TW200836009A - Chemical amplification-type positive-working or negative-working photoresist composition for low-temperature dry etching and method for photoresist pattern formation using the same - Google Patents

Abstract

To provide a chemical amplification-type positive-working or negative-working photoresist composition satisfying requirements (1) that any crack attributable to thermal shock does not occur even under exposure to low temperatures of ≤ 0 DEG C, (2) that a film having a large thickness of ≥ 5 μm can be formed, (3) that high sensitivity can be attained, and (4) that easy separation with a conventional solvent is possible. The chemical amplification-type negative-working photoresist composition for low-temperature dry etching comprises (A) a photoacid generating agent, (B) at least one resin component selected from novolak resins, polyhydroxy styrene resins and acrylic resins, (D) at least one plasticizer selected from acrylic resins and polyvinyl resins, (F) a crosslinking agent and (E) an organic solvent.

Description

200836009 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to a chemically enhanced positive or negative photoresist for low temperature dry etching using a dry etching process step under low temperature conditions suitable for fabricating MEMS devices and through electrodes. A composition, and a method of forming a photoresist pattern using the same. [Prior Art] High-transformation must be applied to the formation of micro-electro-mechanical systems (MEMS) components, small machines (micromachines) for assembling MEMS components, and through electrodes for high-density mounting. The tantalum substrate processed by the (hole depth/opening diameter), and the processing of the tantalum substrate is a photolithography method using a photoresist composition. Conventionally, since the conventional photoresist composition for photolithography can be made to have low dry etching resistance of the photoresist composition, a high aspect ratio germanium substrate structure can be formed by repeating the photolithography step. However, repeating this step causes a poor yield, and the amount of the chemical liquid used for the photoresist is increased, and it is impossible to avoid the use of the high. Further, there is a problem that irregularities are generated on the side wall of the pattern, and residue is retained at the bottom of the processing substrate. Moreover, recently, in order to obtain the high uranium engraving rate characteristic of the tantalum substrate, it is a method of performing a dry etching step at a low temperature of 0 or less, but the step at such a low temperature becomes a load on the photoresist pattern, due to the photoresist pattern. The temperature change (thermal shock) of the type causes difficulty in peeling off the photoresist pattern, cracking in the photoresist pattern, and deterioration in the dimensional fineness of the photoresist pattern. -4- 200836009 In order to be suitable for the formation of a structure of a tantalum substrate under such low temperature conditions, the following characteristics are required for the photoresist composition. That is, (1) cracks (with crack resistance) due to thermal shock even when exposed to a low temperature of 0 ° C or less, and (2) since the ruthenium substrate is subjected to deep etching treatment of 50 μm or more, it can be formed. A thick film of 5 μm or more, (3) a high sensitivity that does not cause an insufficient sensitivity due to the photoresist of the original film, and (4) a requirement that the solvent can be easily peeled off in general. Further, as a conventional resistive film for forming a thick film, a positive photosensitive resin composition having a quinonediazide group-containing compound for forming a pump and forming a wiring has been disclosed (Patent Document 1). Further, various positive chemically amplified resist compositions for thick films for plating are disclosed (Patent Documents 2 to 6). Further, as for the conventional photoresist for forming a thick film, various negative-type chemically-enhanced photoresist compositions for forming thick films for forming pumps and forming wirings have been disclosed (Patent Documents 7 and 8). [Patent Document 1] JP-A-2004-258776 [Patent Document 3] JP-A-2004-09775 [Patent Document 3] JP-A-2004-309776 [Patent Document 5] JP-A-2004-309777 [Patent Document 6] JP-A-2004-3 09778 (Patent Document 7) JP-A-2002-003 6-8 (Patent Document 8) Japanese Laid-Open Patent Publication No. 2 003 - 1 1 45 3 No. 200836009 SUMMARY OF THE INVENTION In order to solve the above problems, in the present invention, it is provided that (1) does not cause thermal shock even when exposed to a low temperature of 〇 °c or less. Cracks, (2) thick films with a thickness of 5 μηι or more, (3) high sensitivity, (4) chemically amplified positive photoresist compositions and chemically enhanced negative light conditions that can be easily peeled off by a general solvent A resist composition and a method of forming a photoresist pattern using the photoresist composition. Further, the present invention provides that the (Β) component is at least one selected from the group consisting of a novolac resin, a polyhydroxystyrene resin, and an acrylic resin which are increased in solubility in alkali by an acid action, and an alkali-soluble phenolic resin. A chemically amplified positive-type photoresist composition for low-temperature dry etching characterized by selecting at least one of a mixed resin of a varnish resin, a polyhydroxy-based vinyl resin, and an acrylic resin. Further, the present invention provides that the (Β) component is at least one selected from the group consisting of an alkali-soluble novolac resin and a polyhydroxystyrene resin, and at least one selected from the group consisting of an acrylic resin which increases the solubility to alkali by an acid action. A chemically amplified positive resist composition for low temperature dry etching characterized by a mixed resin. The above-mentioned problems are solved by the chemically amplified positive-type photoresist composition for low-temperature dry etching provided by the present invention. According to the present invention, it is provided that (1) cracks are not caused by thermal shock even when exposed to a temperature lower than 〇 ° C, (2) a thick film of 5 μm or more is formed, and (3) high sensitivity, ( 4) A chemically-enhanced positive-type photoresist composition for low-temperature dry etching using a solvent which can be easily peeled off in general -6 - 200836009, and a method of forming a chemically-enhanced photoresist composition using the low-temperature dry etching. Further, the low temperature dry uranium engraving resist composition according to the present invention is also selected from the group consisting of (A) photoacid generator, (B lacquer resin, polyhydroxy styrene, and acrylic resin selected from the resin component (C) A chemically-reinforced negative-type photoresist composition for low-temperature dry etching using a plasticizer such as an acrylic resin and a polyethylene resin, (D) a crosslinking agent, and (E) organic solvent. Further, the present invention is also provided on a substrate. Coating the low-chemically-enhanced negative-type photoresist composition onto the film to form a film having a thickness of 5 to 200, and forming a resist pattern of the obtained photoresist film by a predetermined reticle patterning process According to the present invention, it is also provided that (1) cracks are not caused by hot stamping even at low temperatures, (2 μηι or more thick film, (3) high sensitivity, (4) is generally easy Chemically Enhanced Negative Photoresist Composition of Peeling Conditions, Photoresist Pattern of Chemically Enhanced Photoresist Composition for Warm Dry Etution [Embodiment] Hereinafter, the present invention will be described in detail based on examples, but it is intended to be described herein. [(A) Photoacid generator] Light of matter Resistance diagram enhanced negative) Select at least one of the at least one of the novolacs for its characteristic temperature dry etching etch with μπι photoresist radiation, into the 〇 °ci) can form a solvent of 5 can be light and use this low The formation method is not limited to 200836009. The (A) photoacid generator used in the chemically amplified positive-type photoresist composition for low-temperature dry etching of the present invention is a substance which directly or indirectly generates an acid via light irradiation (including radiation). The first aspect of such a photoacid generator may be exemplified by 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-trisole, 2,4-bis(trichloromethyl). -6-[2-(2-furyl)vinyl]-3-trisole, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furanyl)ethylene Base]-s_tris, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furanyl)ethyl bromide]_s_trisole, 2,4-double (Trichloromethyl)-6-[2-(5-propyl-2-furyl)vinyl]_s·trisole, 2,4-bis(trichloromethyl)-6-[2-(3 ,5-dimethoxyphenyl)vinyl]-s-triazine, 2.4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)vinyl]-s- Three tillage, 2,4-bis(trichloromethyl)-6·[2-(3,5-dipropoxyphenyl)vinyl]-s-three tillage, 2.4-bis(trichloromethyl)- 6-[2-(3-Methoxy-5-ethoxyphenyl)vinyl]-s-trin, 2.4-bis(trichloromethyl)-6-[2-(3-methoxy- 5-propoxyphenyl)vinyl]-S·tris, 2.4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)vinyl]-s-three Plough, 2.4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl)-s-triterpene, 2.4-bis-trichloromethyl-6- (3 - 4-methoxy)phenyl-s-triazine, 2.4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4·double -trichloromethyl-6-(2-bromo-4-methoxy)styrene phenyl-s-tris-8 - 200836009 2,4-di-dichloromethyl-6- (3 - desert - 4-methoxy) phenyl phenyl-s-dioxa-2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2- (4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-trimethyl, 2-[2-(2-furyl)vinyl]-4,6-double (trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)vinyl]-4,6-bis(trichloromethyl)-1, 3,5-triterpene, 2-[2-(3,5-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1 , 3,5 -triazine, 2- [2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxy Phenyl)-4,6-bis(trichloromethyl)-1,3,5-tris(tris(1,3-dibromopropyl)-1,3,5-three tillage, three (2,3) a general formula (al) of a halogen-containing triterpene compound such as dibromopropyl)-1,3,5-triazine or the like, and tris(2,3-dibromopropyl)isocyanurate Contained Pigment three coax compound.

