoquinonediazide- 5-sulfonyl chloride, ■, 2-naphthoquinonediazide 4-sulfonyl chloride or 1゜2-benzoquinonediazide-4-
It can be obtained by condensing with sulfonyl chloride at an equivalent ratio of 0.125 to 1.

The 1,2-quinonediazide compound represented by the above general formula (n) is, for example, 2,3.4-)dihydroxydiphenylmethane, 2,4.6-)dihydroxydiphenylmethane, 2.3.4-)dihydroxy-5- Chlorodiphenylmethane, 2,4.6-dolihydroxy-3-bromodiphenylmethane, 2.3.4-)dihydroxy-5-methyldiphenylmethane, 2.4.6-)dihydroxy-3
-Cyanodiphenylmethane, 2.3.4-)dihydroxy-5-nitrodiphenylmethane, 2,3゜4-trihydroxy-4'-methyldiphenylmethane, 2,4.6
-) dihydroxy-4'-methyldiphenylmethane, 2
, 3.4-trihydroxy-4'-t-butyldiphenylmethane, 2,3゜4.5-tetrahydroxy-phenylmethane, 2゜3.4.6-tetrahydroxydiphenylmethane, 2.5-dihydroxydiphenylmethane, 2
．． 4-dihydroxydiphenylmethane, 2.4-dihydroxy-4'-methyldiphenylmethane, 2゜5-dihydroxy-4'-t-butyldiphenylmethane, 1-
(2,3,4-)dihydroxy)-1-phenylpropane, 1-(2,4,6-trihydroxyphenyl)-
1-phenylpropane, 1-(2,3,4-trihydroxy-5-chloro)-1-phenylpropane, 1-
(2,3,4-trihydroxy-5-methyl)-1-phenylpropane, 1-(2,4,6-1-dihydroxy-3-cyanophenyl)-1-phenylpropane, 1-
(2,3,4-)dihydroxy-5-nitrophenyl)
-1-phenylpropane, l-(2,3゜4-trihydroxyphenyl)-1-(p-1-lyl)propane, 1
- (2,4,6-)dihydroxyphenyl)-1-(
4-t-butylphenyl)propane, 1-(2,3,
4,5-tetrahydroxyphenyl)-1-phenylpropane, ■-(2,3,4,6-tetrahydroxy)-
1-phenylpropane, 1-(2,5-dihydroxy)-1-phenylpropane, 1-(2,4-dihydroxy)-1-phenylpropane, L-(2,4-dihydroxyphenyl)-1-(p -) Polyhydroxy compounds such as propane and 1,2-naphthoquinonediazide-
5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, or 1,2-benzoquinonediazide-4-sulfonyl chloride in an equivalent ratio of 0.1.
It can be obtained by condensing 25-1.

1 represented by the above general formula (1) or (II).

Details of the 2-quinonediazide compound are described in Japanese Patent Application No. 58-230328 filed by the present applicant.

The 1,2-quinonediazide compound represented by the above general formula (I [゜3.4-1-dihydroxybenzoyl)benzene, m-bis(2,4,6
-1-dihydroxybenzoyl)benzene, p-bis(
4-hydroxy-3-chlorobenzoyl)benzene, p
-bis(2,3゜4-trihydroxy-5-methylbenzoyl)benzene, p-bis(2,4,6-)dihydroxy-3-nitrobenzoyl)benzene, p-bis(2
,3,4-1-dihydroxy-5-cyanobenzoyl)
Benzene, 1,3,5-tris(2,5-dihydroxybenzoylbenzene, 1,2,3-tris(2,3,4
-trihydroxybenzoyl)benzene, 1,2.4-
1-Lis(2,4,6-trihydroxybenzoyl)benzene, 1,2゜4.5-tetrakis(2,3,4-1
-dihydroxybenzoyl)benzene, α,α′-bis(2°3.4-)dihydroxybenzoyl)-p-xylene, α,α′,α′-tris(2,3,4-trihydroxybenzoyl)mesitylene, 1.2-bis(2,3
, 4-trihydroxybenzoyl)naphthalene and 1,2-naphthoquinone diazide.
5-sulfonyl chloride, 1.2-naphthoquinonediazide-4-sulfonyl chloride or 1.2-benzoquinonediazide-4-sulfonyl chloride in an equivalent ratio of 0.0.
It can be obtained by condensation with 83 to 1, and the details are described in Japanese Patent Application No. 58-243583 filed by the present applicant.

