TWI226509B - Positive resist composition - Google Patents

Abstract

The present invention is to provide a resist composition useful in the production of semiconductor devices and excellent in resolution, a resist composition having high resolution and good reproducibility of isolated line width, and a resist composition for electronic or X-rays and having high resolution, high sensitivity and good profile. A positive resist composition comprises a high-molecular compound having in the side chain a fluoro-aliphatic group derived from a fluoro-aliphatic compound produced by telomerization or oligomerization, and a chemically amplified positive resist composition for electronic or X-rays comprises an alkali soluble resin of specified structure having a weigh average molecular weight in the range of 3,000 to 300,000 or a resin which is decomposable by the action of an acid and thereby whose solubility in an alkali developing solution is increased.

Description

1226509 V. Description of the Invention (1) [Technical Field] The present invention relates to a chemical amplification system for a semiconductor manufacturing process such as a lithographic printing plate or an IC, a circuit substrate manufacturing such as a liquid crystal, a hot needle, and other photoresist application projects. Type photoresist composition, more specifically, relates to a kind of ultraviolet rays, excimer laser light (F2, XeCl, KrF, ArF) and other extreme ultraviolet rays, electron rays, molecular rays, r rays, ytterbium, etc. Photoresist composition for photoresist for step-by-step accelerating irradiation of Is-rays for localized body circuits. [Prior art] In order to increase the integration degree of local integrated circuits, it is necessary to process ultra-fine patterns with a line width of less than half a micrometer in manufacturing semiconductor substrates such as ultra-LSI. In order to achieve the necessary resolution, the wavelength of the exposure device used in photolithography is shortened, and far-ultraviolet light or excimer laser light (XeCl, KrF, ArF, etc.) is also currently being reviewed. In addition, we also review direct exposure by electron beams or exposure through a photomask. In addition, with the high integration of integrated circuits and the etching method of wafers, since the wafers are moved from dry etching to conventional etching, they must have etching resistance and heat resistance. Although the photoresist formed by the conventional phenolic lacquer resin and naphthoquinonediazide compound has good dry etching resistance and heat resistance, when it uses ultraviolet light or excimer laser light to form a lithography pattern, The phenolic lacquer resin and naphthoquinonediazide have strong absorption in the ultraviolet range, so light does not easily reach the bottom of the photoresist, and it is not possible to obtain a cone pattern with low sensitivity. . To solve the above problems, there are U.S. Patent No. 449 1 628, European Patent No. 1226509 V. Description of Invention (2) Lee No. 249 1 39, Japanese Patent Laid-Open No. 59-43439, Polym. Eng. Sci. 23 (18) '1 0 1 2 (1 983) and other chemically amplified photoresist compositions. The chemical amplification type positive photoresist composition is irradiated with radiation such as far ultraviolet light, generates an acid in the exposed portion, and reacts with the acid as a catalyst to change the irradiation portion of the active radiation to the non-irradiated portion. Pattern-forming material that has solubility in liquids and forms a pattern on a substrate. The positive-type chemically amplified photoresist composition is divided into a two-component system made of a compound (photoacid generator) that generates an acid by radiation exposure and an alkali-soluble resin having an acid-decomposable group (US Patent 4 4 9 1 6 2 8 etc.), 3-component system (Europe patent) which reacts with alkali-soluble resin, photoacid generator and acid catalyst to form alkali-soluble dissolution preventing compound (acid-decomposable dissolution inhibitor). 249 1 39, JP 2-24895 3, etc.). Any of these is the same as a photoresist made of a phenolic resin and a naphthoquinonediazide compound. In order to achieve a high resolution, it is necessary to increase the difference in dissolution rate between the exposed and non-exposed areas. In addition, a multi-component system in which an alkali-solubility-inhibiting compound is added to the two-component system can be used. When microfabrication is used and any exposure light source is used, a photoresist composition having high resolution and excellent line width reproducibility of isolated lines is sought. An isolated line is a line that has a large space in the adjacent line. With fine processing, the isolated line will fly away from the substrate interface and disappear. In the chemically amplified photoresist composition, a surfactant may be blended in general in order to prevent the occurrence of streaks and improve coating properties. General surfactants include, for example, polyethylene oxide alkyl ethers, polyethylene oxide alkyl allyl ethers, 1226509 5. Description of the invention (3) Polyethylene oxide-polypropylene oxide block copolymer Type, sorbitol fatty acid esters, polyethylene oxide sorbitol fatty acid esters and other non-ionic surfactants, and fluorine-based surfactants, organosiloxane polymers or acrylic or methacrylic ( Co-polymeric polymers, etc. In addition, Japanese Patent Publication No. 7-2 1 626 discloses a photoresist composition for semiconductor microfabrication, which is characterized by containing an alkali-soluble resin, an organic solvent of at least a mono-oxidized monocarboxylic acid ester, a fluorine-based surfactant, and a radiation-sensitive substance. Made. In addition, Japanese Patent Application Laid-Open No. 7-24687 discloses a combination of a solvent having a specific structure and a fluorine-based surfactant, and Japanese Patent Application Laid-Open No. 2000-1 62768 discloses a chemically amplified photoresist composition using a fluorine-based surfactant having a specific structure. . However, even when the above-mentioned surfactant is used, it is not possible to improve the coatability of the case such as the appearance of streaks and the function of flying out the isolated lines, and the line width reproducibility of the isolated lines has been sought. Moreover, in the pattern generation technology of the next generation or the next generation of electron beams or X-rays, it is sought to develop a photoresist composition having a high resolution, a high sensitivity, and a rectangular outline, but a positive electron beam or an X-ray photoresist The agent is susceptible to the effects of alkaline pollutants in the atmosphere or exposed to the inside and outside of the irradiation device. The surface is difficult to dissolve and a T-To p shape is formed when the line pattern is formed (the surface is a T-shaped awning). It is a contact hole. When patterning, the surface may have a groove shape (a awning is formed on the surface of the contact hole). In addition, in order to prevent a groove shape or a T-Top shape, the film edge may be caused when the adhesive is hydrophilic. [Disclosure of the invention] Therefore, the object of the present invention is to provide a photoresist composition with excellent resolution, especially for manufacturing semiconductor devices. Excellent photoresist composition and photoresist composition for electronic or X-rays with high resolution and good contour shape. As a result of intensive research, the present inventors have found that by adding a specific fluorine-based polymer to the photoresist composition, a photoresist composition having high resolution and excellent line width of the isolated line and excellent linearity can be obtained. The present inventor is based on the insights on the manufacturing process, structure, and composition distribution of those who have reviewed fluorinated aliphatic groups in detail. The inventors focused on the development of copolymerization components or the substitution numbers of fluorinated aliphatic groups. Different technical ideas of the photosensitive layer technology of the polymer. In other words, the following positive-type photoresist composition of the present invention having the structure (1) or (2) is based on the above-mentioned technical problems that exhibit excellent effects, have high resolution, do not reduce sensitivity, and can suppress the problem of isolated line flying away. Insights. This invention is comprised by the following structures. (1) A positive photoresist composition, characterized by containing (A) (1) a resin which is decomposed by an acid to increase solubility in an alkali developing solution, (2) an alkali-soluble resin and Compounds that decompose and increase the solubility in alkaline imaging solution by acid action, or. (3) Resins that decompose and increase the solubility in alkali imaging solution by acid action and decompose and increase Low-molecular-weight compounds that are soluble in alkaline imaging solutions, (B) compounds that generate acids by irradiation with active light or radiation 'and (C) fluoroaliphatic compounds produced by short-chain polymerization or oligomerization Compound 1226509 5. Description of the invention (5) A polymer compound derived from a fluorinated aliphatic group on a side chain. (2) a type of positive photoresist composition, which is characterized by containing (A) (1) a resin that is decomposed by an acid to increase the solubility in an alkali developing solution, (2) an alkali-soluble resin and a resin Compounds that are decomposed by an acid to increase the solubility in an alkali developer, or (3) resins that decompose by an acid to increase the solubility in an alkali developer, and decomposed and increased by an acid. Low-molecular-weight compounds that are largely soluble in an alkali imaging solution, (B) a compound that generates an acid by irradiation with active light or radiation, and (C) have a fluorine represented by the following general formula (F 1) on the side chain Aliphatic polymer compound, and the polymer compound is mixed with a base of general formula (F1) in which η is 3, 4, 5, and 6; at this time, the component of the base of η = 4 is η = 3, The composition of 4, 5, and 6 is 40 to 97 mol% in total, or the composition of η = 3 is 40 to 97 mol% in total for η = 3, 4, 5, and 6 Molecular compound | 2Υ——XfC —)-(CF2CF2) n F (F1) I m r3 1226509 5. Description of the invention (6) (wherein 'R2 and R3 each represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms 'X means single bond or 2 valence For bonding groups, γ represents the polymer main chain, m represents an integer of 0 or more, and η represents an integer of 1 or more). As a component of (1) or (2), a polymer having a fluorinated aliphatic group on a side chain is particularly excellent when compared with conventional ones. The reason is currently unknown, and the following possibilities are considered. . (1) The effect of using a fluorinated alkyl group produced by a short-chain polymerization method or an oligomerization method is another typical manufacturing method. It has an aliphatic alkyl group with a structure different from that of the electrolytic fluorination method, or has a broader composition distribution. Very beneficial effect. For example, it is possible to use the advantageous effect of mixing fluorinated alkyl groups having different carbon numbers, or mixing aliphatic fluorinated alkyl groups having a partially branched alkyl structure. The excellent constitutional requirements of (2) are the proponents of the inventors' opinions. The typical fluorinated aliphatic group of the general formula (1) is centered on a specific carbon number, and those who use the composition distribution can obtain excellent results. Effect. (3) A type of positive photoresist composition for chemical amplification of electron rays or X-rays, which is composed of (a) a compound that generates an acid by irradiation with electron rays or X-rays, and (13) a weight average molecular weight of 3,000 to 3,000,000 alkali-soluble resins that can satisfy the following conditions (1) and (2), (1) at least one aromatic ring having 6 to 20 carbon atoms, and the aromatic ring is directly or via a bonding group connected to the aromatic ring A repeating unit derived from a monopolymer having an ethylenically unsaturated group '(b) The following relationship is established between the electron of the aromatic ring and the non-shared electron pair of a substituent on the aromatic ring: 1226509

V. Description of the invention (7) (Formula 1) + 2 Ni〇ne g 1 〇 (wherein N 7Γ represents the total number of V electrons' N i. Ne represents a straight chain having 1 to 12 carbon atoms as a substituent, Total number of branched or cyclic alkoxy, alkenyloxy, aryloxy, aralkoxy, or non-shared electron pairs of hydroxy groups. Two or more adjacent oxo groups or hydroxy groups are bonded to each other. In order to form a ring structure with more than 5 carbons, except for the benzodioxazole structure, and the substituent does not contain a hydroxyl group when N 7Γ = 6). (4) The electron beam or X-ray chemical amplification type positive photoresist composition according to the above (3), wherein (b) the alkali-soluble resin has at least one type repeated as shown in the following general formulae (1) to (5) Structural units as constituents,

-(〇Rc) n (ORb) m 1226509 V. Description of the invention (8)

Rioi — (-ch2c-) — {Rd〇) p-, (〇Rg) s ⑵- (〇Rh) t (Re〇) q (Rf〇) r (OR)

(〇Rf) r (〇Ri) t (RgO) (〇Rh) t (3) (Rd〇) p (ReO)

-fCH2C

(ORk) v (Rt〇) r (Rg〇) s \ (° R ^ (ORi) (ORfOt ⑷ -10- 1226509) V. Description of the invention (9)

(Where, R π) represents a hydrogen atom or a methyl group, and L represents a divalent bonding group. Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, R1 are -11. -1226509 V. Description of the invention (10) is a linear, branched, or cyclic alkyl, alkenyl, aryl, aralkyl, or hydrogen atom each independently representing a carbon number of 1 to 12 In addition, these can be connected to each other to form a ring of 5 or more carbons with a carbon number of 24 or less. 1, 1, m, η, p, q, r, s, t, u, v, w, and x are integers of 0 to 3. , Satisfiable, 3, p + cj + r two 0, 1, 2, 3, s + t + u = 0, 1, 2, 3, v + w + x = 0, 1, 2, 3, only In the formula (1), Ra, Rb, and Rc cannot be hydrogen atoms and in the general formula (1), except for the benzodioxine structure. (5) A chemically amplified positive photoresist composition for electron or X-rays, characterized in that it contains (a) a compound that generates an acid by irradiation with electrons or X-rays, and (b ') a weight average molecular weight of 3,000 ~ 300,000 Resins which can satisfy the following conditions (1) and (2) to increase the solubility in alkali developing solution by acid action and decomposition, (1) at least one aromatic having 6 to 20 carbon atoms Ring and a repeating unit derived from a monomer having an ethylenically unsaturated group bonded directly or via a bonding group on the aromatic ring, (2) the 7Γ electron of the aromatic ring and the substituent on the aromatic ring are not shared The following relationship is established between the electron pairs: (Formula υΝ7Γ + Ni〇ne -12-1226509 V. Description of the invention (11) is a substituent, and the total number of susceptible oxygen groups is 5 carbons or less. Let the following (where Nττ represents the total number of 7Γ electrons, and NUne represents the linear, branched, or cyclic alkoxy, aryloxy, aralkoxy, or hydroxyl group of carbon number 1 to 2 of f The non-shared electron pairs are all. Two or more adjacent alkoxy groups or hydroxyl groups are bonded to each other to form an upper ring structure. Except for the benzodioxazole structure, and the N 7Γ group does not contain a hydroxyl group.) (6) The chemically amplified 2 composition for electron or X-rays as described in (5) above, wherein (b ′) the alkali-soluble resin is at least A repeating structural unit represented by the general formulae (1) to (5) as a constituent, -13 ----- 1226509 V. Description of the invention (12) R1

⑴ (RaO) l-(〇Rc) n (〇Rb) m

Ri -fCH2i (Ming (Re〇)

(〇Rh) t ⑵ (Rp) r (〇 取

? 101 CH2c-)-

(ORF) r (ORJu ⑶ 4- 1226509

1226509 V. Description of the invention (14) are linear, branched, or cyclic alkyl, alkenyl, aryl, aralkyl, hydrogen atom, or acid decomposable groups each independently representing a carbon number of 1 to 12. 'In addition, these can be connected to each other to form a ring of 5 or more carbons with a carbon number of 24 or less. 1, 1, m, n, p, q, r, s, t, u, v, w, and X are 0 to 3 Integer, can satisfy 1 + m + n = 2,3, p + q + r = 0,1,2,3, s + t + u = 0,1,2,3, v + w + x: z〇 , 1,2,3, except that Ra, Rb, and Rc in the general formula (1) cannot be hydrogen atoms and in the general formula (1) (except for the benzodioxazole structure). (7) The positive-type photoresist composition for chemical amplification of electron rays or X-rays as described in (3) above, wherein (b) the molecular weight distribution of the test-soluble resin is 1.0 to 1.5 as described above (8) 5) The chemical amplification type positive photoresist composition for electron or X-rays, in which (b ′) the molecular weight distribution of the resin which increases the solubility in the alkali developing solution by the action of acid is decomposed to 1.0. ~ 1.5. (9) The chemical amplification type positive photoresist composition for an electron beam or an X-ray according to any one of (3) to (8) above, further containing (c) having a base decomposed by an acid and by Acidic action increases compounds' solubility in alkaline imaging solutions and low molecular weight dissolution preventing compounds with molecular weights below 3,000. (10) The chemical amplification type positive photoresist composition for electron or X-rays according to any one of (3) to (9) above, further containing (d) a compound having a cation polymerizable function. (1 1) The chemical amplification type positive photoresist composition for electron or X-rays according to any one of (3) to (10) above, wherein (d,) is at least one selected from the group consisting of an ethylene compound, a ring Paraffinic compounds, cyclic ether compounds, lactone compounds, aldehydes-16-1226509 5. Compounds of the compound of the invention (15). (1 2) The chemical amplification type positive photoresist composition for electron or X-rays as described in (1 1) above, wherein (d ') is a compound represented by general formula (A), and general formula ㈧

/ 0-¾ \ R〇 (wherein Ra, Rb, and Rc represent the same or different hydrogen atom, an alkyl group or an aryl group which may have a substituent, and 2 of these may be bonded to form a saturated or olefin (Unsaturated ring, Rd means alkyl or substituted alkyl). (1 3) The chemical amplification type positive photoresist composition for electron or X-rays according to any one of (3) to (1 2) above, wherein (a) the acid or The compound system contains at least one compound represented by the following general formulae (I) to (III). -17-1226509 V. Description of the invention (16

R

29 D

R 35 X (III) (/, in which Rl represents the same or different hydrogen atom, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, hydroxyl, halogen Atom, or -s-r38, where r38 represents a linear, branched, or cyclic alkyl or aryl group. Two or more of R ^ Rm, R16 ~ R27, and R28 ~ R37 form a single bond, At least one or two or more selected from the group consisting of oxygen, sulfur, and nitrogen

-18- 1226509 V. Description of the invention (17) X-is an ion which does not extend the acid). (1 4) The chemical amplifying positive photoresist composition for electronic or X-rays as described in (1 3) above, wherein x_ represents a compound having at least one member selected from at least one fluorine atom and at least one fluorine-substituted direct photoresist composition. Chain, branched or cyclic alkyl, at least one linear, branched or cyclic alkoxy substituted with fluorine, at least one alkynyl substituted with gas, at least one substituted with fluorene Oxygen, at least one sulfonyl group substituted with fluorine, at least one sulfonyl group substituted with fluorine, at least one sulfonyl group substituted with fluorine, at least one aryl group substituted with fluorine, at least one substituted with fluorine Anions of aralkyl, and at least one fluorine-substituted alkoxycarbonyl benzenesulfonic acid, naphthalenesulfonic acid, and anthracenesulfonic acid. (1 5) The chemically amplifying positive photoresist composition for electronic or X-rays according to any one of (3) to (1 4) above, wherein the solvent mainly contains propylene glycol monomethyl ether acetate. (16) The chemical amplification type positive photoresist composition for electron rays or X-rays according to any one of the above (3) to (15), which further contains (e) an organic basic compound 〇 (1 7) is as described above (3) ~ (16) The positive amplification composition of the chemical amplification system for electronic or X-rays, further containing (f) a fluorine-based and / or silicon-based boundary-19-1226509 V. Invention Note (18) Surfactants. [Implementation Mode of the Invention] [I] First, the positive-type light composed of the above-mentioned (丨) and (2) regarding the photoresist composition having high resolution and excellent solitary line width and then linearity will be described in detail Resistance composition. First, a polymer compound having a fluorinated aliphatic group on the side chain (referred to as "fluorine polymer") of the component (C) will be described. The fluorine-based polymer used in the present invention can be in the form of most polymers satisfying the requirements contained in (1) and (2). Specific forms include acrylic resin, methacrylic resin, styrene resin, polyester resin, polyurethane resin, polycarbonate resin, polyamide resin, polyacetal resin, phenol / formaldehyde condensation resin, Polyvinylphenol resin, maleic anhydride / α-olefin resin, α-heterocyclic substituted methacrylic resin, and the like. Among them, acrylic resin 'methacrylic resin' styrene resin, polyester resin, and polyurethane resin are preferable, and acrylic resin, methacrylic resin, and polyurethane resin are more preferable. One of the fluorinated aliphatic groups used in the side chain of the present invention is a derivative of a fluorinated aliphatic compound manufactured by a short-chain polymerization method (that is, a short-chain polymer method) or an oligomerization method (that is, an oligomer method). By. For the manufacturing method of these fluorinated aliphatic compounds, for example, "Synthesis and Function of Fluorochemical Compounds" (Supervision: Yannan Ishikawa, Issue: Siemsi (Transliteration), 1 987) Page 1 1 7 ~ 1 1 8 , Or "Chemistry 〇f Organic Fluorine Compound II" (Monograph 187 ^ Ed by Milos Hudlicky and Attila E. -20-1226509 V. Description of the Invention (19) Pavlath, American Chemical Society 1995), pages 747-752. The short-chain polymerization method is a method of synthesizing a short-chain polymer by using a halogenated alkyl group having a large chain shift constant, such as iodide, as a short-chain polymerization agent, and performing radical polymerization of a fluorine-containing ethylene compound such as ethylene tetrafluoride and ethylene. S cheme-1 example). Scheme *! R —I + n F2C = CF2-^ R- ^ CF2CF ^ ~ \ The resulting terminally iodinated short-chain polymer is usually an appropriate terminal chemical modification such as [Scheme2], and is introduced into a fluorinated aliphatic compound . These compounds are used, if necessary, in the manufacture of fluorinated aliphatic group-containing polymers transformed into the desired monomer structure.

Scheme2

R- ^ CF2CF2y-CH2CH2—I R- ^ CF2CF2 ^ CH2CH-CH2 R- ^ CF2CF2j-,

CH2CH2—OH R ~ f-CF2CF2j—CH = CH2 \ / n

R ~ ^ CF2CF2j-C02H In the present invention, the compound introduced into the side chain of a polymer compound having a fluorinated aliphatic group on the side chain is suitably produced by the short-chain polymer method described above.

-21-1226509 V. Description of the invention (2) Specific examples of the compounds are fluorine-based chemicals sold by Lai Jin (Transliteration) Chemical Products Sales Co., Ltd. Ya-1620, A-2020, A-1260, A-1460, A-1660, A-1860, A-1435, A-1635, A-1835, A-1473, A-1637, A- 1820, Please refer to lines 1 to 26 of the original P29, or manufactured by Mecton Dragon (Transliteration) Co., Ltd., DCHEMINOX FA, FA-M, FAAC, FAAC-M, FAMAC, FAMAC-M, etc., etc. The main component structure of a fluorine-based chemical is represented by the following general formula TM-1 (where ^ represents an integer from 0 to 20). -22- 1226509 V. Description of the invention (21 t- (cf2) -z —T -CF3 ——CF2CF3 a cf2cf2cf3 f3c, CF— / f3c —cf2cf2h —Z —ch2oh —ch = chch2oh —CH2CH2OH —CH2CHICH2OH Ten CH7 OH ——OCF2 (CF3) CH2OH —co2h —I ——COCI -Br —ch2ch—ch2 V —ch2ch2i —ch2i —ch = ch2 —ch2nh2 \ ch2 o— ^ 0 \ ch2—o— ^ 0 —ch2ch2 ~ o— / o —CH2CH2-o— ^ oo —CH2CH (OH) -CH2—〇— / o These fluorine-based chemicals can be easily introduced into the side chain with fluorination by a method known to those skilled in the art. Aliphatic polymer compound. -23-12126509 V. Description of the invention (22) The compound represented by the formula -Z in the general formula TM-1 below -Z has a propylene fluorenyl group or methacryl fluorene group at the molecular end, so The polymer compound having a fluorinated aliphatic group according to the present invention can be more simply produced by ethylene polymerization, so it is desired.

In addition, the present invention preferably uses a polymer compound having a fluorinated aliphatic group on a side chain of a fluorine-based chemical product obtained by a short-chain polymerization method, which is generally referred to as "perfluoroalkyl-containing oligomer", It is commercially available and used. This chemical product is, for example, MEGAFAC F-178K, MEGAFAC F-470, MEGAFAC F-473, MEGAFAC F-475, MEGAFAC F-476, MEGAFAC F_472, MEGAFAC R-08 manufactured and sold by Dainippon Ink Chemical Co., Ltd. Or SURFLON SdSl'S-SSS'SdQS'S-lOl'S-iOS, etc. manufactured by Asahi Glass Co., Ltd. Among them, MEGAFAC F-178K (hereinafter referred to as P-1), -24-1226509 V. Description of the invention (23) MEGAFAC F-470 (hereinafter referred to as P-2), MEGAFAC F- 47 3 (hereinafter referred to as P-3), MEGAFAC F-475 (hereinafter referred to as P-4), MEGAFAC F476 (hereinafter referred to as P-5), and MEGAFAC F-472 (hereinafter referred to as P-6), will not cause the problem of sensitivity reduction It ’s better. In the present invention, a fluorinated aliphatic compound produced by a polymerization method is preferred. The oligomerization method uses gallium fluoride or selenium fluoride as a catalyst to polymerize ethylene tetrafluoride free radical in a polar solvent such as dichloride to produce an oligomer (Scheme3), and the above short-chain polymer In the same manner, a reactive group (unsaturated bond) in the oligomer obtained by polymerization is used to introduce a polymer compound having a fluorinated aliphatic group into a side chain through appropriate chemical modification. Scheme3 KF F2C = CF2 _ 'diglyme CF3CF3 c2f5 C2F5

etc. Except for short-chain polymerization and oligomerization, typical fluorinated aliphatic compounds are produced by electrolytic fluorination and indirect fluorination. In other words, perfluorinated octyl sulfonate fluoride (Sc hem e4) and the fluorine-based chemicals introduced into it have been commercially very successful by electrolytic fluorination, and they have been more commonly used by users since ancient times. The present inventors have found that a better result can be obtained when a fluorine-based chemical produced by a short-chain polymerization method or an oligomerization method is used instead.

