TW538313B - Positive photoresist composition - Google Patents

Abstract

Provided is a positive photoresist composition which may decrease the occurrence of development deficiency during the manufacture of semiconductor devices. A positive photoresist composition comprises a resin which contains repeating units of a specific structure, the rate of the resin dissolving in an alkaline solution being increased by the action of an acid, and a compound which generates an acid upon irradiation with actinic rays or a radiation.

Description

538313 V. Description of the invention (1) Technical field The present invention relates to a positive-type anti-corrosion composition for ultra-fine microlithography engineering or other photoresist application engineering used in the manufacture of ultra-LSI or high-capacity microcrystalline wafers. More specifically, it relates to a positive-type photoresist composition with reduced display defects. 0 Advanced technology In recent years, in order to further increase the integration of integrated circuits, semiconductor substrates such as super LSIs must be made by half a micron. Ultra fine pattern processing with the following line width. In order to meet this necessity, the wavelength of the exposure device used in lithography is shortened, and far-violet external light or excimer laser light (X eC, KrF, ArF, etc.) is currently under review. When the lithographic resin pattern is formed in this wavelength range, the user is a chemically amplified resist. 0—Generally, chemically amplified resists can be divided into 2 component systems, 2.5 component systems, and 3 component systems. Wait for 3 categories. The two-component system is a combination of a compound that generates an acid by photodecomposition (hereinafter referred to as a photoacid generator) and a binder resin. 0 This binder resin is decomposed by the action of an acid, and has a resin in the molecule that makes the image visible. Resin that increases the solubility group (acid-decomposable group) in the liquid. The 2.5 component system is composed of a low-molecular compound having an acid-decomposable group in the 2 component system. The 3 component system contains a photoacid generator and The alkali-soluble resin and the above-mentioned low-molecular compound. The above-mentioned chemically amplified resist is suitable as a photoresist for ultraviolet or far-ultraviolet irradiation. However, fi ^,: must have additional characteristics corresponding to the requirements of j -3-. 538313 V. Description of the invention (2) Proposed combination of photoresist composition for A r F light source (partially hydroxylated styrenic resin) (meth) acrylic resin produces less acid by light Resistance composition. For example, JP-A No. 7-1, 99467, and No. 7-2, 52324. Japanese Unexamined Patent Publication No. 6-2 8 9 6 1 5 discloses a resin in which a tertiary carbon organic group is bonded to the oxygen ester of the carboxyl group of acrylic acid. In addition, Japanese Unexamined Patent Publication No. 7-2345 1 discloses that acrylate or fumarate is an acid-decomposable resin having a repeating structural unit, but the pattern appearance and the adhesion of the substrate are insufficient, and satisfactory performance cannot be obtained. . In addition, another resin has been proposed in which an alicyclic hydrocarbon site is introduced for the purpose of dry etching resistance. Japanese Patent Application Laid-Open No. 9-7 3 1 73, Japanese Patent Application Laid-Open No. 9-90637, Japanese Patent Application Laid-Open No. 10-ΐ 6 1 3 1 3 describes the use of a base-soluble group containing a cycloaliphatic group-protected structure, and the base A resist material that is an acid-sensitive compound that dissolves a soluble group into an alkali-soluble building block by dissociation of an acid. In addition, Japanese Unexamined Patent Publication Nos. 9-90637, 10-207069, and 10-2 7 4852 describe an antitumor composition containing an acid-decomposable resin having a specific lactam structure. The lithography process for manufacturing displays using design rules of 0.18 // m and 0.1 3 / ζ m, since most of the light with a wavelength of 193 nm is used as the exposure radiation, so it is not expected to contain ethylenic unsaturation. Resist polymer. Japanese Unexamined Patent Publication No. 10-10739 and Japanese Unexamined Patent Application No. 10-30740 show that those who can improve the transparency to the wavelength of 193nm, but it cannot be said to have high sensitivity. 538313 V. Description of the invention (3) Consider 0.1 3 // Insufficient anti-hunger performance such as insufficient resolution in lithography below m. Japanese Unexamined Patent Publication No. 1 0 _ 1 3 0 3 4 0 discloses a chemically amplified corrosion inhibitor of a tripolymer containing a specific repeating structural unit having an original norbornene structure on the main chain. Japanese Patent Application Laid-Open No. 1 丨 _ 3 0 5 4 4 4 discloses a resin containing a repeating structural unit having an adamantane structure in a side chain and a repeating structural unit having maleic anhydride. Further, Japanese Patent Application Laid-Open No. 1 1 to 09632 discloses the use of a resin containing a cycloaliphatic functional group containing an polar group and an acid-decomposable group as a radiation-sensitive material. However, this chemically amplified resist has defects during development, so there is no room for improvement. _Invention_ _Problems to be Solved Therefore, the object of the present invention is to provide a positive type photoresist composition which can reduce the occurrence of development defects when manufacturing a semiconductor device. The inventors have repeatedly studied the constituent materials of the positive-type chemically amplified resist composition, and found that the purpose of the present invention can be achieved by using an acid-decomposable resin having a repeating structure containing a specific structure and completed this invention. The above-mentioned object can be achieved by the following constitution. (1) A positive type photoresist composition, which is characterized by (A) -containing a repeating structural unit represented by the following general formula (1), the following general formula 538313 Resin showing a repeating structural unit and a repeating structural unit represented by the following general formula (II-2) and increasing the dissolution rate of an alkali developing solution by an acid action, and (B)-an acid is generated by active light or radiation Of compounds,

R

(I) [0013] [化 6]-(• ch2— ~

A one COO one W ⑴-2)

Ri -f ch2—C) —

In the general formula (I), Rn to R14 each independently represent a hydrogen atom or an alkyl group which may have a substituent, a represents 0 or 1, and in the general formula (Π-1), R represents a hydrogen atom or a methyl group. A represents a single bond, alone or in combination of two or more selected from the group consisting of alkylene, cycloalkyl, ether, thioether, carbonyl, and ester groups. 538313 V. Description of the invention (0 w means at least one Hydrocarbon R — ^ c- \: z,, — / 6 I 8 R11C1R1 of the alicyclic constituent RN RN represented by the following general formulae (ρ I) to (ρ VI)