The 1,2-quinonediazide compound represented by the above general formula (IV) is, for example, ethylene glycol di(2-hydroxybenzoate), diethylene glycol di(2,
3-dihydroxybenzoate), triethylene glycol-di(2,6-dihydroxybenzoate), ethylene glycol-di(3,4,5-)dihydroxybenzoate), diethylene glycol-di(2,4,6-
trihydroxybenzoate), triethylene glycoludi(2-hydroxy-3-methylbenzoate),
Ethylene glycol rouge (4-chloro-2-hydroxybenzoate), polyethylene glycol rouge (5-bromo 2-hydroxybenzoate), propylene glycol rouge (3-chloro-4-hydroxybenzoate), styrene glycol rouge (2-hydroxy- 3-methoxybenzoate), poly-10 pyrene glycoluge (2-hydroxy-5-methoxybenzoate), poly-3,3-bistarolologothyloxetane glycoluge (3-hydroxy-4-methoxybenzoate), 1.
3-propanedioludi(3゜4.5-1-dihydroxybenzoate), 1,4-butanedioludi(3
-hydroxybenzoate), polytetrahydrofuran glycol di(3,4,cJ-)dihydroxybenzoate), and 1,2-naphthoquinonediato-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride. Or 1.
It can be obtained by condensing with 2-benzoquinone diazide-4-sulfonyl chloride at an equivalent ratio of 0.17 to 1.

The 1,2-quinonediazide compound represented by the above general formula (V) is, for example, ethylene glycol-monomethyl-mono (3,4,5-) dihydroxybenzoate), ethylene glycol-monoethyl-mono (2,4,6- )
dihydroxybenzoate), diethylene glycol
Monoethyl-mono(2,3-dihydroxybenzoate), triethylene glycol-monoethyl-mono(3,
5-dihydroxybenzoate), ethylene glycol-monophenyl-mono(3,4,5-trihydroxybenzony)), 1,2-benzenedimethanol-monoethyl-mono(3,4,5-)dihydroxybenzoate), etc. p polyhydroxy compound and 1,2-naphthoquinonediazide-5-sulfonyl chloride, l,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-
It can be obtained by condensing benzoquinone diazide-4-sulfonyl chloride at an equivalent ratio of 0.3 to 1.

Details of the 1゜2-quinonediazide compound represented by the above general formula (IV) or (V) can be found in the applicant's Japanese Patent Application No.
It is described in the specification of No. 2521.

Examples of the 1,2-quinonediazide compound represented by the above general formula (V[) include 1.2.3-)lihydroxybenzene, 1,2.3-)dihydroxy-4-chlorobenzene, 1.2.3-) -) Lihydroxy-4-ethylbenzene, 1.2.3-trihydroxy-4,6-dichlorobenzene, 1.2.3-trihydroxy-4,5-dimethylbenzene, 'L2.4-trihydroxybenzene, 1 ．．
2.4-trihydroxy-5-bromobenzene, 1,2
゜4-trihydroxy-5-t-butylbenzene, 1.
3. Polyhydroxy compounds such as 5-1-lihydroxybenzene, 1,3゜5-trihydroxy-4-chlorobenzene, 1゜3.5-trihydroxy-4-isopropylbenzene and 1,2-naphthoquinonediazide. 5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-
It can be obtained by condensation with sulfonyl chloride or 1,2-benzoquinonediazide-4-sulfonyl chloride at an equivalent ratio of 0.3 to 1, and the details are described in the specification of Japanese Patent Application No. 167979/1989 filed by the present applicant. has been done.

In addition, 1,2-quinonediazide sulfonic acid of at least one natural pigment selected from α-pyrone compounds having a hydroxyl group, γ-pyrone compounds having a hydroxyl group, diazine compounds having a hydroxyl group, and quinone compounds having a hydroxyl group. Esters can also be used.