Scheme4

C8H17—S02X

HF c8f17-so2f e -25-1226509 V. Description of the invention (24) The working principle of the effect of the present invention is not clear. The short-chain polymerization method or oligomerization method of the present invention, which uses an aliphatic compound corresponding to electrolytic fluorination or an indirect fluorination method as a production raw material, and controls the C-fluorene bond fluorination system by polymerizing and preparing a fluorinated olefin, Those who have obtained fluorinated aliphatic compounds can obtain better results for any reason. For example, a fluorinated aliphatic compound obtained by a short-chain polymerization method or an oligomerization method usually results in a chain length distribution of the polymerization reaction process, so a mixture of compounds having different alkyl chain lengths is formed, and if necessary, it has branched chains. Alkyl constructor. This may be related to the working principle of the present invention. In addition, the partially fluorinated chemical products manufactured by the electrolytic fluorination method used in the past are substances with low biodegradability and high bioaccumulation, although the degree is slight, fearing reproductive toxicity and developmental toxicity. The fluorine-based chemical product of the present invention by the short-chain polymerization method is a substance having high environmental safety, which is advantageous in terms of industry. Based on the hypothesis of this operation, the inventors have carried out a detailed review and found that another method for achieving a better photoresist composition is to use the composition of (2) above. In other words, the other to the fluorinated aliphatic group used in the side chain of the present invention is the one represented by the general formula (F 1), and the side chain portion is represented by the general formula (F2), especially The composition shown by n = 4 is the sum of the components of n = 3 ~ 6 and the mixture of '= 40 ~ 97 mole%, or the composition of n = 3 which has 40 ~ 97 mole% has excellent performance. -26- 1226509 V. Description of the invention (25) ——x + c— (CF2CF2) n F (F2) | mr3 Among them, R2 and R3 each represent a hydrogen atom and 1 to 4 carbon atoms (Cl to C4) Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a butyl group, and the like, preferably a hydrogen atom, a methyl group, and more preferably a hydrogen atom, X represents a common bond or a divalent bonding group (organic group) that connects a substituent (F2) with a polymer side chain. A preferred X represents _〇-, -S-, -N (R4 )-, -C0-, directly or via a divalent bonding group, are bonded to the polymer main chain. Here, R4 represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and 3-butyl groups. Preferred are a hydrogen atom and a methyl group. X may be any of the above, but -0-is preferred. M is an integer of 0 or more, an integer of 2 to 8 is preferable, and m is more preferable. When m is 2 or more, functional groups on adjacent carbons are bonded to form an aliphatic ring. η is an integer of 1 or more, and an integer of 1 to 10 is preferable. Here, η is more preferably 3 to 6, and it is preferable that at least η is 3,4,5,6 in the polymer compound. In particular, the component (polymer component) represented by η = 4 is 40 to 97 mol% or η = 3 for the total of the components of η = 3 to 6 (where η is each component of 3, 4, 5, and 6). The components shown are preferably 40 to 97 mole% for the sum of the components of η = 3 to 6 (11 is each component of 3, 4, 5, 6). The better ^ = 4 shows -27-1226509 V. Description of the invention (26) The sum of the components n = 3 to 6 is 60 to 95 mole%, and the best is 70 to 90 mole%. If it is less than 40 mol%, the isolated line will fly away, and if it is greater than 97 mol%, the isolated line will also fly away, so it is not desirable. The polymer main chain of Y is, for example, the compounds exemplified below. Next, a more specific method for producing a polymer compound having a fluorinated aliphatic group according to the present invention will be described. The fluorine-based polymer used in the present invention may be in the form of all polymers satisfying the requirements described in (A) and (B) above. Specific forms include acrylic resin, methacrylic resin, styrene resin, polyester resin, polyurethane resin, polycarbonate resin, polyamide resin, polyacetal resin, phenol / formaldehyde condensation resin, Polyvinylphenol resin, maleic anhydride / α-olefin resin, α-heterocyclic substituted methacrylic resin, and the like. Among them, acrylic resin, methacrylic resin, styrene resin, polyester resin, and polyurethane resin are useful, and acrylic resin, methacrylic resin, and polyurethane resin are more preferable. These resins can be obtained by using a polymerizable monomer, and can be easily produced by methods known to those skilled in the art, such as polycondensation, addition polymerization, and ring-opening polymerization. In order to satisfy the requirement (A), a fluorine-containing monomer raw material can be appropriately selected at this time, and in order to satisfy the requirement (B), a raw material for monomer manufacturing, polymerization can be appropriately selected, and mixed or polymerized as required. Of polymers. The polymers most useful in the following, for example, acrylic resins and methacrylic acid resins, which are also excellent in manufacturing suitability, will be described in more detail with respect to the configuration (B). • 28-1226509 5. Description of the invention (27) A preferred embodiment of the acrylic resin used in the present invention is, for example, a unit having a unit not constituted by the following general formula (F3) as a copolymerization unit.

H2C C / 1, \ r2 \ C——γ〇- Η —c- 'I 0 I Ra － (CF2CF2) nF (F3) 1ΊΊ where' R i represents hydrogen atom, halogen atom (such as fluorine atom, bromine atom ) Or a methyl group which may have a substituent, YQ represents a divalent organic group, X, r2, R3, m, and η are synonymous with those of the general formula (F2), and the divalent organic group represented by Υ () is, for example, the above-mentioned X The same specific example. The specific structure of the perfluorinated alkyl group-containing monomer of the general formula (F3) used in the present invention is as follows. -29- 1226509 V. Description of the invention (28

0 〇-CH2CHr (CF2CF2) 4F (F-1)

0-CH2CH2 * (CF2CF2) 4F (F-7), CH3

〇-CH2CH2- (CF2CF2) 4F 〇

H (F-2) -〇-CH2- (CF2CF2) ^ F cr (F-8)

H (F-4) -o-ch2ch2ch2- (cf2cf2) 4f o OH3 o (F-9) -〇-CH2CH2CH2CH2- (CF2CF2) 4F (F-10)

H

H CH3 〇 • N—CH2CH2- (CF2CF2) 4F ch3 (F-5) -o-c 〇

HCH- (CF2CF2) 4F ch3 CF-ll) ΑΗ5 -N-CH2CH2- (CF2CF2) 4F ° CaH9

ch3 0-CH- (CF2CF2) 4F 〇 (M2) 3 Specific examples -30-1226509 V. Description of the invention (29) Η

Cl 0 ~ CH2CH2 ** (CF2CF2) 3F (F-13)

-〇-CH2CH2- (CF2CF2) 3F o (F-19)

o-ch2ch2- (cf2cf2) 3f

H (F-14) -〇-CH2- (CF2CF2) 3F 0, (F-20) .CH3

H

-S-CH2CH2- (CF2CF2) 3F

-〇-CH2CH2CH2- (CF2CF2) 3F o o (F-15) (F-21)

-N—CH2CH2- (CF2CF2) 3F o

H

0-CH2CH2CH2CHr (CF2CF2) 3F (F-16) (F-22)

H

〇 N-CH2CH2- (CF2CF2) 3F ch3 (F-17)

ch3 0-CHCH- (CF2CF2) 3F ch3 (P-23), C2H5 \ —N—CH2CH2- (CF2CF2) 3F c4h9

Specific examples of n = 5 -31 1226509 V. Description of the invention (30)

0-CH2CHr (CF2CF2) 5F (F-25)

Cl

0-CH2CH2- (CF2CF2) 5F (F-31) yCH3

o-ch2ch2- (cf2cf2) 5f (F-26) 0-CH2- (CF2CF2) 5F 〇 (F-32)

(F-28)

H

0-CH2CH2CH2- (CF2CF2) 5F

3

o-ch2ch2ch2ch2- (cf2cf2) 5f

(F-33) (F-34)

H ch3 N-CH2CH2- (CF2CF2) 5F ch3 〇 -〇-CHCH- (CF2CF2) 5F ch3 (F-29) (F-35)

yC2H5 N—CH2CH2- (CF2CF2) 5Fy I C4H9

ch3 0-CH- (CF2CF2) 5F

Specific examples of n-2 -32- 1226509 V. Description of the invention (31) Η

Cl 0-CH2CH2- (CF2CF2) 6F (F-37)

-〇CH2CH2- (CF2CF2) 6F 〇 (F-43)

0-CH2CH2- (CF2CF2) 6F (F-38)

o-ch2- (cf2cf2) 6f

S-CH2CH2- (CF2CF2) 6F

N-CH2CH2- (CF2CF2) 6F H (F〇9) (F-44)

(F-46)

(F-40)

H

N-CH2CH2- (CF2CF2) 6F ch3

ch3 0-CHCH- (CF2CF2) 6F ch3 (F-41) (F-47) 〇 c2h5

N-CH2CH2- (CF2CF2) 6F c4h9

ch3 0-CH- (CF2CF2) 6F (F-48) In the polymer compound of the present invention, the above monomers are preferably a mixture of different chain lengths of perfluorinated alkyl groups. In particular, in the general formulae (F 1) and (F3), the components represented by n = 4 and the components of n = 3 to 6 (where η is each component of 3, 4, 5, and 6)

-33- 1226509 V. Description of the invention (32) 40% to 97 mole%, or n = 3 to n = 3 to 6 (n = 3, 4, 5, 6) ) The sum is preferably 40 to 97 mole%. More preferably, the component represented by η = 4 is 60-93 mole% with respect to the sum of the components of η = 3-6, and the most preferable is 70-90 mole%. This mixture can be prepared by mixing the monomers represented by the above monomers (F-1) to (F-1 2) and η2 3, η = 5, and η = 6. In addition, after the perfluorinated alkyl group of the raw material is synthesized by short-chain polymerization to obtain mixtures with different chain lengths, the component of η = 4 can be prepared within the above-mentioned range by distillation, column separation, extraction, etc. to produce monomers. mixture. In addition, a mixture of η = 3 to η = 3 to 6 (where η is 3, 4, 5, and 6) can be mixed with a mixture of 40 to 97 moles of the above monomers (F- 13) The monomers shown in (F-24) are prepared with η = 4, η = 5, and η-6. In addition, after the raw materials of the perfluorinated alkyl group are synthesized by short-chain polymerization to obtain mixtures with different chain lengths, the component of η = 3 can be prepared and manufactured by the methods of distillation, column separation, and extraction within the above-mentioned range to produce monomer mixture . #The amount of these fluorinated aliphatic group-containing monomers used in the fluoropolymer used in the invention is 1% by weight or more, preferably 3 to 70% by weight, more based on the weight of the fluorinated polymer. Preferably, it is 7 to 60% by weight. Since the present invention uses a fluorinated aliphatic group S 'structure or composition distribution of a specific fluorinated polymer, the present invention can be used in any combination of conventional techniques such as copolymerization to a specific fluorinated aliphatic substitution number. Example 1 The polymer compound containing a perfluorinated alkyl group of the present invention is preferably used with a monomer copolymer having a polyepoxy group. Polyalkylene oxides such as polyepoxide-34-1226509 V. Description of the invention (33) Eyuan, Polypropylene oxide, Polybutylene oxide, Poly (Ethylene oxide · propylene oxide) None Regular copolymerization groups, poly (ethylene oxide • propylene oxide) block copolymerization groups, etc. Specific examples of these alkylene oxides are, for example, Japanese Patent Laid-Open No. 6 2-1 7 0 95 0, Japanese Patent Laid-Open No. 62-226 1 43, Japanese Patent Laid-Open No. 3_ 丨 72849, and Japanese Patent Laid-Open No. 8-15858. Gazette and others. In order to sufficiently achieve the purpose of the present invention, the molecular weight of the polyalkylene oxide is preferably 500 to 3000. The polyalkylene oxide unit is preferably at least 10 mol% in the polymer compound. In addition, the polymer used in the present invention can copolymerize a monomer having an acidic hydrogen atom. As the group having an acidic hydrogen atom, for example, any of the conventionally known acidic groups can be used as a carboxyl group or a phenolic hydroxyl group. Examples of known acidic groups include J.A. Dean ed., Lange's Handbook of Chemistry 3rd. Ed. 1985 Mcgraw-Hill Book Co .. In addition, a specific structure of the acidic hydrogen atom of these acidic groups bonded to the acidic group of a nitrogen atom is, for example, the following structures (A 1) to (A7). -S02NH2 (A 1) -S02NH-(A 2)-CONHS 02- (A3)-CONHCO— (A4) —S 〇2ΝΗ— S 〇2— (A 5) —C0NHS〇2NH — (A 6) -NHC0NHS02- (A7), and the acidic group described in Japanese Patent Application Laid-Open No. 8-1 5 8 5 8 is extremely useful. Including the nitrogen-containing proton having a coupling structure described in Japanese Patent Application Laid-Open No. 7-248628 -35-1226509 5. The heterocyclic structure of the invention (34). Examples of such nitrogen-containing heterocyclic structures are shown in (H) and (1) below.

Similarly, an acidic group having a hydrogen atom bonded to a carbon atom adjacent to an electron attracting group described in Japanese Patent Application Laid-Open No. 2000-19724 is extremely useful. Others such as kaiping 1 1-3 5268 1, kaiping 1 1-327 1 42, kaiping 1 1-327 1 3 1, kaiping 1 1-327 1 26, kaiping 1 1-339948, kaiping 1 0 -207052, Japanese Patent Application Laid-open No. 1 0-1 86642, Japanese Patent Application Laid-open No. 1 0-1 6 1 303 are also very suitable. These single systems having an acidic hydrogen atom use ethylene monomers having a freely polymerizable unsaturated group. Preferred among these ethylene monomers are acrylate, methacrylate, acrylamide, methacrylamide, styrene-based, and vinyl-based. A preferred structure is, for example, a compound described in Japanese Patent Application Laid-Open No. 104 42778. The content of the monomer having an acidic hydrogen atom in the fluorinated aliphatic group-containing polymer compound of the present invention is 0 to 50 mole%, preferably 0 to 40 mole%, and more preferably 5 to 30 mole%. . In addition, 'other copolymerization components are monomers having bridge bonds described in Japanese Patent Application Laid-open No. 4_222805, or the side chains of -36-1226509 described in Japanese Patent Application No. 10-1 42778. 5. Description of the invention (35) Yes Copolymerization of acrylate, methacrylate, acrylamide, or methacrylamide monomers with aliphatic groups having 9 or more carbon atoms or aromatic groups substituted with aliphatic groups having 2 or more carbon atoms. In addition, the present invention can be suitably applied to the urethane-based polymers described in JP 10-1088640, JP 10-186641, JP 2000-3032, JP 2000-304 0, and the like, Or the polycondensation and polymer addition system polymers disclosed in Japanese Patent Application Laid-Open Nos. 1 1 to 3 27 1 29. Furthermore, (meth) acrylic acid ester monomers having two or three perfluorinated alkyl groups of 3 to 20 in the molecules described in JP 2000-1 873 1 8 are also applicable to the present invention. The fluorine-based polymer of the present invention can be produced by a conventional method. For example, a (meth) acrylic acid ester having a fluorinated aliphatic group, a (meth) acrylic acid ester having a polyoxyalkylene group, and an acidic group-containing ethylene monomer bonded to an acidic hydrogen atom or a nitrogen atom are used in organic A general radical polymerization initiator is added to the solvent, and it is produced by thermal polymerization. Or, if necessary, another addition polymerizable unsaturated compound is added, and it is produced by the same method as described above. In addition, other addition-polymerized unsaturated compounds that are required to be used are, for example, those described in PolymerHandbook 2nd ed., J. Brandrup, Wiley Interscience (1 975) Chapter 2 Page 1 to 483. These include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethyl chloride (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and propylene oxide (meth) acrylate. (Meth) acrylates, (meth) acrylamide, N-methylol (meth) acrylamide, n- (p-hydroxyphenyl) _methacrylamine, etc. ( Meth) acrylamidonium, allyl acetate, allyl propionate, allene-37-1226509 V. Description of the invention (36) Allyl compounds such as propyloxyethanol; ethyl is allyl ether, propyl Vinyl ether, butyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, benzyl vinyl ether, Tetrahydrofuryl vinyl ether, phenyl vinyl ether, tolyl vinyl ether, diethylamino ethyl vinyl ether, and other vinyl ethers; vinyl acetate, vinyl butyrate, vinyl hexanoate, vinyl chloride acetate, Vinyl methoxyacetate, phenyl vinyl acetate, ethyl vinyl acetate, vinyl benzoate, benzyl chloride Vinyl esters such as vinyl acid esters; styrene, α-methylstyrene, methylstyrene, dimethylstyrene, chloromethylstyrene, ethoxymethylstyrene, hydroxystyrene, chlorinated Styrenes such as styrene and brominated styrene; ketenes such as methylketene, ethylketene, propylketene, and phenylketene; olefins such as isobutene, butadiene, and isopentene; Others include butyl citrate, dimethyl itaconate, diethyl itaconate, dimethyl maleate, diethyl fumarate, N-vinylpyrrolidone, N-vinylpyridine, acrylonitrile, etc. . The specific structure of the fluorine-based polymer of the present invention is described below. In addition, the numbers in the formula represent the mole ratio of each component. -38- 1226509 V. Description of the invention (37

30

70 C〇2 —CH2CH Ten CF2CF Seven F co2 Ten CH2CH2〇) ^ CH3 (P · 7) Division 2. , C02-CH2CH2 * (~ CF2CF2 ^ -f CO 乂 一 ch2ch2o) ^ ch3 (P-8) Women-_ C〇2 十 CH2CH2〇) ^ CH3 6〇2 ~ fC3H6〇) -7CH3 C02-CH2CH (0H) CH2- ^ CF2CF2 BU F (P-9)

40

60 CF3 C02-fcH2CH2c) * ^ C3H6C ^ (CH2CH20 | -CH3 C〇2 ~ CH2CH2 ^ ~ OF 2CF —CF—CF3 n'1 (P-10) (a + b + c = 12) f51 19 26 C02CH3 co2ch2ch2oh C02CH2CH (CH3) 2 CF. 3 (P-11) C〇2-CH2CH (OH) CH2- ^ CF2CF24—CF-cf3 -39-1226509

1226509 V. Description of Invention (39) (P-7) The production method will be a fluorine-based chemical product manufactured by short-chain polymerization (FM-1, where η is a mixture of 3, 4, 5, and 6, and η = 3% After the acrylic monomer (F-48) was introduced into the acrylic monomer (F-48) at a rate of 41% and a content ratio of η = 4, it was polymerized by copolymerization with other components. co2h = \

, C02-CH2CH2 ^ ~ CF2CF2 | ^ F ho_ch2cfv (-cf2cf2) ~ f-• H20 F «48 FM-1 (P-8) is produced using a fluorine-based chemical product (FM -2, n = 4, purity 95%) After introducing a methacrylic acid monomer (F-49), it is polymerized with other components by copolymerization. HO—CH, CH ten CF〇CFv} -n C02H ‘-H20 FM-2 co2-ch2ch2-(-cf2cf2) ^ f F49

Me (P-9) is produced by using a fluorine-based chemical product (FM-3, 'purity 95%') produced by a short-chain polymerization method. After introducing a methacrylic acid monomer (F-50), it is co-existed with other components. Polymerize to polymerize. H2C-CHCH2-f-CF2CF2) ^ F ---- ==== ^ C02-CH2CH (0H) CH2-(-CF2CF2) ^ F 〇 FM-3 F-50 -41-1226509 V. Description of the invention (4〇) The method of (P -1 0) uses a fluorine-based chemical product (FM-3, n = 3, purity 80%) produced by a short-chain polymerization method, and is introduced into a methacrylic acid monomer (F-51), followed by other components. Polymerization is performed by copolymerization. cf3 HO—CH2CH2 ^ ~ CF2CF2] —CF—CF3 n-1

co2h FM-4 -h2o C02-CH2CH2-f-CF2CF2f-cF-CF3 n-1 F-51 (P-1 1) Production method uses a fluorine-based chemical product (FM-5, n = 3,4,5,6 mixture, n = 4 content 60%) After introducing methacrylic acid monomer (F-52), it is polymerized with other ingredients by copolymerization. CF, H2C-CHCH2 ^ CF2CF2f.cF_cF3 〇 n-1 co2h -h2o FM-5

cf3 C〇2 ^ CH2CH (OH) CH2 ^ CF2CF2) —CF- CF——CF3 F-52 (p-l 2) Production method uses a fluorine-based chemical product (FM _ 6, n = 3 of -42-1226509 V. Description of the invention (41) Content 96%) After introducing methacrylic acid monomer (F_53), it is polymerized with other components by copolymerization. co2h HOH2C CF2CF2—h — FM-6 · Η2〇SC〇2-CH2 十 CF2CF2) -h F.53 (P-1 3) Production method uses a fluorine-based chemical product (FM- 7. The content of n = 4 is 93%) After introducing diol (F-54), it is polymerized with other diols and diisocyanate components through polycondensation. HO,

H02C BU CF2 CF2 BU F

N——H

H2ocH FM-7 0 -H2

H2C CH0F2 2N1C—C H2, ‘C \-

Production method of F -5 (P-1 4) A fluorine-based chemical product (FM-3) produced by a short-chain polymerization method is used to react with formazan / formalin resin to introduce a fluorinated aliphatic side chain. (? -16, 17, 18, 19, 20) The production method is a mixture containing n = 3,4,5,6, each of which has the following composition: P-16: n = 4 60% -43 ~ 1226509 V. Description of the invention (42) p_17: n = 4 is 80% of the sum of other ingredients P-18: n = 4 is 90% of the sum of other ingredients 19: n = 4 component is 95% for the sum of other components P-20: n = 3 component is 50% for the sum of other components The molecular weight range of the fluorine-based polymer used in the present invention is generally 10,000 to the weight average molecular weight The molecular weight of 200,000, more preferably 3,000 to 100,000 ° can be obtained by, for example, the GP method using a polystyrene standard material. Moreover, the addition amount of the fluorine-based polymer used in the present invention to the composition except for the solvent is 0.001 to 1% by weight, and more preferably 0. 0 to 1 to 5 weight%. %. In addition, the fluoropolymer of the present invention can be used in two or more kinds, and most of them can be used with a surfactant. In addition to the fluorine-based polymer used in the present invention, the essential components are (A) (1) a resin that is decomposed by an acid to increase solubility in an alkali developing solution, or (2) an alkali-soluble resin, and Low-molecular compounds that are decomposed by an acid and increase the solubility in an alkali imaging solution, or (3) resins that decompose by an acid, increase the solubility in an alkali imaging solution, and decomposed by an acid. , A low-molecular compound which increases solubility in an alkali imaging solution, and (B) a compound which generates an acid by irradiation with active light or radiation. The resin related to the component (A) which is decomposed by the action of acid to increase the solubility in the alkali developing solution will be explained. -44- 1226509 V. Description of the invention (4 3) (1) The resin which is decomposed by the action of acid and increases the solubility in the alkali imaging solution is achieved by protecting the alkali-soluble group with an acid-decomposable group. purpose. The alkali-soluble group is preferably a phenolic hydroxyl group or a carboxylic acid group. The protective groups of these alkali-soluble groups are acetal group, ketal group, 3-butyl ester group, 3 -butoxycarbonyl group, etc. are preferred, and more preferred are acetal group, 3 -butyl ester group, In particular, the acetal group is preferred in terms of sensitivity, sensitivity change to exposure time after exposure, and dimensional change stability (PED). In addition, when the exposure light source is A rF, the absorption of the phenol structure is high, and the acetal ester having a 3-butyl ester group or a carboxyl group is preferred. In particular, hydroxystyrenes are preferred for dry polymers that introduce appropriate acid-decomposable groups under KrF excimer laser light and electron beam exposure. The hydroxystyrenes and 3-butyl acrylate or Copolymer of acid-decomposable (meth) acrylates such as 3-butyl methacrylate. In addition, for the purpose of adjusting the alkali solubility of the dry polymer, a non-acid-decomposable group may be introduced. The method of introduction is a method of copolymerizing styrenes, (meth) acrylic esters, ammonium (meth) acrylic acid, or a method of protecting hydroxyl groups of hydroxystyrenes with non-acid-degradable substituents. Better. The non-acid-degradable substituents are preferably ethylamyl, mesylsulfonyl, tolylsulfonyl and isopropoxy, but are not limited by these. In addition, acid-decomposing groups having different acid-decomposability include, for example, coexistence of a 3-butoxy group, a 3-butoxycarboxy group, a tetrahydrofuranoxy group, and a tetrahydrofuranoxy group in the same main chain. It is better to adjust the sensitivity and contour. Suitable K rF excimer laser light and electron beam exposure are suitable for acid decomposition -45-1226509 V. Description of the invention (44) The general formula (E) of the polymer is as follows. General formula (E) H ^ c Jr ^ rd O — CH I o—r4

OH

Cl

Rs .c • c, 〇 少, 〇-Re

O, N-R7 I Re (wherein R3 'each independently represents a hydrogen atom, a methyl group, and several r3s may be the same or different. R4 represents a straight chain, a branched chain, or a cyclic carbon number of 1 to 12 unsubstituted or optionally substituted alkyl groups, or 6 to 18 unsubstituted or substituted aromatic groups, or 7 to 18 unsubstituted or substituted carbons Aralkyl group. Linear, branched or cyclic carbon number ～~ 12 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, 2-butyl , 3-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, cyclopropyl, cyclopentyl, 1-adamantylethyl, etc.) Substituents have, for example, hydroxyl atoms, fluorine, chlorine, bromine, iodine, etc., amine groups, nitro groups, cyano groups, carbonyl groups, ester groups, alkoxy groups, cycloalkyl groups which may contain hetero atoms, aryloxy groups, Substituent for sulfofluorenyl. Here, the fluorenyl group is preferably substituted with a fluorenyl group and an aromatic substituted fluorenyl group, the acetic acid group is substituted with a sulfonyl group and an aromatic substituted ester group, and the alkoxy group is methoxy and ethoxy A group, a propoxy group, a 3-butoxy group and the like are preferred. Examples of the cycloalkyl group include cyclohexyl, adamantyl, cyclopentyl, and cyclopropyl, and those having a hetero atom include, for example, a chelating group. Aryloxy, such as phenoxy, etc., may have substituents on this aryl group -46-1226509 V. (45) group of the invention description. Examples of the substituent having a sulfofluorenyl group include a methylsulfonyl group such as a methylsulfonyl group and an ethylsulfonyl group, and an arylsulfonyl group such as a phenylsulfonyl group. Examples of the aralkyl group include benzyl, phenethyl, benzhydryl, and naphthylmethyl. Among these aralkyl groups, those described as a substituent having an alkyl group may be used as the substituent. Examples of the aromatic group include a group derived from a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. These aromatic group rings may have, as substituents, those described in the substituents having the above-mentioned alkyl group. A hydrogen atom, a straight chain, a branched alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, propyl, butyl, 2-butyl, 3-butyl, etc.), straight chain, branch Alkoxy groups with 1 to 4 carbon atoms (such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, 2-butoxy, 3-butoxy, etc.), Acetyloxy, methanesulfonyloxy, tolyloxy, 3-butoxycarbonyloxy, 3-butoxycarbonylmethoxy, tetrahydrofuranoxy or tetrahydropyranyloxy. 3-Butyl, ethylfluorenyl, isopropoxy, and tetrahydrofluororanyloxy are preferred. R6 is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an aromatic group having a substituent having 6 to 12 carbon atoms, or a substituent having 7 to 18 carbon atoms The aralkyl group is preferably a 3-butyl group, a 1-methoxycyclohexyl group, or the like. R7 and R8 each independently represent a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an aromatic group which may have a substituent having 6 to 12 carbon atoms, or an aromatic group having 7 to 18 carbon atoms Aromatic radicals of substituents. Specific examples of the alkyl group, aromatic group, and aralkyl group of R0 to R8 are those in the above-mentioned carbon number range in the above-mentioned R3'-47-1226509. (46) Examples. a, b, c, d, and e each represent the mole% of each monomer unit, and OS a / (a + b) S 0.6 is better, and more preferably OS a / (a + b) S 0.5 The best is 0.05 $ a / (a + b) S0.5. 0Sc / (a + b + c) S0.3 is preferred, and even more preferred is 0Sc / (a + b + c) S 0.2 ° ° Sd / (a + b + d) S0.4 is preferred, 0Sd / (a + b + d) S 0.3 ° is better, 0Se / (a + b + e) S0.4 is better, and 0Sd / (a + b + d) S 0.3 ° is better than The above description is a preferred example of an acid-decomposable polymer. However, "i_Bu" means isobutyl, "n-Bu" means n-butyl, and "Et" means ethyl.