2 R ly 一 ΪΟ--CH

I 2224 R R1XR22 >

5, 2 R ——CIR (pl ^ 26 * 727 〇 II II—C—CH—C—R28 I ^ 29 〇R \ '一 II, —c—〇—C ί * \ Z Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, or 2-butyl group. Z represents an atomic group necessary to form a carbon atom and an alicyclic hydrocarbon group. R j 6 ~ R2 () Each independently represents a linear or branched alkyl group (pV) with 1 to 4 carbon atoms (pV) (pV!) 538313 5. Description of the invention (0 or alicyclic hydrocarbon group, but at least one of R! 6 ~ RI 8 or R 1 9. Any of R2Q is an alicyclic hydrocarbon group, and R 2 1 to R 2 5 each independently represent a linear or branched chain or alicyclic hydrocarbon group having 1 to 4 carbon atoms, but at least R 2 1 to R 25 One is an alicyclic hydrocarbon group and one of R 2 3 and R 2 5 is a linear or branched chain or alicyclic hydrocarbon group having 1 to 4 carbon atoms, and R26 to R29 each independently represent a carbon number of 1 to 4 Straight or branched alkyl or alicyclic hydrocarbon groups, but at least one of R26 to R29 is an alicyclic hydrocarbon group. In the general formula (Π-2), Ri is the same as in the general formula (π-1). R! Is synonymous. R2 ~ R4 each independently represent a hydrogen atom or a hydroxyl group, but in R2 ~ R4 (2) The positive photoresist composition according to (1) above, wherein the resin (A) further contains a repeating structural unit represented by the following general formula (III),

Among them, "Z2" represents -0- or -N (R3) ·, R3 represents a hydrogen atom, a hydroxyl group or -OS〇2_R4_, and I represents an alkyl group, a halogenated alkyl group, a cycloalkyl group or a camphor residue. (3) The positive-type photoresist composition according to the above (1) or (2), further comprising (D) an organic basic compound, (E) a fluorine-based and / silicon-based surfactant. Invention Embodiment

538313 V. Description of the invention (7) The ingredients used in the present invention will be described in detail in the following. [1] (A) Resin that increases the dissolution rate in an alkali developing solution by an acid action (hereinafter also referred to as "acid-decomposable resin") General formula for repeating structural units of acid-decomposable resin (I) 'Rn ~ R, 4 represents a hydrogen atom or an alkyl group which may have a substituent,

The alkyl group of Rm ~ RI4 is preferably a carbon number of 1-12, and more preferably a carbon number of 1-10. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, and isobutyl. , 2-butyl, 3-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl are preferred. Examples of the substituent of the alkyl group include a hydroxyl group, an alkoxy group, and an alkoxyalkoxy group. These alkoxy and alkoxyalkoxy groups preferably have a carbon number of 4 or less. A is 0 or 1 in the general formula (I). In the general formula (11_ 丨) representing a repeating unit of an acid-decomposable resin, R1 represents a hydrogen atom or a methyl group. The alkylene group of A in the general formula (I I-1) is, for example, a group represented by the following formula. -[C (Rf) (Rg)] r- wherein R f and Rg each represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl, butyl and the like, and more preferably selected from methyl, ethyl, propyl, and isopropyl. Examples of the substituent of the substituted alkyl group include a mesityl group, a prime atom, and an oxygen group. The oxy group includes, for example, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group having a carbon number of 4 to 4. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r is an integer from 丨 to 10 538313 V. Description of the invention (8). In the general formula (I I-1), a cycloalkyl group of A is, for example, one having 3 to 10 carbon atoms, and there are cyclopentyl, cyclohexyl, and cyclooctyl. W of the general formula (II-1) represents at least one partial structure containing an alicyclic hydrocarbon represented by the general formulae (pI) to (pVi). The alkyl groups of R10 to R29 in the general formulae (pi) to (pVI) may be substituted or unsubstituted linear or branched alkyl groups having 1 to 4 carbon atoms. The examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl, and the like. Further, the other substituents of the alkyl group include, for example, 1 to 4 carbon atoms; t-oxyl, halogen atom (fluorine, chlorine, bromine, iodine), fluorenyl, fluorenyl, cyano, Hydroxyl, carboxyl, alkoxycarbonyl, nitro and the like. The alicyclic hydrocarbon group of R15 to R29 or the alicyclic hydrocarbon group which Z forms with a carbon atom may be monocyclic or polycyclic. Specifically, it is a base having a monocyclic, bicyclic, tricyclic, tetracyclic structure having a carbon number of 5 or more. Its carbon number is preferably from 6 to 30, and more preferably from 7 to 25. These alicyclic hydrocarbon groups may have a substituent. Examples of the structure of the alicyclic portion in the alicyclic hydrocarbon group are shown below. -10- 538313

538313

538313 V. Description of the invention (11) In the present invention, the preferred alicyclic moiety is gold-alkyl, normantyl, decalinyl residue, tricyclodecenyl, tetracyclododecyl, Protobornyl, cedar, alcohol, cycloheptyl, sulfanyl, hexadecyl, and cyclododecaline. Preferred are adamantyl, decalinyl, probornyl, cedarenol, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl. The substituents of these alicyclic hydrocarbon groups are, for example, alkyl groups, substituted alkyl groups, cycloalkyl groups, alkenyl groups, halogen atoms, fluorenyl groups, hydroxyl groups, carboxyl groups, and alkoxycarbonyl groups. The alkyl group is preferably a lower alkyl group such as methyl, ethyl, propyl, isopropyl, or butyl, and more preferably methyl, ethyl, propyl, or isopropyl. Examples of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. The alkoxy group (an alkoxy group including an alkoxycarbonyl group) includes, for example, one having 4 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Specific examples of the monomer of the repeating structural unit represented by the general formula (I) are shown below, but they are not limited thereto.

-13- 538313

538313 V. Description of Invention (13)

538313 V. Ling Cangming's Explanation (14)

-16-538313 5. Description of the invention (15) In the general formula (II-2), R is synonymous with R! Of the general formula (11-1). At least one of R2 to R4 represents a meridian group. The non-repeating structural unit represented by the general formula (I-2) is preferably a dihydroxy compound or a monohydroxy compound, and more preferably a dihydroxy compound. The (b) acid-decomposable resin of the present invention may further contain a repeating unit represented by the general formula (I Π). In the general formula (III), Z2 represents -0 or -N (R3)-. R3 represents a hydrogen atom, a radical, or -C) -S02-R4. R4 refers to the radicals, halogenated radicals, transport radicals or camphor residues. The above alkyl group of R4 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. Methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl. Examples of the halogenated alkyl group of R4 include trifluoromethyl, naphthalene sulfide butyl, pentafluorooctyl, and trichloromethyl. Examples of the cycloalkyl group of R4 include cyclopentyl, cyclohexyl, and cyclooctyl. Specific examples of the monomer of the repeating structural unit represented by the general formula (III) are shown below, but are not limited thereto. -17- 538313 V. Description of the invention (16 ^ rt)-0 ο [ΗΜ] ο

-18- 538313 V. Description of the invention (17)