In the above general formula (al), Rla, R2a, and R3a are each independently a halogenated alkyl group. -9 - 200836009 Further, the second aspect of the photoacid generator may be exemplified by α-(p-toluenesulfonyloxyimino)phenylacetonitrile or α-(phenylsulfonyloxyimino)_2,4_2. Chlorophenylacetonitrile, α-(phenylsulfonyloxyimino)-2, dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, (ethanesulfonate)醯 oxyimino)-1-cyclopentenylacetonitrile, and a compound of the following general formula (a2) which contains an oxime sulfonate group.

In the above general formula (a2), R4a is a monovalent, divalent or trivalent organic group, and R5a is a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic compound group, and η is a repeat unit. In the above-mentioned general formula (a2), the aromatic compound is a group of a compound which exhibits a characteristic physical or chemical property to the aromatic compound, and examples thereof include an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, and a furan group. Base, the base of the temple. It may also have an appropriate substituent such as one or more of a tooth atom, an alkyl group, an alkoxy group, or a nitro group on the ring. Further, R5a is particularly preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. Particularly, a compound in which R4a is an aromatic compound group and R5 a is a low alkyl group is preferred. The photoacid generator of the above formula (a2), when n=l, R4a is any one of a phenyl group, a methylphenyl group and a methoxyphenyl group, and the ruler 53 is a methyl group. In the case of ^-(methylsulfonyloxyimido)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1 -(p-methylphenyl)acetonitrile, -10- 200836009 --(Methanesulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, [2-(propanesulfonyloxyimino)-2,3-dihydroxythiophene-3-ylidene] (o-tolyl) acetonitrile and the like. When n = 2, the photoacid generator represented by the above general formula may specifically be an acid generator represented by the following chemical formula.

C2H5—S〇2—〇——C=N—〇—S02—C2H5

CN CN

F3C—S〇2—〇- N=〒—C=N~〇—S〇2—CF3 CN CN More, the third aspect of the photoacid generator is an oxygen lance salt having a naphthalene ring in the cation portion. . The term "having a naphthalene ring" means having a structure derived from naphthalene, and means a structure of at least two rings, and maintaining such aromaticity. The naphthalene ring is a substituent which may have a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. The structure derived from the naphthalene ring may be a monovalent group (the free valence is one), and may also be a divalent group (the free valence is two or more), but is desirably a monovalent group (however, at this time, the removal and the above The substituent binding moiety counts the free atomic valence) -11 - 200836009. The number of naphthalene rings is preferably from 1 to 3. Such a cation portion having an oxo salt of a naphthalene ring in the cation portion is preferably a structure represented by the following general formula (a3).

In the above general formula (a3), at least one of R6a, R7a and R8a is a group represented by the following general formula (a4), and the remainder is a linear or branched alkyl group having 1 to 6 carbon atoms. Further, it may have a phenyl group, a hydroxyl group or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of R6a, R7a, and R82 is a group represented by the following general formula (a4), and the remaining two are independently a linear or branched chain alkyl group having 1 to 6 carbon atoms, respectively. The terminal can be combined into a ring shape.

(R9a, iR1〇a, and the above general formula (a4), R9a and R1Ga are each independently a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear chain of 6 carbon atoms. Or a branched chain alkyl group, Rlla is a single bond or a linear or branched chain of 1 to 6 carbon atoms which may have a substituent, and p and q are each independently an integer of 〇 or 1 to 2 , p + q is 3 or less. However, when R1Ga is present, it may be the same or different from each other. Further, when there are several R9a, they may be the same or different from each other. - 200836009 In the above R6a, R7a, and R8a, the total number of the general formula (a4) is preferably one from the viewpoint of the stability of the compound, and the remaining one is a linear or branched chain having 1 to 6 carbon atoms. An alkyl group or a phenyl group which may have a substituent, and these terminal groups may be bonded in a ring shape. In this case, the above-mentioned two stretching groups constitute a 3 to 9 member ring containing a sulfur atom. The number of the sulfur atom-containing atoms is preferably from 5 to 6. Further, the substituent which may have an alkylene group may, for example, be an oxygen atom (in this case, a carbon atom constituting an alkylene group) Further, a carbonyl group, a hydroxyl group, etc. may be formed. Further, the substituent which the phenyl group may have may be a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a straight number of 1 to 6 carbon atoms. The alkyl group having a chain or a branched chain, etc., as the suitable ones of the cations, may be exemplified by the following chemical formulas (a5) and (a6), and particularly preferably the structure represented by the chemical formula (a6).

The cation portion may be an iron iodide salt or a phosphonium salt, but is preferably a sulfonium salt in terms of acid production efficiency and the like. Therefore, the anion portion having an oxo salt of a naphthalene ring in the cation portion is suitably an anion capable of forming a sulfonium salt. -13- 200836009 The anion portion of such a photoacid generator is a part or all of a fluorinated fluoroalkylsulfonate ion or an arylsulfonate ion of a hydrogen atom. The alkyl group in the fluoroalkylsulfonic acid ion may be a linear or branched or cyclic ring having a carbon number of 1 to 2, and the carbon number is 1 to 1 in terms of the bulkiness of the acid to be generated and the diffusion distance thereof. One is better. In particular, it is preferable that the branch or the ring has a short diffusion distance. Specifically, from the viewpoint of inexpensive synthesis, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group or the like is preferable. The aryl group in the arylsulfonic acid ion is an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group which may be substituted by an alkyl group or a halogen atom. Since the synthesis is inexpensive, the carbon number is 6 to 10 The aryl group is better. Specifically, a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, a methylnaphthyl group and the like are preferable. In the fluoroalkylsulfonate ion or the sulfonic acid ion, a fluorination ratio when a part or all of the hydrogen atoms are fluorinated is preferably from 10 to 100%, more preferably from 50 to 100%, particularly all When a hydrogen atom is substituted by a fluorine atom, it is preferable because the strength of the acid is increased. Specific examples of such a substance include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, and perfluorobenzenesulfonate. Among them, preferred anion moieties are as shown in the following general formula (a7). R12aS03- (a7) In the above general formula (a7), examples of R12a include the structures shown by the following general formulas (a8) and (a9), and the structures represented by the chemical formula (a10). -14- 200836009

In the above general formula (a8), 1 is an integer of 1 to 4, and in the general formula (a9), R13a represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a carbon number. 1 to 6 linear or branched alkoxy groups, and m is an integer of 1 to 3. Among them, trifluoromethanesulfonate or perfluorobutanesulfonate is preferred from the viewpoint of safety. Further, the anion portion may also be a nitrogen-containing one represented by the following chemical formulas (all) and (al2).

In the above formulas (all) and (al2), Xa is a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and the alkyl group has 2 to 6 carbon atoms, preferably 3 ~5, the best is 3 carbon numbers. Further, each of Ya and Z2 is independently a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the carbon number of the alkyl group is 1 to 1 unit, preferably 1 to 7, more preferably It is 1~3.

The smaller the carbon number of the alkyl group of Xa or the carbon number of the alkyl group of Ya or Za, the better the solubility in the resist solvent is. -15- 200836009 Further, in the alkyl group of xa or the alkyl group of Ya or za, the more the number of hydrogen atoms is substituted, the stronger the strength of the acid is. The proportion of fluorine atoms in the group, i.e., the fluorination rate, is preferably from 70 to 90% to 100%, and most preferably all of the hydrogen atoms are alkyl groups or perfluoroalkyl groups having a fluorine atom. Such a cationic moiety has a compound of the naphthalene ring oxysulfide salt (a 1 3 ) and ( a 1 4 ). The alkyl group or the alkane is 100% by the fluorine atom, and more preferably the substituted perfluoro is the following chemical formula.