-48- 1226509

1226509

1226509

1226509

1226509

(B-22)

OH (B-23)

(B-24)

-53- 1226509 V. Description of the invention (52) The weight average molecular weight of the above polymer can be determined by gel permeation chromatography (GPC), and the molecular weight (Mw) of polystyrene conversion is preferably 2,000. ~ 200,000, more preferably between 4,000 and 50,000, and the best between 7,000 and 30,000. If the molecular weight is more than 200,000, the solubility is poor and the resolution is lowered. 'If the molecular weight is less than 2,000, the film tends to be edged. A polymer having a narrow molecular weight distribution (weight average molecular weight / number average molecular weight) (1.03 to 1.40) is preferable in terms of resolution. In addition, the above polymers may be combined with two or more different polymers, or polymers of the same kind, different molecular weights, or different composition ratios may be combined, and sensitivity, resolution, etc. may be adjusted. In the aspect (1) of the present invention, when it is used for KrF excimer laser light and electron beam exposure, it can be added to the acid-decomposable polymer described above, and can be used in the positive photoresist composition without acid-decomposable groups. Alkali soluble resin, which can improve local sensitivity. The above-mentioned alkali-soluble resin containing no acid-decomposable group (hereinafter simply referred to as alkali-soluble resin) is a resin that is soluble in alkali, and for example, polyhydroxystyrene, phenolic resin and derivatives thereof are preferred. In addition, any copolymer resin containing para-hydroxystyrene units that has alkali solubility can be used. Among them, poly (p-hydroxystyrene), poly (p- / m-hydroxystyrene) copolymer, poly (p-hydroxy / o-hydroxystyrene) copolymer, poly (p-hydroxystyrene / benzene Ethylene) copolymers are preferred. In addition, poly (4-hydroxy-3-methylstyrene), poly (4-hydroxy-3, 5-dimethylstyrene) poly (alkyl-substituted hydroxystyrene) resins, and partial phenolic properties of the above resins The hydroxyl group is alkylated or -54-1226509 V. Description of the invention (53) Acetyl-based resins are preferred as long as they are alkali-soluble. In addition, when hydrogenating part of the phenol nuclei of the above resin (less than 30 mol% of all phenol nuclei), it is preferable to improve the transparency, sensitivity, resolution, and form a rectangular outline of the resin. In the form of (1) in the present invention, the addition amount of the alkali-soluble resin containing no acid-decomposable group to the composition is preferably 2 to 60% by weight based on the total weight of the solid content of the entire composition. ， Better 5 ～ 30% by weight. 〇 In addition, it is decomposed by the acid action corresponding to the exposure of A rF excimer laser light to decompose the resin which increases the solubility in the alkali developing solution, for example, in the resin main chain and / Alternatively, a resin having an alicyclic structure in a side chain may be a conventional polymer prepared by a conventional technique. A suitable resin is, for example, a polymer containing a repeating structural unit represented by the following general formula (F) and / or a repeating structural unit represented by the following general formula (G).

(Among them, RU ~ RM each independently represents a hydrogen atom or an alkyl group which may have a substituent, and a represents a 0 or 1, and an alkyl group of R 1! To R i 4 is preferably one having 1 to 12 carbon atoms. More preferably, it is 1 to 10, and specific examples include methyl, ethyl, propyl,

55-1226509 V. Description of the invention (54) Isopropyl, n-butyl, isobutyl, 2-butyl, 3-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl are preferred . Examples of the substituent of the alkyl group include a hydroxyl group, an alkoxy group, and an alkoxyalkoxy group. In the general formula (G), R3 represents a hydrogen atom or a methyl group. The "a" represents two or more kinds selected from a single bond, an alkylene group, a cycloalkylene group, an ether group, a sulfurized ether group, a fluorenyl group, and an acetic acid group, alone or in combination. W represents a group represented by -C (Ra) (Rb) (Rc) or a group represented by -CH (Rd) -0-Re. Here, each of Ra, Rb, and Rc may have a halogen atom, an alkoxy group, an alkoxycarbonyl group, a fluorenyl group, or a fluorenyl group as a substituent. The carbon number is 1 to 20 linear or branched alkyl groups or carbon Number 3 to 20 cycloalkyl. However, Ra and Rb can be bonded to each other to form an alicyclic monocyclic ring. Rd means a hydrogen atom or an alkyl group. The Re system represents a linear or branched alkyl group having 1 to 20 carbon atoms or a cycloalkane having 3 to 20 carbon atoms having a halogen atom, an alkoxy group, an alkoxycarbonyl group, a fluorenyl group, or a fluorenyl group as a substituent. base. The polymer may further include a repeating structural unit represented by the following general formula (H)

(Where Z2 represents -0- or -N (R3)-, where R3 represents a hydrogen atom, a hydroxyl group, an alkyl group, a halogenated alkyl group, or -0s〇2_R4, and L represents an alkyl group, a halogenated alkyl group, Cycloalkyl or camphor residue) The following are specific examples of monomers having a repeating structural unit represented by the general formula (F), -56-1226509

5. Description of Invention (55) Except for these restrictions. Q 'W HO HO H0

The following are specific examples of monomers having repeating structural units represented by the general formula (G) ', but are not limited thereto. -57- 1226509 V. Description of the invention (56)

58- 1226509

1226509 V. Description of Invention (58)

Ο

For the purpose of the resolution, heat resistance, sensitivity, etc. of the resistance to standard or standard imaging solution, substrate adhesion, profile of the resist, and general necessary characteristics of photoresist, various repeating structural units may be included. The repeating structural unit is, for example, the following repeating structural unit of a monomer, but is limited by these. This can finely adjust the properties required for acid-decomposable resins, especially (1) the solubility of the coating solvent, -60-1226509 5. Description of the invention (59) (2) Film-forming properties (glass transition temperature), ( 3) Inspection of imaging, (4) film edges (hydrophilicity, alkali-soluble group selection), (5) adhesion to the substrate of the unexposed part, (6) dry etching resistance, and other fine adjustments. The monomers include, for example, acrylates, methacrylates, ammonium acrylates, ammonium methacrylate, allyl compounds, vinyl ethers, vinyl esters, and the like. Unsaturated compounds, etc. Specifically, the following monomers are mentioned, for example. Examples of the acrylates include alkyl acrylates (preferably alkyl acrylates having 1 to 10 carbon atoms in the alkyl group): methyl acrylate, ethyl acrylate, propyl acrylate, pentyl acrylate, and cyclohexyl acrylate , Ethylhexyl acrylate, octyl acrylate, 3rd-octyl acrylate, ethyl chloride acrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxybenzoyl acrylate Ethyl esters, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, methyl acrylate, tetrahydromethyl acrylate and the like. For example, methacrylic acid esters Alkyl esters (preferably alkyl methacrylates having 1 to 10 carbon atoms): methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, methyl ester Methyl acrylate, hexyl methacrylate, -61-1226509 5. Description of the invention (60) Cyclohexyl methacrylate, benzyl methacrylate, benzyl methacrylate chloride, octyl methacrylate Esters, 2-hydroxy methacrylic acid Ethyl ester, 4-hydroxybutyl methacrylate, 5-hydroxybenzyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate , Pentaerythritol monomethacrylate, methyl methacrylate, tetrahydromethyl methacrylate, etc .; acrylamides: acrylamide, N-alkylacrylamide (alkyl groups are 1 to 10 carbon atoms, Such as methyl, ethyl, propyl, butyl, 3-butyl, heptyl, octyl, cyclohexyl, hydroxyethyl, etc.), N, N-dialkylpropenamide (alkyl is the number of carbons) 1 to 10, such as methyl, ethyl, butyl, isobutyl, ethylhexyl, cyclohexyl, etc.), N-hydroxyethyl-N-methacrylamide, N-2 -vinylfluorenamine Ethyl-N-ethenylacrylamide and the like. Methacrylamides: Methacrylamides, N-alkylmethacrylamides (alkyl groups are 1 to 10 carbon atoms, such as methyl, ethyl, 3-butyl, ethylhexyl, Hydroxyethyl, cyclohexyl, etc.), N, N-dialkylmethacrylamide (alkyl is ethyl, propyl, butyl, etc.), N-hydroxyethyl-N-methylmethacrylamine Amine, etc. Allyl compounds: Allyl esters (eg allyl acetate, allyl hexanoate, allyl hexanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate Propyl ester, allyl acetate, allyl lactate, etc.), allyloxy ethanol, etc. -62- 1226509 V. Description of the invention (61) Vinyl ethers: Alkyl vinyl ethers (such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethyl Oxyethyl 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, diethyl amino ethyl vinyl ether, butyl amino ethyl vinyl ether, benzyl vinyl ether, tetrahydrofluorenyl vinyl ether, etc. Vinyl esters: Vinyl butyrate, vinyl isobutyrate, trimethyl vinyl acetate, diethyl vinyl acetate, vinyl decanoate, vinyl hexanoate, vinyl chloride chloride, vinyl dichloride, methoxy Vinyl Acetate, Butoxy Vinyl Acetate, Ethyl Vinyl Acetate, Vinyl Lactate, Vinyl-Phenyl Butyrate, Vinyl Cyclohexyl Carboxylate, etc .; Dialkyl Itaconates: Itaconic Acid Dimethyl ester, diethyl itaconic acid, dibutyl itaconic acid, etc. Others include citric acid, itaconic acid, maleic anhydride, horse Amidine, acrylonitrile, methacrylonitrile, maleonitrile, etc. Other addition polymerizable unsaturated compounds that can be copolymerized with the monomers of the various repeating structural units described above are copolymerized. In acid-decomposable resins, each repeats The molar ratio of the structural unit is appropriate in terms of the required dry etching resistance of the photoresist, the standard developing solution suitability, the substrate adhesion, the photoresist profile, and the resolution and heat resistance of the general requirements for photoresist. -63- 1226509 V. Description of the invention (62) The content of non-repeating structural units of general formula (F) in acid decomposable resins suitable for A r F exposure applications is 25 to 70 moles in all repetitive structural units. The ear% is preferably, more preferably 28 to 65 mole%, and most preferably 30 to 60 mole%. The content of the repeating structural unit represented by the general formula (G) in the acid-decomposable resin is repeated all over. The structural unit is preferably 2 to 50 mol%, more preferably 4 to 45 mol%, and most preferably 6 to 40 mol%. In addition, the general formula (树脂) in the acid decomposable resin is repeated. Content of tectonic unit 20 to 80 mol% is preferred, 25 to 70 mol% is more preferred, and 30 to 60 mol% is most preferred. The repeating structural unit based on the monomer constituting the copolymerization component described above is The content in the resin can be appropriately set depending on the desired photoresist performance. Generally, the repeating structural unit represented by the general formula (F) and the general formula (G) is 99 mol for the total mol. % Or less is preferred, more preferably 90% or less, and most preferably 80% or less. The molecular weight of the above acid-decomposable resin is weight average (Mw: polystyrene conversion by GPC method), It is preferably 1,000 to 1,000,000, more preferably 1,500 to 500,000, even more preferably 2,000 to 200,000, and the most preferable 2,500 to 1,00,000. The larger the heat resistance is, etc., In addition, the developability can be reduced, and the balance 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). The following is a preferred specific example of a repeating structural unit combining an acid-decomposable resin suitable for A F exposure applications. -64- 1226509 V. Description of the invention (63) —0¾—CH-

CH 3 —CH-CH— ο (1) —CH2—CH- CHjCHari0 —CH-CH—〇 ~ > = 〇 C2)

—CH-CH— 〇 person 〇x ^ 〇 ⑶ Ο Ο

M) (5)

-CH2—CH— CH2CH3ViQ—CH—CH— * 〇 = v = 〇 * —CH2—CH—I c—o II o ⑹ C (CH3) 3 -65-1226509 5. Description of the invention (64 -CH2—CH— CH3Γ multiple CH—CH0 ** = k > 〇 (7) 〇CH factory CH— C—0—CH2CH2OCH3II0 ο —CH2—CH— CH2CH3 c—οIIο

—CH—CH—〇 ~ > = 〇 ⑻ * —ch2—ch ~ ° o -CH2—CH— CH3c " ° i9 II o—CHj—CH—CH3 C—0-CII I o ch3

—CH—CH— 0 = k Λ = 〇 O —CH—CH—

o -CH5—CH ⑼ CH3 oo (10) * —CH2—CH-r ° <500 〇-66-1226509 V. Description of the invention (65) CH3 _ch2—C—c—〇II 〇ΙΠ3—CH—CH — 〇 = ^ 〇 ^ = 〇 (11) ch3 • CH2—0 &quot; · C—0fl 0 ch2ch3i9 —CH—CH—〇 ~ &gt; = 〇 (12) ch3 -ch2—C— CH3ΓΪ0 —CH-CH—Φ 〇 &lt; 0 &gt; 〇 (13) * _CHj-CH- f {-〇 ^ 2 (QH2hCHz 0

* —CH2—c—— (14) C—〇—CH2CH2〇CH3 o In the positive photoresist composition of the present invention, when the above-mentioned acid-decomposable resin is in the form of (1), the whole photoresist composition is compounded. The amount is preferably 40 to 99.99% by weight of the total solid content, and more preferably 50 to 99.97% by weight. Next, the combination of (A) component (2) form alkali-soluble resin and -67-1226509 V. Description of the invention (66) Low-molecular-weight compounds that decompose by acid action and increase the solubility in the developing solution. Alkali-soluble resins are alkali-soluble resins, such as polyhydroxystyrene, phenolic lacquer resin, and derivatives thereof. In addition, any copolymer resin having para-hydroxystyrene units having alkali solubility can be used. Among them, poly (p-hydroxystyrene), poly (p- / m-hydroxystyrene) copolymer, poly (p-hydroxy / o-hydroxystyrene) copolymer, and poly (p-hydroxystyrene / benzene Ethylene) copolymers are preferred. In addition, poly (4-hydroxy-3 -methylstyrene), poly (4-hydroxy-3, 5-dimethylstyrene) poly (alkyl-substituted hydroxystyrene) resins, and some of the phenolic properties of the above resins A resin having a hydroxyl group alkylated or acetylated is preferred as long as it is alkali-soluble. For example, a styrene-maleic anhydride copolymer or a resin described in Japanese Patent Application No. 6-9867 1 or a carboxyl group-containing methacrylic resin and derivatives thereof are not limited thereto. The weight-average molecular weight of these alkali-soluble resins according to the present invention (polystyrene equivalent 测定 measured by gel permeation chromatography) is preferably from 1,000 to 100,000. If it is less than 1,000, the unexposed portion will lose a large amount of film after development, and if it is more than 1,000, the development speed will decrease. Especially preferably 2,000 to 50,000. In the positive-type photoresist composition of the present invention, in the form of (2), the compounding amount of the acid-decomposable resin in the entire photoresist composition is 40 to 99.99% by weight of the total solid content. 50 to 99.97% by weight. Next, low-molecular compounds which are decomposed by the action of an acid to increase the solubility in an alkali developing solution will be described. -68- 1226509 V. Description of the invention (67) These compounds with a certain molecular weight of 3,000 or less are preferred, and a compound with a single structure is introduced with a base that decomposes by acid, decomposes by acid action, and has alkali-soluble compounds . A compound having at least two acid-decomposable groups in its structure and having the furthest distance between the acid-decomposable groups in addition to the acid-decomposable group and having at least 8 bonding atoms is preferred. More preferably, 10 or 12 compounds, or at least 3 acid-decomposable groups, and at least the position between the acid-decomposable groups has at least a position other than the acid-decomposable group. Compounds with 9 bonded atoms, more preferably 10 compounds, and most preferably 11 compounds. In addition, the preferable upper limit of the above-mentioned bonding atoms is 50, and the more preferable number is 30. In the present invention, when the acid-decomposable dissolution inhibiting compound has three or more acid-decomposable groups, preferably four or more, or when it has two acid-decomposable groups, the decomposable groups have a certain distance or more from each other, Can significantly improve the solubility of alkali-soluble resins. In addition, the distance between the acid-decomposable groups may indicate the number of bonded atoms in addition to the acid-decomposable group. For example, in the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonded atoms each, and in the case of the compound (3), 12 bonded atoms. 2 3 B〇-〇 〇 ‘B〇 ⑴-2CH2-3CH2-4CH2-COO-A0 (2) -69-1226509 V. Description of the invention (68)

Acid-decomposable group: "COO-A0, -0-B0" In addition, the "dissolution preventing compound of the present invention may have several acid-decomposable groups on one benzene ring, preferably one on one benzene ring A compound formed by the structure of an acid-decomposable group. In addition, the molecular weight of the dissolution preventing compound of the present invention is preferably 3,000 or less, more preferably 500 to 3,000, and most preferably 1,000 to 2500. In a preferred embodiment of the present invention, a group decomposed by an acid, that is, a group containing -COO-A (), -0-BG, for example, -a (), -R2G ()-COOA (), or -ArOB ° The base shown. Among them, A ° represents-C (R (n) (R〇2) (R〇3), -Si (R () I) (R〇2) (R03), R03, R () 4, RQ5 represents each the same or different hydrogen atom, straight chain radical, branched alkyl, cyclic alkyl, alkenyl or aryl, and R06 represents straight linear or branched alkyl. Or aryl groups, but any two of R01 ~, or any two of ?? 1 ~, R (m ~ R06) can be bonded to each other to form a ring. R () represents a divalent aliphatic group which may have a substituent. Or aromatic hydrocarbon group, -Ar- represents a monocyclic or polycyclic divalent aromatic group which may have a substituent. -70-1226509 V. Description of the Invention (69) Here, the alkyl group is methyl, ethyl, or Propyl, n-butyl, 2-butyl, and 3-butyl have 1 to 4 carbon atoms. Cycloalkyl is cyclopropyl, cyclobutyl, cyclohexyl, and adamantyl. Numbers 3 to 10 are preferred. Alkenyl is preferably vinyl, propenyl, allyl, butenyl. Numbers 2 to 4 are preferred. Aryl is phenyl, tolyl, tolyl, Cumene, naphthyl, and anthracenyl have 6 to 14 carbon atoms. Examples of the substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, and iodine). , Nitro, cyano, the above-mentioned alkyl, methoxy · ethoxy · hydroxyethoxy · propoxy · hydroxypropoxy · n-butoxy · isobutoxy • 2nd-butoxy • 3rd-Alkoxy groups such as butoxy, methoxycarbonyl and ethoxycarbonyl groups, alkoxycarbonyl groups such as benzyl, phenethyl, and cumyl groups, aralkyloxy groups, and methylamino groups Fluorenyl groups such as ethenyl, butyryl, benzyl, cyano and pentamyl, ethoxy of butyryl, the alkenyl, vinyloxy, allyloxy, allyloxy, and butene Alkenyloxy group of oxy group 3, aryloxy group such as aryl group, phenoxy group, aryloxycarbonyl group such as benzamyloxy group, etc. The groups decomposed by acid are silyl ether group, cumyl group, condensation Aldehyde group, tetrahydropyranyl ether group, ethanol ether group, ethanol ester group, tertiary alkyl ether group, tertiary alkyl ester group, tertiary alkyl carbonate group are preferred. Tertiary alkyl ester group is more preferred A tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group are preferred. Specific examples of preferred compound structures are described below. 1226509 V. Description of the invention (70)

-72- 1226509 V. Description of the invention (71)

-73- 1226509 V. Description of the Invention (72)

(11)

-74- 1226509 V. Description of the Invention (73)

-75- 1226509 V. Description of the invention (74)

OR OR

(16)

OR

-16- 1226509 V. Description of the Invention (75)

(19)

-77- 1226509 V. Description of the invention (76)

OR OR OR

(twenty two)

OR OR OR

(twenty three)

OR OR OR

(24) -78- 1226509 V. Description of the invention (77)

OR OR OR

-79- 1226509 V. Description of the Invention (78)

OR

OR

-80- 1226509

1226509 V. Description of Invention (80)

OR

RO

CH 3 CH. -82- 1226509 V. Description of the invention (81)

OR OR

-83- 1226509 V. Description of the invention (82)

-84- 1226509 V. Description of the Invention (83)

OR OR

In the above compounds (1) to (43), R represents a hydrogen atom and the following group: -85-1226509 V. Description of the invention (84) a ch2- coo-c (ch3) 2c6h5, a CH2-COO-C4H9 ( t) ·, one co0-C4H9 ⑴, but at least two or three depending on its structure are groups other than hydrogen atoms, and each substituent R may be the same group. Those suitable for use as the Ai: F excimer laser photoresist are, for example, a dissolution preventing compound shown in [3] (C) described in Japanese Patent Application No. 2000-248658, but are not limited thereto. In the case of the form (2) in the present invention, the content of the dissolution preventing compound is 3 to 45% by weight based on the total weight of the composition (excluding the solvent), preferably 5 to 30% by weight, and more preferably 10 to 20% by weight. The morphology shown in (3) is a resin containing an acid that is decomposed by the action of (1) as described above and has increased solubility in an alkali developing solution, and a resin that is decomposed and increased by the action of acid as shown in (2) above. Both soluble compounds in alkaline imaging solution. In addition, in order to adjust the sensitivity or the influence of a fixed wave, an alkali-soluble resin can be added. When in the form of (3), the content of each component is a resin that can be decomposed by the action of acid in the form of (2) above to increase the solubility in the alkali developing solution, and decomposed by the action of acid to increase the Each content of the soluble low-molecular-weight compound in the alkali imaging solution and the alkali-soluble resin for adjusting sensitivity or the influence of a fixed wave has the same range. The compounds used in the present invention to generate acids by irradiation with active light or radiation (photoacid generators: compounds containing acids generated by electron rays) are -86-1226509 V. Description of the invention (85) Photocationic polymerization Photo-initiator, photo-radical polymerization photo-initiator, photochromic agent for pigments, photochromic agent, or microphotoresist used in conventional light (ultraviolet light of 400 ~ 200nm, especially g-line, h-line , I-line, KrF excimer laser light), ArF excimer laser light, F2 excimer laser light, electron rays, X-rays, molecular rays or ion beams to generate acid compounds and appropriately select these mixtures. In addition, other photoacid generators such as diazonium salts, ammonium salts, phosphorus salts, iodide salts, selenium salts, selenium salts, arsenic salts, organic halogen compounds, organic metal / organic halides, ortho-nitro groups are used. The benzyl-type protective group photo-generating agent, sulfamate and other typical photo-decompositions produce sulfonic acid compounds, diazones, diazo compounds, and the like. In addition, compounds which generate an acid group by light or introduce a compound into the main or side chain of a polymer can be used. Alternatively, VNRPillai, Synthesis, (1), 1 (19080), A. Abad eta1, Tetrahedron Lett., (47) 4555 (1971), DHR Barton et al, J. Chem. Soc. (C), 329 (1970), US Pat. No. 3,799,778, and European Patent No. 1 26,7 1 2 are compounds which generate acid by light. The following is a description of those who are particularly effective among the compounds which generate an acid by electron beam or X-ray irradiation. (1) A trihalomethyl substituted oxazole derivative represented by the following general formula (PAG 1) or an S-Sanken derivative represented by the general formula (PAG2). -87- 1226509 V. Description of the invention (86) N-N〆, 〇 ′, _ (PAG1)

C (Y) 3 (PAG2) (wherein represents a substituted or unsubstituted aryl, alkenyl, R2 () 2 represents a substituted or unsubstituted aryl, alkenyl, alkyl, -C (Y) 3. Y represents a chlorine atom or a bromine atom. Specifically, for example, there are the following compounds, but the present invention is not limited by these. 0 -88-1226509 V. Description of the invention (87) (M1-1) Λ = ν N CH.CH- 0, ^ 'c CH-CH-C ^^ C-CO, CHi-

H-H U 1 «_C, #C

HftCO- CB #, ringing-^ CH ^ CH-C: 〇: C_ C〇3 (WC1-3) [^^ CHeCH one of them. (PACl-δ) (P / Cl-4) co- m〇aa CHmCH ^^ CC, a CC ^ CH-l ⑽H) &lt; PACl-7) a P · 1 n (⑽ · "〇3〇 ^ Ν ^ ((FAC2-2)

a

C ^ C

l CH »CH Λ N Λ A

CH-C

scW j A CPAC2-9) CCJ, (PAC2-10) (2) An iodized salt represented by the following general formula (PAG3), or a green salt represented by the general formula (PAG4). ,, A /: ιΘ ζΘ r2〇3 R ^-^ S®

Z Θ (PAG3) R205 (PAG4) -89- 1226509 V. Description of the invention (88) (wherein A r 1 and A r 2 each represent an independently substituted or unsubstituted aryl group, R203, R204, The R205 series each independently represents an unsubstituted alkyl group or aryl group, which is substituted by 仵 | | substituting μ. The Z- series represents a counter anion, such as BF4-, AsF6-, PF6-,,,

Condensed polynuclear aromatic sulfonic acid anions such as perfluoroalkanesulfonic acid anions, pentafluorobenzenesulfonic acid anions, naphthalene-1 -sulfonic acid anions, such as SiF6-, C104-, CF3S03-, etc. Dyes and the like, but the present invention is not limited by them. In addition, at least two of R203, R204, and R205 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 -90-1226509 V. Description of the invention (89)

CiiH, 5 (PAG3-1) 〇- · Θ-〇 C4Hg

ΟτΆ CfsS0p 1 -sof (PA63-2) (PAC3-3) (ms-4): ©

-91-1226509 V. Description of the Invention (90) (PACW2) iCHjCHiCHa

H3COOC

ac ^ xy 外 &quot; Ο (PAC3-13) sop (PAG3-14) \} ~ or Q ^ O ^^^-8 ° 30 &lt; (PAC3-15) • 1E)

(PAC3-18)

(FAC3-19) \ jj \ _) ο- · ^ α Θ C4F9S〇3 (PAG3-21) -92-1226509 V. Description of the invention (91)

F F F (PAG3-22) CF3S03 Θ

OfO · —Qr side ©

nh-so3 θ (PAG3-23) (PAG3-24) (PAG3-25) -93- 1226509 V. Description of the invention (92)

5 ^ (PA04-1) L /) ~ s0 ^ PAW-3)

CFjSpj® ° 12Ημ / / _y \ _ * (Qj-S® (PAG4-i) -1) (PAG4-2) CH3

(PAG4-6) sc &gt; 3G HgC A rr # CtF17SP3e (〇Vs0 f

F F

F F hQ-I ^ oc, ^ (PAG4-7) cf3so3 ©

HiC HO (PAG4-9)

Θ Γ㈣SbF kg CH,

CFaSO ^ (PAG4-8) Θ -S-CHb CHa (PAG4-10) CM Θ (PAG4-11) (PAG4-12) c4iv

Kicq HO H ^ CO -94- 1226509 V. Description of the invention (93 (ηϊΟ, Ηο HO (η) 04Ηα (PAG4-14) e, \ w / ▼, / BF‘e ch, (FAG4-15)

sw Ο

H3C CH ^ Qg (PAC4-16) 〇0 Θ o ~ s 0 (PAM-17) 〇 一 CHj sbFee / == ^ Khan CH, ^ J ^ c ^ -seJ pFee (PAC4-1S) CQiCHjCHjCHjCH. Sound bar ) 2 (PAM-20) Q ^ Lch,-^) pp. E ^ Q-sof

Cf- ^ CHaCI ^ Cf ^ O- 〇 (PAG4'21) (PAG4-22): household (PAW-23) (FA64-24) ^ 2η, 5 (PAG4-25) -95-122526 5. Description of the invention ( 94)

-96- 1226509 V. Description of the invention (95 -Ph2 eo3s-cf3 (PAG4-38) MeO — ^^-1-Ph2 0o3s-c4f9 (PA64-39) e〇3S-CF3 (PA64-40) Ph2 θ〇3δ —C4F9 (PAG4-41) — ^^-S ~ Ph2 e〇3S--Q ^ CH3 (PAG4-42)!-Ph2% ShQ) -CH3 (PA64-43) S-Ph2 e〇3S—CF3 (PA64 -44) e〇3S-C4F «(PAG4-45) -97-1226509 V. Description of the invention (96)

〇3s-〇 ~ CH3 (PAG4-46) —0 ~ S-Ph2 (-+ Ois (-Wi?-+ 〇- * s &quot; ph2% S-CF3 circle-47) eo3s-c4fs (pa_ e〇3S- CF3 (PAG4- 49) e〇zS-CAf% (PA64-50) 0〇3S-CF3 (PAG4-51) e〇3S-C4F9 (PA64-52) (where Ph is phenyl) General formula (PAG3 ) And (PAG4) are synthesized by the methods described in US Pat. Nos. 2,807,648 and 4,247,473, 53-10, 1,33 1, etc. (3) The second mill derivative represented by the formula (PAG5), or the iminosulfonate derivative represented by the general formula: Ar3—S02-S02—Ar4 R206—s〇2—〇—N (PAG5) (PAG6)

(Among them, A1 · 3 and A4 represent independent substituted or unsubstituted aryl groups. For example, JP-A (PAG6) is substituted-98-1226509. V. Description of the invention (97) R2Q6 are each independently represented A substituted or unsubstituted alkyl group and aryl group. A represents a substituted or unsubstituted alkylene group, an alkenyl group, and an arylene group. Specific examples include the compounds shown below, but the present invention is not limited thereto. Waiting Limit-SOf (PAG5-1)

CHa (PAC5-2)

HjC

CJ (ΡΑβδ-4) (PA6S-3)

Qj〇a5 HC HaC F f F F (PAG5-13)

caJ (PACS-6) (PAG6-i) a

(PAC5-1D)

(PAB5-12) (PAG5-M) a

^^ SO ^ SOj— SOj- (PAG5-15) -99- 1226509 V. Description of the invention (⑽) 〇

° (PAG6-3) (PAG6-S) ° (PAG6-2) Ο Ο (PAG6-4) ° (ΡΑΒδ-ε)

fi M-O-SC ^ -CjHs ° &lt; PA «-7) Ο

_ · 1Z) • 100- 1226509

1226509 V. Description of the invention (100 P 0 ^ Jn-〇-ShQhcH3 (PA66-21) Fly 〇 〇 〇 N—〇 One S—CF3 II 〇 ° (PAG6-22) 〇 i? N—O—S—CHj * 〇Art

(PAG6-23) Ο Ο? (PAG6-24) CH3 (PAG6-25)

(PAG6-26) (PAG6-27) -102- 1226509 5. Description of the invention (

(PA66-2B)

N-〇-S-C3H7 (PAG6-29) N-〇-S-C4H9

(PAG6-30) (PAG6-32) (PAG6-33) (PAG6-34) fu N-〇-S-^^-CH3 (PAG6-31) (4) The weight shown by the following general formula (PAG7) Azadiapine derivative compound -103-1226509 V. Description of the invention (102)

Ο Ο (PAG7) (wherein R is each a linear, branched or cyclic alkyl group, or an aryl group which may have a substituent) Specific examples include the following compounds, but are not limited thereto.