-19-538313 V. Description of the invention (18) The acid-decomposable resin of component (A) is in addition to the above-mentioned repeating structural unit, in order to adjust the dry etching resistance or the standard developing solution suitability, the substrate adhesion, the resist shape, When the resolution, heat resistance, and sensitivity of the general requirements of the resist are used, copolymers with repeating units of various monomers can be used. The repeating unit is equivalent to, for example, the repeating unit of the following monomers, but is not limited by these households. This makes it possible to fine-tune the properties required for the above resins, in particular (1) solubility in coating solvents, (2) film forming properties (glass transition temperature), (3) alkali developability, (4) Around the membrane (choice of hydrophilic and hydrophobic, alkali-soluble groups), (5) Adhesion to the substrate of the unexposed part, (6) Dry-type full-saturation resistance. The comonomer has, for example, an addition selected from the group consisting of acrylates, methacrylates, ammonium acrylates, ammonium methacrylates, allyl compounds, vinyl ethers, and ethyl acetate. Form polymerizable unsaturated bonds. Specifically, for example, the following monomers can be used. Acrylates (the carbon number of the alkyl group is preferably from 1 to 10): alkyl acrylates, such as methyl acrylate, ethyl acrylate, propyl acrylate, pentyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, Octyl acrylate, 3-butyl acrylate, ethyl chloroacrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate Esters, pentaerythritol monoacrylate, -20-538313 V. Description of the invention (19) Benzyl acrylate, methoxybenzyl acrylate, methyl acrylate, tetrahydro methacrylate, etc. For example, the hospital base (the carbon number of the hospital base is preferably 1 ~ 10): methacrylate (such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, propyl methacrylate) , Amyl methacrylate Λ hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, ethyl methacrylate, octyl methacrylate, methacrylic acid 2- Hydroxyethyl ester, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate > 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylol monomethylpropionate Propane ester, pentaerythritol monomethacrylate, methacrylic acid methyl ester, tetrahydrofluorene methacrylate, etc.); acrylic acid amines such as fluorene methacrylate, N-alkyl fluorene methacrylate (the carbon number of the alkyl group is Carbon number 1 ~ 10 is preferred, for example, methyl, ethyl, propyl, butyl 3rd--butyl, heptyl, octyl, cyclohexyl, hydroxyethyl, etc.) \ Ν, Ν- dialkyl Ammonium acrylate (alkyl groups are 1 to 10 carbon atoms, such as methyl, ethylbutyl, isobutyl, ethylhexyl, cyclohexyl, etc.), N-hydroxyethyl-N-methacrylate , N-2-vinylamine ethyl-N-ethyl fluorenyl acrylate, etc. j methacrylic acid amines such as methacrylic acid amines, N-alkyl methyl acrylic acid amines (alkyl such as carbon Numbers from 1 to 10, such as methyl, ethyl, 3-butylethylhexyl, hydroxy Ethyl, cyclohexyl, etc.), Ν, Ν-dialkylmethylpropanamide (alkyl is ethyl, propyl, butyl, etc.), N-hydroxyethyl-Ν-methyl methyl Methacrylic acid methacrylate, etc .; -21-538313 V. Description of the invention (20) Allyl compounds are, for example, allyl esters (for example, allyl acetate, allyl hexanoate, allyl heptanoate, alkenyl laurate Propyl ester, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc.), allyloxyethanol, etc .; vinyl ethers such as There are alkyl vinyl ethers (such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxy vinyl ether, ethoxy vinyl ether, chlorinated ethyl vinyl ether, 1-methyl -2, 2-Dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylamino ethyl vinyl ether, diethylamino Ethyl vinyl ether, butylamino ethyl vinyl ether, benzyl vinyl ether, tetrahydrofluorenyl vinyl ether, etc.); vinyl esters such as vinyl butyrate, ethyl isobutyrate Esters, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl valerate, vinyl hexanoate, vinyl chloride chloride, vinyl dichloride, vinyl methoxyacetate, butoxyacetic acid Vinyl esters, ethylene vinyl acetate, vinyl lactate, vinyl / 3-phenylbutyrate, vinyl cyclohexyl carboxylate, etc .; dialkyl itaconates (such as dimethyl itaconate, itaconic acid) Diethyl acid, dibutyl itaconic acid, etc.); others include, for example, citric acid, itaconic acid, acrylonitrile, methacrylonitrile, and maleonitrile. Any other addition polymerizable unsaturated compound that can be copolymerized with the monomers of the above-mentioned various repeating structural units may be copolymerized. In acid-decomposable resins, the other repeating unit structures contain mol ratios of -22 to 538313. 5. Description of the invention (21): Oxygen plasma etching resistance, sensitivity, and pattern crack prevention of the desired resist. The resolution, heat resistance, etc. of the adhesiveness of the substrate, the appearance of the anti-corrosive agent, and the general requirements of the resist are appropriately set. The content of the repeating structural unit represented by the general formula (1) in the acid-decomposable resin is 25 to 70 mol%, preferably 28 to 65 mol%, and more preferably 30 to mol of all the repeating structural units. ~ 60 mol%. In the present invention, the content of the repeating structural unit represented by the general formula (II-1) in the acid-decomposable resin is 5 to 40 mol%, preferably 10 to 35 mol% of all the repeating structural units, More preferably, it is 15 to 30 mol%. In the present invention, the content of the repeating structural unit represented by the general formula (II-2) in the acid-decomposable resin is 3 to 30 mol%, preferably 5 to 25 mol% of all the repeating structural units, More preferably, it is 8 to 20 mol%. The content of the repeating structural unit represented by the general formula (I Π) in the acid-decomposable resin is 20 to 80 mole%, preferably 25 to 70 mole%, and more preferably 30 to 30 mole% of all the repeating structural units. ~ 60 旲%. In addition, the content of the resin in the repeating structural unit based on the monomers of the other copolymer components described above can also be appropriately set according to the desired resist performance, but in general, the general formulae (I), (II- 1) and (II-2) The total number of moles of the repeating structural unit is preferably 99 mole% or less, more preferably 90 mole% or less, and most preferably 80 mole%. . The molecular weight and weight average of the acid-decomposable resin (Mw ·· polystyrene conversion by gel permeation chromatography method), preferably 10,000 to 1,000,000, more The best is 1,500 to 500,000, and the most preferred is 2,000 to 200,000 -23 to 538313. 5. Description of the invention (22), the best is 2,500 to 100, 000. When the weight average molecular weight is larger, not only The heat resistance can be improved, and the developability can be reduced. The balance of these properties can be adjusted to a better range. The acid-decomposable resin used in the present invention can be synthesized by a conventional method (for example, radical polymerization). In the positive type photoresist composition of the present invention, the compounding amount of the entire resist composition of the acid-decomposable resin is preferably 40 to 99.99% by weight, and more preferably 50 to 99.97% by weight in the total solid content. . Preferred specific examples of the following combination of repeating structural units of the acid-decomposable resin of the component (A) of the present invention are described below.