Moreover, other aspects of the photoacid generator can be enumerated! Dimethylmethane, di(1,1-dimethylethenyl bis(cyclohexylsulfonyl)diazomethane, bis(2,4-di)diazomethane, etc. Nitrogen methane; p-i benzyl ester, p-toluenesulfonic acid-2,6-dinitrobenzyl benzyl ester, nitric acid dinitrobenzyl benzene sulfonate, nitric acid sulfonate, nitrate nifedipine carbonate a nitrobenzyl derivative such as an ester; a pyrogallol triterpene trimethyl sulfonate, a benzyl toluene extended acid ester, a sulfomethoxy amber succinimide, an N-trichloromethyl sulfonate , N-phenylsulfonyloxymaleimide, N-methylsulfonium oxysulfonate; N-hydroxy quinone imine, N-hydroxynaphthalene dimethyl I (p-toluene) diazomethane , 2-phenyltoluenesulfonate, methyl carbonate, dimesylate, pyrosulfonate, N-methylammonium iminoimide, etc. Amine et al. 3-16-200836009 fluoromethanesulfonic acid) phenyl iodonium gun trifluoromethane) diphenyl decyl fluorene trifluoromethyl α-methyl benzene $ t-diphenyl ester and the like. The above compound () has 1 to 8 carbon atoms and is substituted with an aromatic unsubstituted alkane. More than the above. Further, (measured by mass of 100 parts by weight.) (Full sensitivity and uniformity [(Β) resin of the present invention; diphenyl iodine hexafluorophosphate, (4-methoxybenzene trifluoromethane sulfonate) Acid ester, bis(p-tert-butyl benzoate, diphenyl thiohexafluorophosphate, (4-methoxybenzoic acid trifluoromethanesulfonate, (p-tert-butylphenyl)) An oxo salt of a sulfonate or the like; a benzoin tosylate of a benzoin toluenesulfonic acid vinegar, a acetoin sulfonate, or the like; an iodine salt, a triphenylsulfonium salt, a phenyldiazonium salt The photoacid generator of the onium salt and the hard group A) component is preferably a general formula (u, preferably η値 is 2, and further preferably, R4a is a divalent substituted or unsubstituted alkylene group, Or a substituted or unsubstituted group, and preferably, R 5a is a substituted or aryl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group, but the component (A) is not limited thereto, and The amount of the component of the component A) may be used in combination with the total amount of the component (B) to be described later, and the amount of the component is 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass. When the amount is more than 20 parts by mass, the solubility solution for the solvent is improved, and the storage stability is improved. Component] Chemically Enhanced Positive Photoresist Composition for Low Temperature Dry Etching -17- 200836009 The component (B) is a resin containing at least one of a novolak resin (B1), a polyhydroxystyrene resin (B2), and an acrylic resin (B3), or may be a mixed resin or a copolymer. The component (B) is at least one selected from the group consisting of an alkali-soluble novolak resin (B 1 -1 ), a polyhydroxystyrene resin (B2-1), and an acrylic resin (B3-1), and is added by an acid action. It is preferred to select at least one of a mixture of a novolak resin (Bl_2), a polyhydroxystyrene resin (B2-2), and an acrylic resin (B3-2) which is soluble in alkali. [(B 1 -1) The alkali-soluble novolac resin (B 1 -1 ) is preferably a mass average molecular weight (hereinafter referred to as a mass average molecular weight) in terms of polystyrene of 1,000 to 50,000. Varnish resin is for example An aromatic compound having a phenolic hydroxyl group (hereinafter, simply referred to as "phenol") can be obtained by addition condensation condensation with an aldehyde under an acid catalyst. Examples of the phenol used in this case include benzoquinone and o- Formic acid, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3, 5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, fluorophenol, hydroxydiphenyl Base, biguanide A' gallic acid, gallic acid ester, ^-naphthol, Θ-naphthoic acid, and the like. Further, examples of the wake-up include, for example, wake-up, wake-up, benzophthalein, nitrobenzone-18-200836009 aldehyde, acetaldehyde, and the like. The catalyst in the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid or the like can be used as the acid catalyst. In the present invention, the flexibility of the resin can be further improved by using ortho-cresol, replacing the hydrogen atom of the hydroxyl group in the resin with another substituent, or using a high-hanging aldehyde. [(B 2 - 1 ) alkali-soluble polyhydroxystyrene resin] The above-mentioned alkali-soluble polyhydroxystyrene resin (B2-1) preferably has a mass average molecular weight of 1,000 to 50,000. The hydroxystyrene compound constituting such a polyhydroxystyrene resin may, for example, be p-hydroxystyrene, α-methylhydroxystyrene or α-ethylhydroxystyrene. Further, the polyhydroxystyrene resin is preferably a copolymer with a styrene resin, and the styrene compound constituting the styrene resin may, for example, be styrene, chlorostyrene, chloromethylstyrene or vinyltoluene. , α-methylstyrene, and the like. [(Β 3 -1 ) alkali-soluble acrylic resin] The alkali-soluble acrylic resin (Β3-1) has a mass average molecular weight of 50 and preferably 〇〇〇800,000. Such an acrylic resin is preferably a monomer derived from a monomer derived from a polymerizable compound having an ether bond and a polymerizable compound having a carboxyl group. The polymerizable compound having an ether bond can be exemplified by 2-methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and (methyl-19-200836009) 3-methoxybutyl acrylate. Bonded (methyl) esters, phenoxy polyethylene glycol (meth) acrylate, (meth) propylene glycol, tetrahydrofurfuryl (meth) acrylate The acrylic acid derivative is preferably acrylic acid 2- or methoxytriethylene glycol acrylate. These compounds may be used alone or in combination of two or more. The polymerizable compound having a carboxyl group may, for example, be a monocarboxylic acid such as acrylenoic acid or crotonic acid, a dicarboxylic acid such as maleic acid or transbutic acid, or 2-methylpropenyloxyethylsuccinene. The oxiranyl ethyl maleic acid, 2-methyl propylene oxiranyl 2-methyl propylene oxy hexahydro phthalic acid, etc. have a carboxyl group, a substance, etc., and acrylic acid and methacrylic acid are preferable. These compounds may be used in combination or in combination of two or more. [(B 1 -2) a lipid which increases the solubility to alkali by an acid action] The above-mentioned phenol (B1-2) which increases the solubility to alkali by an acid action, has a mass average molecular weight of 1〇〇〇 ～5 0000 is a resin represented by the following general formula (b1) as such a novolac resin which increases the solubility to alkali. Alcohol ester, (the olefinic methoxy group has an ether bond and the ester methoxyethyl ester is used alone, and the acid, methacrylic acid, clothing, 2-methylpropane phthalic acid, ester bond compound can be used alone酉 aldehyde varnish tree aldehyde varnish resin is good. (B1-2 ), " OR1b η

-20- 200836009 In the above general formula (b 1 ), R1 b is an acid dissociable dissolution inhibiting group, and R2b and R3b are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and η means a repeating unit. Further, the acid dissociable dissolution inhibiting group represented by the above R 1 b is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms represented by the following general formula (b2) or (b3). , tetrahydropyranyl, tetrahydrofuranyl, or trialkylformamyl is preferred.

Fi4b Ο -C-〇-R6b (b2) -fCH2^C-〇-R7b (b3) In the above general formulas (b2) and (b3), R4b and R5b are each independently a hydrogen atom or a carbon number of 1 to 6 a linear or branched alkyl group, R0b is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and R7b is a linear, branched or cyclic ring having 1 to 6 carbon atoms. Alkyl, 〇 or 1. Further, examples of the linear or branched alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group and isobutyl group. Examples of the pentyl group, the neopentyl group and the like include a cyclopentyl group, a cyclohexyl group and the like. Here, the acid dissociable dissolution inhibiting group represented by the above general formula (b2) may specifically be methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl or n-butoxy Ethyl, isobutoxyethyl, tert-butoxyethyl, cyclohexyloxyethyl, methoxypropyl, ethoxypropyl, 1-methoxy-1-methylethyl, 1-ethoxy -1 -methylethyl or the like, and the acid dissociable dissolution inhibiting group of the above formula (b 3 ) may, for example, be a third butoxycarbonyl group or a third butoxycarbonylmethyl group. Further, in the above-mentioned trialkylcarbenyl group, each of the alkyl groups such as trimethylmethanyl group and tri-t-butyldimethylformyl group has 1 to 6 carbon atoms. [(B 2 - 2 ) Polyhydroxystyrene resin which increases the solubility to alkali by the action of an acid] The above-mentioned polyhydroxystyrene resin (B2-2) which acts by acid to increase the solubility to alkali, The mass average molecular weight is preferably from 1,000 to 5 Å. As the polyhydroxystyrene resin (B2-2), a resin represented by the following general formula (b4) can be used.

In the above general formula (b4), R8b is a hydrogen atom or an alkyl group having a carbon number of 丨~6, R9b is an acid dissociable dissolution inhibiting group, and n is a repeating unit. Further, the linear or branched alkyl group having 1 to 6 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, a pentyl group or a different group. Examples of the pentyl group, the neopentyl group and the like include a cyclopentyl group, a cyclohexyl group and the like. The acid dissociable dissolution inhibiting group represented by the above R9b can be used in the same manner as those exemplified in the above general formulas (b 2 ) and (b 3 ), and the above-mentioned acid acts to increase the base. The soluble polyhydroxystyrene resin (B 2 -2 ) may contain other polymerizable compounds as constituent units for the purpose of moderately controlling chemical properties. Examples of such a polymerizable compound include a known radical polymerizable compound and an anionic polymerizable compound. Examples thereof include monoacids such as acrylic acid, methacrylic acid, and crotonic acid; and dicarboxylic acid 2-methacryloxyethyl succinic acid such as maleic acid, fumaric acid, and itaconic acid. 2·methacrylic acid having a carboxyl group and an ester bond, such as methacryloyloxyethyl cis succinic acid, 2-methyl propylene oxy oxy phthalic acid, 2-methyl propylene methoxy hexahydro phthalic acid Derivatives of alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; hydroxyethyl (meth)acrylate, (methyl) (Alkyl (meth)acrylates such as 2-hydroxypropyl acrylate; phenyl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; and diethyl maleic acid; Dicarboxylic acid diesters such as esters, fumarate, etc.; styrene, methylstyrene, styrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, (nonylhydroxystyrene, a vinyl-containing aromatic compound such as α-ethylhydroxystyrene; a vinyl-containing fat such as vinyl acetate a conjugated diene such as butadiene or isoprene; a polymerizable compound containing a nitrile group such as acrylonitrile or acrylonitrile; a chlorine-containing polymerizable compound such as vinyl chloride or vinylidene; a polymerizable compound containing a decylamine bond of acrylamide or methacrylamide. [(Β3 -2 ) an acrylic resin which increases the solubility to alkali by an acid action] Acrylic tree carboxylic acid y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y y 500000 is preferable. The acrylic resin (B3-2) can be a resin represented by the following general formulas (b5) and (b7).