Examples of the α-pyrone compound having a hydroxyl group include hispidine, 2',3'-dioxy-dibenz-α-pyrone, ellagic acid, gluterdine, and osboraftone. Examples of the γ-pyrone compound having a hydroxyl group include Eunigen,
Brassillin, hematoxylin, euxanthone, gentimin, chrysin, tringin, a glycoside of chrysin,
Primethin, abigenin, abiin, a glycoside of abigenin, luteolin, quercetin, quercitrin, isoquercitrin, quercitrin, a glycoside of quercetin, rutin, hyperin, carangin, kaempferol,
Fisetin, morin, rhamnetin, myricetin, cycadoflavone, naringenin, brasilin, a glycoside of naringenin, sakuranetin, hesperitin, alpinone, daidzein, prunetin, prunidrine, a glycoside of prunetin, isogenin, a glycoside of isogenin. Examples include prunidrine, isogenin, and isogenin glycosides such as irisine, osazine, belargonidine, cyanidin, and leucodelphinidin. Examples of the diazine compound having a hydroxyl group include xanthopterin, leucopterin, entropterin, chrysopterin, and iodinine. Examples of the quinone compound having a hydroxyl group include polyboric acid, atromentin, leucomelone, muscarfine, osborein, nigerone, echituchrome A1 spinone A1 subinochrome N, alizarin, purpurin, emodin, carminic acid, kermesic acid,
Skylin, pyromycin, etc. can be mentioned.

The 1,2-quinonediazide sulfonic acid ester of the natural dye is a combination of the natural dye and 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1.2-naphthoquinonediazide-4-sulfonyl chloride, or 1.2-benzoquinonediazide-4. -sulfonyl chloride in an equivalent ratio of 0.
It can be obtained by condensing 3 to 1.