--CH2-CH-CH3-CH-CH- *

ch2—

-24- 538313 V. Description of the invention (μ

CH2 — CH 0 = k J = 0 (4) 〇

—CH-CH— * OH

One CH—CH— * J = 0 (5)

12 一 CH— CH; C —0 —C — II I 〇 Chl ·

CH2 —CH — 〇

-ch2—

⑹ OH

[2] (B) Compounds that generate acids by irradiation with active light or radiation (photoacid generators) The photoacid generators used in the present invention are compounds that generate acids by irradiation with active light or radiation. -25- 538313 V. Description of the invention (24) The photoacid generator used in the present invention can use a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photochromic agent for pigments, Conventional light used in photochromic agents or microresists (400 to 200 η ultraviolet, especially g-line, h-line, 1-line, K r F excimer laser light), A r F excimer laser light, electrons X-rays, X-rays, molecular rays or ion beams to generate acid compounds and select these mixtures appropriately. In addition, other photoacid generators used in the present invention include diazide, ammonium, scale, ferric iodide, selenium, iron selenium, arsenic, organic halogen compounds, organic metal / organic halides , Photo-generators with ortho-nitrobenzyl-type protective groups, sulfamates and other typical photodecomposition compounds that produce sulfonic acids, diazide, diazide dimaple compounds, etc. Furthermore, these are compounds which generate an acidic group by light or introduce a compound into the main chain or side chain of a polymer. Alternatively, VNRPniai, Synthesis, (1), 1 (1980), A. Abad eta 1, Tetrahedron Lett., (47) 4555 (1971) ^ DHR Barton et al ^ J. Chem. Soc., ( C), a compound which generates an acid by light, as described in 3 29 (1 70), U.S. Patent No. 3,799,7 78 and European Patent No. 1 26, 7 1 2. Those which are particularly effective among the above-mentioned acid generating compounds are described below. (1) A trihalomethyl-substituted oxane derivative represented by the following general formula (PAG 1) or an S-trioxo derivative represented by the general formula (PAG2). -26- 538313 V. Description of Invention (25)

(PAG1)

(Y) aC

(PAG2) C003 where R2 () 1 represents a substituted or unsubstituted aryl or alkenyl group, and R2 () 2 represents a substituted or unsubstituted aryl, alkenyl, alkyl, -C (Y) 3. The Y system represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited to these. -27- 538313 V. Description of the invention (26) a ^ —, NN V- CH-CH- 〇 [〇α3 CHs ο (PAG1-1) Ν ^ Ν ί / ο CH-CH- ^ C- * 00½ 0 ( PAG Bu 2)

Ch ^ CH-C… C ~ CBr3 (ah noisy 〇 (PAG1-3) N ~ Nch * ch — c… c- ea3 o (PAGl-i) .〇

NN chuch — Formula 0, c- ccj3 << 0, c- ca3 (FAG1-5) (PAG1-0 a &gt;-CH-CH- C, &lt; C- CC 丨 3 o- CH * CH -a- OCf -b (FAC1-8) (PAG1-7) 0 ^ 0 CCl ^ g NN; ΛΝΑ〇〇13 X (PAG2 ^ 1) CI3C 乂 '㈨ 人 ca3 (PAG2-2) NΛ ADN (PAG2-3) N ^ NΛ Λ rla3c n coi3 (PAG2-4)

a och3

CH = CH

CH-CH Λ,

N N CH-CH Λ

N N

CloC ^ N times CCI3 a3C N 'CCl3 CI3C ^ N into CCI3 (FAC2-B) (_2-9) (PAG2-10) (2) Iodine phosphonium salt represented by the following general formula (PAG3), or general formula ( PAG4) Yu salt -28- 538313 V. Description of the invention (27

Ar \ ιΘ ζΘ R203 R205 (PAG3) (PA64) Wherein, Ar1 and Ar2 each independently represent a substituted aryl group; unsubstituted aryl groups, and R2G3, R2.4, R2.5 are each independently unsubstituted. Valence ~ attack unsubstituted academic and aryl groups. Z1 is an anion such as BF4 ·, AsF6 ·, PIV, SbIV, SiF / ·, CIO, CFJO3 · and other perfluoroalkanesulfonic acid anions, pentafluorobenzenesulfonic acid anions, naphthalene-1 -sulfonic acid anions Isocondensation polynuclear aromatic acid expanding anions, anthraquinone sulfonic acid anions, sulfonic acid group-containing dyes, etc., but the present invention is not limited by these. In addition, at least two of R2Q3, R2 ° 4, and R2 ° 5, and Ari'Ar2 may each be a single bond or bonded through a substituent. Specific examples are the compounds shown below, but the present invention is not limited by these ^ 29- 538313 V. Description of the invention (28)

^-&gt; 0-hQ 0 ~, 6l ~ Q

c12h2S (PAD3-1)

SO Θ

si of (PAG3-2)

Or

Θ (PAG3-3)

SbF6v Θ (PAG3-4) CFgSOfi

(PAG3-S)

© 〇3s

(PAG3-10) OCH3 〇CHa (PAG3-11) -30- 538313

538313 V. Description of Invention (30)

(PAG3-23) CF3SO3

(PAG3-25) © (PAG3-24) -32- 538313 V. Description of the invention (31

Oh Θ C12 ^ 25

SO-, Θ (PAG4-1) Θ h3c-0-s fPAG4-2) CH3 Θ S03

Of s ASF ® 3 (PAG4-3), Θ s CF3S03® (PAG4-5) (PAG4-2)

s〇30 H3C

Or • s

© F

F F 0〇2Η5 (PAG4-7) 0 CF3S〇r (PA04-8)

C,] CF3S〇3® / 2 HO (PAG4-9) h3c / = = \ Θ ho-A r H3Q ch3 SbF6 (PAG4-11) CH3 ch3 (PAG4-10) C4H9 pf6 Θ

HO

S © (PAG4-12) c4H9

SO?