(PAG7-5)

Additionally, No. 2000-24 1 45 7, No. 2000-240060, No. 2000-23473 No. 3, No. 2000-1 502 1 No. 7, No. 2000-1 88077, No. 2000- 62 3 78 Photoacid generator. The addition amount of these photoacid generators is based on the solid content in the composition, and is usually 0.1 to 30% by weight, preferably 0.3 to 20% by weight, and more preferably 0.5 to 10% by weight. -104- 1226509 5. Description of the invention (103) If the amount of photoacid generator is less than 0.1% by weight, the sensitivity will tend to decrease, and if it exceeds 30% by weight, the light absorption of the photoresist will be too high and the profile will deteriorate. 2. The scope of the project (especially the firing process) is narrow, so it is not desired. A basic compound may be added to the composition of the present invention. The preferred basic compound system usable in the present invention is an organic basic compound having a stronger basicity than phenol. Among them, nitrogen-containing organic basic compounds are preferred. By adding organic basic compounds, the sensitivity change over time can be improved. The organic basic compound is, for example, a compound having a structure shown below. R251 R250—N—r252 — (A) (wherein 'R25 (), R251, and R252 are independent hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, fluorenyl alkyl groups having 1 to 6 carbon atoms, and carbon number 丨A hydroxyalkyl group of ~ 6 or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, in which R2 "and R 2 5 can be bonded to each other to form a ring.) -N-0 = 4 ^ 1 —… (B) 1 |… (c) -CN ~… (D) r253 γ, r… (E) R —C ~ N—C—R256 (where R253, R254, R255, and R256 are the same or different Alkyl group of 1 to 6 carbon atoms) -105-1226509 V. Description of the invention (10) The compound of the more soil is a nitrogen-containing alkali with one to two points in the middle to the middle, and has two different chemical environments. The most preferred compound is 'one or not', which means that there are two groups containing a substituted or unsubstituted amine group. Chemical compounds. Preferred examples are substituted or unsubstituted guanidine, substituted: unsubstituted aminopyridine, substituted or unsubstituted aminopyridine, substituted or unsubstituted amino Zyrrolidine, substituted or unsubstituted: Azole, substituted or unsubstituted pyrazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted: purine, substituted or unsubstituted imidazoline , Substituted or unsubstituted, pyrazoline, substituted or unsubstituted piperidine, substituted or unenacted morpholine, substituted or unsubstituted aminomorpholine, etc. 2 Generation In the sense of the meaning, the substitution of an amino group, an amino alkyl group, an alkylamino group, an amine aryl group, an aryl group is an alkyl group, an alkyl group, an alkoxy group, a fluorenyl group, an alkoxy group, an aryl group, Aryloxy, peptyl, hydroxy, cyano. Compounds that are more preferred include guanidine, 丨, dimethyl guanidine, 1, 1 '3,3-tetramethylguanidine, 2-aminopyridine, 3 -Aminopyridine, 4-Aminopyridine, 2-methylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine methyl) , 2-fl female group-3-methyl group ratio, 2-amino group "4 'methylpyridine B, 2-month female group-5-methyl group ratio π group, 2-amino group-6 -Methyl hydrazine D, q ^ J January feminine ethylpyridine, 4-amine Ethylpyridine, 3-aminopyridine, piper belly, N- (2-aminoethyl) piperidine, N- (2-aminoethyl) piperidine, 4-amino, 9, 2, 6, 6-

Tetramethylpiperidine, 4-pyranylpiperidine, 2-iminopiperidine,. D 1 · (2-Aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-3_-10 6-1226509 5. Description of the invention (105) P-Tripyrazole, Pycnogenol, 2 aminomethyl I 5 _methylpyridine, pyrimidine, 2,4-monoaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3 -Pyridinoline, N-aminomorpholine, N_ (2-aminoamino) morpholine, 丨, 5_diazobicyclo [4.3 · 0] -5 -nonene, 1,8- Diazobicyclo [5 · 4 · 0] -7-undecene, 1,4-diazobicyclo [2.2 · 2] octane, 2,4,5-triphenylimidazoline, N- Tertiary morpholine derivatives such as methylmorpholine, N-ethylmorpholine, ν-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinylethylthiourea (CHMETU), Tokaihei 1 1-52 57 Hindered amines described in Gazette No. 5 (as described in [0005] in the Gazette), etc. are not limited by these. More specific examples include 1, 5 -diazobicyclo [4.3.0]-5 · nonene, 1, 8 -a diazo- [5.4 · 0] -7 -undiple storage (DBU), 1,4-diazobicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, pyrrole, pyrazole, Tertiary morpholines such as imidazoles, pyridazines, pyrimidines, CHMETU, and hindered amines such as bis (1,2,2,6,6-pentamethyl-4-piperidinyl) decanoate and the like. Among them, 1,5-diazobicyclo [4 · 3.0] -5-nonene, 1,8-diazobicyclo [5 · 4 · 0] -7-undecene, 1,4-diene Azobicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, 4,4-dimethylimidazoline, CHMETU, bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) decanoate and dicyclohexylmethylamine are preferred. These organic basic compounds can be used alone or in combination of two or more. The amount of the organic basic compound used is generally 0.001 to 10 parts by weight, preferably 0.01 to -107 · 1226509 for 100 parts by weight of the total solid content of the photoresist composition. 5. Description of the invention (106) 5 Parts by weight. If it is less than 0.001 part by weight, the effect of adding an organic basic compound cannot be obtained. Further, if it is more than 10 parts by weight, the sensitivity tends to decrease and the developability of the non-exposed portion tends to deteriorate. The positive-type photoresist composition of the present invention may contain other fluorine-based and / or silicon-based surfactants in addition to the fluorine-based polymer of the present invention. The positive-type photoresist composition of the present invention may contain any one of a fluorine-based surfactant, a silicon-based surfactant, a surfactant containing both a fluorine atom and a silicon atom, or two or more kinds thereof. Such surfactants include, for example, JP-A-Sho 62-3 6663, JP-A-Sho 6 1-226746, JP-A-Sho 6 1-226745, JP-A-Sho 62-1 70950, and JP-A-Sho 63-34540. The surfactants described in Japanese Patent Application Laid-Open No. 7-230 1 65, Japanese Patent Application Laid-Open No. 8-62834, Japanese Patent Application Laid-Open No. 9-5988 can also be used directly as described below. Commercially available surfactants include, for example, Yebei Dunpu (transliteration) EF30 1, EF3 03 (produced by Shin Akita Kasei Co., Ltd.), Floraton FC430, FC431 (Sumitomo Shriyem (transliteration) (stock) System), Mercat F1 7 1, F 1 7 3, F 1 7 6, F189, R08 (made by Dainippon Ink Co., Ltd.), Safron S-382, SC101, SCI 02, SCI 03, SCI 04, SCI 05, SCI 06 (made by Asahi Glass Co., Ltd.) and other fluorine-based surfactants or silicon-based surfactants. In addition, polysiloxane polymer KP-34 1 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant. The compounding amount of these surfactants is based on the total composition of the composition of the present invention -108-1226509 V. Description of the solid component of the invention (107) The standard is usually 0.001 ~ 2% by weight, preferably 0 · 01 ~ 1% by weight. These surfactants may be used singly or in combination. Specific examples of other surfactants include polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide hexadecyl ether, polyethylene oxide oleyl ether and the like. Ethers, polyethylene oxide alkyl aryl ethers such as polyethylene oxide octyl phenol ether, polyethylene oxide nonyl phenol ether, polyethylene oxide · polypropylene oxide block copolymers Class, sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate, sorbitol monostearate Esters such as sorbitol fatty acid esters, polyethylene oxide sorbitol monolaurate, polyethylene oxide sorbitol monopalmitate, polyethylene oxide sorbitol monostearate, Non-ionic surfactants such as polyethylene oxide sorbitol trioleate, polyepoxide sorbitol fatty acid esters, etc. Methacrylic (co) polymerized polyfuron (transliteration) No. 75 'No. 95 (Gongrong Company Fat Chemical Industry Co., Ltd.) and so on. The compounding amount of these other surfactants is usually 2 parts by weight or less, preferably i% by weight or less, based on 100 parts by weight of the solid content in the composition of the present invention. Compounds having two or more phenolic OH groups that promote solubility in a developing solution, such as polyacryl compounds, preferably polyhydroxy compounds, among which are benzene, resorcinol, fluorinated saccharin, 2, 3 4,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, ^, 61: ,, ^ '(4-hydroxyphenyl) -1,3,5-tris Cumene, 4- (4-hydroxyphenyl) methane, 4- (4-hydroxyphenyl) -109-1226509 5. Description of the invention (1 08) yl) ethane, 1,1'-bis (4-hydroxybenzene) Group) cyclohexane. In the chemically amplified photoresist composition of the present invention, the above components are dissolved in a solvent and coated on a carrier. The solvent used here is dichloroethylene, cyclohexanone, cyclopentanone, 2-heptanone, 7 -Butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether Methyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate , N, N-dimethylformamide, dimethylarylene, N-methylpyrrolidone, tetrahydrofuran and the like are preferred, and these can be used alone or in combination. In addition, N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl It is used for high boiling point solvents such as kiln and benzyl ether. The above-mentioned chemically amplified photoresist composition can be coated on a substrate (such as silicon / silicon dioxide coating) used in manufacturing precision integrated circuit components by a suitable coating method such as a spinner, a roller, etc. The hood is exposed, and a good photoresist pattern is obtained by firing and developing. The developing solution of the chemically amplified photoresist composition of the present invention can use, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methylsilicate, ammonium water, ethylamine, n-propylamine, etc. Primary amines, secondary amines such as diethylamine, di-n-propylamine, tertiary amines such as triethylamine, methyldiethylamine, alcohol amines such as dimethylethanolamine, triethanolamine, methylformamide or acetamidine Isoamidine, tetraammonium hydroxide, tetraethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydrogen-110-1226509 V. Description of the invention (109) oxide, tetraethylammonium hydroxide Compounds, tributylmethylammonium hydroxide, tetraethanolammonium hydroxide, methyltriethanolammonium hydroxide, benzyldiethanolammonium hydroxide, benzyldimethylethanolammonium hydroxide, benzyl Aqueous solutions of quaternary ammonium such as triethanolammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide, and cyclic amines such as pyrrole and piperidine. The positive 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 from 0.2 · 1.2 to 1.2 // m. In the present invention, a commercially available inorganic or organic antireflection film may be used as necessary. As the anti-reflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon dioxide, or an organic film type made of a light absorbing agent and a polymer material can be used. The former must use equipment such as a vacuum evaporation apparatus, a CVD apparatus, and a sputtering apparatus for film formation. The organic antireflection film is, for example, a product formed from a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin, an alkali-soluble resin, and a light-absorbing agent described in Japanese Patent No. 7-6 96 1 1 or US Patent No. 5,294,680. Reactant of maleic anhydride copolymer and diamine-type light absorbing agent, Japanese Patent Application Laid-open No. 6-1 1 863 No. 1 containing resin binder and methylolmelamine-based thermal crosslinking agent, Japanese Patent Application Laid-open No. 6-1 1 86 An acrylic resin-type antireflection film having a carboxylic acid group, an epoxy group, and a light-absorbing group in the same molecule described in Japanese Patent Publication No. 56, which is described in Japanese Patent Application Laid-Open No. 8-871 15 by methylolmelamine and dibenzoyl A ketone-based light absorbing agent is prepared by adding a low-molecular-weight light absorbing agent to a polyethylene glycol resin described in JP-A No. 8-1 79509. The organic anti-reflection film can also use the DUV30 series or DUV-40 series made by Newark Sainz (Transliteration), AC_2 -111-1226509 made by Western Ray (Transliteration). 5. Description of the invention (110), AC-3 Wait. The above photoresist liquid is applied to a substrate (such as a silicon / silicon dioxide coating) used in manufacturing precision integrated circuit components (on a substrate provided with the antireflection film as required) by a spinner, a roller, etc. After being coated by an appropriate coating method, it is exposed through a predetermined hood, and a good photoresist pattern is obtained by firing and developing. Here, light, X-rays, and electron rays having a wavelength of 150 nm to 250 nm of exposure light or radiation are preferred. Specifically, there are, for example, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), X-rays, and electron rays. [Π] Next, a photoresist composition for an electron or X-ray with high resolution, high sensitivity, and good contour shape according to the present invention will be described. The typical photoresist for electron or X-rays of the present invention constituted by the above (3) to (1 4) is a compound containing a component (a) which generates an acid when irradiated with electrons or X-rays. As the component (a), any compound that generates an acid by electron beam or X-ray irradiation can be used, but compounds represented by the general formulae (I) to (I Π) are preferred. -112- 1226509

R3I ^ 32 卩 37 feet 36 X- In the general formulae (I) to (III), the linear or branched alkyl group is, for example, a methyl group, an ethyl group, a propyl group, an isobutyl group, a second group -Butyl and 3 -butyl have 1 to 4 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group having 3 to 8 carbon atoms which may have a substituent. Examples of linear and branched alkoxy groups of R and R37 include methoxy, ethoxy, hydroxyethoxy, propoxy, n-butoxy, isobutoxy, and 2-butoxy- 113-1226509 V. Description of the invention (112) group, 1-but 4-carbon number such as 3-butoxy. The cyclic alkoxy group is a cyclopentyloxy group, and examples thereof include a cyclopentyloxy group and a cyclohexyloxy group. The halogen atom of R! To R37 includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The aryl group having a size of 38, for example, a phenyl group, a tolyl group, a methoxyphenyl group, or a naphthyl group may have 6 to 14 carbon atoms. The substituents of this # are 1 to 4 carbon atoms, halogen atoms (fluorine atom, chlorine atom, iodine atom), 6 to 10 carbon atoms, 2 to 6 alkenyl groups, and cyano groups. , Hydroxyl, carboxyl, carboxycarbonyl, nitro, etc. In addition, 'R] ~ R] 5, R] 6 ~ R27 or R28 ~ R37 may form a ring containing one or two or more kinds selected from single bonds, carbon, oxygen, sulfur, and nitrogen. There are pyran ring, dihydropyran ring, pyran ring, trihydropyran ring, thiophene ring, pyrrole ring and the like. In the general formulae (I) to (I I I), X-is an anion of a sulfonic acid. In addition, 'such as condensation polynuclear aromatic anions such as perfluorinated alkane sulfonic acid anions such as CF3S03-, pentafluorobenzenesulfonic acid anions, naphthalene-1 sulfonic acid anions', i. But not limited by these. Among them, X 'is more preferably an anion having benzenesulfonic acid, naphthalenesulfonic acid' or quinonesulfonic acid having at least one selected from the following groups. At least one fluorine atom, at least one linear, branched or cyclic alkyl substituted with fluorine, -114-1226509 V. Description of the invention (113) At least one linear, branched or cyclic substituted with fluorine Alkoxy, at least one fluorenyl substituted with fluorine, at least one fluorenyl substituted with fluorine, at least one sulfonyl substituted with fluorine, at least one sulfonyl substituted with fluorine, at least one substituted with fluorine Sulfonylamino, at least one aryl substituted with fluorine, at least one arylalkyl substituted with fluorine, and at least one alkoxycarbonyl substituted with fluorine The number of carbon atoms is 1 to 1, and 2. 1 to 25 fluorine atoms are preferred. Specific examples include trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, pentafluoropropyl, heptafluoroisopropyl, perfluorobutyl, perfluorooctyl, perfluorododecyl , Perfluorocyclohexyl and so on. Among them, perfluoroalkyl groups having 1 to 4 carbon atoms which are all substituted with fluorine are preferred. The linear, branched, or cyclic alkoxy group is preferably 1 to 12 carbon atoms, and is preferably substituted with 1 to 25 fluorine atoms. Specific examples include trifluoromethoxy, pentafluoroethoxy, pentafluoroisopropoxy, perfluorobutoxy, perfluorooctyloxy, perfluorododecyloxy, perfluorocyclohexyloxy and the like. Among them, perfluoroalkoxy groups having 1 to 4 carbon atoms which are all substituted with fluorine are preferred. The above fluorenyl group is preferably those having 2 to 12 carbon atoms and being substituted with 1 to 23 fluorine atoms. Specific examples include trifluoroacetamido, fluorinated ethidium, pentafluoropropionyl, pentafluorobenzyl, and the like. The above fluorenyloxy group is preferably those having 2 to 12 carbon atoms and substituted with 1 to 23 fluorine atoms. -115-1226509 V. Description of the invention (114). Specific examples include trifluoroacetamyloxy, fluorinated acetamyloxy, pentafluoropropamyloxy, pentafluorobenzyloxy and the like. The sulfofluorenyl group is preferably one having 1 to 12 carbon atoms and one having 2 to 5 fluorine atoms substituted. Specific examples include trifluoromethanesulfonyl, pentafluoroethanesulfonyl, perfluorobutanesulfonyl, perfluorooctanesulfonyl, perfluorobenzenesulfonyl, 4-trifluoromethylbenzenesulfonyl, etc. . The sulfonyloxy group is preferably one having 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms. Specific examples include trifluoromethanesulfonyloxy, perfluorobutanesulfonyloxy, and 4-trifluoromethylbenzenesulfonyloxy. The sulfonamide group is preferably one having 1 to 12 carbon atoms and substituted with 1 to 25 fluorine atoms. Specific examples include trifluoromethanesulfonamido, perfluorobutanesulfonamido, perfluorooctanesulfonamido, and pentafluorobenzenesulfonamido. The above-mentioned aryl group is preferably 6 to 14 carbon atoms and substituted with 1 to 9 fluorine atoms. Specific examples include pentafluorophenyl, 4-trifluoromethylphenyl, pentafluoroallyl, nonafluoro, 4-chlorophenyl, 2,4-dichlorophenyl, and the like. The above aralkyl system is preferably one having 7 to 10 carbon atoms and substituted with 1 to 15 fluorine atoms. Specific examples include pentafluorophenylmethyl, pentafluorophenylethyl, perfluorobenzyl, perfluorophenethyl and the like. The alkoxycarbonyl group is preferably one having 2 to 13 carbon atoms and substituted with 1 to 25 fluorine atoms. Specific examples thereof include a difluoro / methoxy iron group, a pentaethoxyloxy group, a pentafluorophenoxycarbonyl group, a perfluorobutoxycarbonyl group, a perfluorooctyloxycarbonyl group, and the like. The most preferred X-series is a fluorine-substituted benzenesulfonic acid anion, of which pentafluorobenzenesulfonic acid anion is more preferred. -1 16-1226509 5. Explanation of the invention (115) In addition, the benzenesulfonic acid, naphthalene acid, or anthracenesulfonic acid having a fluorine-containing substituent may be linear, branched, or cyclic alkoxy, and fluorene. Group, fluorenyl group, sulfonyl group, sulfonyl group, sulfonyl group, aryl group, aralkyl group, alkoxycarbonyl group (these carbon numbers are the same as above), halogen (except fluorine) , Hydroxyl, nitro, etc. The following are specific examples of the compound represented by the general formula (I).

-117- 1226509 V. Description of the Invention (116)

〇 丨 + cf3 0 -118-1226509 V. Description of the invention (117)

cf3so3 'α -15)

C4F9S03

CgF ^ SOs

C11F23SO3

(I-20) CH3

-119- 1226509 V. Description of the invention (118)

(I-23) 〇C4H9

(Bu 27)

C4F9SO3 -120- 1226509 V. Description of the invention (彳 19) h3c

COOCH2CH2CH2CH3 (Bu 30)

(Bu 32) The following are specific examples of compounds represented by the general formula (I I) -121-1226509 V. Description of the invention (12)

-122- 1226509 V. Description of the Invention (121)

ch3 The following are specific examples of the compound represented by the general formula (I I I). -123- 1226509 V. Description of the Invention (122 / Οη_ηΟ &quot; 4ά ^ (ΠΜ)

F CF3

(ΙΙΙ-3)

OzS

〇ρ

• 〇3S • CF3 (III-5)

jF = ^ \ H 〇 NHCOCbH17 卞 C4F9 • o

MeO

-o3s

Br F -124- 1226509 5. Description of the invention (123 Οκ_ι + · ηΟ cp3S〇3 &quot; ㈣0 '^ ^ —1 + ~ ^ ^ c8f17so3 〈〉 —— 丨 +-^ ^ C11F23S03Q_r ^ fs〇3- <〉-1+ ~ ^ ^ ~ 〇CH3 CF3SO3 <^ ^ ~ 〇CH3 C4F9SO3 N5- &gt; +-q N [} ~ | + 0 ^ 02 cf3so3_ H3C- ~ ^ ^ -1 +-^ ^ ~~ CH3 CF3SO3 H3c-^ ^ —Γ ~ ^ ~ CH3 CF3SO3 o2n NO, CF3S03 (III-9) M-10) 11-11) I M2) I M3) 11-14) I BU 15) 11-16) 11-17) 11-18 ) (111-19) h3c C7H15 (n) Cl CH3 ~ Guang ~~ (π) 〇7Η15 CF3SO3 (Ml-20) CF3SCV (IN-21) -125- 1226509 V. Description of the invention (124) f3c— ^ ^ —丨 + ~ ^ ~ ^ ~ CF3 cf3so3 cf3so3 1

h3co〇c cooch3

Cl

CF3S03 tBu CF3SO3 tBu C4F9SO3

CF3SO3 (111-22) (111-23) (111-24) (II Bu 25) (111-26) (111-27) (111-28) (111-29) -126- 1226509 V. Description of the invention ( 125 〇3s ^ δΗιι (η)

H ^ co- —OCH3 (MI-30) 0 ~ r_0 (111-31) dll-32) (MI-33)

Cl (MI-34)

0 ~, + _ {D

03S—4 A—OC2H5 NH'〇3δΌ0 (n) C5H1

(111-35) The following are acid generators other than the compounds represented by the general formulae (I) to (I I I) -127-1226509 V. Description of the invention (126)

(n) C4H9 CF3SO3

(n) C4H9 cf3so3 ~

ch3

C02Me -128- 1226509 V. Description of the invention (127)

-129- 1226509 V. Description of the invention (128) —〇; 0 ^ —CHrf—⑼W CF3S03- (n) C4H9 • 〇3S s + —ch2ci ch3 Compounds of general formula (I) and general formula (in) can be used alone Or two or more kinds. The compounds of the general formula (I) and the general formula (II) are reacted with a substituted or unsubstituted phenylsulfenyl group, for example, by using an aryl Grignard reagent such as an arylmagnesium bromide, and the obtained triarylsulfonyl group is reacted. Method for exchanging halide with corresponding sulfonate, or condensing substituted or unsubstituted phenylimine with corresponding aromatic compound using acid catalyst such as methanesulfonic acid / pentaoxophosphate or aluminum chloride The method of salt exchange is synthesized by using a diaryl iodonium salt and a diaryl sulfonate to condense using a catalyst such as ketone acetate, or a salt exchange method. The compound of the general formula (I I I) can be synthesized by reacting an aromatic compound with a periodate. The sulfonic acid or sulfonate used in the salt exchange can be prepared by hydrolyzing a commercially available chlorinated sulfonic acid, a method of reacting an aromatic compound with chlorosulfonic acid, and an aromatic compound with an aminosulfonic acid. Prepared by reaction methods and the like. A method for synthesizing a specific compound of the general formulae (I) to (III) will be specifically described below. -1 30-