(b7) In the above general formulas (b5) to (b7), R1Gb to R17b are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom or a carbon number of 1 to 6 a linear or branched fluorinated alkyl group (however, Ri ib is not a hydrogen atom) 'X is a hydrocarbon ring having a carbon number of 5 to 20 together with the carbon atom to which it is combined. Y may also have a substituent. An aliphatic cyclic group or an alkyl group, η means a repeating unit, ρ is 0 to 4, and q is 0 or 1. Further, the linear or branched alkyl group having a carbon number of 1 to 6 may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group or an isobutyl group, a tert-butyl group, a pentyl group or an isoprene group. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group. Further, the fluorinated alkyl group is one or a part of the hydrogen atom of the alkyl group substituted by a fluorine atom. The above Rllb is excellent in high contrast, resolution, and wide depth of focus, and is preferably a linear or branched alkyl group having 2 to 4 carbon atoms, and the aforementioned Rl3b, Rl4b, Rl6b, and R17b are A hydrogen atom or a methyl group is preferred. The above xb is an aliphatic cyclic group having a carbon number of 5 to 20 in combination with carbon atoms bonded thereto. Specific examples of such an aliphatic cyclic group include a group in which one or more hydrogen atoms are removed from a polycycloalkane such as a monocyclic alkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specific examples thereof include monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The group in which one or more hydrogen atoms are removed from the polycycloalkane. In particular, it is preferred to remove one or more hydrogen atoms (and more preferably a substituent) from cyclohexane or adamantane. Further, when the aliphatic ring formula of Xb has a substituent on the ring skeleton, examples of the substituent include a polar group such as a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (=〇), and a carbon number of 1 to 4 linear or branched low alkyl groups. The polar group is particularly preferably an oxygen atom (=0). The above-mentioned Y is an aliphatic cyclic group or an alkyl group, and examples thereof include a group in which one or more hydrogen atoms are removed from a polycycloalkane such as a monocyclic alkane, a bicycloalkane, a tricycloalkane or a tetracycloalkane. Specific examples thereof include monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The group or the like from which one or more hydrogen atoms are removed from the polycycloalkane. In particular, it is preferred that the radical of one or more hydrogen atoms (and more preferably a substituent) be removed from adamantane. Further, when the aliphatic ring form of the above Yb has a substituent on the ring skeleton, examples of the substituent include a polar group such as a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (=〇), and a carbon number of 1 to 4 linear or branched low alkane-25-200836009 base. The polar group is particularly preferably an oxygen atom (=〇). Further, when 丫*^ is an alkyl group, a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 6 to 15 carbon atoms is preferred. Such an alkyl group is particularly preferably an alkoxyalkyl group, and examples of such an alkoxyalkyl group include 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-isopropyloxyethyl , 1-n-butoxyethyl, 1-isobutoxyethyl, 1-tert-butoxyethyl, 1-methoxypropyl, 1-ethoxypropyl, 1-methoxy-methyl-ethyl , 1-ethoxy-1-methylethyl and the like. Preferable specific examples of the acrylic resin represented by the above general formula (b5) include the following general formulas (b5-1) to (b5-3).

(B5-1) (B5-2} (B5-3) R18b in the above general formula (b5-1) to (b5-3) is a hydrogen atom or a methyl group, and η is a repeating unit. The above general formula (b6) Preferable specific examples of the acrylic resin shown are as shown in the following general formulas (b6-1) to (b6-28). -26- 200836009 CH3 广广 u n_i ch3 八1 Λ 广11 /^11 Cri2 C CH2 CH Cri2 C CH2 CH C=0. nc=o. n C=0. nc=o.

(b6-1)

(b6-2)

" CH3 Ί 1 3 Am OM2 CH 0=0 n CH2—CH

CH2—C

(b6-8) (b6-5) CH3 (b6-6) (b6-7) CH3 CH2—c- C=0 CH2—CH— C=0 ch2—C—CH2—CH— C=0

-27 200836009 CH3 广LI 广ΓΜ_Ι dJ ch3 a· · Cr»2 C Crlo GH ‘ I CH2〒 CH2 CH c=o. η L c=oJ n c=o. n C=0.

CH,

(b6-17) HCp-CH3 Ο

0

(b6-18) CH2—CH— C=0 I o ch3 HC-CH3 o

Ch2-c- CH,

0 1 ch2 o (b6>19b)q CH2_c~

Ch2-ch— c=o Io ch2

c=o 0 HC-CH HC-CH 〇 I CH, 〇 I CHo

R19b)c Preferred examples of the acrylic resin represented by the above general formula (b7) include the following general formulas (b7-1) to (b7-22). -28· 200836009

(b7-1) CH3 —CH2—c— T ^

——CH2—CH— +=0 〇

C=0 0 1 ch2

(b7-4) ch3 —ch2—c—

(b7-5)

—CH2—CH—C-O- n

c=o I 0 1 CH2

(b7^) -29- 200836009

(b7-11)

-ch2-ch- (b7-13)

(b7-12) (b7-14)

-30- 200836009

(b7-21) (b7-22) Further, the acrylic tree (b3-2) which increases the solubility to alkali by the action of an acid, and the composition of the above general formula (b5) to (b7) It is preferred that the unit is a resin composed of a copolymer further comprising a structural unit derived from a polymerizable compound having an ether bond. Such a constituent unit is a constituent unit derived from a polymerizable compound having an ether bond. The polymerizable compound having an ether bond can be exemplified by 2-methoxyethyl (meth)acrylate, 2·ethylhydroethyl (meth)acrylate, (methyl)propene-31 - 200836009 methoxy ethoxylate Alcohol ester, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxy poly(meth)acrylate A radically polymerizable compound such as a (meth)acrylic acid derivative having an ether bond or an ester bond such as a propylene glycol ester or a tetrahydrofurfuryl (meth)acrylate, preferably 2-methoxyB (meth)acrylate Ester, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate. These compounds may be used alone or in combination of two or more. Further, the acrylic resin (b3-2) which increases the solubility in alkali by the action of an acid may contain other polymerizable compounds as a constituent unit for the purpose of appropriately controlling physical properties and chemical properties. Examples of such a polymerizable compound include a known radical polymerizable compound and an anionic polymerizable compound. Examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and 2-methylpropenyloxyethyl amber. Acid, 2-methyl propylene oxiranyl maleic acid, 2-methyl propylene oxy oxy phthalic acid, 2-methyl propylene oxyethyl hexahydro phthalic acid, etc. having a carboxyl group and an ester bond Methacrylic acid derivatives; alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate; 2-hydroxy(meth)acrylate Ethyl (meth) acrylate such as ethyl ester or 2-hydroxypropyl (meth)acrylate; decyl (meth)acrylate such as phenyl (meth) acrylate or benzyl (meth) acrylate Dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyl toluene , hydroxyphenylethyl-32-200836009 suspected, α-methyl-based phenyl benzene, α-ethyl phenyl benzene, etc. a vinyl-containing aliphatic compound such as vinyl acetate; a conjugated dilute such as butyl sulphate or an isoprene; a polymerizable compound containing a nitrile group such as a nitrile or a methacrylonitrile; A chlorine-containing polymerizable compound such as vinyl chloride; a polymerizable compound containing a guanamine bond such as acrylamide or methylamine. Among the above (Β) components, in the alkali-soluble resin components represented by (Bl-1), (Β2-1), and 1), combinations (Β 1 -2 ), ( ), and (Β 3 - 2 ) The mixed resin shown to increase the alkali-soluble tree by acid action is preferred. More preferably, the above (Β) component is added to the alkali-soluble resin component represented by (Bl-1), (Β2-1), and 1) by an acid action as shown by the combination (Β2-2) and ( ). The mixing of the alkali-soluble resin component is preferred. In particular, the alkali-soluble resin component increases the alkali by an acid acting as (Β 1 - 1 ) and (alkali-soluble novolac resin and alkali-soluble polyhydroxystyrene represented by Β2- 1 and (Β3-2) A mixed resin of a soluble propylene resin is preferred. Among the above alkali-soluble novolak resins (Β 1 -1 ), a composition of a combination of phenolic cresol and p-cresol is preferable, particularly, m-cresol and iphenol are used. The mass ratio = 50: 50 to 70: 30 is preferably a combination of alkali-soluble novolac. The alkali-soluble polyhydroxystyrene resin (B2-1) is preferably a copolymer of styrene and hydroxystyrene. In particular, styrene is a propylene glycol propylene propylene propylene (B3-B2-2 condensed into a [B3-B3-2 resin) resin acid 乂 - 时 时 时 甲 甲 甲 甲 - - - - -33- 200836009 hydroxy styrene It is preferable to use an alkali-soluble polyphenylene styrene resin having a mass ratio of 100: 〇~75:25. The above-mentioned acrylic resin (B3-2) which is increased in alkali solubility by an acid action also has the above-mentioned general a constituent unit represented by the formula (7) and a structure derived from a polymerizable compound having an ether bond Units, and (meth) acrylic acid units, units of the copolymers of (meth) acrylic acid alkyl ester formed of the preferred. Such copolymers preferably the following general formula the copolymer (b 8) of FIG.