-33-538313 V. Description of the invention (32 (n) 〇4H9 HO (n) C ^ H9 ja rig pf6 e CH3 (PAG4-15)

(PAG4-14)

(PAG4-16)

CbF ^ SC ^ Θ 〇 / = \ II ® 〇 ^ ^-C--CH2--s--CH3 SbF6u ch3 (PAG4-18) (PAG4-17) &lt; ^^ C-CH-S © J pF &amp; ( PAG4-19) COsCHjCi ^ C ^ CHo ch3ch2ch2ch2o- &lt; ^^-s ''-^^^ &gt;) 2 o-1 〇 (PAG4-20) C12H25 ch2— (PAG4-21) .C- CH2— S © (PAG4-22) 〇-so? C-CH2—s® (n) C4H9 —ca) ceHi7S〇3 Θ pf6 © (PAG4-23) (n) C4H9 (PAG4-24) 〇-sQ ~ s0 ~ ( O! C12H25

Θ so (PAG4-25) -34- 538313 V. Description of the invention (33)

-35- 538313 V. Description of the invention C 34) PAG4-37

CF3SO3

e〇3s — CF3 (PAG4-38) e〇3S — C4F9 (PA64-39) e〇3S — CF3 (PAG4-40) ~ 〇3S ~ ~ C4F 9 (PAG4-41)

S ~ Ph2 ° 03S-CH3 (PAG4-42) ° -〇- | -ph2 '0〇3S- &lt; Q) -CH3 (PAG4-43) 〇 ^ Q &gt; -S ~ Ph2 G〇3S-CF3 (PAG4 -44) 〇 ~~ S-Ph2 ㊀〇3S-C4F9 (PAG4-45) -36- 538313 Five invention descriptions (35) -0-es-Ph2 "QS-Ph2 e〇3s ^ 0 ~ ch3 (PAG4-46 ) e〇3S-CF3 (PAG4-47) e〇3S-C4F9 (PAG4-48) e〇3S-CF3 (PAG4-49)

e〇3S-C4F9 (PAG4-50) e〇3S-CF3 (PAG4-51) ξ-Ph e〇3S-C4F9 (PAG4-52) where Ph represents phenyl. The above-mentioned phosphonium salts represented by the general formulae (PAG3) and (PAG4) are known substances, and there are methods described in, for example, U.S. Patent Nos. 2,807,648 and 4,247,473, Japanese Patent Application Laid-Open No. 5301, 3 31, and the like. The synthesized ° (3) diamidine derivative represented by the following general formula (PAG5), or an iminosulfonic acid ester derivative represented by the general formula (PAG6).

Ar3-S02-S02-Ar4 R2〇6_s〇2-〇-N: (PAG5) (PAG6) 〇 -37- 538313

-38- __- ^ 538313 V. Description of the invention (37

CI —S〇2 ~ S02 ~ (P / lG5 ~ 1)

Cl H3C ~ Qr S〇2 ~ S〇2 (PAG5-2)

CHn

H3CO JOr f3c. So2— so; (PA65-3) so2— S02 ~ 、

OCH3 H3C

S〇2 一 S〇2 (PAGS-4) so2 ~~ SOL

Cl

Cl (PAG5-5)

Cl

(PAG5-6) ^ so-so2— ^ (PAG5-8) S〇21 SOj (PAG5-10)

Cl

OCH3

H3C (PAG5-13) so: (PAG5-12)

so2— so2— ^ (PAG5-14)

S02— S〇2— \ H (PAG5-15) -39- 538313

538313

538313 V. Description of the invention (40) 〇 〇 0 N_〇- 〇 (PAG6-21) 〇

〇 II N —〇—S — CF3 IIο (PAG6-22) Ν —Ο—S — CH2-IIο (PAG6-23) 1. 〇 II s-c4f9 〇 (PAG6-24) 〇

N-0-i ^ O ~ CH3 (PAG6-25) (PAG6-26) (PAG6-27) -42- 538313 V. Description of the invention (41

(PAG6-28)

N ~ 0 ~ S ~ C3H7 n-0-i ~ 0 ^ cH2 (PAG6-29)

(PAG6-30) (PAG6-31)

(PAG6-32) N-0-S—CH2

(PAG6-34)

(PAG6-33) -43- 538313 V. Description of the invention (42) (4) Diazide difluorene derivative represented by the following general formula (PAG7) 0 μ 0 I! ^ II RS-11 ~ S-R II II 0 〇 (PAG7) wherein R is each a straight-chain, branched-chain or cyclic alkyl group, and an aryl group which may be substituted. Specific examples are the compounds shown below, but the present invention is not limited by these.

(PAG7-1)

Ο-

〇 Μ 〇 II ^ 2 ι S-υ-S_ II II 〇 〇

(PAG7-2) (PAG7-3) (PAG7-4) (PAG7-5) -44- 538313 V. Invention Description C 43)