As the 1,2-quinonediazide sulfonic acid ester of the natural pigment obtained in this way, for example, hispirin-
1,2-naphthoquinonediazide-5-sulfonic acid diester, hisvidine-1. 2 = naphthoquinonediazide
5-sulfonic acid monoester, 2',3'-dioxy-
Dibenz-α-pyrone-1,2-naphthoquinonediazide-5-sulfonic acid diester, ellagic acid-1,2-naphthoquinonediazide-5-sulfonic acid tetraester, ellagic acid-1,2-naphthoquinonediazide-5-sulfonic acid triester, gluterdine-1,2-naphthoquinonediazide-5-sulfonic acid monoester, osporactone-1,2-naphthoquinonediazide-5-sulfonic acid monoester, eugenin-1,2-naphthoquinonediazide-5-sulfonic acid monoester ester, brasilin-1,
2-naphthoquinonediazide-5-sulfonic acid triester, hematoxylin-1,2-naphthoquinonediazide
5-sulfonic acid pentaester, hematoxylin-1,
2-naphthoquinonediazide-5-sulfonic acid tetraester, hematoxylin-1゜2-naphthoquinonediazide-5-sulfonic acid triester, hematoxylin-1,
2-naphthoquinonediazide-5-sulfonic acid diester, euxanthone-1,2-naphthoquinonediazide-5
-sulfonic acid diester, kentimine-1,2-naphthoquinonediazide-5-sulfonic acid diester, chrysin-1,2-naphthoquinonediazide-5-sulfonic acid diester, trangine-1,2-naphthoquinonediazide-
5-sulfonic acid diester, primethine-1,2-naphthoquinonediazide-5-sulfonic acid diester, abigenin-1,2-naphthoquinonediazide-5-sulfonic acid triester, abiin-1,2-naphthoquinonediazide-5-sulfonic acid Triester, luteolin-1゜2
-Naphthoquinonediazide-5-sulfonic acid triester, quercetin-1,2-naphthoquinonediazide-5-sulfonic acid pentaester, quercetin-1,2-naphthoquinonediazide-5-sulfonic acid tetraester, quercetin-1,2-naphtho Quinonediazide-5-sulfonic acid triester, quercetin-1,2-naphthoquinonediazide-5-sulfonic acid diester, quercetin-1゜2-naphthoquinonediazide-5-sulfonic acid monoester, quercetin-1,2-naphthoquinonediazide-4 −
Sulfonic acid tetraester, quercetin-1,2-benzoquinonediazide-4-sulfonic acid tetraester, quercitrin-1,2-naphthoquinonediazide-5-sulfonic acid tetraester, isoquercitrin-1,2-naphthoquinonediazide-5- sulfonic acid tetraester,
Quershiftrin-1,2-naphthoquinonediazide-5-
Sulfonic acid tetraester, rutin-1,2-nafdoquinonediazide-5-sulfonic acid diester, piperine-
1,2-naphthoquinonediazide-5-sulfonic acid tetraester, carangin-1,2-naphthoquinonediazide-5-sulfonic acid triester, kaempferol 1,2
-Naphthoquinonediazide-5-sulfonic acid triester, soicetin-1,2-naphthoquinonediazide-5=sulfonic acid triester, serine-1,2-naphthoquinonediazide-5-sulfonic acid tetraester, serine-1
, 2-naphthoquinonediazide-5=sulfonic acid pentaester, rhamnetin-1゜2-naphthoquinonediazide-
5-sulfonic acid triester, myricetin-1,2-naphthoquinonediazide-5-sulfonic acid pentaester,
Cycas flavone-1,2-naphthoquinone diazide-5-
Sulfonic acid tetraester, naringenin-1゜2-naphthoquinonediazide-5-sulfonic acid triester, naringin-1,2-naphthoquinonediazide-5-sulfonic acid diester, zakranetin-1,2-naphthoquinonediazide-5-sulfonic acid diester, hesperitin
1,2-naphthoquinonediazide-5-sulfonic acid diester, alpyran-1,2-naphthoquinonediazide-5
-sulfonic acid diester, catechin-1,2-naphthoquinonediazide-5-sulfonic acid tetraester, daidzein-1,2-naphthoquinonediazide-5-sulfonic acid monoester, prunetin-1゜2-naphthoquinonediazide-5-sulfonic acid diester, prunidrine-1,
2-naphthoquinonediazide-5-sulfonic acid diester, biligenin-1,2-naphthoquinonediazide-5-sulfonic acid diester, iridine-1,2-naphthoquinonediazide-5-sulfonic acid diester, osazine-1,
2-naphthoquinonediazide-5-sulfonic acid diester, belargonidine-1,2-naphthoquinonediazide-5
-Sulfonic acid triester, cyanidin-1,2-naphthoquinonediazide-5-sulfonic acid tetraester, leucodelphicodin-1,2-naphthoquinonediazide-
5-sulfonic acid pentaester, xanthopterin-1
゜2-naphthoquinonediazide-5-sulfonic acid diester, leucopterin-1,2-naphthoquinonediazide-
5-sulfonic acid triester, entropterin-1,
2-naphthoquinonediazide-5-sulfonic acid triester, chrysopterin-1゜2-naphthoquinonediazide-
5-sulfonic acid diester, iodinine-1,2-naphthoquinonediazide-5-sulfonic acid diester, polyboric acid-1,2-naphthoquinonediazide-5-sulfonic acid diester, atromenthine-1,2-naphthoquinonediazide-5-sulfonic acid triester ester, leucomelon-1,2-naphthoquinonediazide-5-sulfonic acid triester, muscarfine-1,2-naphthoquinonediazide-5-sulfonic acid diester, osborein-1
．． 2-naphthoquinonediazide-5-sulfonic acid triester, nigerone-1,2-naphthoquinonediazide-5-
Sulfonic acid monoester, Ekitsuchrome A-1゜2-
Naphthoquinonediazide-5-sulfonic acid tetraester, Subinone A-1,2-naphthoquinonediazide-5-sulfonic acid tetraester, Spinchrome N-1,2-
naphthoquinonediazide-5-sulfonic acid triester,
Alizarin-1゜2-naphthoquinonediazide-5-sulfonic acid diester, purpurin-1,2-naphthoquinonediazide-5-sulfonic acid diester, Emodin-1゜2-naphthoquinonediazide-5-sulfonic acid diester, carminic acid-1, 2-naphthoquinonediazide-5-sulfonic acid triester, kermesic acid-1,2-naphthoquinonediazide-5-sulfonic acid triester, skylin-1,2-naphthoquinonediazide-5-sulfonic acid hexaester, pyromycin-1,2 -naphthoquinonediazide-5-sulfonic acid triester, etc.
Details of the 1,2-quinonediazide sulfonic acid esters of these natural dyes are described in Japanese Patent Application No. 18287/1987 filed by the present applicant.