1226509 V. Description of the invention (129) (Synthesis of tetramethylammonium pentafluorobenzenesulfonate) Dissolved in 100 g of methanol in 25 g of pentafluorobenzenesulfonyl sulfonyl chloride under ice-cooling, and slowly add 100 g 25% tetramethylammonium hydroxide in water. After stirring at room temperature for 3 hours, a solution of tetramethylammonium pentafluorobenzenesulfonate was prepared. The solution was exchanged with a salt of a salt of iodonium and iodonium. (Synthesis of triphenylethenyl pentafluorobenzenesulfonate: Synthesis of specific examples (〗 _ 丨)) 50 g of diphenylsulfenyl sulfonate was dissolved in 800 ml of benzene, 200 g of aluminum chloride was added thereto, and refluxed for 24 hours. The reaction solution was slowly poured into 2 L of ice, 400 ml of concentrated hydrochloric acid was added thereto, and the mixture was heated at 70 ° C. for 10 minutes. The aqueous solution was washed with 500 ml of ethyl acetate, filtered, and 400 ml was added to dissolve 200 g.砩: Money changer. The precipitated powder is filtered, washed with water, washed with ethyl acetate, and dried to obtain 70 g of triphenyl iodide. 30.5 g of triphenyl iodide is dissolved in 10 In 〇m 1 methanol, 19.1 g of silver oxide was added to the solution, and the mixture was stirred at room temperature for 4 hours. The solution was filtered, and an excessive solution of tetramethylammonium pentafluorobenzenesulfonate was added thereto. The reaction solution was concentrated and dissolved in 500 ml of dichloromethane, and the solution was washed with a 5% tetramethylammonium hydroxide aqueous solution and water. The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain Triphenyl pentafluorobenzene sulfonate (I-1) ° (Synthesis of triaryl pentafluorobenzene sulfonate: Synthesis of specific examples (I-9) and (II-1)) 50 g of triaryl Dissolved in base chloride (made by Fluka, 50% of triphenyl chloride) 131-1226509 V. Description of the invention (13〇) Aqueous solution) Dissolved In 500m 1 of water, an excessive amount of a solution of tetramethylamine pentafluorobenzenesulfonate was added to the solution to precipitate an oily substance. The upper liquid solution was removed with decane, and the obtained oily substance was washed with water and dried to obtain a triaryl group. Pentafluorobenzenesulfonate (Specific examples (I-9), (II-1) as main components). (Synthesis of di (4--3-pentylphenyl) iron iron pentafluorobenzenesulfonate: Synthesis of Specific Example (III-1)) 60 g of 3-pentylbenzene, 39.5 g of potassium iodate, 81 g of acetic anhydride, and 170 ml of dichloromethane were mixed, and 66.8 g of the solution was slowly dropped thereinto under ice-cooling. Sulfuric acid. After stirring under ice-cooling for 2 hours, it was stirred at room temperature for 10 hours. 500 ml of 1 water was added to the reaction solution under ice-cooling, and the mixture was extracted with dichloromethane. The organic phase was washed with sodium bicarbonate and water. It was concentrated to obtain bis (4-thi-methylphenyl) iodoferric sulfate. The sulfate was added to an excess of tetramethylammonium pentafluorobenzenesulfonate solution. 500 m of water was added to the solution to make it It was extracted with dichloromethane, and the organic phase was washed with 5% tetramethylammonium hydroxide aqueous solution, absorbed in water, and concentrated to obtain two (4-3- Pentylphenyl) iodopentafluorobenzenesulfonate. Other compounds can also be synthesized using the same method. Other acid generators that can be used as component (a) in the photoresist composition for electron or X-rays of the present invention, As the component (a), in addition to the above-mentioned preferred acid generators, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photochromic agent, and a photochromic agent may be appropriately selected and used. Or the photo-resistive compounds used in micro-resistance, etc. to generate acid compounds and these mixtures' are more specific. For example, the photoresist composition described above -132-1226509 5. In the description of the invention (131), those exemplified as photoacid generators . Further, the compound represented by the general formula (I) to the general formula (II) of the component (a) may use another photoacid generator. The amount of the acid generator used with the compound represented by the above-mentioned general formulae (I) to (III) according to the present invention is based on the odor ratio (compounds represented by the general formulae (I) to (III) / other acid generators) It is usually 100/0 ~ 20/80, preferably 100/0 ~ 40/60, and more preferably 100/0 ~ 50/50. The total content of the component (a) is generally 0.1 to 20% by weight, preferably 0.5 to 10% by weight, and more preferably all of the solid components of the positive electron beam or X-ray photoresist composition of the present invention. It is 1 to 7% by weight. The photoresist composition for an electron beam or X-ray of the present invention contains an alkali-soluble resin or an acid-decomposable resin as a component (b) or (b,). Alkali-soluble resins are aqueous resins that are insoluble in water and soluble in alkaline aqueous solutions (referred to as alkali-soluble resins). The alkali-dissolving rate of these alkali-soluble resins is preferably 20 A / sec or more at 0 · 26 1 N tetramethylammonium hydroxide (TMAH) measurement (23 ° C). More preferably, it is 200 A / sec or more (A is Angstrom). The acid-decomposable resin has a base which is decomposed by an acid, and becomes an alkali-soluble resin by the action of an acid. The alkali-soluble resin and the acid-decomposable resin used in the photoresist composition for electron or X-rays of the present invention can also satisfy the following conditions (1) and (2). (1) Derived from -133-1226509 derived from at least one aromatic ring having 6 to 20 carbon atoms and a monomer having an ethylenically unsaturated group bonded directly or through a bonding group on the aromatic ring. V. Description of the invention ( 132) The repeating unit, (2) The relationship between the 7 ^ electrons of the aromatic ring and the non-shared electron pair of the substituent on the aromatic ring is the formula (1). (Formula 1) Ν7Γ + Ni〇ne = 1 Here, N 7Γ represents the total number of π electrons, and N1 () ne represents a linear, branched, or ring having 1 to 12 carbons as a substituent. Alkoxy, alkenyloxy, aryloxy, aralkoxy, or total number of electrons of non-shared electron pairs of hydroxyl groups, 2 or more adjacent alkoxy groups or hydroxyl groups are bonded to each other to form 5 or more carbon atoms Ring structure. Except for benzodioxazole. Moreover, when N 7Γ = 6, the substituent does not contain a hydroxyl group. In particular, N 7Γ + (1/2) NUne in the formula (I) is preferably in the range of 10 to 40 because it is easy to generate secondary electrons. Preferred aromatic rings are, for example, benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, biphenyls, etc., and preferred substituents on the aromatic rings are, for example, hydroxy, methoxy, ethoxy, isopropyl, and the like. In addition, when the total number of '7Γ electrons N7Γ is 10 or more aromatic rings (such as naphthalene ring, I stomach ring, biphenyl ring, biphenyl aromatic ring), the substitution of 8 stomachs on the aromatic ring does not have non-shared electron pairs ( NUne = 0), such as hydrogen, saturated alkyl, etc. M If ffij stomach The alkali-soluble resin and acid-decomposable resin of the present invention are preferably composed of repeating units represented by WS (1) to (5). -134- 1226509 V. Description of the invention (彳 33) -e I1: CH2C-) — ⑴ (Ra〇) |-^ dr— (° Rc) n {〇Rb) r

Ri〇1 — (-CH2C-)-(ORg) s (2)

(Rf〇) r (〇Ri) i (〇Rh) t

(ORF) r (〇Ri) i ⑶

-135- 1226509 V. Description of the invention (134

^ 101-^ CH ^ ~ L (〇Rj) v (Rd〇) P (Ming

⑷ (Rf〇) r (Rg °) s \ (〇R ^ (ORi) (〇Rh) t R101 — ^ ch2c ^ (〇Rk) w (5)

(Called 丄: ^ (called (Re〇) q- ^ 3? &Gt; ^ (〇Rh) t (RfO) r ^ \ RiL Ιί, OCO, 0 ^ 0,0¾

Divalent bond group, Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj -136-1226509 5. Description of the invention (135), Rk, R 1 each independently represent a carbon number of 1 ~ 1 2 is a linear, branched, or cyclic alkyl, alkenyl, aryl, aralkyl, or hydrogen atom. Moreover, these may be bonded to each other to form a ring of 5 or more carbons having 24 or less carbon atoms, 1, m, η, P, q, r, s, t, u, v, w, and χ are integers of 0 to 3, which can satisfy l + m + n = 2,3, p + q + r = 0,1,2,3, s + t + u = 0,1,2,3, v + w + x20, 1, 2, 3 o Only Ra, Rb, Rc in the general formula (1) is not hydrogen atom. Moreover, the general formula (1) is other than benzodioxazole.

Examples of Ra, Rb, and Rc include hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 3-butyl, pentyl, octyl, hexyl, cyclohexyl, octyl, Decyl, dodecyl, allyl, benzyl, phenyl, cumyl, etc. Moreover, for example, to form a methyl-substituted dioxocyclic ring, an ethyl group to replace a U-oxocyclic ring, a phenyl-substituted dioxocyclic ring, a dimethyl-substituted dioxocyclic ring, hi!

Kd, Re, R f, Rg, ethyl, propyl, isopropyl, butyl, isobutyl '帛 3-butyl, pentyl, octyl, hexyl, cyclohexyl, octyl, diglycerine Hexyl, decyl, dodecyl, allyl, benzyl, phenyl, cumyl and other radicals such as Rd ~ Rf, Rg ~ Ri, or Rj ~ R1, for example, are bonded to each other to form a methyl group instead of monomethyl Dioxane, ethyl substituted dioxocyclic ring, phenyl substituted dioxocyclic ring, dimethyl πτ7 α methyl substituted dioxocyclic ring, and dioxane ring -C00-L has a single bond, -CH2-, -〇CH2-, -CONH-, etc. • C〇〇CH2-, -〇CH2CH2〇-, -137-1226509

1226509 V. Description of the invention (137) oc—c H2c H2c CIC——c H3

〇

ο — (ch29h)-— (ch2ch)-', och3 ^ Κ ^ 〇〇2Η5 h3co

c2h5o

— (Ch2ch) —

Y ^ o I 〇 -139-1226509 V. Description of the invention (138)

c2h5〇 &quot; ta〇 -140-1226509 V. Description of the invention (139 — (ch2ch)-h3co

OCH 3 OCH3 —j-CH2CH] — — (CH2CH) — — (-CH2CHf-1, 〇CH3 H3C〇v ^ k ^ 〇CH3

h3co, 〇ch3 och3 — (ch2ch) —

och3

och3 — (ch2ch)-h3co ^ y 0 〇v ^ — (ch2ch |-〇

〇

H3CO, 0CH3 C2H50 T 〇 〇ch3 ch3 — (-ch2ch) -coo -fCH2C-)-

coo

H3CO, 〇ch3 H3CCT 〇ch3 och3 OCH3 -141-1226509 V. Description of the invention (14〇

-fCHsCHj- O -fCH2CH |-

O 00 o

OH — (-ch2ch |-o o

OCH3 ^ ch2ch ^-

— (-Ch2ch-) — ch2ch-) —

OH

OCH3 -142- 1226509

1226509 V. Description of the invention (1 42 ch2ch-) — — (CH2CH &quot;) — coo coo

och3 ch2ch-) — — (-ch2ch-) — — (-ch2ch-) — 'ί φο ¢ 0 OH OH OC2H5

— ^ Ch2ch-] — ^ ch2ch-] — — ^ ch2ch

oc2h5 -144- 1226509 V. Description of the invention (143-(ch2ch-)-COOόο coo

OH CH3-(-ch2ch ·) — CH2CH ^ —-(-CH2C-) — coo coo

coo00 och3 och3

1226509 V. Description of the invention (144 —CH2CH-) — — (CH2CH-)-— ^ ch2ch-)-

och3

0 〇c2h5 0

-(ch2ch-)--(ch2ch ·)-o o o o

OH

och3

-14 6- 1226509

1226509 V. Description of the invention (146 ch2ch-) — — (ch2ch-) — —f ch2ch ·) — coo OCH3 OC2H5 -CH2CH-) — — (; CH2CH-) — — (-CH2CH-j— coo coo coo oc2h5 och3 -148- 1226509

1226509 V. Description of the invention (148)

-150- 1226509 V. Description of the invention (149) — (-ch2ch-)-0

OCH3

(-ch2ch ^ —

• CH2CH ^ —

-151-1226509 V. Description of the invention (15〇)

1226509 V. Description of the invention (151 ch3 — (-ch2ch-) — — (* CH2CH-}-—f-CH2C-^ — coo coo coo

OCH3

OCH3 CHc

ch2ch-) — —CH2C-)-

CH2〇H * ^-o 0 '

coo

〇c2h5 The acid-decomposable resin is a group that is decomposed into an alkali-soluble group by the action of an acid, even if the alkali-soluble group is protected by an acid-decomposable group. -153- 1226509 5. Description of the invention (152) The alkali-soluble group is preferably a phenolic hydroxyl group or a carboxylic acid group. These acid-decomposable groups which are protective groups of the alkali-soluble group are preferably an acetal group, a ketal group, a tertiary carboxylic acid ester group, and a tertiary carbonate group. Tertiary carboxylic acid ester groups include, for example, 3-butyl ester and 2-methyl-2-adamantyl ester. The tertiary carbonate group includes, for example, a 3-butoxycarboxylic acid ester. Among them, acetal and tertiary carboxylic acid ester are more preferable, and acetal is more preferable. The group in which the alkali-soluble group is protected by an acid-decomposable group may be a substituent (any one of Ra to R 1 is an acid-decomposable group) in the repeating unit of the above (1) to (6), or may exist in the constituent acid Among other repeating units of the decomposable resin, the proportion of the repeating unit having an acid-decomposable group in the acid-decomposable resin is usually 5 to 40 mol%, preferably 10 to 30 mol%. Specific examples of the acid-decomposable resin are exemplified in the following, but are not limited thereto. In the following, R is an alkyl group, an aralkyl group, or an aryl group. —F-CH ^ CH-i--i-CH ^ CH-^ —

— (-CH2CH ·)-f CH2CH ^ —

-154- 1226509 V. Description of the invention (153 —f-CH2CH-)-{· CH2CH *) —

H3CCT got OCH3 OCH3 0 丫 0R — (· οη2〇η-)-(-ch2ch ·) —

0CH3 OCH3

— ^ CH2CH ^ — ^ CHsCH ^ .OCH3 ^

H3CO

'〇 、 .OR — (-ch2ch-)-(· ch2ch ^ —

Hr ^ CCT 〇 〇CH3 och3

— (&Quot; CH2 &lt; pH ^ ^ CH2CH ^ ', och3 J-

och3 OChU O ^ / OR — (-CH2CH-)-f-CH2CH *) —

〇 丫 OR -155- 1226509

1226509

1226509 V. Description of the invention (156) —f-CH2CH-)-f-CH2CH-) —

COO

0… OR — (-ch2ch) — —f ch2ch) —coo

OR

-158- 1226509

1226509

1226509 V. Description of Invention (彳 59)

〇ch3 —f-CH2CH-)-(-CH2CH ^ —

-161-1226509 V. Description of the invention (16)-(CH2CH-)-f-CH2CH-) I, 0

—F-CH2CH-)-f-CH2CH-) — 〇 〇〇〇—f-CH2CH)-

〇, / OR

— [Ch2ch ^ —

Cy〇R — {· CH2CH · Bu--f-CH2CH ·) — CH 2

—F-CH2CH-j-{-CH2CH-) —

OH

〇 O

CX / OR -162- 1226509 V. Description of the invention (161) — (-ch2ch | —

-163- 1226509

1226509

The alkali-soluble resin of the present invention can be synthesized by conventional methods such as radical polymerization, cationic polymerization, and anionic polymerization. Free radical polymerization is the easiest way to combine the corresponding monomers.

-165- 1226509 V. Description of the invention (164) Synthesis by anion and anion polymerization is better. Moreover, depending on the kind of polymerization initiation, when a reaction other than the polymerization of the monomer is caused, a monomer having an appropriate protective group introduced can be polymerized, and after the polymerization, a desired polymer can be obtained by deprotection. In addition, a polymer having an alkoxy group can also be obtained by subjecting a hydroxyl group of a polymer having a corresponding hydroxyl group to an ether reaction to obtain a desired polymer. About the polymerization method, such as the lecture on experimental chemistry 28, polymer synthesis, the lecture on new experimental chemistry 19, and high molecular chemistry [I]. The molecular weight of the alkali-soluble resin and the acid-decomposable resin of the present invention is 3,000 to 1,000,000. A preferred weight average molecular weight is 3,000 to 500,000. It is preferably 300,000 or less, more preferably 1 50,000 or less, even more preferably 100,000 or less, and most preferably 50,000 or less. The molecular weight distribution (Mw / Mn) of the alkali-soluble resin that can be synthesized by the above-mentioned synthesis method is preferably 1.0 to 1.5, whereby the photoresist can be highly sensitive. The molecular weight distribution resin can be synthesized by living anionic polymerization in the above synthesis method. Moreover, other alkali-soluble resins can be used. Other alkali-soluble resins used in the present invention include, for example, phenolic resin, hydrogenated phenolic resin, acetone-pyrophenol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, Hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, p-polyhydroxybenzene The hydroxyl group of ethylene is partially ortho-alkylate (for example, 5 ~ 3 0-16 6-1226509. V. Description of the invention (165) Mole% of o-methylate, o- (1_methoxy) ethyl Compound, ortho- (1_ethoxy)) ethylate, ortho-2-tetrahydropyranide, ortho-3-butoxycarboxyl) methylate, etc.) or ortho-fluorenylate (e.g. 5 to 3 0 mol% o-fluorenyl compound, o- (3-butoxy) fluorenyl compound, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylbenzene Ethylene-hydroxystyrene copolymers, carboxyl-containing methacrylic resins, and derivatives thereof are not limited thereto. More preferred alkali-soluble resins are phenolic resins, o-polyhydroxystyrene, m-polyhydroxystyrene, p-hydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partially Polyhydroxystyrene ortho-alkylated, or alpha-methylstyrene-hydroxystyrene copolymer. This phenolic lacquer resin is obtained by adding and condensing aldehydes in the presence of an acidic catalyst with the monomers specified below as a main component. The specified monomers can be used alone or in combination of two or more types of cresols such as phenol, m-cresol, o-cresol, and p-cresol, 2,5-xylylene hydrazone, 3,5-xylenol, Dimethylphenols such as 3,4-xylenol, 2,3-xylenol, m-ethylphenol, p-ethylphenol, o-ethylphenylhydrazone, p-third-butylphenol, p-phenol -Octylphenol, 2,3,5-trimethylphenyl hydrazone, etc. classification of benzene, p-methoxyphenol, m-methoxyphenol, 3,5-monomethoxybenzoic acid, 2- Methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxybenzidine, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, p-butoxy Alkoxyphenols such as phenol, dialkylphenols such as 2-methyl-isoisopropyl basic acid, m-chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxy-167-1226509 5. Description of the invention (166) Hydroxy aromatic compounds such as biphenyl, bisphenol A, phenylphenol, resorcinol, naphthol, etc., but are not limited by these. Examples of the aldehydes include formaldehyde, p-formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, A-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-aldehyde -Hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p_nitrobenzaldehyde, o-methylbenzaldehyde , M-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p-n-butylbenzaldehyde, furfural, chloroacetaldehyde, and acetals such as chloroacetamidaldehyde Diethyl acetal and the like are preferably formaldehyde. These aldehydes can be used alone or in combination of two or more. Acidic catalysts include hydrochloric acid, sulfuric acid, formic acid, acetic acid, and oxalic acid. The weight-average molecular weight of the phenolic lacquer resin thus obtained is preferably 1,000 to 30,000. If it is less than 1,000, the exposure portion will be large after the development, and if it is more than 30,000, the development speed will be small. The better is 2,000 ~ 20,000. The weight average molecular weight of the polyhydroxystyrene, its derivatives and copolymers other than the phenolic lacquer resin is 2,000 or more, preferably 2,000 to 30,000, and more preferably 2,000 to 20,000. Here, the weight average molecular weight is defined in terms of polystyrene conversion ratio of gel permeation chromatography. In the present invention, these alkali-soluble resins or acid-decomposable resins may be used in combination of two or more kinds. The amount of alkali-soluble resin used is based on the entire photoresist composition -168-1226509 V. Description of the invention (167) The weight is generally 30 to 90% by weight, preferably 50 to 80% by weight 〇 Base of the characteristic component of the present invention The amount of the soluble resin or acid-decomposable resin used is based on the total weight of the photoresist composition (except for the solvent), and is usually 30 to 90% by weight, preferably 50 to 80% by weight. The photoresist composition for an electron beam or X-ray of the present invention may also contain a low-molecular compound (referred to as "low-molecular acid-dissolving dissolution") "Block compounds" or "(c) ingredients"). The preferred (c) component to be incorporated in the photoresist composition for an electron wire or X-ray of the present invention is to have at least two groups decomposed by an acid in its structure, and the distance between the acid-decomposable groups is the farthest. Compounds that have at least 8 atoms bonded to them at positions other than acid-decomposable groups. More preferably, the component (c) has at least two groups decomposed by an acid in its structure, and the distance between the acid-decomposable groups passes through at least 10 at the furthest position (preferably 11). 12 or more) Compounds that bond to atoms other than acid-decomposable groups, or have at least 3 acid-decomposable groups in their structure, and the distance between the acid-decomposable groups is the farthest A compound having at least 9 (preferably 10, more preferably 11) bonded atoms other than the acid-decomposable group at the position of. In addition, the upper limit of the above bonding atoms is preferably 50, more preferably 30. The amount of the compound of the component (C) in the photoresist composition for electronic or X-rays of the present invention is 3 to 45% by weight compared to -169-1226509 for the solid content of the entire composition. 5. Description of the invention (168) The best and better are 5 to 30% by weight, and the best is 10 to 30% by weight. In the photoresist composition for an electron beam or X-ray of the present invention, a cationically polymerizable compound ((d) component) is preferably used. In the present invention, cationic polymerization refers to the addition polymerization of positive ions in which the growth chain is a carbon iron ion or an oxygen ion. The present invention refers to a compound having a cationic polymerizable function in a monomer obtained by the cationic polymerization. For example, in the case of an ethylene compound, the cationic polymerizability of the ethylene monomer is Q-e 値 used for free ion polymerization. In other words, the cationic polymerizability which e 値 is about less than -0.3 is known. In addition, the cationically polymerizable compounds are characterized by (1) 7Γ-carbon-carbon unsaturated bonds of the donor, and (2) η-cohard hybrids seen in some (mostly saturated) heterocyclic compounds. Non-shared electron pairs of ring atoms (oxygen, sulfur, nitrogen, phosphorus), (3) alkane can be seen under special conditions σ-the donor has a carbon-containing single bond. (1) is ethylene, vinylidene compound, vinylidene compound, and the like. (2) It is a lactone compound, a cyclic ether compound, and an oxazoline type, an azacyclopropane type, a cyclic siloxane, etc. For example, isobutene, isoprene, butadiene, cyclopentadiene, cyclohexadiene, ortho-sadiene, styrene, indene, naphthalene, benzofuran, p-methoxystyrene, α -Methylstyrene, vinyl ether, N-vinylcarbazole, N-vinylpyrrolidone. Among them, an ethylene compound is preferably used. The amount of the compound (d) in the photoresist composition for electronic or X-rays of the present invention is 0.5 to 50% by weight -170-1226509 for the total weight (solid content) of the composition. 169) It is preferably 3 to 30% by weight. In addition, the photoresist composition for electron or X-rays according to the present invention contains at least one compound ((d ') component) selected from the group consisting of an ethylene compound, a cycloalkane compound, a cyclic ether compound, a lactone compound, and an aldehyde compound. good. As the vinyl compound, the following vinyl ether compounds, styrene, α-methylstyrene, m-methoxystyrene, p-methoxystyrene, o-chlorostyrene, and m-chlorostyrene can be used. , P-chlorostyrene, o-nitrostyrene, m-nitrostyrene, p-brominated styrene, 3, 4-dichlorostyrene, 2,5-dichlorostyrene, -Styrenes such as dimethylaminostyrene, 2-isopropenylfuran, 2-vinylbenzofuran, 2-vinyldibenzofuran, 2-isopropenylthiophene, 2-vinyl Vinylthiophenes, such as phenothiones, N-vinylazoles, ethylene naphthalene, ethylene anthracene, ethylene naphthyl and the like. As the cycloalkane compound, phenylcyclopropane, helix [2,4] heptane, helix [2,5] octane, helix [3,4] octane, and 4-methyl helix [2,5] octane can be used. , Helix [2,7] decane, etc. As the cyclic ether compound, dioxanes such as 4-phenyl-1,3-dioxane, 3,3-dichloromethyl oxide cyclobutanes, trioxane, and 1,3-dioxide can be used. Cyclopropane and other compounds. In addition, glycidyl ethers such as allyl glycidyl ether, phenylglycidyl ether, glycidyl acrylate, glycidyl methacrylate, etc. can be used. ) Commercially available bisphenol A epoxy resin, tetrabromobisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac resin type epoxy resin, cresol novolac resin type Ring-171-1226509 V. Description of the invention (17〇) Oxygen resin and other compounds. As the lactone compound, propiolactone, butyrolactone, valerolactone, caprolactone, -methyl- / 3-propiolactone, α, α-dimethylpropiolactone, α-methyl- / 3 -Compounds such as propiolactone. As the aldehyde compound, aliphatic saturated aldehyde compounds such as valeraldehyde, hexanol, heptanol, octanol, nonanol, decanol, cyclohexylaminoformaldehyde, and phenylacetaldehyde, methacrylaldehyde, crotonaldehyde, 2-Methyl-2-butenal, 2-butynyl alcohol, crocetin and other aliphatic unsaturated aldehyde compounds, benzaldehyde, tolualdehyde, cinnamaldehyde and other aromatic aldehyde compounds, acetaldehyde tribromide, 2 , 2,3-trichlorobutyraldehyde, halogenated aldehyde compounds such as butyraldehyde, benzaldehyde, glyceraldehyde, aldol, salicylaldehyde, m-hydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 4-hydroxy -3 -Hydroxy and alkoxy-substituted aldehyde compounds such as methoxybenzaldehyde, piperaldehyde, amines and nitro-substituted aldehyde compounds such as aminobenzaldehyde, nitrobenzyl, succinaldehyde, glutaraldehyde Dialdehyde compounds such as aldehydes, phthalic acid aldehydes, terephthalic acid, etc., acetal compounds such as phenylglyoxal, benzamylacetaldehyde, and their derivatives. The relationship between the (d) cationically polymerizable compound and (d ') an ethylene compound, a cycloalkane compound, a cyclic ether compound, a lactone compound, and an aldehyde compound is any one of the following 1) to 3). Those which are (d) cationic polymerizable compounds, not (d ') ethylene compounds, cycloalkane compounds, cyclic ether compounds, lactone compounds, and aldehyde compounds are (d') ethylene compounds, cycloalkane compounds, Cyclic ether compounds, lactone compounds, aldehyde compounds, and those other than (d) cationic polymerizable compounds -172-1226509 5. Description of the invention (171) is (d) cationic polymerizable compounds and (d,) ethylene Compounds, cycloparaffin compounds, cyclic ether compounds, lactone compounds, and aldehyde compounds. In addition, the compounds suitable for the present invention are the three types mentioned above, all of which have the same effects as the present invention. However, as described below, the effect of the ethylene compound is remarkable. In view of the remarkable effect of the (d ') compound, an ethylene compound is preferred, and a vinyl ether compound is more preferred, and a compound represented by the general formula [A] is particularly preferred. In the general formula (A), when Ra, Rb and Rc are aryl groups, they generally have 4 to 20 carbon atoms, and may be alkyl, aryl, alkoxy, aryloxy, fluorenyl, fluorenyl, Alkylthiol, aminofluorenyl, carbonylalkoxy, nitro, sulfofluorenyl, cyano, or halogen atoms are substituted. Here, the aryl group having 4 to 20 carbon atoms includes, for example, phenyl, tolyl, xylyl, biphenyl, naphthyl, anthryl, and phenanthryl. When Ra, Rb and Rc are alkyl groups, they represent saturated or unsaturated straight-chain, branched-chain or alicyclic alkyl groups having 1 to 20 carbon atoms, and may be a halogen atom, a cyano group, an ester group, an oxy group, an alkoxy group, or an aromatic group. Oxy or aryl substitution. Here, the saturated or unsaturated linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, or 3-butyl , Pentyl, isopentyl, neopentyl, hexyl, isohexyl, octyl, isooctyl, nonyl, decyl, eleven-yuan, ten- · yuan, twelve-yuan, fourteen-yuan , Ethylene, propenyl, butenyl, 2-butenyl, 3-butenyl, isobutenyl, pentenyl, 2-pentyl, hexyl, heptenyl, octyl, cyclopropyl Cyclobutyl-173-1226509 V. Description of the Invention (172) Cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentenyl, cyclohexenyl and the like. Moreover, any two of Ra, Rb and Rc are bonded to form a saturated or ethylenically unsaturated ring. Specifically, the cycloalkane or cycloalkene is usually 3 to 8, preferably 5 or 6 rings. In the general formula (I) of the present invention, one of Ra, Rb, and Rc is preferably a methyl group or an ethyl group, and the remainder is an ethanol ether having a hydrogen atom. More preferably, all of Ra, Rb, and Rc are hydrogen atoms. The following general formula [A-1]. General formula [A— 1] CH 2 = CH— 0 — R (where R: alkyl group, substituted alkyl group) Here, the alkyl group is a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. The substituted alkyl group is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms. Examples of the linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms include ethyl, linear, branched, or cyclic propyl, butyl, pentyl, hexyl, heptyl, and octyl Base, nong base, decyl base, ~ ί • base, 12 base, 13 base, 14 base, 15 base, 16 base, 17 base, 18 base, 10 base Nine alkyl, eicosyl and the like. Examples of the other substituents of the alkyl group include a hydroxyl group, an alkyl group, an alkoxy group, an amine group, a nitro group, a halogen atom, a cyano group, a fluorenyl group, a fluorenyl group, a sulfonyl group, a sulfonyloxy group, and a sulfonyl group. Amino group, aryl group, aralkyl group, fluorenimine group, hydroxymethyl group, -174-1226509 V. Description of the invention (173) -0, 1, -c (= 〇) -r2, -0 ~ c (= 0) one 3, one C (&gt; 〇) one one; r4, -s ~ r5, -C (= S) one R6, -〇 ~ C (= S) one r7, -c (= s) —〇-r8, (and other substituents. Here, 1 ^ ~ 1 ^ each independently represents a linear, branched or cyclic; U group, pentoxide, amine, nitro, halogen Atom, cyano, fluorenyl, sulfonyl, sulfonyloxy, sulfonamido, sulfinamido,-(CH2CH2-〇) n-R9 (where 'η is an integer from 1 to 20, and R9 is It means a hydrogen atom or an alkyl group), an aryl group or an aralkyl group which may have a substituent (here, the substituent is, for example, a linear, branched or cyclic alkyl group, an alkoxy group, an amine group, a nitro group , Halogen atom, cyano, fluorenyl, aryl, aralkyl) The compound represented by the general formula (A) is, for example, the following Preferred form, but not limited these.