ο n2 〇ch3 / ^ ν II II II 1 (Vs-^ — S —C-CHs (PAG7-8) W 丨 丨 ii I 〇o ch3 CH t—〇 ^ CH3 _-9) 〇〇 Such light The amount of the acid generator to be added is based on the solid content of the composition, and is usually 0.01 to 30% by weight, preferably 0.3 to 20% by weight, and more preferably 0.5 to 10% by weight. If the addition amount of the photoacid generator is less than 0.01% by weight, the sensitivity tends to decrease, and if the addition amount is more than 30% by weight, the light absorption of the resist is too high, the appearance is deteriorated, and the engineering (especially Baking) range is narrow, so it is not desirable. [3] (D) Organic test compound The preferred (D) organic basic compound used in the present invention is a compound which is more basic than phenol. Among them, a nitrogen-containing basic compound is preferred. By adding (D) an organic basic compound, the sensitivity change over time can be improved. (D) An organic basic compound is, for example, a compound having a structure shown below. -45- 538313 V. Description of the invention (44) R252… (A) Among them, R25 (), R251 and R252 may be the same or different carbon atoms, alkyl groups having 1 to 6 carbon atoms, and amines having 1 to 6 carbon atoms Alkyl group, hydroxy group of carbon number 丨 ~ 6, or substituted or unsubstituted aryl group of 6 ～ 20, and R251 and R2 ″ may be bonded to each other to form a ring. * N—C = N —… (B ) 1 1… (C)… (D) R254 〇255 1 1 * 7 », 253 1 * 1—C—N—c—R256… (E) R 2 5 3, R 2 5 4, R 2 5 5 and R256 may be the same or different carbon numbers of 1 to $. A better compound is a nitrogen-containing basic compound having two or more nitrogen atoms in different chemical environments in one molecule, and more preferably a compound containing Take = or = lightly substituted amine group and nitrogen atom ring structure _ compounds or compounds with amines, preferred specific examples are substituted or unsubstituted guanidinium or unsubstituted amines, substituted Or unsubstituted amines ;: -pyridine, substituted or unsubstituted aminopyrrolidine: substituted mirim, substituted or unsubstituted Zhuang; unsubstituted or unsubstituted -46- 538313 V. Hair Description (45 / generation of pyridine, substituted generation or unsubstituted pyrimidine, substituted purine, substituted $ unsubstituted pyrazoline, substituted 4 unsubstituted and unsubstituted piperidine Morpholine with substituted spheres, substituted with ~ unsubstituted amine groups, amines that have good substituents, amine groups, amino amine groups, aryl aryl groups, amine groups, Oxy, fluorenyl, fluorenyl, aryl, aryloxy, nitro:, cyano. Preferred specific examples of the basic nitrogen compound include guanidine, 1, K dimethylguanidine, 1,1 , 3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, laminidine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, diethylamine Pyrimidine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2.amino-5_methylpyridine, 2-amine -6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperidine, N-(2-aminoethyl) piperidine, n- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 · tetramethylpiperidine, 4-pyridine Piperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5_methylpyrazole, 5-amino-3-methyl- 1-p-Tripyrazole, Pyrazine, 2- (Aminomethyl) -5-methylpyridine, pyrimidine, 2, 4-diaminopyrimidine, 4, 6-dihydroxypyrimidine, 2-pyrazole Tertiary morpholine derivatives such as phenanthroline, 3-pyrazoline, N-aminomorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMETU) , Hindered amines described in JP-A No. 1 1-5 257 5 (the ones described in [0 0 0 5] in the publication), and the like are not limited by these. More specific examples are 1, 5 -diazidebicyclo [4.3.0.-5] -nonene, 1,8--47-538313. V. Description of the invention (46) — * 宜 热 一 * fe [ 5.4.〇] -7-Eleven 'commission (DBU), 1,4-1 · Azide 1 * Wang Ai [2 · 2 · 2] Wu Yuan, 4-dimethylamino p ratio 卩, six Methylenetetramine, 4,4-dimethylimidazoline, pyrrole, pyrazole, imidazole, pyridyl, pyrimidine, CHMETU and other morpholine, bis (1,2, 2, 6 , 6-pentamethyl-4-piperidinyl) decanoate and other hindered amines. Among them, 1,5-diazidebicyclo [4.3.0b 5-nonene, 1,8-diazidebicyclo [5.4.0b7-undecene, l, 4-diazidebicyclo [2.2.2] Octane, 4-dimethylaminopyridine, hexamethylenetetramine, CHMETU, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) decanoic acid Esters are preferred. These nitrogen-containing basic compounds may be used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is usually 0.001 to 5% by weight, preferably 0.01 to 5% by weight, based on the solid content of the entire composition of the photosensitive resin composition. When the content is less than 〇. 〇 丨 丨 wt%, the above-mentioned addition effect of the nitrogen-containing basic compound cannot be obtained. Moreover, when it is more than 10% by weight, the sensitivity tends to decrease and the developability of the non-exposed portion tends to deteriorate. [4] (E) Fluorine-based and / or sand-based surfactant It is preferred that the positive-type photoresist composition of the present invention contains a fluorine-based / silicon-based surfactant. The positive-type photoresist composition of the present invention preferably contains a fluorine-based surfactant, a silicon-based surfactant, and a surfactant having a gaseous species and sand atoms, or two or more kinds thereof. Such surfactants include, for example, JP-A-Sho 62_ 3 6 6 6 3, JP-A-Sho 6 1-2 2 6 7 4 6, JP-A-Sho 6 1-2 2 6 7 4 5, JP-A-Sho 6 2-1 7 0 9 5 〇-48- 538313 V. Description of the invention No. C 47), JP 6 3-34540, JP 7-2 3 0 1 6 5 and JP 8-6 2 834 JP-A-9-54432, JP-A-9-5988, U.S. Patent No. 5405 720, the same as 5 3 60692, the same as 5 52988 1, the same as 5 2 96330, the same as 5436098, the same as 5576 1 43, The surfactants described in the same as 52945 1 1 and 5 82445 1 can also be used directly as described below. Commercially available surfactants can be used, for example, EF 3 0 1, EF 3 0 3 (made by Shin Akita Kasei Co., Ltd.), Floraton FC43 0, and FC431 (made by Sumitomo 3M Co., Ltd.) , Mekafak F171, F173, F176, F189, R08 (made by Dainippon Ink Co., Ltd.), Safron S- 3 8 2, SCI 01, SCI 02, SCI 03, SC 104, SC 105, SC 106 (Asahi Glass Co., Ltd.), Dunron Irolu (transliteration) S-3 6 6 (Dun Longyi Chemical Co., Ltd.) and other fluorine-based surfactants or silicon-based surfactants. In addition, polysiloxane polymer KP-3 4 1 (made by Shin-Etsu Chemical Industry Co., Ltd.) can also be used as a silicon-based surfactant. The compounding amount of the surfactant is usually 0.001 to 2% by weight, preferably 0.01 to 1% by weight based on the solid content in the composition of the present invention. These surfactants can be used singly or in combination of several kinds. Specific examples of other surfactants include polyethylene oxide alkylene oxide, polyethylene oxide stearyl ether, polyethylene oxide hexadecyl ether, polyethylene oxide oleyl ether, and the like. Ethers, polyethylene oxide alkyl aryl ethers, polyethylene oxide octyl phenol ether, polyethylene oxide nonyl phenol ether, polyethylene oxide • polypropylene oxide ether block copolymers Class, sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol dioleate, sorbitol monostearate Esters of sorbitol fatty acid esters, polyethylene oxide sorbitol monolaurate, polyethylene oxide sorbitol monopalmitate, polyethylene oxide sorbitol monostearate, -49- 538313 V. Description of the invention C 48) Polyepoxide sorbitol fatty acid esters such as polyethylene oxide sorbitol trioleate, polyethylene oxide sorbitol tristearate, etc. And other non-ionic surfactants. The compounding amount of these other surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less based on 100 parts by weight of the solid content in the composition of the present invention. The positive resist composition of the present invention uses at least one kind selected from propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, and alkyl lactates such as methyl lactate and ethyl lactate. , Propylene glycol monomethyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol Ethylene glycol monoalkyl ether acetates such as alcohol monoethyl ether acetates, alkoxypropanes such as 2-heptanone, r-butyrolactone, methyl methoxypropionate, ethyl ethoxypropionate, etc. Acid alkyl esters, alkyl pyruvate esters such as methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, dimethylimide, etc. cover. Preferred examples include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl lactate, and ethyl lactate. These solvents can be used singly or in combination, but it is more preferable to use a mixture of at least one selected from the group consisting of propylene glycol monoalkyl ether acetates and alkyl lactates in order to reduce the number of developing defects. Here, the mixing ratio is preferably a weight ratio of 95/5 to 30/70. In the present invention, the solid content of the solid component of the resist composition containing the above-mentioned components in the above-mentioned solvent is preferably 3 to 25% by weight, and more preferably 5 to 50 to 538313. V. Description of the invention (49) ~ 22% by weight, and the best is 7 ~ 20% by weight. The positive photoresist composition of the present invention may further contain an acid-decomposable dissolution preventing compound, a dye, a plasticizer, a surfactant, a photosensitizer, and a compound that promotes solubility in a developing solution, etc., as necessary. . The photopositive photoresist composition of the present invention is coated on a substrate to form a thin film. The film thickness of the coating film is preferably 0. 