Furthermore, as described in JP-A-58-17112, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4- Sulfonyl chloride or 1,2-benzoquinonediazide-4-sulfonyl chloride at equivalent ratio o, ooi ~ 0.5
A resin condensed with can also be used as the quinonediazide compound (a).

These quinonediazide compounds can be used alone or in combination of two or more.

Compound (b) used together with the quinonediazide compound (a) in the positive radiation-sensitive composition of the present invention
is a compound having the following basic structure.

2H-pyrido(3,2-b)-1,4oxazine-3 [
4H]on(2H-Pyrido (3,2-b) -1,4-
oxazine-3[4H]oneH0-pyrido(3,
2-b) (1,4]-benzothiazine (10H-Pyrido (3,2-b) (1
, 4] benzothiazine) urazol (
Urazole Hydantoin Barbituric acid
Glycine anhydride
) l-hydroxybenzothizole (1-hydroxybenzothizole hy
(drate) Alloxan Maleimide H These compounds (b) may be derivatives of these compounds, that is, these compounds, and examples of derivatives of these compounds include 1-methylurazol, , 1-phenylurazole, 3-methylurazole, 3-p-tolylurazole, 5゜5-diphenylhydantoin, 5
, 5-dimethylhydantoin, 5-methyl-5-phenylhydantoin, 5-methyl-5-p-tolylhydantoin, l-methylhydantoin, l-phenylhydantoin, 1-methyl-5-methylhydantoin, 5-methylhydantoin, 5-ethyl-5-p-tolylhydantoin, 5,5-diethylhydantoin, 5-ethyl-5
-p-) Lylbarbituric acid, 5-nitrobarbituric acid, 5.5-dimethylbarbituric acid, 5.5-diphenylbarbituric acid, ■-methylglycine, I-phenylglycine, Examples include 2-methylglycine, 2.2-dimethylglycine, 5-methyl-1-hydroxybenzotriazole, 5.6-dimethyl-1-hydroxybenzotriazole, ■-methylalloxane, 1-phenylalloxane, 3-phenylmaleimide, etc. It will be done.

The amount of the compound (b) to be added is 1-100 parts by weight, preferably 4 to 60 parts by weight, per 00 parts by weight of the quinonediazide compound (i).If it is less than 1 part by weight, the radiation sensitivity of the composition will not be improved. On the other hand, if the amount exceeds 100 parts by weight, the film thinning phenomenon in the non-irradiated areas becomes large during development of the composition when used as a resist.

The positive radiation-sensitive composition of the present invention usually contains a film-forming resin. As this film-forming resin, an alkali-soluble resin is generally used, and examples of the alkali-soluble resin include an alkali-soluble novolak resin, polyhydroxystyrene or its derivatives, styrene-maleic anhydride copolymer, cellulose acetate hydrogen phthalate, polyvinyl Examples include hydroxybenzoate, polyhydroxybenzal, and carboxyl group-containing acrylic resin.

Among these alkali-soluble resins, particularly preferred are alkali-soluble novola resins and polyhydroxystyrene or derivatives thereof.

Here, the alkali-soluble novolak resin contains an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as "phenol") and an aldehyde, preferably an aldehyde per mole of the phenol! It is obtained by addition condensation under an acid catalyst at a ratio of 0.7 to 1 mole. The phenols used at this time include phenol, 0-cresol, m-cresol, p-cresol, 0-ethylphenol, m-ethylphenol, p-ethylphenol, 0-butylphenol, m-butylphenol, p-
7'Tylphenol, 2,3-xylenol, 2,4-
Xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,6-xylenol, p-phenylphenol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, hydroxydiphenyl, bisphenol A1 bisphenol C1 bis Examples include derivatives of phenols such as phenol S, gallic acid, gallic acid ester, α-naphthol, and β-naphthol. These phenols may be used singly or in combination, taking into consideration the alkali solubility of the novolac resin to be produced.