-175- 1226509

1226509 V. Description of the invention (175) A —15 A —16 A —17 A —18 A —19 A-20 A — 21 A—22 A — 23 〇 ^ \ ^ 〇 \ / ^ 〇 ^ \ ^ · 〇, Product o ^^ nh2 / Product N 〇 = * 4 ^ 20

1226509 V. Description of the invention (176) A-24 produces 0 ~ 〇v〇 A — 25 A — 26 A-27. ~. A-28 A-29 0 11 ~ 々0 0 A — 30 The method for synthesizing the compound represented by the general formula [A-1] can be, for example, Stephen. C Europe Lapin, Polymers Paint Colour Journals' 1 79 (423 7), 3 2 1 (1 988) The method described is the synthesis of alcohols or phenols with -178-1226509 V. Description of the invention (177) Ethylene, or the reaction of alcohols or phenols with halogenated alkyl vinyl ethers. It can also be synthesized by reacting a carboxylic acid compound with a halogenated alkyl vinyl ether. The addition amount of the compound (d ′) in the photoresist composition for electron or X-rays of the present invention (preferably, the compound represented by the general formula (A)) is based on the total weight (solid content) of the composition. 0.5 to 50% by weight is preferable, and 3 to 30% by weight is more preferable. In addition, the electron beam or X-ray photoresist composition of the present invention preferably contains the above-mentioned organic basic compound. More preferred compounds are, for example, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine '3-aminopyridine, 4-aminopyridine, 2- Dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino 4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrole Alkane, piperin, N- (2-aminoethyl) piperin, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-pyranylpiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5 -methylpyrazole, 5-amino-3 -Methyl-1 -p-triazolium, pyrenol, 2-(aminomethyl) -5 -methyllazine, chelation, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine , 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, diazobicyclononene, diazobicycloundecene, etc. , But not limited by these. These (e) organic basic compounds can be used alone or in combination of two or more. -179-1226509 V. Description of the invention (178) Use. The amount of the organic basic compound used is generally 0. 01 to 10 mol%, preferably 0.1 to 5 mol for the compound of the present invention (a) which generates an acid by irradiation with electron rays or X rays. %. If it is less than 0 · 0 1 mol%, its addition effect cannot be obtained. On the other hand, if it is more than 10 mol%, the sensitivity tends to decrease or the image developability of the non-irradiated portion tends to deteriorate. The photoresist composition for an electron beam or X-ray of the present invention preferably contains the above-mentioned fluorine-based and / or silicon-based surfactant as a surfactant. The addition amount is also the same. The photoresist composition for electronic or X-rays of the present invention may further contain dyes, pigments, plasticizers, photosensitizers, and two for promoting solubility in a developing solution, as required. Compounds of the above phenolic groups and the like. The compound having two or more phenolic groups usable in the present invention is preferably a phenol compound having a molecular weight of 1,000 or less. In addition, it is necessary to have at least two phenolic hydroxyl groups in the molecule. If it is greater than 10, the improvement effect of the development range is lost. When the ratio of the phenolic hydroxyl group to the aromatic ring is less than 0.5, the correlation between the film thickness and the imaging range is narrow. When the ratio is more than 1.4, the stability of the composition is not good and it is difficult to obtain high resolution and good film thickness correlation, so it is not desirable. The preferable addition amount of the phenol compound is 2 to 50% by weight, and more preferably 5 to 30% by weight for the (g) alkali-soluble resin. If it is more than 50% by weight, the development residue is deteriorated, and a new defect that the pattern is deformed during development is not desirable. -180 · 1226509 V. Description of the invention (彳 79) Examples of phenol compounds having a molecular weight of less than 1 000 are, for example, Japanese Patent Laid-Open No. 4-122938, Japanese Patent Laid-Open No. 2-28531, US Patent No. 49 1621 0, European Patent No. 2 The methods described in No. 9294 and the like can be easily synthesized by those skilled in the art. Specific examples of the phenylhydrazone compound are not described in "F", but the compounds usable in the present invention are not limited thereto. Such as resorcinol, chlorophenol, 2, 3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4,3 ', 4', 5. Pentahydroxybenzophenone, acetone-pyrophenol condensation resin, fluorinated saccharin, 2,4,2 ', 4'-biphenylfuran, 4,4'-thiobis (1,3-di (Hydroxyl) benzene, 2,2 ', 4,4'-tetrahydroxydiphenyl ether, 2,2', 4,4'-tetrahydroxydiphenylimine I, 2,2 ', 4,4' -tetra Hydroxydiphenyl mill, ginseng (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl), cyclohexane, 4,4- (α-methylphenylene) bisphenol, α ", Α ', α" -Shen (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, ", 0', ^"-Shen (4-hydroxyphenyl) -1-ethyl- 4-cumene, 1,2,2-gins (hydroxyphenyl) propane, 1,1,2-gins (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2,5, 5- (4-hydroxyphenyl) hexane, 1,2- (4-hydroxyphenyl) ethane, 1,1,3-(4-hydroxyphenyl) butane, p- [α, α , Α ', α'-(4-hydroxyphenyl)]-xylene, etc. The composition of the present invention is made by dissolving the above components in a solvent. Medium 'is coated on the carrier. The solvents used here are ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, r-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate -181-1226509 5. Description of the invention (180), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N -di Methylformamide, dimethylimine, N-methylpyrrolidone, tetrahydrofuran, linear ketones having 6 to 9 carbons, 7-butyrolactone, etc. are preferred. These solvents can be used alone or in combination. In the present invention, the coating solvent is preferably propylene glycol monomethyl ether acetate, thereby making the in-plane uniformity excellent. When pursuing a more advanced semiconductor, in addition to its inherent high resolution and other properties, the sensitivity, Various viewpoints, such as coatability, minimum required coating amount, adhesion to the substrate, heat resistance, and storage stability of the composition High-performance components are required. Recently, in order to increase the absolute amount of wafers, large-diameter wafers have been used to create devices. However, when coating on large-diameter wafers, coating properties, especially If the uniformity of the film thickness in the plane is reduced, it is required to improve the uniformity of the rear surface of the film for large-caliber wafers. The method for confirming the uniformity is to measure the film thickness at most points in the wafer. Calculate the standard deviation of each measurement, and confirm the homogeneity by 3 times the 値. The smaller the 値, the higher the in-plane uniformity. The 3 times the standard deviation is preferably 100 or less, and more preferably 50 or less. In the manufacture of photolithography photomasks, the linearity of CD is the most important factor, and the thickness in-plane uniformity of the inner film of the blank is required to be improved. The photoresist composition for electronic or X-rays of the present invention can be dissolved in a solvent and then -182-1226509 V. Description of the invention (181) Filtration. Therefore, the filter to be used may be selected from those used in the photoresist field. Specific filter materials are those containing polyethylene, dragon-resistant or poly-maple. More specifically, for example, Microcarton (Transliteration), Microcarton Plus, Microcarton Mininicum-D, Microcarton Mininicum-D PR, Miri Boa Obu Kimiara (Transliteration), DEV / DEV-C, Miribo Ao Bugimara 16/1 4, Ulukiboa (Transliteration) N66, Bo Kiran (transliterated), Nailong Farukon (transliterated), etc. The pore size of the filter can be confirmed by the following method. In short, PSL standard particles (polystyrene latex bead particle size 0.100V m) were dispersed in ultrapure water, and a tube pump was used to continuously circulate at a constant flow rate on the primary filter side, and calculated from the particles. The device measures the range concentration, and can capture more than 90% as a pore size of 0.1 / 1 m filter. The photoresist composition for electronic wires or X-rays of the present invention is applied to a substrate (such as a silicon / silicon dioxide coating) used in manufacturing precision integrated circuit components (as required, on a substrate provided with the above-mentioned antireflection film) ) After coating by a suitable coating method such as a rotator, a roller, etc., it is exposed through a predetermined hood, baked, and a good photoresist pattern is produced by development. The developing solution of the composition of the present invention can use inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methyl silicate, ammonium water, primary amines such as ethylamine, n-propylamine, and diethylamine. , Secondary amines such as di-n-propylamine, tertiary amines such as triethylamine, methyldiethylamine, alcohol amines such as dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc. Basic ammonium salts, cyclic amines such as pyrrole, pyridine and other alkaline aqueous solutions. -183- 1226509 V. Description of the invention (182) In addition, an appropriate amount of alcohol and surfactant may be added to the above-mentioned alkaline aqueous solution. [Examples] The present invention will be described in more detail by examples and the like in the following, but the present invention is not limited by these. Moreover,% means weight% unless otherwise specified. Synthesis Example 1 32.4 g (0.2 mol) of p-ethoxyloxystyrene was dissolved in 120 ml of butyl acetate, and under a nitrogen atmosphere with stirring, 0.03 3 g of azobisisobutyronitrile (AIBN) was added 3 times at 83 ° C, and finally stirred for another 6 hours to perform a polymerization reaction. The reaction solution was poured into 1,200 ml of hexane to precipitate a white resin. The obtained resin was dried and then dissolved in 150 ml of methanol. 7.7 g (0.19 mol) of sodium hydroxide / 50 ml of an aqueous solution was added thereto, and the mixture was hydrolyzed by heating and refluxing for 3 hours. In addition, 200 m 1 of water was dissolved and diluted, and neutralized with hydrochloric acid to precipitate a white resin. This resin was filtered, washed with water, and dried. It was dissolved in 200 ml of tetrahydrofuran and dropped into 5 L of ultrapure water with vigorous stirring to perform reprecipitation. This reprecipitation operation was repeated 3 times. The obtained resin was dried in a vacuum dryer at 120 ° C for 12 hours to obtain poly (p-hydroxystyrene) [resin R-1]. The obtained resin had a weight average molecular weight of 1 3,000. Synthesis Example 2 35.25 g (0.2 mol) of p-th-butoxystyrene monomer dehydrated and distilled and purified based on a conventional method and 5.21 g (0.05 mol) of styrene-184-1226509 Description of the invention (183) The monomer is dissolved in 100 nl of tetrahydrofuran. Under a nitrogen atmosphere and stirring, 0.033 g of azobisisobutyronitrile (AIBN) 'was added 3 times at 83 ° C over 3 hours and stirred for another 6 hours to perform the polymerization reaction. The reaction solution was poured into 1200 ml of hexane to precipitate a white resin. After the obtained resin was dried, it was dissolved in 150 ml of tetrahydrofuran. 4N hydrochloric acid was added thereto, and the mixture was hydrolyzed by heating and refluxing for 6 hours, and then reprecipitated in 5L of ultrapure water, and the resin was filtered, washed with water, and dried. In addition, 200 m 1 of tetrahydrofuran was dissolved, and 5 L of ultrapure water was dripped under vigorous stirring to perform reprecipitation. This reprecipitation operation was repeated 3 times. The obtained resin was dried in a vacuum dryer at 120 ° C for 12 hours to prepare a poly (p-hydroxystyrene / styrene) copolymer [Resin R-2]. The weight average molecular weight of the obtained resin was 1 1,000. Synthesis Example 3 40 g (0.33 mole p-hydroxystyrene) and 10.7 g (0.08 mole) of 3-butyl acrylate were dissolved in 50 g of dioxane To the mixture, 8 g of azobisisobutyronitrile (AI BN) was added, and the mixture was stirred for 8 hours at 60 ° C under a nitrogen gas stream. The reaction solution was poured into 1,200 ml of hexane to precipitate a white resin. After the obtained resin was dried, it was dissolved in acetone and dropped into 5 L of ultrapure water under vigorous stirring to perform reprecipitation. This reprecipitation operation was repeated 3 times. The obtained resin was dried in a vacuum dryer at 120 ° C for 2 hours to prepare a poly (p-hydroxystyrene / 3-butyl acrylate) copolymer [Resin R-3]. The weight average molecular weight of the obtained resin was 21,000. Synthesis Example 4 -185-1226509 5. Description of the Invention (184) 24 g of poly (p-hydroxystyrene) manufactured by Soda Co., Ltd. (molecular weight: 8,000) was dissolved in 100 nl of dioxane, and then foamed in nitrogen 3 〇minutes. To this solution was added 13. lg of di-third-butyl-dicarbonate, stirred and 36 g of triethylamine was added dropwise. After the dropping was completed, the reaction solution was stirred for 5 hours. This reaction solution was dropped into a 1% by weight aqueous ammonium solution, and a polymer was precipitated. After the obtained resin was dried, it was dissolved in acetone and dropped into 5 L of ultrapure water with vigorous stirring to perform reprecipitation. This reprecipitation operation was repeated 3 times. The obtained resin was dried in a vacuum drier at 120 ° C for 12 hours to obtain a poly (p-hydroxystyrene / p-3-thoxybutoxycarbonyloxystyrene) copolymer [Resin R -4]. The weight average molecular weight of the obtained resin was 8,300. Synthesis Example 5 After dissolving 70 g of poly (p-hydroxystyrene) manufactured by Soda Co., Ltd. (molecular weight 8,000) in 320 g of propylene glycol methyl ether acetate (PGMEA), 0. 3.5 g of p-toluenesulfonic acid was added. Pyridine salt, dissolved by heating at 60 ° C. This mixture was depressurized to 20 mmHg at 60 ° C, and about 40 g of a solvent remained in the system, followed by distilling off with water. It was cooled to 20 ° C, and 18.9 g of benzyl alcohol was added and dissolved. Then, 17.5 g of di-third-butyl vinyl ether was added, and stirring was continued for 5 hours at 20 ° C. An additional 5.5 g of pyridine was added, and 5.9 g of acetic anhydride was added, followed by stirring at 20 ° C for 1 hour and 30 minutes. To the reaction mixture, 280 ml of ethyl acetate, 140 ml of water and 12 ml of propidium were added to perform an extraction operation. After repeating the water washing operation three times, the water was distilled off at 60 ° C and 20 mmHg to remove water from the system. In addition, the obtained resin solution was diluted with acetone and precipitated in a large amount of hexane. -186-1226509 V. Description of the invention (185) A white resin was prepared. This operation was repeated 3 times, and the obtained resin was heated and dried at 4 ° C. for 24 hours in a vacuum dryer to obtain poly (p-hydroxystyrene / p- (1-benzyloxyethoxy) ) Styrene / p-acetoxybenzyl) copolymer [Resin R-5]. Weight average molecular weight is 8, 400. Synthesis Example 6 Except using 70 g of poly (p-hydroxystyrene) [alkali soluble resin R- 1], except that 2 2 · 0 g of phenylethanol was used in place of benzyl alcohol, the same operation was performed as in Synthesis Example 5 above to obtain poly (p-hydroxystyrene / p- (1-phenethylethoxy) styrene / P-Ethyloxystyrene) copolymer [Resin R-6]. Weight-average molecular weight is 13,800. Synthesis Example 7 70 g of poly (p-hydroxystyrene / styrene) [alkali-soluble resin R-2] Dissolved in 3 20g of PGMEA, added another 0.35g of p-toluenesulfonic acid pyridine salt, and dissolved by heating at 60 ° C. The mixture was depressurized to 20mmHg at 60t, and about 40g of solvent remained in the system together with water. Distilled off. After cooling to 20 ° C, 8.7 g of ethyl vinyl ether was added and dissolved. Then, stirring was continued at 2 ° C for 5 hours. After adding 0.3 g of triethylamine, 280 ml of ethyl acetate was added to the reaction mixture, and 140 ml of water and 12 ml of acetone were added to perform the extraction operation. After repeating the water washing operation three times, it was distilled off at 60 ° C and 20 mmHg to remove the water in the system to prepare a poly (pair -Hydroxystyrene / p- (ethoxyethoxy) styrene / styrene) copolymer [Resin R-7]. Weight average molecular weight is 2,600. Synthesis Example 8 -187-1226509 V. Invention Explanation (186) Except that 70 g of poly (p-hydroxystyrene / dibutyl acrylate) [resin R-7] was used, the same operation as in the above Synthesis Example 7 was performed to prepare a poly (p-hydroxybenzidine / p-- (1-ethoxyethoxy) styrene / 3-butyl propionate) copolymer [Resin R-8]. The weight-average molecular weight is 22,000. Synthesis Example 9 Protospinene, 2- Methyl-2 -adamantyl acrylate and maleic anhydride are added to the reaction vessel at a molar ratio of 3 5/3 0/3 5 and dissolved in methyl ethyl ketone, and adjusted to a solution having a solid content of 60%. It was heated to 60 ° C under a nitrogen stream. The reaction temperature was stabilized, and 1.5 mol% of Wako Pure Chemical Industries, Ltd.'s starting agent V-6601 was added to start. Reaction. After 10 hours of reaction, the reaction mixture was diluted twice with methyl ethyl ketone, and then poured into a large amount of 3-butyl formic acid to precipitate a white powder. The crystal powder was filtered, taken out, and dried to obtain Resin [R-9] of the target object The molecular weight of the obtained resin [R-9] was measured by GPC, and the polystyrene conversion was 9700 (weight average). In addition, by the composition of the resin [R-9] in the NMR spectrum, the orthospinene / 2-methyl-2 -adamantyl acrylate / maleic anhydride of the present invention has a molar ratio of 32/28/40. Synthesis Example 10 42.4 g (0.10 mole) of 1- [methyl · α- (4'-hydroxyphenyl) ethyl] -4- [α ,, α'-bis (4 ”-hydroxyphenyl) Ethyl] benzene was dissolved in 300 ml of N, N-dimethylformamide, and 49.5 g (0.35 mole) of potassium carbonate and 84.8 g (0.33 mole) of cumyl bromide bromide were added. Then, at 120 ° Stir for 7 hours at C. Put the reaction mixture into 2 L of ion-exchanged water and neutralize -188-1226509 with acetic acid. 5. After the description of the invention (187), extract with ethyl acetate. The ethyl acetate extract is concentrated, refined, and prepared. 70 g of an acid-decomposable dissolution preventing compound [I-1] was obtained (the hydrogen atoms of the hydroxyl group were all replaced with -CH2COOC (CH3) 2C6H5 group). Synthesis Example 11 44 gl, 3, 3, 5-methyl- (4-hydroxyl Phenyl) pentane was dissolved in 250 ml of N, N-dimethylformamide, and 70.7 g of potassium carbonate and 90.3 g of 3-butyl bromoacetate were added and stirred at 12 ° C for 7 hours. The reaction The mixture was poured into 2 L of ion-exchanged water, and the viscous substance was washed with water. 87 g of an acid-decomposable dissolution preventing compound [1-2] was prepared by column chromatography, and all hydrogen atoms of the hydroxyl group were replaced by -CH2COOC4H9 (t). Together Example 1 2 20ga, α, α ', α', α ", α" -L (4-hydroxyphenyl) -1,3,5-triethylbenzene was dissolved in 400 ml of diethyl ether. 400 ml of dimethyl ether In this solution, 42.4g of 3,4-dihydro-2H-pyran under nitrogen atmosphere, add hydrochloric acid in contact with coal, and reflux for 24 hours. After the reaction is completed, add a small amount of sodium hydroxide to filter. Concentrate the filtrate Then, it was purified by column chromatography to obtain 55.3 g of an acid-decomposable dissolution preventing compound [I-3] (all hydroxyl groups are THP groups). Synthesis Example 13 Drying in an oven and using argon Purified Schlenk tubes were filled with (pre-dried overnight under vacuum at 60 ° C) 3-butyl deoxycholate (2g, 4.457 mmol), (distilled from CaH2) N- Methylmorpholine (1.1 mL, 10 mmol) and methyl chloride (8 mL) to synthesize 3-butyldeoxycholate-189-1226509 5. Description of the invention (188) 〇Cool to 0 At ° C, the glutamine dichloride (0.552 g, 4.324 mmol, 97 mole%) of distillate was added slowly using an airtight injector. When the addition was completed, salt precipitation started The resulting slurry was stirred, warmed to room temperature within 30 minutes, and heated at 40 ° C. for 30 minutes. Then, the mixture was poured into a solution containing methyl chloride (40 mL) and water (40 mL). Organic The layer was washed 4 times with a dilute ammonium acetate aqueous solution, and then concentrated to obtain a solid. This solid was freeze-dried from dioxane to obtain a powder. This powder was dispersed in water (100 mL) and stirred for 1 hour. It was filtered, and the powder was recovered and dried in vacuum. The yield was 1.5 g (64% yield). When this method was repeatedly used with tetrahydrofuran (THF), the yield was 1.7 g (yield 74%). Using this oligomer as an acid-decomposable dissolution preventing compound [I_4]. Example 1 a to 16 a (Preparation and evaluation of radiation-sensitive resin composition: K rF excimer laser exposure) 8 g of the components shown in Table-1 below were dissolved in PGMEA (propylene glycol monomethyl ether acetate) Medium, filtered through a 0.1 / 1m m Teflon filter to modulate the photoresist solution. (The resin obtained from the PGMEA solution is expressed in terms of solid content concentration.) The photoresist composition solution was coated on a silicon wafer to which hexamethyldisilanes was applied by a spin coater, and vacuum-adsorbed at 130t. The hot plate is heated and dried for 90 seconds to form a photoresist film with a film thickness of 0 · 4 // m. KrF excimer laser stepped exposure device (NA = 0.63) was used for pattern exposure on this photoresist film -190-1226509 V. Description of the invention (189) Light's vacuum adsorption type heat at 110 ° C after exposure The plate was heated for 60 seconds. In addition, it was immersed in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with pure water for 30 seconds, and dried. The obtained pattern was observed with a scanning electron microscope 'and the photoresist performance described below was evaluated. Sensitivity is determined by the exposure energy that enables resolution of 0.2 5 m lines and space (pitch 1: 1). Resolution is expressed in terms of the critical resolution at which this exposure can be resolved. At the same time, the remaining 0 · 20 // m isolated line (pitch 1: 1) pattern is observed. Those who have no pattern flying away at all are 0, those with more than 1/2 remaining are △, and most of the pattern flying away are x. -191-1226509 V. Description of the invention (190) Table-1 Formulas of positive photoresist composition (Executive power and comparative examples) Resin (addition amount) Acid decomposable dissolution preventing compound: Photoacid generator (addition amount ) Organic basic compound (addition amount) Example of high molecular compound containing fluorinated aliphatic group la R-3 (1.6 g) M J \ W Dl (0.06 g) El (0.005 g) Pl (10 ppm) Example 2a R-4 (1.6g) y \ w D-2 (0.07g) E-2 (0.005g) P-3 (100ppm) Example 3a R-4 (1.6g) ^ frrr II &quot;: D-3 (0.08g) M / 1 / 1NP-4 (100ppm) Example 4a R-5 (1.6g) Dl / D / 3 (0.04 / 0.04g) E-3 (0.005g) P-6 (150ppm) Example 5a R-6 (1.6g) and j \\\ Dl (0.08g) El (0.005g) P-7 (5ppm) Example 6a R-6 (1.6g) MJ \ w D_2 (0.08g) E-2 (0.003g) P-10 (20ppm) Example 7a R-6 / R-1 (1.0g / 0.5g) without D-3 (0.08g) E-3 (0.006g) P- ll (40ppm) Example 8a R-6 / R-1 (1.0g / 0.5g) yiw D-2 / D-3 (0.05 / 0.03g) El (0.002g) P-12 (150ppm) Example 9a R -7 (l.6g) M j \\\ Dl (0.06g) M j \\\ P-13 (350ppm) Example 10a R-7 (1.6g) M (0.43g) D-2 (0.03g) El (0.005g) P-14 (500ppm) Example 11a R-8 (90g) M / »\ N D-3 (0.10g) E-2 (0.005g) P-8 (1000ppm) Example 12a R-8 (1.6g) 1-2 (0.20g) Dl (0.05g) E-3 (0_007g) P -16 (500ppm) Example 13a Rl (1.5g) 1-3 (0.43g) D-2 (0.08g) El (0.005g) P-17 (300ppm) Example 14a R-2 (1.6g) 1- 1 (0.44g) D-3 (0.07g) M / INN P-18 (50ppm) Example 15a R-3 (1.6g) 1-2 (0.20g) Dl (0.08g) El (0.005g) P- 19 (5ppm) Example 16a R-4 (1.6g) 1-3 (0.20g) D-2 (0.06g) E-2 (0.005g) P-20 (3ppm) Comparative example la R-4 (l .6g) MJ »N \ D-3 (0.09g) E-3 (0.005g) M Comparative Example 2a R-5 (1.6g) Without Dl (0.08g) El (O.OOlg) Comparative Example 3a R- 6 (1.6g) yiw D-2 (0.08g) E-2 (0.004g) PR-1 (5ppm) Comparative example 4a R-7 (1.6g) 1-1 (0.43g) Dl / D-3 (0.04 / 0,04g) E-3 (0.005g) PR-2 (150ppm) Comparative Example 5a R-K1.5) 1-2 (0.43g) D-2 / D-3 (0.05 / 0.03g) El (0.005 g) ° R-3 (500ppm) Comparative Example 6a R-2 (1.6g) 1-3 (0.44g) D-3 (0.08g) None j \ \\ Comparative Example 7a R-2 (1.6g) I- KO.20g) Dl (0.05g) E-2 (0.005g) PR-4 (1000ppm) *: Add concentration to resin ppm