2 to 1. 2 μΐΏ. In the present invention, a commercially available inorganic or organic antireflection film may be used as necessary. The anti-reflection film can be made of inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon, and organic film type made of light absorbing agent and polymer material. Equipment such as melting equipment, CVD equipment, and sputtering equipment. The organic anti-reflection film is, for example, a product made of a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin, an alkali-soluble resin, and a light absorbing agent as described in Japanese Patent No. 7-696 ii, or US Patent 5 2 9 4 6 8 Reactant of maleic anhydride copolymer and diamine-type light absorbing agent described in No. 0, JP-A 6-1 1 863 No. 1 containing a resin binder and a hydroxymethylmelamine-based thermal cross-linking agent, described in JP-A 6 -1 1 8656 Acrylic resin type anti-reflection film having a residual acid group, an epoxy group and a light absorbing group in the same molecule, JP 8-87 1 1 5 Those formed by amines and benzophenone-based light absorbers include those in which a low-molecular-weight light absorber is added to the polyethylene glycol resin described in JP-A No. 8-1 79509. In addition, the organic anti-reflection film can also use DUV30 series or DUV-40 series manufactured by Newark Sainz Co., Ltd., AC-2 and AC-3 manufactured by Western Lightning Co., Ltd., etc. -51-538313 V. Description of the invention (so) The above-mentioned resist solution is used on a substrate (such as sand / silicon dioxide coating) used in manufacturing precision integrated circuit components (if necessary, the above-mentioned antireflection film is provided) (On the substrate), after being coated by a suitable coating method such as a spinner and a roller, it is exposed through a predetermined photomask, baked, and a good resist pattern is produced by development. Here, the exposure light source is preferably light having a wavelength of 150 nm to 250 nm. Specifically, for example, there are KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (I57 nm), X-ray, electron beam, and the like. The imaging solution can use inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methylsilicate, and ammonium water, and primary amines such as ethylamine and n-propylamine. Class I female temple Class I female II secondary amines such as diethylamine, methyl monoethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, fourth class such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Ammonium salts, basic aqueous solutions such as cyclic amines such as pyrile and piperidine. Alternatively, an appropriate amount of an alcohol or a surfactant may be added to the alkaline aqueous solution. Examples The present invention will be specifically described in the following examples, but the present invention is not limited to the following examples. (1) The synthesis of resin (1) makes orbornene, 2-methyl-2 -adamantyl acrylate, maleic anhydride, 3,5-dihydroxyadamantyl acrylate at a molar ratio of 3 0/3 0/3 0/1 0 added to the reaction vessel and dissolved in methyl ethyl ketone 'adjusted to a solid content of 60% -52--^ 538313 V. The solution of the invention (51). It was heated to 60 under a stream of nitrogen. When the reaction temperature was stabilized, 1.5 mole% of Wako Pure Chemicals (strand) initiator v_601 was added to start the reaction. After 10 hours of reaction, the reaction mixture was diluted twice with methyl ethyl ketone and was 'put into a 5-fold amount of a 3-butyl methyl ether / hexane = 1/1 mixed solvent' to precipitate a white powder. The crystal powder is filtered, taken out, and dried to obtain the target resin (1). The molecular weight of the obtained resin (1) was measured by GPC, and it was 1,700 (weight average) in terms of polystyrene. In addition, according to the composition of the tree moon purpose (1) of the NMR spectrum, the orbornene / 2-methyl-2-adamantyl acrylate / maleic anhydride / 3,5-dihydroxyadamantyl acrylate of the present invention The esters have a molar ratio of 24/31/38/7. Resins (2) to (7) were prepared in the same manner as described above. Specific examples (1) to (7) of the above-mentioned resins represent repeating structural units constituting these resins. Table 1 Resin original borneol alicyclic (meth) acrylic acid anhydride passed through Mw 2 29 19 36 16 14 500 3 25 24 39 12 14 900 4 28 25 37 10 1 5700 5 27 21 34 18 14 400 6 29 24 38 9 14300 7 28 19 36 17 14200 -53- 538313 V. Description of the invention (52) Examples 1 to 16 and comparative examples (modulation and evaluation of positive photoresist composition) 2 g each of the above synthesis examples (Table 2 below) (Shown) The resin, photoacid generator shown in Table 2, 5 mg of organic basic compound, 5 mg of interfacial active agent, each dissolved in the solvent shown in Table 2 in a proportion of 10% by weight of the solid content. It was filtered with a 0.1 micron micro filter to prepare the positive resist composition of Examples 1 to 16. In addition, in Comparative Example 1, the resin (R) shown in Table 2 (Resin A4 obtained in Synthesis Example 11 of JP-A No. 1 1-3 0 5444) and a photoacid generator (PAG-R: 4-methylbenzene) were used. Except for diphenylsulfonium trifluoromethane dibasic acid ester) and solvent, a positive resist composition was prepared in the same manner as in Example 1. The solvents are: S 1: propylene glycol monomethyl ether acetate S2: propylene glycol monomethyl ether propionate S 3: ethyl lactate 54: butyl lactate 55: 2-heptanone 56: propylene glycol monomethyl ether S7: ethoxy Ethyl propionate 58: τ-butyrolactone 59: Ethyl carbonate S 1 0: Noctyl carbonate The surfactant is: -54- 538313 V. Description of the invention (53) W -1 ·· Meika method Gram (transliteration) F 1 7 6 (made by Dainippon Ink Co., Ltd.) (fluorine-based) W-2: Mekafak (transliteration) R 0 8 (made by Dainippon Ink Co., Ltd.) (fluorine-based and polymer) Siloxane type) W-3: Polysiloxane polymer-KP-341 (made by Shin-Etsu Chemical Co., Ltd.) W-4: Polyethylene oxide nonylphenyl ether W-5 Lu (transliteration) S- 3 66 (made by Dunlong Chemical Co., Ltd.) (fluorine) Organic basic compounds are: 1: DBU (1,8-diazide ring [5. 4 · 0]-7- Undecene) 2: 4-DMAP (4-dimethylaminopyridine) 3: TP 1 (2,4,5-triphenylimidazoline) 4: 2,6-diisopropylaniline-55- 538313 V. Description of the invention (μ) Table 2 Example (A) Resin component (B) Photoacid generator (addition amount, mg) Solvent * 1 (E) Interfacial activity Agent (D) Organic Basic Compound 1 Resin (1) PAG4-5 (40) SI 5 1 2 Resin (2) PAG4-36 (42) SI 1 2 3 Resin (3) PAG4-52 / PAG7-3: (36) / (8) SI 3 3 4 resin (4) PAG4-50 / PAG7-5 = (35) / (10) SI 2 2 5 resin (5) PAG4-39 / PAG6-19 = (33) / (10) SI 1 1 6 resin (6) PAG4-52 / PAG7-8 = (40) / (4) S2 2 2 7 resin (7) PAG4-6 / PAG4-51: (30) / (6) S5 / Sl = 50/50 3 1 8 Shed purpose (1) PAG4-41 (50) SI / S4 two 75/25 3 2 9 resin (2) PAG4-45 (43) Sl / S6 = 88/12 5 3 10 Resin (3) PAG4-52 / PAG4-51 = (40) / (8) Sl / S7 = 80/20 5 3 11 Resin (4) PAG4-48 (40) Sl / S8 = 92/8 3 3 12 Resin (5) PAG4-48 / PAG4-47 = (35) / (7) Sl / S4 / S9 = 75/20/5 3 2 13 Resin (6) PAG4-39 (39) S1 / S7 / S10 two 80 / 16/4 2 1 14 Resin (7) PAG4-52 (42) SI 1 2 15 Shed purpose PAG4-51 (41) SI 4 3 16 Resin (1) PAG4-50 (45) SI te 1 Comparative example 1 Resin (R) PAG-R (40) SI 4 * 1: The ratio when mixing solvents is (weight ratio). -56- 538313 V. Description of the invention (55) (Evaluation test) [Development defect]: Each 0.3-micron resist film is coated on a 6-inch Ba re S i substrate, and a vacuum adsorption hot plate is used at 135 t Dry for 60 seconds. Then, via 0.16 micro