Examples of aldehydes include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.

As the acid catalyst, for example, inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, oxalic acid, and acetic acid are used.

For details of these alkali-soluble novolak resins, see JP-A No. 55-123614, JP-A No. 57-101834, JP-A No. 57-101833, and JP-A No. 5B-1711.
No. 2, US Pat. No. 4,404,357, and the like.

These alkali-soluble novolac resins may be those obtained by an addition condensation reaction of phenols and aldehydes and may be used as they are, or may be used after being subjected to appropriate post-treatment. As described in Japanese Patent Application No. 59-45146 of the present applicant, the post-treatment referred to here means, for example, that an alkali-soluble novolac resin synthesized according to a conventional method is treated with a polar solvent such as methanol, ethanol, acetone, etc. , methyl ethyl ketone, dioxane,
Dissolve in tetrahydrofuran etc., then add this solution to water.
List a treatment in which the resin content is precipitated by placing it in a polar solvent mixed precipitant or a non-polar solvent precipitant such as pentane or hexane, so that the mono- to trinuclear content of the alkali-soluble novolak resin becomes less than 10% by weight. Can be done.

In addition, examples of polyhydroxystyrene or its derivatives include poly-m-hydroxystyrene, poly-m-
Hydroxystyrene, poly-p-hydroxystyrene,
Poly-α-methyl-〇-hydroxystyrene, poly-α
Examples include -methyl-m-hydroxystyrene, poly-α-methyl-p-hydroxystyrene, and partially acetylated and silylated products thereof. The number average molecular weight of these polyhydroxystyrenes or their derivatives in terms of standard polystyrene is preferably 3,000 to 200,0.
00, particularly preferably 5,000 to 100,000.

In the positive radiation-sensitive composition of the present invention, the amount of the film-forming resin blended is generally 200 to 4.000 parts by weight, preferably 250 to 4.000 parts by weight, based on 200 parts by weight of the quinonediazide compound (iH00). If the amount of the film-forming resin is too large, the amount of the quinonediazide compound (a) will be relatively small, so the amount of carboxylic acid produced by the quinonediazide compound absorbing radiation will be reduced, and the resist When used as a coating film, it is impossible to differentiate the solubility of the irradiated and non-irradiated areas of the composition coating in a developer consisting of an alkaline aqueous solution.
Buttering becomes difficult.

On the other hand, when the amount of this compound decreases, the amount of quinonediazide compound (a) becomes relatively large, so when irradiated with radiation for a short time, most of the quinonediazide compound still remains in the same form, so it is difficult to use it as a resist. In this case, the insolubilization effect in a developer consisting of an aqueous alkaline solution is so high that it becomes difficult to develop a coating film of the composition, and the film-forming ability and mechanical properties of the coating film are reduced.

The positive radiation-sensitive composition of the present invention can be obtained by dissolving the quinonediazide compound (a), the compound (b), and a film-forming resin blended as necessary in an organic solvent.

Examples of the solvent used in this case include glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol dibutyl ether, and diethylene glycol dimethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate,
Cellosolve esters such as butyl cellosolve acetate, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexane, cyclopentanone, acetonylacetone, acetophenone, and isophorone, benzyl ethyl ether, 1°2 - Ethers such as dibutoxyethane and dihexyl ether, fatty acids such as caproic acid and caprylic acid, alcohols such as 1-octatool, 1-nonanol, 1-decanol, and benzyl alcohol) LtW
t, H ethyl acetate, butyl acetate, 2-ethylhexyl acetate, benzyl acetate, benzyl benzoate, diethyl oxalate, diptyl oxalate, diethyl malonate, dimethyl maleate, diethyl maleate, diptyl maleate, dibutyl phthalate, dimethyl phthalate , esters such as ethylene carbonate and propylene carbonate, and cyclic lactones such as γ-butyrolactone. These organic solvents are
One type or a combination of two or more types may be used.

The amount of this organic solvent used varies depending on the required film thickness when applying the composition liquid, but is generally 100 to 2,000 parts by weight, preferably 200 parts by weight, based on 100 parts by weight of the composition.
~1.500 parts by weight.