-192- 1226509 V. Description of the invention (191) Photoacid generator

-193- 1226509

1226509 V. Description of the invention (193), reached; Number of polymer compound with fluorinated aliphatic group on the side chain-Fluorine polymer fluorinated aliphatic side chain P-1-manufactured by Zuo Dan Mo Chemical Co., Ltd. MEGAFAC F-178K contains C8F17 based P-2 manufactured by short-chain polymerization method. Made by Ink Chemical Industry Co., Ltd. MEGAFAC F-470 contains C8F17 based P-3 manufactured by short-chain polymerization method. Zuo Dan ^ Ink Chemical Industry Co., Ltd. MEGAFAC F-473 containing C8F17 group P-4 manufactured by short-chain polymerization method _ ^ Dan MEGAFAC F-475 containing C8F17 group P-5 manufactured by short-chain polymerization method Gudancha MEGAFAC F-476 manufactured by Dimo Chemical Industry Co., Ltd. contains C8F17 based P-6 manufactured by short chain polymerization method MEGAFAC F-472 manufactured by Dimo Chemical Industry Co., Ltd. contains C8F17 based P-7 manufactured by short chain polymerization method The weight-average molecular weight of 50,000 contains the C8F17 group produced by the short-chain polymerization method P-8. The weight-average molecular weight of 10,000 contains the C8F17 group produced by the short-chain polymerization method. The P-9 is described as containing C8F17 produced by the short-chain polymerization method. P-10 βϋΐ is described as containing C8F17 group produced by short-chain polymerization. P-11 is a weight-average molecule. 20,000 P-12 recorded weight average molecular weight 15,000-P-13 — continuous system 111 already loaded weight average molecular weight 20,000 P-14 ----- ^ 11 recorded weight average molecular weight 0.6 million P-16 --- ~ ^ Recorded weight average molecular weight 20,000 P * 17 ------ Recorded weight average molecular weight 30,000 P-18 --- ^ Recorded weight average molecular weight 25,000 JM9 Recorded weight average molecular weight 15,000 Recorded weight average molecular weight 20,000 Ith ^ PR -2 (Comparison) _ MEGAFAC F-177 made by Daikoku Ink Chemical Industry Co., Ltd. ___ The formula containing C8F17 manufactured by electrolytic fluorination method is the same as P-16 ~ P-20, and the weight average molecular weight is 27,000 η = 3,4,5,6 mixture, η = 4 component content is 35 mol% for these components in total ΙίΤ (comparative), and η = 3 component content is 28 mol% ___ = The formula is the same as P-16 ~ P_20, with a weight average molecular weight of 210,000 η = a mixture of 3, 4, 5, 6 and the content ratio of η = 4 is 98.5 Mo for these components in total (Comparison) Ear% ___ ^ The formula is the same as P-16 ~ P-20, with a weight average molecular weight of 23,000, η = 3,4,5,6, and η = 3. For example, it is 98.5 mol% -195-1226509 V. Description of the invention (194) Table-3 Evaluation of photoresistance performance Resolution (# m) The isolated line flies away from Example la 0.21 〇 Example 2a 0.22 〇 Example 3a 0.21 〇 Example 4a 0.21 〇 Example 5a 0.22 〇 Example 6a 0.21 〇 Example 7a 0.20 〇 Example 8a 0.21 〇 Example 9a 0.21 〇 Example 10a 0.21 〇 Example 11a 0.22 〇 Example 12a 0.21 〇 Example 13a 0.20 〇 Example 14a 0.22 〇 Example 15a 0.21 〇 Example 16a 0.22 〇 Comparative Example la 0.23 X Comparative Example 2a 0.23 X Comparative Example 3a 0.24 X Comparative Example 4a 0.24 X Comparative Example 5a 0.23 X Comparative Example 6a 0.23 X Comparative Example 7a 0.24 Δ -196- 1226509 V. Description of the invention (195) Examples 17a to 28a (Modulation and evaluation of radiation-sensitive resin composition: electron beam exposure) 8.2 g of the components shown in Table-4 below were dissolved in PGMEA, and · 1 // m Teflon filter to modulate the photoresist solution. Each sample solution was coated on a silicon wafer using a spin coater, and dried at 12 ° C. for 90 seconds with a vacuum adsorption hot plate to obtain a photoresist film having a thickness of 0.5 // m. The photoresist film was irradiated with an electron beam scanning device (pressurized electric speed: 50kV). After the irradiation, each was heated on a vacuum adsorption hot plate at 110 ° C for 60 seconds, with 2.38% tetramethylammonium The hydroxide (TMAH) aqueous solution was immersed for 60 seconds, rinsed with water for 30 seconds, and dried. The cross-sectional shape of the obtained contact hole pattern and line and space pattern was observed with a scanning electron microscope. -197- 1226509 V. Invention Explanation (196) Table-4 Formulas of positive photoresist composition (Solenoid and Comparative Examples) Resin (addition amount) Acid-decomposable dissolution preventing compound Photoacid generator (addition amount) Organic basic compound (addition) Amount) Polymer compound containing fluorinated aliphatic group Example 17a R-4 (1.5g) M J \ w D-5 (0.07g) El (0.005g) P-2 (100ppm) Example 18a R-4 (l.5g) e.g. D-6 (0.08g) μy \\\ P-3 (100pprn) Example 19a R-5 (1.6g) M D-4 (0.04g) E-3 ( 0.005g) P-4 (150ppm) Example 20a R-6 (1.6g) / 1 1 1 1 *. &Quot; ittT: D-4 (0.08g) E-2 (0.005g) P-5 (5ppm) Example 21a R-6 (1.6g ) M / \\\ D-5 (0.08g) El (0.003g) P-6 (20ppm) Example 22a R-6 / R-1 (1.0 / 0.5g) te y \\\ D-6 (0.05 g) E-2 (0.002g) P-12 (150ppm) Example 23a R-7 (1.6g) M D-5 (0.06g) te P-13 (350ppm) Example 24a R-7 (1.3g ) 1-1 (0.43g) D-4 (0.03g) El (0.005g) P-14 (500ppm) Example 25a R-8 (90g) / D-4 (0.10g) E-2 (0.005g) P-7 (1000 ppm) Example 26a R-8 (1.6g) 1-2 (0.20g) D-6 (0.05g) E-3 (0.007g) P-16 (500ppm) Example 27a R-2 ( 1.6g) 1-1 (0.44g) D-4 (0.07g) M j \\\ P-18 (50ppm) Example 28a R-3 (1.6g) 1-2 (0.20g) D-5 ( 0.08g) El (0.05g) P-19 (5ppm) Comparative Example 8a R-4 (1.6g) fiE D-4 (0.09g) E-3 (0.005g) MJ \ w Comparative Example 9a R- 5 (l.6g) te j \\\ D-5 (0.05g) El (O.OOlg) M Sichuan N Comparative example 10a R-6 (l.6g) M j \\\ D-4 (0.08g) E-2 (0.004g) PR-1 (5ppm) Comparative Example 11a R-7 (1.6g) 1-1 (0.43g) D-4 (0.04g) E-3 (0.005g) PR-2 (150ppm) Comparative Example 12a Rl (1.5g) 1-2 (0.43g) D-5 (0.08g) El (0.005g) PR-3 (500ppm) Comparative Example 13a R-2 (1.6g) 1-3 (0.40g) D-6 (0.08g) M j \\\ M j \\ Comparative Example Ma R-2 (1.6g) 1-1 (0.2g) D-4 (0.05g) E-2 (0.005g) PR-4 (lOOppm) *: Adding concentration to resin ppm -198- 1226509 V. Description of the invention (197) Photoacid generator

(D-4) (D-5) Using the line and space system to make 0. 2 // m design size 1 as the sensitivity, when the exposure dose can be resolved to the maximum, observe the remaining 0. 1 5 / / π solitary line (in the case where the pattern is flying away is 0, the remaining is more than 1/2, the disappearing is X. (D-6): the minimum irradiation of 1 resolution, the size is the resolution. Same as 1: 1 0) No pattern at all, most of the patterns fly away -199-1226509 V. Description of the invention (198) Table-5 Evaluation of photoresistance performance Resolution (#m) Isolated lines fly away Example 17a 0.10 〇 Example 18a 0.09 〇 Example 19a 0.10 〇Example 2 〇a 0.11 〇Example 21 a 0.09 〇Example 22a 0.11 〇Example 23a 0.11 〇Example 24a 0.10 〇Example 25a 0.11 〇Example 26a 0.09 〇Example 27a 0.11 〇Example 28a 0.10 〇 Comparative Example 8a 0.12 X Comparative Example 9a 0.12 X Comparative Example 10a 0.12 X Comparative Example 11a 0.13 X Comparative Example 12a 0.12 X Comparative Example 13a 0.12 X Comparative Example 14a 0.12 Δ-200-1226509 V. Description of the Invention (1 &quot;) Example 29a ~ 34a (Modulation and evaluation of radiation-sensitive resin composition ... A rF excimer (Radiation exposure) 2 g of the resin shown in Table 6, a photoacid generator, 200 mg of an acid decomposable dissolution preventing compound, 5 mg of an organic basic compound, and a quantitatively compounded polymer compound containing a fluorinated aliphatic group, each of After dissolving the component in weight percent in PGMEA, it was filtered through a 0 · 1 A m micro filter to prepare a positive photoresist composition. -201-1226509 V. Description of the invention (200) Table-6 Formulas of positive photoresist composition (1 f force and comparative example) Resin acid decomposable dissolving photoacid generator organic basic compound containing fluorine Macromolecular compound of an aliphatic compound (addition amount) blocking compound (addition amount) (addition amount) Example 29a R-9 and j \ w D-7 &gt; fnT-ιΠΓ y »ν \ Ρ-3 45mg (lOOppm ) Example 30a R-9 Μ j \\ D-8 El P-6 45mg (20ppm) Example 31a R-9 te D-9 E-2 P-12 60mg (150ppm) Example 32a R-9 te j \ D-7 E-1 P-14 45mg (500ppm) Example 33a R-9 1-4 D-8 E-3 P-16 200mg 45mg (500ppm) Example 34a R-9 D- 9 Ε-1 P-19 40mg (50ppm) Comparative Example 15a R-9 te D-7 Ε-3 j ^ 45mg Comparative Example 16a R-9 te j \ w D-8 Ε-2 PR-1 60mg (50ppm) Comparative Example 17a R-9 te J \ w D-9 Ε-3 PR-2 45mg (150ppm) Comparative Example 18a R-9 1-4 D-7 Ε-1 PR-3 200mg 40mg (1000ppm) Comparative Example 19a R -9 1-4 D-8 Ε-2 PR-4 200mg 45mg (500ppm) *: Addition concentration to resin ppm-202-1226509 V. Description of the invention 2〇1)

CF3SO3- (D-9) Coat an anti-reflection film AR-19 manufactured by Siple Corporation on a silicon wafer, fire it at 215 ° C for 90 seconds, and apply it at a thickness of 850A. The thus-prepared photoresist was coated on the substrate thus obtained, and fired at 1 35 ° C for 90 seconds to obtain a film thickness of 0.30 // m. The wafer obtained in this way was equipped with a resolution mask in an ArF excimer laser stepped exposure device (ArF exposure machine 9300 manufactured by IS Company), and the exposure amount was changed and exposed. Then, it was heated in a greenhouse at 150 ° C for 90 seconds, and then developed with tetramethylammonium hydroxide imaging solution (2.88% by weight) for 60 seconds, washed with ultrapure water, and dried. And make a pattern. -203-1226509 V. Description of the invention (202) Use line and space system to make 0.1 6 // m design size 1: 1 minimum exposure as the sensitivity and the minimum size that can be resolved by the exposure as the resolution . At the same time, observe the residual 0.1 2 // m isolated lines (spacing 1 ·· 1 0). Those who have no pattern flying away at all are 0, those with more than 1/2 remaining are △, and those with most patterns flying away are X. . Table-7 Evaluation of photoresistance __ Resolution (# m) The isolated line flies away from Example 29a 0.13 〇Example 30a 0.13 〇Example 31a 0.125 〇Example 32a 0.125 〇Example 33a 0.13 〇Example 34a 0.13 〇Comparative Example 15a 0.14 X Comparative Example 16a 0.14 X Comparative Example 17a 0.14 X Comparative Example 18a 0.145 X Comparative Example 19a 0.135 Δ ^ It is understood that the present invention provides a solution capable of improving the resolution of a chemically amplified photoresist, and particularly capable of suppressing isolated patterns. Fly away photoresist composition. Secondly, it is a photoresist composition for electron or X-rays. 1. Synthetic examples of constituent raw materials (1) Compounds that generate acids by electron or X-rays-204-1226509 V. Description of the invention (203) (1-1) Synthesis of pentafluorobenzenesulfonic acid tetramethyl salt In 100 ml of methanol, 25 g of pentafluorobenzenesulfochloride was dissolved, and 100 g of 25% tetramethylammonium hydroxide was slowly added thereto. After stirring at room temperature for 3 hours, a tetramethylammonium pentafluorobenzenesulfonate solution was prepared. This solution was exchanged with a salt of a phosphonium salt and an iodonium salt. (1-2) Synthesis of triphenylpentafluorobenzenesulfonic acid salt 50 g of diphenylene was dissolved in 800 ml of benzene, 200 g of aluminum chloride was added thereto, and the mixture was refluxed for 24 hours. The reaction solution was slowly poured into 2 L of ice, 400 ml of concentrated hydrochloric acid was added thereto, and the mixture was heated at 70 ° C for 10 minutes. The aqueous solution was washed with 500 ml of ethyl acetate, and after filtration, 400 ml of 200 g of ammonium iodide was dissolved. The precipitated powder was filtered, washed with water, washed with ethyl acetate, and dried to obtain 70 g of triphenyl erythroiodide. 30.5 g of triphenyl erythroiodide was dissolved in 1000 ml of methanol, and 19.1 g of silver oxide was added to the solution, followed by stirring at room temperature for 4 hours. The solution was filtered, and an excessive solution of tetramethylammonium pentafluorobenzenesulfonate was added thereto, and the reaction solution was concentrated and dissolved in 500 ml of dichloromethane, and the solution was adjusted to 5% tetramethylammonium hydroxide Wash with water and water. The organic phase was dried over anhydrous sodium sulfate, and then concentrated to obtain triphenylpentafluorobenzenesulfonic acid salt (I-1) ° (1-3) bis (4- 3rd-fluorenylphenyl) pentafluoro Synthesis of ferric iodobenzene besylate 60 g of 3-pentylbenzene, 39.5 g of potassium iodate, 81 g of acetic anhydride, and 170 ml of dichloromethane were mixed, and 66.8 g of concentrated sulfuric acid was slowly added thereto under ice-cooling. After stirring under ice-cooling for 2 hours', it was stirred at room temperature for 10 hours. -205-1226509 V. Description of the invention (204) 500 ml of water was added to the reaction solution under ice cooling, and the mixture was extracted with dichloromethane. The organic phase was washed with sodium bicarbonate and water and concentrated to obtain two (4 -3 -pentylphenyl) iodophosphonium sulfate. This sulfate was added to an excess of tetramethylammonium pentafluorobenzenesulfonate solution. 500 m of water was added to the solution, and the solution was extracted with dichloromethane, and the organic phase was washed with 5% tetramethylammonium hydroxide aqueous solution, washed with water, and concentrated to obtain di (4-thi-pentylphenyl). ) Iodophosphonium pentafluorobenzenesulfonate (III-1). The acid generators PAG-1 and PAG-2 shown below were also synthesized in the same manner as described above. (Other acid generators)

Br I CH2CHCH2Br

Br BrCH2CHCH2

Br I CH2CHCH2Br PAG-1: PAG-2: (2) Synthesis of soluble resin (1 ^ 1): 16.4 g (0.1 mol) of 3,4-dimethoxystyrene, 158.7 g (0.9 Moore) Ren 3rd-butoxystyrene is dissolved in dry THF and heated to 701 under a stream of nitrogen, and 2 mole% of the total moles of the above monomers are added. Starter V-60 1. After reaction-206-1226509 V. Description of the invention (205) 8 hours, the reaction solution was diluted with THF, precipitated in hexane, purified, and the polymer was taken out. (P _ 1) is produced by acid decomposition by a common method. The weight average molecular weight (Mw) and molecular weight dispersion (Mw / Mn) were determined by G P C measurement. (1-2) Using the same method as above, and using a protected monomer (example: 4-benzyloxystyrene), cationic polymerization was performed by BF3 · Et〇2 to synthesize (P-1,) , (P-Γ,), (P-2) ~ (P-51). (1-3) Dissolve 1.64 g (0.01 mole) of 3,4-dimethoxystyrene and 15.9 g (0.09 mole) of 4 -3 -butoxystyrene at -78 ° C In dry THF, 1 millimolar 2-butyllithium was used at -78 ° C in a sealed tube, the glass seal was broken, and the reaction was started. The powders concentrated in a large number of hospitals were refined. (P-1 ') was prepared by acid treatment by a conventional method. (3) Synthesis of dissolution preventing compound (Synthesis Example of Dissolution Preventing Compound-1: Synthesis of Compound 18) 42.4 g (0.10 mole) of 1- [α-methyl-α_ (4, -hydroxyphenyl) Ethyl] -4-[α, α'-bis (4 ”-hydroxyphenyl) ethyl] benzene was dissolved in 300 ml of N, N-dimethylacetamide, and 49.5 g (0.35 mole) of carbonic acid was added Potassium and 84.8 g (0. 33 mol) of cumyl bromide bromide were stirred at 120 ° C. for 7 hours. The reaction mixture was poured into 2 L of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate. The ethyl acetate extract was concentrated and purified to obtain 70 g of compound 18 (all R is -CH2COOC (CH3) 2C6H5 group). ○ (Synthesis Example 2 of Dissolution Inhibitor Compound: Synthesis of Compound Example 42) 20 g α, α, α ,, α ', α ,,, α ,,-Lu (4-hydroxyphenyl) -1,3,5--207-1226509 V. Description of the invention (206) Diethylbenzene dissolution Dimethyl ether at 400 m. In this solution, 42.4 g of 3,4-dihydro-2H-pyran under nitrogen atmosphere, add hydrochloric acid in contact with coal, and reflux for 24 hours. After the reaction is completed, add a small amount Hydroxide It was filtered. The filtrate was concentrated and purified by column chromatography to obtain 55.3 g of compound 42 (all R are THP groups). (Synthesis Example 3 of Compound for Dissolution Inhibitor: Compound Example 42-2 Synthesis) 20 g of α, α, α ', α', α ", α" -L (4-hydroxyphenyl) -1,3,5-triethylbenzene was dissolved in 200,001 ^^ dimethyl To acetamide, 28.2 g of potassium carbonate and 3 6.0 g of butyl bromoacetate were added, and the mixture was stirred at 120 ° C. for 7 hours. The reaction product was put into 2 L of ion-exchanged water, and the viscous product was washed with water. 37g of the above-mentioned compound Example 42-2 (all R is -CH2COOC4H9 (t)) was purified by chromatography analysis method. (4) Synthesis example of compound represented by general formula (A) (Synthesis Example-1) A-22 above Synthesis of (benzyloxyethyl vinyl ether) 244 g (2 moles) of benzoic acid was dissolved in 300 ml of toluene, and 320 g of 2-chloroethyl vinyl ether was added, and 88 g of sodium hydroxide and 25 g of tetrahydrofuran were added. Butyl ammonium bromide, 100 g of triethylamine, and heating and stirring at 120 ° C for 5 hours. The reaction solution was washed with water and reduced under pressure I to remove excess 2-ethyl ethyl chloride; (: Hexyl ether and toluene. Since The obtained oil content was distilled off under reduced pressure to obtain 300 g of the desired benzophenoxyethyl vinyl ether. (Synthesis Examples-2 to 8) The synthesis of the above A-23 to A-29 and the above A- 22 The above-mentioned A-23 to A-29 were synthesized in the same manner. 2. Examples [Examples, Comparative Examples]-208-1226509 V. Description of the invention (207) Coating of photoresist 8.2 g of the components shown in Tables 8 to 11 below were dissolved in propylene glycol monomethyl ether acetate 'Oil through a 0.1 m Teflon sprinkler to prepare a photoresist solution. Each sample solution was coated on a silicon wafer using a spin coater, and dried at 120 ° C. for 90 seconds with a vacuum adsorption hot plate to obtain a photoresist film having a thickness of 0.5 // m. Preparation of Photoresist Pattern This photoresist film was irradiated with an electron line scanner (50 kV applied voltage). After the irradiation, each was heated on a 1 1 (TC vacuum adsorption hot plate for 60 seconds', immersed in a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried. The obtained contact hole pattern and the cross-sectional shape of the line and space pattern were observed with a scanning electron microscope. (3) Evaluation of sensitivity and resolution The critical resolution (minimum diameter of the hole) of the contact hole pattern was used as the resolution to make the critical The minimum irradiation energy for resolution is used as the sensitivity. Furthermore, the exposure amount for 0. 20 // m-line (line: space = 1: 1) is the sensitivity, and the smallest size that can be resolved at this exposure amount is the resolution. -209-1226509 V. Description of the invention (208) Table-8 Photoresist film-line and space acid generator test soluble resin (d) or (d,) dissolution inhibitor organic alkaline compound surfactant 氺 implementation Example 1 (ΠΙ-1) 0.072g (P-1) 〇.78g None /> w (42-2) 0.36g B-1 0.002g Wl 1000ppm Example 2 Ibid (P-1) 0.60g (A- 22) 0.18g Ibid. Ibid. Example 3 Ibid. (P-1,) 0.60g Ibid. Ibid. Ibid. Example 4 as above (P-1 ,,) 0.60g Ibid. Ibid. Ibid. Example 5 Ibid. (P-1, I.) 0.60g Ibid. Ibid. Ibid. Example 6 Ibid. (P-2) 0.60g Ibid. Ibid. Same as above Example 7 Same as above (P-3) 0.60g Same as above Same as above Same as above Example 8 Same as above (P-3,) 0.60g Same as above Same as above Ibid Example 9 Same as above (P-4) 0.60g Same as above Ibid Same as above Example 10 Same as above (P-5) 0.60g Same as above Same as above Example 11 Same as above (P-5 ,,) 0.60g Same as above Same as above Example 12 Same as above (P-6) 0.60g Same as above Same as above Example 13 Same as above (P -6 ，） 0.60g Ibid. Ibid. Ibid. Example 14 Ibid. (P-6 ,.) 0.60g Ibid. Ibid. Ibid. Example 15 Ibid. (P-7) 0.60g Ibid. Ibid. Ibid. Example 16 Ibid. (P-8 ) 0.60g as above, same as above, Example 17 Same as above (P-9) 0,60g as above, same as above, as above Example 18 as above (P-10) 0.60g, as above, as above, Example 19, above (P-11) 0.60g as above Ibid ibid ibid Example 20 Same as above (P-12) 0.60g Same as above Same as above Example 21 Same as above (P-13) 0.60g Same as above Same as above Example 22 Ibid (P-10,) 0.60g Same as above Same as above Example 23 Same as above (P-10 ”) 0.60g Ibid. Ibid. Ibid. Example 24 Ibid. (P-12,) 0.60g Ibid. Ibid. Ibid. Example 25 Ibid. (P-14) 0.60g Ibid. Ibid. Ibid. Example 26 Ibid. (P- 15) 0.60g, as above, same as above, Example 27, same as above (P-16), 0.60g, as above, same as above, Example 28, as above (P-17), 0.60g, as above, as above, and Example 29, as above (P-18), 0.60g, as above Ibid. Ibid. Example 30 Ibid. (P-19) 0.60 g Ibid. Ibid. Ibid.-210-1226509 V. Description of the invention (209) Table-9 Photoresist film-line and space acid generator alkali-soluble resin (d) or (d,) Dissolution inhibitor organic basic compound surfactant * Example 31 (m-1) 0.072g (P-20) 0.60g (A-22) 0.18g (42-2) 0.36g B-1 0.002 g Wl 1000 ppm Example 32 Ibid (P-21) 0.60 g Ibid Ibid Same as above Example 33 Same as above (P-22) 0.60g Same as above Same as above Same as above Example 34 Same as above (P-23) 0.60g Same as above Ibid Same as above Example 35 Ibid (P-24 0.60g Same as above Ibid Same as above Example 36 Ibid ( P-25) 0.60g Ibid. Ibid. Ibid. Example 37 Ibid. (P-26) 0.60g Ibid. Ibid. Ibid. Example 38 Ibid. (P-27) 0.60g Ibid. Ibid. Ibid. Example 39 Ibid. (P-28) 0.60 g Same as above Same as above Example 40 Same as above (P-29) 0.60 g Same as above Same as above Example 41 Same above (P-30) 0.60 g Same as above Same as above Example 42 Same as above (P-31) 0.60 g Same as above and above Example 43 Ibid. (P-32) 0.60g Ibid. Ibid. Ibid. Example 44 Ibid. (P-33) 0.60g Ibid. Ibid. Ibid. Example 45 Ibid. (P-34) 0.60g Ibid. Ibid. Ibid. Example 46 Ibid. (P-35) 0.60g Ibid. Ibid. Ibid. Example 47 Ibid. (P-36) 0.60g Ibid. Ibid. Ibid. Example 48 Ibid. (P-37) 0.60g Ibid. Ibid. Ibid. Example 49 Same (P-38) 0.60g Ibid. Ibid. Ibid. Example 50 (PAG-1) 0.072g (P-1) 0.60g Ibid. Ibid. Ibid. Comparative Example 1 (1-1) 0.072g P-101 0.78g-( 18) 0.36g — — Comparative Example 2 (PAG-1) 0.072g P-102 1.14g — — — — Comparative Example 3 (II-3) 0.072g P-103 0.78g One (42) 0.36g — — Comparative Example 4 (PAG-2) 0.072g P-104 0.78g-(42-2) 0.36g —-* Constant composition -211-1226509 V. Description of the invention (210) Table-1 0 Photoresist film-line and space acid Generator alkali-soluble resin (d) or (d,) dissolution inhibitor organic basic compound surfactant * Example 51 (m-1) 0.072g (P-1) 〇.78g None (42-2) 0.36g B-1 0.002g Wl 1000ppm Example 52 Ibid. (P-1) 0.60g (A-22) 0.18g Ibid. Ibid. Example 53 Ibid. (Pn 0.6.g Ibid. Ibid. Ibid. Example 54 Ibid. (P- 1 ,,) 0.60g, as above, same as above, Example 55 55, as above (P-1 ,,,) 0.60g, as above, same as above, Example 56, as above (P-2) 0.60g, as above, as above, and Example 57 as above (P- 3) 0.60g Ibid Ibid Ibid Example 58 Same as above (P-3,) 0.60g Same as above Same as above Example 59 Same as above (P-4) 0.60g Same as above Same as above Example 60 60 Same as above (P-5) 0.60g Same as above Same as above Example 61 Same as above (P -5 ,,) 0.60g, as above, same as above, Example 62 62, as above (P-6), 0.60g, as above, same as above, Example 63, as above (P-6,) 0.60g, as above, as above, and above Example 64 as above (P-6) 0.60g Same as above Same as above Example 65 Same as above (P-7) 0.60g Same as above Same as above Example 66 Same as above (P-8) 0.60g Same as above Same as above Example 67 Same as above (P-9) 0.60g Same as above Same as above Example 68 Same as above (P-10) 0.60 g Same as above Same as above Example 69 69 Same as above (P-11) 0.60 g Same as above Same as above Example 70 Same as above (P-12) 0.60 g Same as above and same as above Example 71 Same as above (P-13) 0.60g Same as above Same as above Example 72 Same as above (P-10,) 0.60g Same as above Same as above Example 73 Ibid (P-10,) 0.60g Same as above and same as above 74 Same as above (P-12) 0.60g Same as above Same as above Example 75 75 Same as above (P-14) 0.60g Same as above Same as above Example 76 76 Same as above (P-15) 0.60g Same as above Same as above Example 77 Same as above (P- 16) 0.60g, as above, same as above, Example 78, same as above (P-17), 0.60g, as above, same as above, Example 79, as above (P-18), 0.60g, as above, as above, Example 80, as above (P-19), 0.60g, as above Same as above Same as above * Anti-solid content -212-1226509 V. Description of the invention (211) Table 1 Photoresist film-line and space acid generator alkali-soluble resin (d) or (d,) Dissolution inhibitor interfacial activity of organic alkaline compound Agent * Example 81 (m-1) 0.072g (P-20) 0.60g (A-22) 0.18g (42-2) 0.36g B-1 0.002g Wl 1000ppm Example 82 Ibid (P-21) 0.60 g Same as above Same as above Example 83 Same as above (P-22) 0.60 g Same as above Same as above Example 84 Same as above (P-23) 0.60 g Same as above Same as above Example 85 Same as above (P-24) 0.60 g Same as above and above Example 86 Ibid. (P-25) 0.60 g Ibid. Ibid. Ibid. Example 87 Same as above (P-26) 0.60g Same as above Same as above Ibid Example 88 Same as above (P-27) 0.60g Same as above Ibid Same as above Example 89 Ibid (P-28) 0.60g Same as above Ibid Same as above Example 90 Ibid ( P-29) 0.60g Same as above Same as above Example 91 Same as above (P-30) 0.60g Same as above Same as above Example 92 Ibid (P-31 0.60g Same as above Same as above Example 93 Ibid (P-32) 0.60g Same as above Same as above Example 94 Same as above (P-33) 0.60g Same as above Same as above Example 95 Same as above (P-34) 0.60g Same as above Same as above Example 96 Same as above (P-35) 0.60g Same as above and same as above Example 97 Same as above (P-36) 0.60g Same as above Same as above Example 98 Same as above (P-37) 0.60g Same as above Same as above Example 99 99 Same as above (P-38) 0.60g Same as above Same as above Example 100 (PAG- 1) 0.072g (P-1) 0.60g Ibid. Ibid. Ibid. Comparative Example 5 (1-1) 0.072g P-101 0.78g (18) 0.36g —-Comparative Example 6 (PAG-1) 0.072g P-102 1.14g — — —-Comparative Example 7 (II-3) 0.072g P-103 0.78g-(42) 0.36g--Comparative Example 8 (PAG-2) 0.072g P-104 0.78g-(42-2) 0.36g--* Anti-solid content -213-1226509 V. Description of the invention (212) The abbreviations used in Tables 8 to 11 are as follows. &lt; Alkali-soluble resin constituting the present invention &gt; (P-1) ^ CH2CH ^ -fCH2CH ^