_CH2 - 0—r c=o. s OH R20b

R21b

(b8) In the above general formula (b8), R2Gb is a hydrogen atom or a methyl group, R21b is a linear or branched alkyl group or alkoxyalkyl group having 1 to 6 carbon atoms, and R22b is a carbon number of 2 to 4. A linear or branched alkyl group, Xa is the same as defined above. Further, in the copolymer represented by the above general formula (b8), s, t, and u are each in a mass ratio, s is 1 to 3 〇 mass%, t is 20 to 70 mass%, and u is 20 to 70. quality%. Further, when the mixed resin of the combination (Bl-1), (B2-1), and (B3-2) is prepared, (B1-1) is (B1-1) 30 to 60% by mass, (82-1) It is preferably from 3 to 20% by mass, and (: 83 to 2) is from 20 to 70%. By using such a component (B), even when dry etching is performed at a very low temperature of -34 to 200836009 at a temperature of 〇 ° C to -1 〇〇 ° C, the resistance to dry etching treatment can be ensured, and even if When it is cooled to a very low temperature at normal temperature, the effect of cracking or the like can be obtained. Further, the component (B) is preferably a glass transition temperature of the entire resin component of 〇 ° C or less, and when a mixed resin or a copolymer is used, the glass transition temperature is calculated by converting into a theoretical glass transition temperature. The theoretical glass transition temperature is calculated relative to the glass transition temperature of each resin or constituent unit, and is multiplied by the mass fraction of each resin or constituent unit, and divided by 1 〇〇 as the theoretical glass transition temperature. . [(Resin component] The (B') resin component used in the chemically-enhanced negative-type photoresist composition for low-temperature dry etching of the present invention is at least a novolak resin (Β·1), a polyhydroxystyrene resin (Β'2) And at least one of an acrylic resin (Β'3). Such a novolak resin (B'l), a polyhydroxystyrene resin (B'2), and an acrylic resin (Bf3) can be selected from those of the resin group corresponding to the above item (B). [(C) Organic Solvent] The (C) organic solvent used in the chemically-enhanced positive-type photoresist composition for low-temperature dry etching of the present invention may, for example, be acetone, methyl ethyl ketone, cyclohexanone or methyl isoamyl ketone. Ketones such as 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetic acid-35-200836009 ester, dipropylene glycol, and dipropylene glycol Monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether and other polyols and derivatives thereof; dioxane-like cyclic ethers; ethyl formate, methyl lactate Ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetate, ethyl acetate, ethyl pyruvate, ethyl ethoxyacetate, methoxypropyl Methyl ester, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 2-hydroxy-3-methylbutyl An ester such as methyl ester, 3-methoxybutyl acetate or 3-methyl-3-methoxybutyl acetate; or an aromatic hydrocarbon such as toluene or xylene. They may be used singly or in combination of two or more. Further, in the chemically-enhanced negative-type photoresist composition for low-temperature dry etching of the present invention, an organic solvent can be appropriately blended as the component (C). Examples of the organic solvent include 1-(3-methoxy)-butyl acetate, 2-ethoxybutyl acetate, 2-carbyl-2-methyl, 2-pyridyl-3-methyl Methyl butyrate, ethyl 2-hydroxypropionate, methyl 2-hydroxypropionate, 2-butanone, 2-heptanone, 2-methyl-3-methoxybutyl acetate, 2-methyl 3-methoxypentyl acetate, 2-methoxybutyl acetate, 2-methoxypentyl acetate, 3-ethyl-3-methoxybutyl acetate, 3-ethoxy Ethyl propyl propionate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate , 3-methoxybutyl acetate, 3-methoxypentyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 4-methyl-2-pentanone , 4-methyl-4-methoxypentyl acetate, 4-methoxybutyl acetate, 4-methoxypentyl acetate, diethyl adipate, dimethyl adipate, Acetaldehyde, acetone, ethyl acetate, ethyl acetate, isopropyl-3-methoxypropan-36-200836009 acid ester, ethanol, ethyl 3-ethoxypropionate, 3-propoxy Propionate B , 3-methoxypropionic acid ethyl ester, ethyl isobutyl ketone, ethyl methyl ketone, ethylene glycol, glycol ether, glycerol ester, ethylene glycol diethyl ether, ethylene glycol dipropyl ether , ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, methyl ethoxyacetate, ethyl oxyacetate, butane, octanol, octane Alkane, xylene, glycerin, diethyl succinate, dimethyl succinate, cyclohexanol, cyclohexanone, cyclohexane, diethyl oxalate, diethyl ether, diethyl ketone, diethylene glycol, two Ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether, diethylene glycol monophenyl ether acetate, two Glycol monobutyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, dioxane, dihexyl ether, tetrahydrofuran, decane, toluene ,Ren Alkane, ethyl pyruvate, butyl pyruvate, propyl pyruvate, methyl pyruvate, butanol, acetone, propylene glycol, propionaldehyde, propionic acid, isopropyl propionate, ethyl propionate, propyl propionate , methyl propionate, propyl 3-methoxypropionate, propylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monopropyl ether acetate Ester, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, hexanol, ethane, heptanol, heptane, benzyl ether, benzyl methyl ether, benzene, pentanol, formaldehyde, diethyl maleate ,methanol, methyl 3-methoxypropionate, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, 7-butyrolactone, ethyl benzoate, formic acid, ethyl formate , octyl methacrylate, butyl formate, A-37-200836009 propyl acrylate, hexyl formate, heptyl formate, amyl formate, acetic acid, isoamyl acetate, isopropyl acetate, ethyl acetate, octyl acetate, Butyl acetate, propyl acetate, hexyl acetate, heptyl acetate, benzyl acetate, amyl acetate, ethyl carbonate , Butyl carbonate, propylene carbonate, dimethyl carbonate, ethyl lactate, octyl lactate, butyl lactate, cyclohexyl lactate, heptyl lactate, pentyl lactate. They may be used singly or in combination of two or more. The organic solvent is used in an amount such that the film thickness of the photoresist layer obtained by using the chemically amplified positive or negative photoresist composition for low-temperature dry etching of the present invention (for example, by spin coating) is 5 μm or more. A component concentration of 30% by mass or more is preferred. Preferably, the film thickness of the photoresist layer obtained by using the composition of the present invention is in the range of 5 μm to 200 μm. In the chemically-enhanced positive or negative-type photoresist composition for low-temperature dry etching of the present invention, the surfactant and the interfacial activity may be optionally blended for the purpose of improving coatability, defoaming property, and leveling property. Examples of the agent may be ΒΜ-1 000, ΒΜ-1100 (all trade names; BM Chemi), Megafac F142D, Megafae F172, Megafac F173, Megafac FI 83 (all are trade names, Dainippon Ink Chemical Industry Co., Ltd. )), Floride FC-135, Floride FC-170C, Floride FC-43 0, Floride FC-431 (all trade names; Sumitomo 3M (share) system), Safuron S-112, Safuron S-113, Safuron S -131, S afuron S-14 1, Safuron S-145 (all are trade names; Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all products The commercially available fluorine-based surfactant of the name: Silicone (manufactured by Silicone Co., Ltd.) is not limited thereto. -38- 200836009 [(D) Polyvinyl Resin] In the chemically enhanced type of low-temperature dry etching of the present invention, if necessary, (D) polyvinyl alkenyl resin may be used as poly(vinyl low alkyl ether). It can be composed of a (co)polymer obtained by singly or in combination of two or more vinyl lower alkyl ethers represented by dl). Hc = ch2 〇 (d1) In the above general formula (dl), Rld is a carbon number or a branched alkyl group. Such a polyvinyl resin is a vinyl compound, and specific examples of such a polyvinyl resin include polychloroolefin, polyhydroxystyrene, polyvinyl acetate, polyvinyl vinyl ether, polyvinyl ether, and poly Vinyl alcohol, polyketone, polyvinyl phenol, copolymers thereof and the like. Among them, the low temperature, preferably polyvinyl ether. The polyethylene-based resin preferably has a mass average molecular weight of preferably from 50,000 to 10,000. By coordinating with this type, it is possible to impart resistance to dry hungry treatment even when it is further treated at a very low temperature of TC. When such a polyvinyl resin is blended, it is 5 to 95 with respect to the first 100 parts by mass. The mass fraction is preferred. The type of photoresist composition is the same as the general formula of the following formula (the mixture is polymerized by a mixture of 6 linear polymers, ethylene, polyphenylethylbenzoic acid, polyvinylpyrrolidine in view of the glassy state. 10000~200000 Polyethylene resin for dry etching (B) Component -39- 200836009 [(D 1 ) Plasticizer] Used by chemically reinforced negative photoresist composition for low temperature dry etching using the present invention ( D') plasticizer, even when dry etching is performed at a very low temperature of 〇 ° C or lower, especially at 0 ° C to -10 ° ° C, the resistance to dry etching can be ensured, and even if it is from room temperature Further, in the present invention, it is preferable that the mass ratio of the component (B1) to the component (Df) is 5: 95 to 95: 5 in the case of cooling to an extremely low temperature. (D') plasticizer can be used by propylene At least one of the resin and the polyvinyl resin is selected. [(D'l) Acrylic resin] The acrylic resin (D'l) preferably has a mass average molecular weight of 50,000 to 800,000. The resin is preferably a monomer derived from a polymerizable compound having an ether bond and a monomer derived from a polymerizable compound having a carboxyl group. The above polymerizable compound having an ether bond can be exemplified by (meth)propionic acid 2 - Methoxyethyl ester, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)propanoate, ethyl carbitol (meth)propionate, ( Methyl)acrylic acid phenoxy polyethylene glycol ester, (meth)acrylic acid methoxypolypropylene glycol ester, (meth)acrylic acid tetrahydrofurfuryl ester, etc. (meth)acrylic acid having an ether bond and an ester bond The derivative or the like is preferably 2-methoxyethyl acrylate or methoxytriethylene glycol acrylate. These compounds may be used alone in the range of -40 to 200836009, or two or more types may be used in combination. The polymerizable compound may, for example, be an acrylic acid or a crotonic acid. Dicarboxylic acid, 2-methylpropenyloxyethyl succinic acid, olefinic oxyethyl maleic acid, 2-methyl propylene oxime, etc. of carboxylic acid, maleic acid, anti-butyric acid Ethylbenzene 2-methylpropenyloxyethyl hexahydrophthalic acid or the like has a carboxyl group, an ester or the like, and is preferably acrylic acid or methacrylic acid. These compounds may be used alone or in combination of two or more. D'2) Polyvinyl resin] The above-mentioned polyvinyl resin (D'2) is preferably an average mass of 10,000 to 200,000. Such a polyvinyl resin is a poly(vinyl low alkyl ether) for the above general formula ( The (co)polymer obtained by polymerizing a mixture of a single or more of the lower alkyl ethers shown in dl). Such a polyvinyl-based resin can be considered to be suitable by the users listed in the above item (D). By blending such a (D') plasticizer, it is possible to impart resistance to dryness even when dry etching is performed at a low temperature of 0 °C. [(E) Acid Diffusion Control Agent] The chemically amplified positive type or composition for low-temperature dry etching of the present invention may further contain an acid diffusion controlling agent as 1, methylmalonic acid, and clothing 2-methylpropane. The combination of dicarboxylic acid and a bond may be preferably a molecular weight alone, and may be selected by a single or two types of ~-100 ° C to treat a negative photoresist E) component -41 - 200836009 Acid diffusion control agent with nitrogen-containing compound Preferably, an organic carboxylic acid or a phosphorus oxyacid or a derivative thereof may be used as needed. [(el) nitrogen-containing compound] The above (e 1 ) nitrogen-containing compound may, for example, be trimethylamine, diethylamine, amine, di-n-propylamine, tri-n-propylamine, tribenzylamine, diethanolamine, triethylamine, n-hexylamine or n-glycol. Amine, n-octylamine, n-decylamine, ethylenediamine N,N,N',N,tetramethylethylenediamine, tetramethylenediamine,hexamethylene,4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl ether, 4,4,-dibenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamidine N,N- Dimethylformamide, acetamide, N-methylacetamide, n,N-diethylammoniumamine, acetamide, benzamide, pyrrolidone, N-methylpyrrole, methylurea, 1 , 1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetraurea, 1,3,diphenylurea, carbazole, benzimidazole, 4·methylimidazole, Quinoquinoline, aziridine, porphyrin, pyrrolidine, piperidine, 2,4,6-tris(pyridine)-S-triazine, morpholine, 4-methylmorpholine, piperidine, 1,4 - Dimethyl tillage, 1,4-dioxinbicyclo[2.2.2]octane, and the like. Among them, triethylamine alkanolamine is preferred. They can be used singly or in combination. When the nitrogen-containing compound (1) or (B') component is 100% by mass, it is usually used in the range of 0 to 5% by mass, more preferably 0 to 3% by mass. Containing triethanolamine, diamine diamine, methylalkanone methyl 8-hydroxy-2-pyridylamine as a use of -42-200836009 [(e2) organic carboxylic acid, or phosphorus oxyacid or The derivative (e2) organic carboxylic acid is preferably malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid or the like, and particularly preferably salicylic acid. Examples of the phosphorus oxyacid or a derivative thereof include a phosphoric acid such as phosphoric acid, di-n-butyl phosphate or diphenyl phosphate or a derivative thereof, a phosphonic acid, a dimethyl phosphonate or a di-n-butyl phosphonate. a derivative of a phosphonic acid such as phenylphosphonic acid, diphenyl phthalate or dibenzyl phosphonate, or a derivative thereof, a phosphinic acid such as phosphinic acid or phenylphosphinic acid, or a derivative thereof, wherein In particular, phosphonic acid is preferred. They may be used singly or in combination of two or more. When the organic carboxylic acid or the oxyacid of phosphorus or a derivative thereof is regarded as 100% by mass in the component (B) or the component (B'), it is usually used in an amount of from 0 to 5% by mass, preferably hydrazine is used. ~3 mass% range. Further, in order to form a salt stably, it is preferred to use the same amount of the organic carboxylic acid or phosphorus oxyacid or a derivative thereof as the above nitrogen-containing compound. Further, in the chemically amplified positive or negative photoresist composition for low-temperature dry etching of the present invention, a tackifier may be further used in order to improve the adhesion to the substrate. The tackifier used is preferably a functional decane coupling agent. The above-mentioned functional decane coupling agent means a decane coupling agent having a reactive substituent such as a carboxyl group, a methacryl fluorenyl group, an isocyanate group or an epoxy group, and specific examples thereof include trimethoxylethane benzoic acid, R-methacryloxypropyltrimethoxydecane, vinyltriethoxydecane, vinyltrimethoxydecane, r-glycidoxypropyltrimethoxydecane, 10,000-(3,4-ring Oxycyclohexyl) ethyl dimethoxy hospital and the like. The amount of the compound is -43 to 200836009. The amount of the component (B) or the component (B') is preferably 2 parts by mass or less. Further, in the chemically-enhanced positive or negative-resistance composition for low-temperature dry etching of the present invention, an acid, an acid anhydride or a high-boiling solvent may be added in order to finely adjust the solubility of the alkali developing solution. Examples of the acid and the acid anhydride include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid, and lactic acid and 2-hydroxybutyric acid. 3-hydroxybutyric acid, salicylic acid, m-carbamic acid, p-benzoic acid, 2-cyanocinnamic acid, 3-cyanocinnamic acid, 4-cyanocinnamic acid, 5-hydroxyisophthalic acid a hydroxy monocarboxylic acid such as diacid or syringic acid, and oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrofurfuric acid, phthalic acid, and isophthalic acid Acid, terephthalic acid, 1,2·cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentane a polyvalent carboxylic acid such as tetracarboxylic acid, butane tetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, triterpene Anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, salic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentane tetracarboxylic dianhydride, benzoic acid Anhydride, pyromellitic anhydride, trimellitic anhydride, Benzophenone tetracarboxylic anhydride, ethylene glycol bis (trimellitate) dianhydride, glycerol tris (trimellitate) anhydride of the acid anhydride. Further, examples of the high boiling point solvent include N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-di Methylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ether, dihexyl ether, acetonitrile acetone, isophorone, hexanoic acid, citric acid, 1-octanol, 1-nonanol, Benzyl alcohol, benzyl acetate, ethyl benzoate, oxalic acid di-44- 200836009 ethyl ester, diethyl maleate, r - butyrolactone, ethyl carbonate, propyl carbonate, phenyl cellosolve Acetate and the like. The amount of the compound for fine adjustment of the solubility of the image forming liquid can be adjusted according to the application and the coating method. The composition can be uniformly mixed, but the composition is 60. The mass% or less is preferably 40% by mass or less. [(F) Crosslinking Agent] The (F) crosslinking agent used in the chemically-enhanced negative-type photoresist composition for low-temperature dry uranium engraving of the present invention is an amine-based compound, and for example, melamine resin, urea resin, guanamine can be used. Resin, ethylene glycol urea-formaldehyde resin, succinylamine-formaldehyde resin, ethylene urea-formaldehyde resin, etc., especially alkoxymethylated amines such as alkoxymethylated melamine resin and alkoxymethylated urea resin A base resin or the like is suitable for use. The above alkoxymethylated amine-based resin can be, for example, a condensate obtained by reacting melamine or urea with formalin in a boiling aqueous solution, and is a low alcohol such as methanol, ethanol, propanol, butanol or isopropanol. Etherification, followed by cooling and precipitation of the reaction liquid, can be produced. The alkoxymethylated amine-based resin described above specifically includes a methoxymethylated melamine resin, an ethoxymethylated melamine resin, a propoxymethylated melamine resin, and a butoxymethylated melamine. Resin, methoxymethylated urea resin, ethoxymethylated urea resin, propoxymethylated urea resin, butoxymethylated urea resin, and the like. The above alkoxymethylated amine-based resins may be used alone or in combination of two or more. In particular, the alkoxymethylated melamine resin has a small amount of change in the size of the photoresist pattern and can form a stable photoresist pattern with respect to the change in the amount of radiation exposure, so that it is preferably -45-200836009, wherein methoxy Methylated melamine resin, ethoxymethylated melamine resin, propoxymethylated melamine resin and butoxymethylated melamine resin are suitable. When the total amount of the components (A), (B'), and (Df) is considered to be 1 part by mass, the crosslinking agent of the component (F) is preferably contained in an amount of 1 to 30 parts by mass. Further, in the chemically-enhanced positive or negative-resistance composition for low-temperature dry etching of the present invention, a smear, a coloring agent, a viscosity adjusting agent or the like may be added as needed insofar as the properties are not impaired. Examples of the filling agent include silica sand, oxidized crystal, talc, bentonite, chromium silicate, powdered glass, and the like. Examples of the coloring agent include body pigments such as tin oxide white, clay, barium carbonate, barium sulfate, and the like, zinc white, lead white, wrong, lead, ultramarine blue, indigo, titanium oxide, zinc chromate, red iron oxide, carbon black. Organic pigments such as inorganic pigments, and Brilliant Kamin 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue, phthalocyanine green, and basic dyes such as magenta and rhodamine, and Direct dyes such as direct scarlet, direct orange, and acid dyes such as roxaline and semi-tanil yellow. Further, examples of the viscosity adjusting agent include bentonite, cerium oxide rubber, and aluminum powder. Preferably, the amount of the additives added is 5% by mass or less based on the positive composition obtained, and 50% by mass or less based on the negative composition. [Adjustment] The chemically-enhanced positive or negative photoresist composition for low-temperature dry etching of the present invention is prepared by mixing and stirring the above-mentioned respective components in a usual manner in the case where no charging agent or pigment is added. However, in the case where the filler or the pigment is not added, it may be dispersed or mixed by using a dispersing machine such as a dissolving rod, a homogenizer, or three roll mills as needed. Further, after mixing, it may be filtered using a sieve, a membrane filter or the like. The chemically-enhanced positive or negative photoresist composition for low-temperature dry etching of the present invention is suitable for forming a photoresist layer having a film thickness of 5 to ΙΟΟΟμηη, preferably 5 to 200 μm, on the support. Also suitable for processing under low temperature conditions [Formation of photoresist pattern] The above photoresist layer can be produced, for example, as follows. (1) Formation of a coating film: a solution of a chemically amplified positive or negative photoresist composition for low-temperature dry etching prepared as described above is coated on a support, and heated to remove a solvent to form a desired coating film. . The coating method on the support to be treated may be a method such as a spin coating method, a slit coating method, a roll coating method, a screen printing method, or an applicator method. The prebaking conditions of the coating film of the composition of the present invention vary depending on the type of each component in the composition, the mixing ratio, the coating film thickness, etc., and are usually 70 to 150 ° C, preferably 80 to 140 °. C, 20~60 minutes or so. (2) Radiation irradiation: For the photoresist layer obtained as described above, the radiation (for example, ultraviolet rays or visible rays having a wavelength of 300 to 50 Onm) is selectively irradiated through a mask of a predetermined pattern to be exposed. The source of such radiation can be a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon laser or the like. The term "radiation" as used herein means ultraviolet rays, visible rays, far ultraviolet rays, X-rays, electron rays, and ion-rays -47-200836009 lines. The amount of the radiation to be irradiated varies depending on the type of each component, the amount of the component, the film thickness of the coating film, and the like. For example, when an ultrahigh pressure mercury lamp is used, it is 100 to 1 0000 mJ/cm 2 , more preferably 100 to 2000 mJ/cm 2 . (3) The development method after development and radiation irradiation is, for example, using a predetermined alkaline aqueous solution as a developing solution, and partially dissolving and removing the specified photoresist pattern. The developing solution can use, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethyl Amine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-dioxinbicyclo[5,4,0]-7-undecene An aqueous solution of a base such as 1,5-dioxabicyclo[4,3,0]-5-decane. Further, an aqueous solution of an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and a surfactant may be used as the developing solution in the aqueous alkali solution. The development time varies depending on the type of the components of the composition, the blending ratio, and the dry film thickness of the composition, and is usually 1 to 30 minutes. Further, the development method may be an overflow method, a dipping method, a paddle method, or the like. Any of the spray imaging methods and the like. After the development, the water is washed for 30 to 90 seconds, and dried using an air gun, a baking oven, or the like. [Examples] [1. Positive-type photoresist composition] 40 parts by mass of the following general formula (Z 1 ), v-cresol and p-cresol and formaldehyde were condensed in the presence of an acid catalyst. 48 parts by mass of the obtained novolac resin and 12 parts by mass of a copolymer of styrene/hydroxystyrene were mixed -48-200836009 to prepare a resin component (B). ' ’ ' ' - -ch2-ch—一 —ch2-ch——CH2—CH— A 1 c=o 1 5 c=o. 45 c=o. OH (0Η2)3〇Η3 (z1)