A surfactant or the like may be added to the positive radiation-sensitive composition of the present invention in order to improve the developability, coatability, and striation of the radiation-exposed area after forming a dry coating film. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene alkyl ether, and polyoxyethylene alkyl phenols such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether. Nonionic surfactants such as ethers and polyethylene glycol dialkyl ethers such as polyethylene glycol dilaurate and polyethylene glycol distearate, FTOP EF301, EF
303 (manufactured by Shinju Kasei ■), Megafac F171, F
173 (manufactured by Dainippon Ink ■), Asahi Guard AG71
0 (manufactured by Asahi Glass ■), a linear fluorine-based surfactant having a fluorinated alkyl group or perfluoroalkyl group exemplified in JP-A No. 57-178242, F-TOP EF352 (manufactured by Shinshuyo Kasei ■) ), Florado FC43
0, FC431 manufactured by Sumitomo 3M), Surflon S
-382,5CIOI 5C102,5C103,5C
Fluorine surfactants containing a fluorinated alkyl group or perfluoroalkyl group in the side chain such as IO4, 5C105, 5C106 (manufactured by Asahi Glass ■), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical ■), acrylic acid type or methacrylic acid System (co)polymer Polyflow Na75
, 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo ■), and the like. The blending amount of these surfactants is usually 0.0001 to 2% by weight, preferably 0.005 to 1% by weight, based on the solid content of the composition.

Furthermore, the positive radiation-sensitive composition of the present invention contains dyes and pigments in order to visualize the latent image in the radiation irradiated area and to reduce the effect of halation during radiation irradiation, and to improve adhesiveness. Adhesion aids can also be added to the adhesive.

Examples of dyes used here include methyl bioleft 2B (C1 42555), malachite green (C1
Magnetic 11005), Victoria Blue B (CIN144
045), Neutral Left (C1 50040)
, Solvent Yellow 2 (CINllI 1020)
, Solvent Yellow 6 (CINQ11390), Solvent Yellow 14 (C11 to 12055), Solvent Yellow 0-15 (CI-18820), Solvent Yellow 16 (C111h12700), Solvent Yellow 21 (CIINQ18690), Solvent Yellow D-
33 (CI fish 47000), solvent yellow 56
(C1111al1021), Solvent Orange 1
(CINal1920), Solvent Orange 2 (C
Solvent Orange 14 (C111)
h26020), Solvent Orange 40, Solvent Red 3 (C1 12010), Solvent Red 8
(CIllh12715), Solvent Red 23 (
C1 26100), Trubentrend 24 (C1 26100)
6105), Solventref F25 (ClNn26
110) ,') Ruhe: / Tre 7 Do 27 (C1 隘26
100), Solvent Red (C111h45170
B), Disperse Red 9 (C1 magnetic 11005), Oil Scarlet 3゜8 (C1 21260), Solvent Brown (C111h12020), Disperse Yellow 1 (C1 10345), Disperse Yellow 3 (C111hl1855), Disperse Yellow 4 (C111h12770), Disperse Yellow 8
(C1 27090), Disperse Yellow 42 (C
1 10338), Disperse Orange 1 (Cl 10338), Disperse Orange 1 (Cl 10338)
1080), Disperse Orange 3 (C1 magnetic 1100
5), Disperse Orange 5 (C111hlllO
O), Disperse Orange 11 (C1 Yang 6075
5), Disper 7, 1/ Rad 1 (C1 magnetic 11
110), Dispersed Red 4 (C1 Yang 60755)
, Dispersed Red 11 (C111h62015),
Oil-soluble dyes such as Dispersed Red 15 (C! 6071o), Dispersed Red 58 (CIN111135), disperse dyes or basic dyes, Miketon Fast.
Methine dyes such as Yellow 7G (manufactured by Mitsui Toatsu Dyes), Miketon Fast Orange 5R (manufactured by Mitsui Toatsu Dyes), Holon (manufactured by Sandoz), Macrolex Yellow 6G (manufactured by Bayer), stilbene, 4. Fluorescent brighteners such as 4-diaminostilbenesulfonic acid derivatives, coumarin derivatives, and pyrazoline derivatives, JP-A-59-142
Examples include hydroxyazo dyes described in Japanese Patent No. 538, and depending on the type of radiation, one type can be used alone or two or more types can be used in combination.