After measuring the test mask with a meter contact hole pattern (D ο 1 e Duty ratio = 1: 3), it was exposed by an A r F excimer stepped exposure device (a rF exposure machine 9300 manufactured by ISI Corporation). Heat at 60 ° C for 90 seconds. Then, the cells were developed with bubbles of 2.38% TMAH (aqueous solution of tetramethylammonium hydroxide) for 60 seconds, and then washed with pure water for 30 seconds and spin-dried. The sample was measured for the number of developmental defects by a KL A-2 2 1 12 machine manufactured by Ken Yale Dieklu (transliteration), and the primary data obtained by &amp; Number of imaging defects. The results of these evaluations are shown in Table 3.

^ ---- 1 538313 V. Description of the invention (56) Examples of development defects 1 15 2 12 3 11 4 11 5 11 6 16 7 11 8 8 9 9 10 8 11 8 12 6 13 6 14 11 15 17 16 25 Comparative Example 1 760 As can be seen from the above Table 3, the positive-type photoresist composition of the present invention has excellent performance in reducing the occurrence of developing defects. -58- 538313 V. Description of the invention (57) Effect of the invention The present invention can provide a positive type photoresist composition which can effectively prevent the occurrence of development defects in the manufacture of semiconductor devices. -59-

Claims (1)

538313 Public table application benefit range No. 9 0 1 1 4 1 4 1A Application patent scope: "Positive Photoresist Composition" patent case (Amended on February 20, 2002) A positive photoresist composition, which It is characterized by containing: (A) 40 to 99.99% by weight of a resin containing a repeating structural unit represented by the following formula (II), a repeating structural unit represented by the following formula (II-1), and the following formula (II-2) Resin showing a repeating structural unit and increasing the dissolution rate of an alkali developer by an acid action, (B) 0.01 to 30% by weight of a compound, which is a compound that generates an acid by active light or radiation, (I ) Rl1R12 R13Rl4 Ri -fCH2—〒 卜 (| H) A—COO-W (II-2) Ri * ^ ch2—— In the formula of the formula (I), Rh ~ Rl4 each independently represents a hydrogen atom or the substitution a represents 0 or 1 '538313 6. In the scope of patent application formula (II-1), h represents a hydrogen atom or A methyl group, A represents a single bond, alone or in combination of two or more selected from the group consisting of an alkylene, a cycloalkyl, an ether group, a thioether group, a carbonyl group, and an ester group, and the W series represents at least one of the following formula I) ~ (p VI) Partial structure of alicyclic hydrocarbons, ^ 15c (pi) z 〒16 • 〒a r17 ^ 18 (pH) 〒19 (pin) 〇I • ch_r2〇 ^ 26 ^ 27 〇 II II / w, one 0 — CH — C — R28 (pV) R 29 〇I! R 15 (pV!) One c one 10-c Z 538313 6. The scope of patent application, r15 Is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a 2-butyl group, and the Z series is an atomic group necessary to form a carbon atom and an alicyclic hydrocarbon group. The Ru ~ R20 series Each independently represents a linear or branched alkyl or alicyclic hydrocarbon group having 1 to 4 carbon atoms, but at least one of R 1 6 to R 1 8 or any of R 1 9 and 20 is an alicyclic hydrocarbon group , R2] ~ r25 each independently represent a linear or branched alkyl or alicyclic hydrocarbon group having 1 to 4 carbon atoms, but at least one of R2! ~ R25 is an alicyclic hydrocarbon group, and one of R23 and R25 It is a linear or branched alkyl or alicyclic hydrocarbon group having 1 to 4 carbon atoms, and R26 to R29 each independently represent a linear or branched alkyl or alicyclic hydrocarbon group having 1 to 4 carbon atoms, but R26 to R29 At least one of R29 is an alicyclic hydrocarbon group. In the formula (II-2), R! Is synonymous with R! In the above formula (II-1), and only 4 are each independently a hydrogen atom or a hydroxyl group, but R2 ~ R4 at least It is a hydroxyl group. 2. The positive photoresist composition according to item 1 of the patent application range, wherein the resin (A) further contains a repeating structural unit represented by the following formula (III), Where Z 2 represents -0-or -N (R 3)-, R 3 represents a gas atom, the radical 538313 VI, the scope of patent application or -0S02-R4-, R4 represents an alkyl group, a halogenated alkyl group, A cycloalkyl or camphor residue. 3. The positive photoresist composition according to item 1 or 2 of the patent application scope, which further contains (D) organic basic compounds, (E) fluorine-based and / or silicon-based surfactants.