CH2CH3 is a compound 1 represented by the following chemical formula (z2) in which a photoacid generator is added to 100 parts by mass of the above-mentioned (B) resin component. 〇 by mass, hydrazine salicylate · 1 part by mass, triethanolamine 0 · 1 part by mass, and propylene glycol monomethyl ether acetate was dissolved, and a chemically amplified positive-type photoresist composition for low-temperature dry etching having a solid content concentration of 40% by mass was prepared. C4H9—S〇2-〇-N=C——〒=Ν—Ο - S02-C4H9 (z2)

Next, on the substrate, the positive photoresist composition for low-temperature dry etching is applied at 10,000 rpm for 25 seconds, and then pre-baked on a hot plate at 10 ° C for 6 minutes to form a film thickness of about 20 μm. Coating film. Next, through the pattern mask, an ultrahigh pressure mercury lamp (USH-250D manufactured by UCO) was used, and ultraviolet exposure was performed at an exposure amount of 1 500 mJ/cm2. After the exposure, the coating film was developed with a developing solution (trade name; P-7G, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Thereafter, the running water was washed, and the pattern-like cured product was obtained by nitrogen gas. The substrate was cooled to -2 (the state of TC, using a reactive gas composed of CF4, SF6, 〇2, and N2, and the pattern-like cured product manufactured by the above-mentioned preparation example 1 was used as a mask. The ruthenium substrate is etched and etched at a depth of up to 180 μm. At this time, the photoresist pattern is in a state where no cracks are generated, and a 180 μm diameter hole shape can be formed for the ruthenium substrate [2. Negative type Photoresist composition] [Synthesis Example 1: Synthesis of (Β') component] m-cresol and p-cresol were mixed at a mass ratio of 60:40, and an aqueous formaldehyde solution was added thereto, using oxalic acid catalyst and The phenolic varnish resin is obtained by a known method of condensation, and the resin is subjected to a classification treatment to remove a low molecular region and obtain a novolak resin having a mass average molecular weight of 10,000 (Z'l [Synthesis Example 2: Synthesis of (B') component] An aqueous formaldehyde solution is added to the cresol, and the phenolic varnish resin is obtained by condensing with a oxalic acid catalyst by a known method. The resin is subjected to a classification treatment, and the low molecular region is removed and a phenolic varnish having a mass average molecular weight of 6,000 is obtained. Fat (z'2) [Synthesis Example 3: Synthesis of (B') component] A flask equipped with a stirring device, a reflux device, a thermometer, and a dropping tank was replaced with nitrogen, and then 200 g of propylene glycol methyl ether acetate was charged. The solvent was started, and stirring was started. Thereafter, the temperature of the solvent was raised to 80 ° C. 2,2'-azobisisobutyronitrile 〇. 5 g, acrylic acid-50- was charged as a polymerization solvent in the dropping tank. 200836009 2-methoxyethyl ester 130 g, benzyl methacrylate 50.0 g, and acrylic acid 20.0 g, stirred until the polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., trade name V-65) was dissolved, and the solution was placed in a flask. The mixture was uniformly dropped for 3 hours, and then polymerization was carried out for 5 hours at 8 01: Thereafter, the resin (zf3 ) was obtained by cooling to room temperature. [Preparation Example 1] The following chemical formula (z ' 4 ) was used as the component (A). The compound 〇·5 parts by mass.