As mentioned above, the blending amount of these dyes that can be used in combination is 0.01% per solid content of the composition per dyestuff.
-6% by weight, preferably 0.3-4% by weight.

In addition, examples of adhesion aids include 3-aminopropyltriethoxysilane, vinyltrichlorosilane, 2-(
Examples include silicon compounds such as 3,4-epoxycyclohexylethyl) trimethoxysilane. The blending amount of these adhesion aids is from 0.001 to 0.001 per solid content of the composition.
4% by weight, preferably 0.01-2% by weight.

Furthermore, the positive radiation-sensitive composition of the present invention may also contain a storage stabilizer, an antifoaming agent, and the like, if necessary.

Examples of the developer for the positive radiation-sensitive composition of the present invention include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propyl Primary amines such as amines, diethylamine, di-n
- Secondary amines such as propylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and quaternary amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Aqueous solutions of alkalis such as grade ammonium salts, virol, piperidine, 1°8-diazabicyclo(5,4,
O”)-7-undecene, 1,5-diazabicyclo(4
, 3,0)-5-nonane and the like are used. When manufacturing integrated circuits where the use of metal-containing developers is a problem, it is preferable to use an aqueous solution of a quaternary ammonium salt or a cyclic amine.

Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant to the aqueous solution of the alkali can also be used as the developer.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Examples 1 to 12 and Comparative Example 1 10 g of an alkali-soluble novolac resin obtained by condensing a mixed cresol with a ratio of m-cresol to p-cresol of 6:4 and formaldehyde, and 2, 3.
2.6 g of a quinonediazide compound obtained by condensing 4-1-lihydroxybenzophenone and 1,2-naphthoquinonediazide-5=sulfonyl chloride and the compound (b) shown in Table 1 were mixed into cellosolve acetate-H5. A positive radiation-sensitive composition solution was prepared by dissolving the solution in .9 g and filtering through a membrane filter with a pore size of 0.2 μm. The obtained solution was applied onto a silicon wafer using a spinner so that the coating film thickness was 1.2 μm, and then the composition was baked in an air circulating oven kept at 90° C. for 25 minutes to obtain a composition coating. Ta.

This composition coating film has equal line width and space width (1L
/lS pattern) Using a test pattern mask, the mask was exposed to ultraviolet light using a PLA501F mask aligner manufactured by Canon ■, developed for 1 minute with a 2.4% by weight aqueous solution of tetramethylammonium hydroxide, and rinsed with running water. The sensitivity and resolution of this resist pattern were determined using an optical microscope. These results are also shown in Table 1.

Similar studies were conducted for Comparative Example 1, in which compound (b) was not added, and the results are also shown in Table 1.

Table 1 'l' 1) Sensitivity at which a 2 μm wide pattern of IL/Is is resolved.

*2) Minimum IL/Is pattern size to be resolved.

*3) Thickness tO1 of the composition coating film after pre-beta and thickness of the composition coating film with a width of 5 μm in IL/Is obtained by exposing and developing the amount shown in the sensitivity section of the table above. Calculated using the following formula based on t.

Remaining film rate (%) = t/t o This is a particularly excellent composition. In addition, the positive radiation-sensitive composition of the present invention can be used as a resist in a curing or hardening process in which the developed resist pattern is irradiated with radiation such as deep ultraviolet rays to harden the resist pattern. too,
The resist pattern is characterized by being difficult to deform. Due to these characteristics, the positive radiation-sensitive composition of the present invention can be suitably used as a resist for microfabrication during the production of integrated circuits.

Claims (1)

[Claims] (1) (a) Quinonediazide compound and (b) 2H
-pyrido[3,2-b]-1,4-oxazine-3[4
H]ones, 10H-pyrido[3,2-b][1,4]
-benzothiazines, urazoles, hydantoins,
A positive radiation-sensitive composition comprising at least one compound selected from the group of barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, and maleimides.