12,000

OCH3 OCH3 OH (P-V) — {-ch2ch) y — (-ch2ch ^-

11,900 och3 och3 oh (Ρ-Γ) — (-CH2CH-) — -f ch2ch ^ j-

12,500 och3 och3 oh (P-r) —f-CH2CH ^ — (ch2ch- ^

5,000 och3 och3 oh

(P-2) ^ ch2ch) ^ --f ch2ch) ^-'H3ccA

OH 11.500

Mw / Mn 1.88 1.89 1.92 1.12 1.79 -214-1226509 V. Description of the invention (213

Mw / Mn

10,200 1.69

h3c〇, och3 OCH3 OH

11,000 1.69 h3cct och3 OCH3 OH (P-r) _ (. CH2CH) ^ -fCH2CH) ^

10.100 2.15

h3cct och3 OCH3 OH (P-4) ^ ch2ch) ^-(ch2ch ^

och3 OCH3

OH (P-5) _ ^ ch2ch ^ -f ch2ch ^-, och3.

H3CO

OH (P-5 *) — ^ c ^ CH ^ -fCH2CH ·) ^, och3 〆

hhCO

OH 7,500 2.33 6,800 2.29 5,200 1.63 -215-1226509 5. Description of the invention (214

Mw / M gate (P-6) ^ ch2ch ^-f ch2ch ^

h3cct ya '〇ch3 och3

5,900 2.15

OH

h3cct ya och3 och3

11.600 2.14

OH (P-6 ^) _ ^ ch2ch) ^-(ch2ch) ^

h3cct got och3 och3

9,300 2.54

OH (P ~ 7) _ (ch2ch) ^ -f ch2ch- / 9〇, 〇ch3 ^

12,500 2.23

OCH3 OCH3 OH (P-8) _ | ch2CH ^ —f-CH2CH ^-

OH 11,800 2.00 -216- 1226509

1226509

1226509 V. Description of the invention (217)

13,100 2.28 10,300 2.49 11,400 1.68 11,600 2.43 13,000 1.77

Mw Mw / Mn

-219- 1226509

1226509 V. Description of Invention (219)

Mw Mw / Mn

12,700 1.76 9,000 1.90 9,800 1.90 10,700 2.22 -221-1226509

1226509

Mw Mw / Mn 11,600 1.91 5.500 2.13 6,100 2.11 4.500 2.13-2 2 3-1226509

1226509 V. Description of the invention (2 of 3 P-103

Mw Mw / Mn

OH 7,500 2.10 P-104

10,000 1.55

OH OH OH Organic basic compounds are described below. 8-1: 2,4,5-triphenylimidazoline B-2: 1,5 · diazobicyclo [4,3,0] non-5-ene B-3: 4-dimethylamine Pyridine B-4: 1,8-diazobicyclo [5,4,0] undec-7-ene B-5: N-cyclohexyl-N'-morpholinoethyl sulfide urea surfactant As described below. w-1: Dun Long Yi Luolu (transliteration) S-366 (Dun Long Yi (transliteration) chemical (stock) system) W-2: Mekafak (transliteration) F 1 7 6 (Da Yueben Ink (stock) )) (Fluorine-based) W-3: Mekafak (translated) R08 (made by Dainippon Ink Co., Ltd.) (fluorine-based and polyoxanthane-based) W-4: polysiloxane polymer- KP-341 (made by Shin-Etsu Chemical Industry Co., Ltd.) w-5: Seflon (transliterated) S-3 8 2 (made by Asahi Glass (Stock))-225-1226509 V. Description of the invention (224) Table 12 3 Eat Resist Film-Contact Hole Sensitivity (&quot; C / cm2) Resolution (// π〇 Pattern Outline Example 1 3.5 0.08 Rectangle 2 2.5 0.09 Rectangle 3 2.0 0.07 Rectangle 4 2.5 0.06 Rectangle 5 2.0 0.05 Rectangle 6 2.5 0.09 Rectangle 7 2.0 0.08 Rectangle 8 2.5 0.07 Rectangle 9 2.5 0.06 Rectangle 10 3.5 0.05 Rectangle 11 3.5 0.05 Rectangle 12 4.0 0.05 Rectangle 13 3.5 0.06 Rectangle 14 3.5 0.06 Rectangle 15 4.0 0.05 Rectangle 16 4.5 0.05 Rectangle 17 2.0 0.05 Rectangle 18 3.5 0.06 Rectangle 19 3.5 0.05 Rectangle 20 2.0 0.06 Rectangle 21 1.5 0.06 Rectangle 22 3.5 0.05 Rectangle 23 2.5 0.05 Rectangle 24 1.5 0.05 Shape 25 1.5 0.06 Rectangle 26 2.0 0.05 Rectangle 27 3.5 0.06 Rectangle 28 3.5 0.06 Rectangle 29 3.0 0.05 Rectangle 30 3.0 0.05 Rectangle-226-1226509 V. Description of the invention (225) Table 13 Light β and film-contact hole sensitivity (# C / cm2) Resolution (# m) Pattern outline example 31 3.5 0.04 Rectangle 32 3.0 0.05 Rectangle 33 3.5 0.05 Rectangle 34 3.5 0.06 Rectangle 35 3.0 0.05 Rectangle 36 1.0 0.06 Rectangle 37 1.0 0.05 Rectangle 38 1.5 0.06 Rectangle 39 1.5 0.05 Rectangle 40 1.5 0.06 Rectangle 41 1.5 0.05 Rectangle 42 1.0 0.05 Rectangle 43 1.0 0.05 Rectangle 44 1.0 0.06 Rectangle 45 1.0 0.05 Rectangle 46 1 .0 0.05 Rectangle 47 1.0 0.05 Rectangle 48 1 .0 0.05 Rectangle 49 1.0 0.05 Rectangle 50 3.5 0.10 Rectangle Comparative Example 1 5.0 0.15 2 8.0 0.20 3 8.0 0.18 4 4.0 0.25-227-1226509 V. Description of the invention (226) Table 14 Photoresist film-line and space sensitivity (# C / cm2) Resolution (ju m) Pattern outline example 51 2.5 0.07 Rectangle 52 1.5 0.08 rectangle 53 1.0 0.06 rectangle 54 1.5 0.05 rectangle 55 1 .0 0.04 rectangle 56 1.5 0.08 rectangle 57 1.0 0.07 rectangle 58 1.5 0. 06 rectangle 59 1.5 0.05 rectangle 60 2.5 0.04 rectangle 61 2.5 0.04 rectangle 62 3.0 0.04 rectangle 63 2.5 0.05 rectangle 64 2.5 0.05 rectangle 65 3.0 0.04 rectangle 66 3.5 0.04 rectangle 67 1.0 0.04 rectangle 68 1.5 0.04 rectangle 69 1.5 0.04 rectangle 70 1.0 0.05 rectangle 71 0.5 0.04 rectangle 72 2.5 0.04 rectangle 73 1 .5 0.04 rectangle 74 0.5 0.04 rectangle 75 0.5 0.05 rectangle 76 1.0 0.04 rectangle 77 2.5 0.05 rectangle 78 2.5 0.05 rectangle 79 2.0 0.04 rectangle 80 2.0 0.04 rectangle-228-1226509 5. Description of the invention (227) Table 1 5 Photoresist Film-Line and Space Sensitivity (# C / cm2) Resolution (// m) Pattern Outline Example 81 2.5 0.04 Rectangle 82 2.0 0.04 Rectangle 83 2.5 0.04 Rectangle 84 2.5 0.05 Rectangle 85 2.0 0.04 Rectangle 86 0.5 0.05 rectangle 87 0.5 0.04 rectangle 88 0.5 0.05 rectangle 89 0.5 0.04 rectangle 90 0.5 0.05 rectangle 91 0.5 0.04 rectangle 92 0.5 0.04 rectangle 93 0.5 0.04 rectangle 94 0.5 0.05 rectangle 95 0.5 0.04 rectangle 96 0.5 0.04 rectangle 97 0.5 0.04 rectangle 98 0.5 0.04 Rectangle 99 0.5 0.04 Rectangle 100 2.5 0.08 Rectangle Comparative Example 5 4.5 0 .14 Inverted tapered, T-Top 6 7.5 0.19 "7 7.5 0.17" 8 3.5 0.23 Inverted tapered, film edge From the results of Table 1 2 ~ 15, it can be seen that the positive photoresist composition of the present invention has high sensitivity, high The resolution and the contour of the rectangular pattern are good.

-229-1226509 V. Description of the invention (228) In addition, by using a compound represented by the general formulae (I) to (III) as an acid generator or a compound represented by the general formula (A-1), it can be further improved. Excellent performance. Examples 1, 8, 9, 18, 19, 20, 23, 29, 30, 39, 40, 41, 51, 58, 59, 68, 69, 70, 73, 79, 80, 89, 90, and 9 1 However, when the organic basic compound is changed from B-1 to B-2, B-3, B-4, and B-5, the same performance can be obtained. Furthermore, Examples 1, 8, 9, 18, 19, 20, 23, 29, .3 0, 39, 40, 41, 51, 58, 59, 68, 69, 70, 73, 79, 80, 89, In 90 and 91, when the surfactant is changed from W-1 to W-2, W-3, W-4, and W-5, the same performance can be obtained. Examples 1, 8, 9, 18, 19, 20, 23, 29, 30, 39, 40, 41, 51, 58, 59, 68, 69, 70, 73, 79, 80, 89, 90, and 9 1 However, when the solvent was changed to propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 80/20 (weight ratio) and the same performance was obtained. (4) In addition, the components shown in Table 16 were dissolved in 8.2 g of propylene glycol monomethyl ether acetate ', and filtered through a Teflon filter of 0.1 m // to prepare a photoresist solution. Each sample solution was coated on a silicon wafer using a spin coater, and dried on a vacuum adsorption hot plate at 120 ° C for 90 seconds to obtain a photoresist film having a film thickness of 0.5 / m. The same irradiation and development were performed as described above, and the cross-sectional shape of the obtained contact hole pattern was observed. The evaluation method is the same as above. -230-1226509 V. Description of the invention (229) Table 16 Acid generator, binder, organic alkaline compound surfactant * Example 101 1-1 0.072g P-41 1.73g B-1 0.002g Wl O.OOlg Example 102 Same as above P-42 Same as above Example 103 Same as above P-43 Same as above Example 104 Same as above P-44 Same as above Example 105 Same as above P-45 Same as above Example 106 Same as above P-46 Same as above Same as above 107 Same as above P-47 Same as above Example 108 Same as above P-48 Same as above Example 109 Same as above P-49 Same as above Example 110 Same as above P-50 Same as above Example 111 Same above P-51 Same as above Same as above 112 Ibid. P-521 Ibid. Ibid. 113 Id. P-53 Id. Ibid. 114 Id. P-54 Id. Id. 115 Id. P-55 Id. Id. 116 Id. P-56 Id. Id. 117 Same as above P-41 Same as above B-2 0.002g Same as above Example 118 Same as above Ibid B-3 0.002g Same as above Example 119 Same Ditto ditto ditto embodiment 0.002g Example 4 B-12〇 ditto ditto B-5 0.002g Comparative Example P-111 101 ditto ditto

-231-1226509

1226509

1226509

1226509

1226509

1226509

1226509 V. Description of the invention (236) Table 17 Sensitivity (# C / cm2) Resolution (U m) Pattern outline example 101 4.5 0.11 Rectangle 102 5.0 0.12 Rectangle 103 4.0 0.11 Rectangle 104 4.5 0.12 Rectangle 105 4.0 0.11 Rectangle 106 5.0 0.12 Rectangle 107 4.5 0.11 rectangle 108 5.0 0.11 rectangle 109 5.0 0.11 rectangle 110 5.0 0. 11 rectangle 111 4.5 0.11 rectangle 112 4.5 0.11 rectangle 113 5.0 0.12 rectangle 114 4.0 0.11 rectangle 115 5.0 0.11 rectangle 116 5.0 0.12 rectangle 117 5.0 0.11 rectangle 118 5.0 0.11 rectangle 119 5.0 0.12 Rectangle 120 5.0 0.11 Rectangle Comparative Example 101 10.0 0.15 Py-2 3 8-

1226509 V. Description of the invention (237) It can be seen from Table 17 that the evaluation items of the composition of the present invention are all excellent. (5) The patterning by equal-time X-ray exposure each uses the photoresist composition of Example 20 and Comparative Examples 丨 and 2 described above to obtain a film thickness of 0.40 / in the same manner as in (1) above. / m of photoresist film. Then 'except for using an equal magnification X-ray irradiation device (gap 2; 20 nm), patterning was performed in the same manner as in (2) above, and the photoresist performance (sensitivity, resolution, and Pattern shape). The evaluation results are shown in Table 1 / R ° Table 18 _Photoresist composition sensitivity (mJ / cm2) Resolution (# m) Pattern shape * Example 20 70 0.10 Comparative example of a rectangular upper blade 1 180 0.18 Conical shape, groove Comparative Example 2 of the upper dagger 230 230 0.17 It can be seen from Table 18 that the photoresist composition of the present invention has extremely excellent performance in X-ray exposure. [Effects of the Invention] The present invention provides a photoresist composition capable of improving the resolution of a chemically amplified photoresist, particularly a photoresist composition capable of inhibiting the flying away of an isolated line, or a high-sensitivity, high-resolution, and excellent-profile-shaped semiconductor semiconductor device. Positive electron wire or X-ray photoresist composition. -2 3 9-

Claims (1)

1226509 VI. Application for Patent Scope No. 901 22094 "Positive Photoresist Composition" Patent (Amended on June 25, 1993) A. Patent Application Scope: 1 · A positive photoresist composition, including: (A ) 40 to 99.99% by weight (1) a resin that is decomposed by an acid to increase its solubility in an alkali imaging solution, (2) an alkali-soluble resin and that is decomposed by an acid to increase its solubility in an alkali imaging solution Compounds that are soluble in the solvent, or (3) resins that are decomposed by the action of acid to increase the solubility in the alkali developer solution, and resins that are decomposed by the action of the acid to increase the solubility in the alkali developer solution. Molecular compounds, (B) 0.1 to 30% by weight of compounds that generate acid by irradiation with active light or radiation, and (C) 0.001 to 10% by weight of acrylic resin, methacrylic resin, styrene resin, polyester Resin, polyurethane resin, polycarbonate resin, polyamide resin, polyacetal resin, phenol / formaldehyde condensation tree, polyvinyl phenol resin, maleic anhydride / (X-olefin resin, OC- Heterocyclic substitution of methacrylic resin selected by short chain polymerization Polymer compounds derived from fluorinated aliphatic compounds produced by the oligomerization method or oligomerization method and having a fluorinated aliphatic group on a side chain. 2. A positive photoresist composition, including: (A) 40 to 99.99 (1) Resin which is decomposed by the action of acid to increase the solubility in alkali developing solution by weight, (2) Alkali soluble resin and which is decomposed by the action of acid to increase solubility in alkali developing solution Compounds, or (3) low molecular compounds which are decomposed by an acid to increase solubility in an alkali imaging solution and low molecular compounds which are decomposed by an acid to increase solubility in an alkali imaging solution, 1226509 Sixth, the scope of patent application (B) 0.1 to 30% by weight of compounds that generate acids by irradiation with active light or radiation, and (C) 0.0 01 to 10% by weight have side formulas with the following general formula (F1 ) Shows a fluorinated aliphatic-based polymer compound, and the polymer compound is mixed with a base of general formula (F1) in which η is 3, 4, 5, and 6, in which case η = 4 The sum of the components of η = 3, 4, 5, and 6 is 40 to 97 mol%, or the components of η = 3 are based on the components of η = 3, 4, 5, and 6 In total, it is a polymer compound of 40 to 97 mole% Υ——X-fc —)-(CF2CF2) n F (F1) I mr3 (where 1 to 2 and 1 each represent a hydrogen atom and a carbon number of 1 ~ 4 alkyl groups, X represents a single bond or a divalent bond, Y represents a polymer main chain, m represents an integer of 0 or more, and η represents an integer of 1 or more). 3. A kind of positive photoresist composition of electron beam or X-ray chemical amplification system, including: (a) 0.1 to 20% by weight of a compound that generates an acid by irradiation with electron beam or X-ray, (b) 30 to 90% by weight of an alkali-soluble resin having a weight average molecular weight of 3,000 to 3000,000 and meeting the following conditions (1) and (2), (1) having at least one aromatic ring having 6 to 20 carbon atoms, and Straight 1226509 on the aromatic ring 6. The patent application scope is a repeating unit derived from a monopolymer with an ethylenically unsaturated group connected through a bonding group, (2) the 7Γ electron of the aromatic ring and the substituent on the aromatic ring The following relationship is established between the non-shared electron pairs of N7Γ 2 Nlone = 10 (wherein N 7Γ represents the total number of electrons, and NUne represents the linear, branched, Or cyclic alkoxy, alkenyloxy, aryloxy, aralkoxy, or total number of electrons of non-shared electron pairs of hydroxyl groups' 2 or more adjacent alkoxy groups or hydroxyl groups are connected to each other to form a 5 carbon number The above ring structure, except for the benzodioxazole structure, and the substituent does not contain a hydroxyl group when Nττ = 6)4 · If the electron beam or X-ray chemical amplification type positive photoresist composition of item 3 of the patent application scope, wherein (b) the alkali-soluble resin system has at least one of the following general formulae (1) to (5) Repeating structural units as constituents, ? 101 Ra (Ra〇) l-(〇Rc) n (〇Rb) m-3-1226509 6. Patent application scope Ri〇1 ch2c-)-(Rd〇) (〇Rg) s-(〇Rh) t ⑵ p (Re〇) q (RP), m (〇Rt) r (〇Rh) t ⑶ (〇Ri) i ~ f CH2Cp L (Rd〇) p (ReO) (ORi) v (ORk) v (Rf〇) r (Rg〇) s \ (〇R · ^ (〇Ri) &gt; (〇Rh) t a 4- ⑷ 1226509 6. Scope of patent application (5) is QCD, O ~ 0O, ^ b (Where R1 () 1 represents a hydrogen atom or a methyl group, L represents a divalent bonding group, and Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, R1 are each independent The ground represents a linear, branched, or cyclic alkyl, alkenyl, aryl, aralkyl, or hydrogen atom having a carbon number of 1 to 12, and these can be linked to each other to form a carbon number of 24 or less Rings above carbon, 1, m, η, mouth, (1, 1 *, 3, 1, 11, ¥, \ ^, 乂 are integers from 0 to 3, which can satisfy l + m + n = 2, 3 , P + q + r = 0, 1, 2, 3, s + t + u = 0, 1, 2, 3, v + w + x = 0, 1, 2, 3, but in the general formula (1) Ra, Rb, and Rc cannot be 5-1226509 6. The scope of the patent application is for a hydrogen atom and in the general formula (1) (except for the benzodioxazole structure). 5 · — A kind of chemical amplification for electron or X-rays Type photoresist composition, including: (a) 0.1 to 20% by weight of a compound that generates an acid by irradiation with an electron beam or X-ray, (b ') A weight average molecular weight of 30 to 90% by weight is 3,000 to 300,000 and can satisfy the following conditions (1) and (2). Resin, (1) at least one aromatic ring having 6 to 20 carbon atoms and a repeating unit derived from a monomer having an ethylenically unsaturated group bonded directly or through a bonding group on the aromatic ring, (2) the The following relationship is established between the π electron of the aromatic ring and the non-shared electron pair of the substituent on the aromatic ring: (Formula υ • N7Γ + 2 Nlone (where N 7Γ represents the total number of 7Γ electrons, and NUne represents the substitution The carbon number of the group is 1 to 12. The total number of non-shared electron pairs of the linear, branched, or cyclic alkoxy, alkenyl, aryloxy, aralkoxy, or hydroxyl groups is 2 or more. Adjacent alkoxy groups or hydroxyl groups are bonded to each other to form a ring structure with more than 5 carbon atoms, except for benzodioxazole structures, and the substituent does not contain a hydroxyl group when Nτγ = 6). Chemical amplification of electronic or X-ray items is a 6-1226509 6. Patent application type photoresist Into the composition, wherein (b ') an alkali-soluble resin having at least one line of the following general formula (1) to (5) the repeating structural unit as a constituent, Rioi ⑴ ^ OR ^ s (2) (^ e〇) q (Rp), (OROu (〇Rt) r (ORDi ⑶ -7-1226509 6. Scope of patent application-(^ Η2 {ρ (〇Rj) v {RdOJp,! ^^ (Re〇) q- ^ 7 ⑷ _r (Rg〇) s \ (0R &amp; (〇Ri) x (〇Rh) t (〇Rk). ^ 101 (5) (Rd〇) p- ^ J '&gt; ^ ^ or9 ^ (Re〇) q ^ j? ^^ (ORh)! (RfO) r Y (〇R〇u (Where R1 () 1 represents a hydrogen atom or a methyl group, L represents a divalent bonding group, Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, -8-1226509 Six, the scope of patent application Ri is a linear, branched, or cyclic alkyl, alkenyl, aryl, aralkyl, hydrogen atom, or acid decomposable group each independently representing a carbon number of 1 to 12; and These can be connected to each other to form a ring of 5 or more carbons with a carbon number of less than 24. l, m, n, p, q, r, s, t, u, v, w, and x are integers of 0 to 3, but Satisfy l + m + n = 2, 3, p + q + r = 0, 1 '2, 3, s + t + u = 0, 1, 2, 3, v + w + x = 0, 1, 2 , 3, except that Ra, Rb, and Rc in the general formula (1) cannot be hydrogen atoms and in the general formula (1) except for the benzodioxazole structure). 7. For example, a positive photoresist composition for an electron beam or a chemical amplification system for X-rays in item 3 of the scope of a patent application, wherein (b) the molecular weight distribution of the alkali-soluble resin is 1 · 0 ~ 1 · 5 0 8 The electron amplification or X-ray chemical amplification system of the fifth item is a positive type photoresist composition in which (b ′) the molecular weight distribution of the resin which increases the solubility in the alkali developing solution by the action of acid and decomposition is 1.0 ~ 1.5. 9. For example, a positive photoresist composition for a chemical amplification system for electron or X-rays in the scope of patent application No. 3 or 5, which additionally contains (c) a group having a base decomposed by an acid and an increase in Solubility in alkali imaging solution, low molecular weight molecular weight below 3000 prevent compounds. 10. A positive photoresist composition, such as a chemical amplification system for electron rays or X-rays, as claimed in item 3 or 5 of the scope of patent application, which further contains (d) a compound having a cationic polymerizable function. U. If the electronic or X-ray chemical amplification type positive photoresist composition is used in the scope of patent application No. 3 or 5, in which (d ') is at least one selected from the group consisting of ethylene 9-1226509 Compounds, cycloalkane compounds, cyclic ether compounds, lactone compounds, and acid compounds. 1 2 · If the electron beam or X-ray chemical amplification system positive photoresist composition is used in the scope of patent application No. 丨 1 (where (d ') is a compound not represented by general formula (A), general formula (A) V / 0-¾ / = c \ (wherein Ra, Rb, and R. represent the same or different hydrogen atoms, optionally substituted alkyl or aryl groups, and 2 of these can be bonded to form saturation Or an olefin type unsaturated ring, and Rd means an alkyl group or a substituted alkyl group). 1 3 · If the electronic or X-rays are chemically amplified positive photoresist compositions for electronic or X-rays in the scope of patent application, where (a) the compound that generates acid by irradiation with electrons or X-rays contains at least one of the following: The compounds represented by the general formulae (I) to (ΠΙ), 1-10-1226509 6. Application scope (I) X (II) (Wherein Ri to R37 represent the same or different hydrogen atom, straight chain, branched or cyclic alkyl group, straight chain, branched or cyclic alkoxy group, halogen atom, or -S- R38, R38 represents a linear, branched or fluorinated alkyl or aryl group, and R ^ Ru, R16 ~ R27, R28 ~ R37 have two or more bonds to form a single bond, at least one or two or more Selected from the group consisting of oxygen, sulfur, and nitrogen, X- represents an anion of a sulfonic acid). -11-