C4h9-so2-o-n=c CN

_= ND — S02-C4H3 CN (z′4) The acrylic resin obtained in Synthesis Example 3 as the (D′) component, 75 parts by mass of the novolak resin (z′l ) obtained in Synthesis Example 1 ( Z'3) 15 parts by mass of hexamethoxymethylated melamine as a component (F) (manufactured by Chemical Co., Ltd., trade name: Nikalac Mw-100) 1 part by mass in propylene glycol methyl ether acetate 1 5 0 After dissolving in a solvent of a mass part, it was filtered using a membrane filter of a pore size of Ι.Οηηι to prepare a negative-type photoresist composition. The composition of this preparation was used to evaluate the characteristics described later. [Modulator 2] In addition to (Β·) The composition is replaced with a novolac resin (ζ'2), and the (D') component is prepared as an alkali-soluble vinyl ether polymer obtained by subjecting ethyl vinyl ether to a catalyst in a gas phase high-temperature high-pressure polymerization reaction. 51 - 200836009 The negative resist composition was prepared in the same manner as in Preparation Example 1, and the characteristics described later were evaluated. [Preparation Example 3] In addition to replacing the component (A) with tris(2,3-dibromopropyl) The same operation as in Modification Example 1 was carried out except that 1 part by mass of cyanurate was used. The photoresist composition was subjected to the characteristics evaluation described later. [Preparation Example 4] The (B') component was replaced with a hydroxystyrene polymer having a mass average molecular weight of 2,500, and the (D') component was made into ethylethylene. The negative-type photoresist composition was prepared in the same manner as in Preparation Example 1 except that the ether-soluble vinyl ether polymer obtained by the vapor phase high-temperature high-pressure polymerization reaction was used in the presence of a catalyst, and the characteristics described later were evaluated. 1 to 4] Using the negative-type photoresist composition for low-temperature dry etching manufactured in the above Preparation Examples 1 to 4, the following characteristics were evaluated. On the tantalum substrate, a low-temperature dry uranium engraved with a negative photoresist was used. After coating at 100 rpm for 25 seconds, it was prebaked on a 1 μC hot plate for 6 minutes to form a coating film having a film thickness of about 20 μm. Secondly, the pattern mask used for the resolution measurement was used. High-pressure mercury lamp (USH-2 5 0D made by UCO) was exposed to ultraviolet light at an exposure of 1 500 mJ/cm2. After exposure, the coating film was visualized with a developing solution (trade name P-7G: manufactured by Tokyo Ohka Kogyo Co., Ltd.). Like -52- 200836009 After that, running water After washing, the pattern-like cured product was obtained by blowing nitrogen gas. The substrate was cooled to -20 ° C, and a reactive gas composed of CF 4 , SF 6 , 〇 2 and N 2 was used, and the patterned cured product was used as the cured product. The mask is etched and the ruthenium substrate is etched to a depth of 180 μm. At this time, the photoresist pattern is in a state where no cracks or the like are formed, and a hole of 180 μm diameter can be formed for the ruthenium substrate. As described above, according to the present invention, it is possible to obtain (1) a crack which is not caused by thermal shock even when exposed to a temperature lower than 〇 ° C, and (2) a thick film of 5 μm or more can be formed. (3) high sensitivity, (4) a chemically amplified positive or negative photoresist composition for low temperature dry etching under conditions in which a general solvent can be easily peeled off, and a photoresist pattern using the photoresist composition Forming method. -53-

Claims (1)

200836009 X. Patent Application Scope 1 A chemically amplified positive photoresist composition for low temperature dry etching, which comprises (A) a photoacid generator, (B) a resin component, and (C) an organic solvent. 2. A chemically-enhanced positive-type photoresist composition for low-temperature dry etching according to the first application of the patent scope, which is a chemically amplified positive-type photoresist composition for dry etching at 0 ° C or lower. 3. A chemically amplified positive-type photoresist composition for low-temperature dry etching according to the first or second aspect of the patent application, which is a chemically enhanced positive type for forming a photoresist film having a film thickness of 5 to 200 μm. Photoresist composition. 4. The chemically amplified positive resistive composition for low temperature dry etching according to claim 1 or 2, wherein the (Β) component is a novolak resin, a polyhydroxystyrene resin, and an acrylic resin. Choose at least one of them. 5. A chemically-enhanced positive-type photoresist composition for low-temperature dry etching according to claim 1 or 2, wherein the (Β) component is a novolak which is increased in solubility to alkali by an acid action. At least one selected from the group consisting of a resin, a polyhydroxystyrene resin, and an acrylic resin, and at least one selected from the group consisting of an alkali-soluble novolak resin, a polyhydroxystyrene resin, and an acrylic resin. 6. The chemically amplified positive-type photoresist composition for low-temperature dry etching according to claim 1 or 2, wherein the (Β) component is a polyhydroxy group which increases solubility in alkali by acid action. At least one of a styrene resin and an acrylic resin is selected, and an alkali-soluble novolac resin, a poly-54-200836009 hydroxystyrene resin, and an acrylic resin are selected from the resin. 7. The low-learned positive-type resist composition according to Item 1 or 2 of the patent application, wherein the (B) is an acrylic resin which increases the solubility to alkali, and a novolak resin and a poly The hydroxystyrene resin is selected to the resin. 8. A low-enhanced positive-type photoresist composition according to claim 1 or 2, wherein a glass transition temperature (Tg) of the resin component of the one (B) is 9 The low-learned positive-type photoresist composition of the first or second aspect of the invention, which further comprises a resin. 10. A chemically-enhanced positive photoresist composition as claimed in claim 1 or 2, which is a further dispersion controlling agent. 1 1 · A method for forming a photoresist pattern, which is characterized by coating a low-temperature-enhanced positive-type photoresist composition according to claim 1 or 2 and forming a film thickness of 5 to 200 μm to obtain a photoresist film. The imaging process is illuminated by a specified pattern mask. 1 2 · A chemically enhanced negative type for low temperature dry etching: characterized by containing a mixture of (Α) photoacid generator, (Β,), polyhydroxystyrene resin, and acrylic resin The dry etching is classified into a composition for mixing and warm-drying etching which is less than one of alkali solubility by acid action, and is selected to be below 〇 ° C. Warm dry etching uses '(D) polyethylene low-temperature dry uranium engraved with 'E) acid on the substrate, dry uranium engraved with chemical photoresist film, and ray, and the photoresist composition, furfural The varnish resin is at least one of -55 - 200836009 resin component, (D'), at least one of a plasticizer, (F) a crosslinking agent, and (C) an organic solvent selected from the group consisting of an acrylic resin and a polyethylene resin. 13. The chemically-enhanced negative-type photoresist composition for low-temperature dry uranium engraving according to claim 12, which is a chemically-enhanced negative-type photoresist composition for dry etching step below 〇 °C. 1 4 . The chemically-enhanced negative-type photoresist composition for low-temperature dry etching according to claim 12 or 13 of the patent application, which is a step of forming a photoresist film having a film thickness of 5 to 200 μm A chemically enhanced negative photoresist composition. 1 . The chemically-enhanced negative-type photoresist composition for low-temperature dry etching according to claim 12 or claim 13, wherein at least one of the (Β') component and the (D') component is selected The glass transition temperature (Tg) is below 0 °C. The chemically-enhanced negative-type photoresist composition for low-temperature dry etching according to the first or second aspect of the patent application, wherein the component (F) is an alkoxymethylated amine-based resin. The chemically-enhanced negative-type photoresist composition for low-temperature dry etching according to claim 12 or 13 of the patent application, which further comprises an (E) acid diffusion control agent. a method for forming a photoresist pattern, characterized in that a chemically-enhanced negative-type photoresist composition for low-temperature dry etching according to the first or second item of the patent application is coated on the substrate and A photoresist film having a film thickness of 5 to 20 μm is formed, and the obtained photoresist film is irradiated with radiation through a predetermined pattern mask, and subjected to development processing. -56 - 200836009 VII designated representative map (1), the designated representative figure of this case is: no (2), the representative symbol of the representative figure is a simple description: no eight, if the case has a chemical formula, please reveal the best display of the characteristics of the invention Chemical formula: none