TWI294557B - Negative resist composition and process for forming resist pattern - Google Patents

Description

1294557 (1) IX. Description of the Invention [Technical Field of the Invention] The present invention relates to a method for forming a negative-type photoresist composition and a photoresist pattern. The present invention is applied to the Japan Patent Office on February 2, 2005. The Japanese Patent Application No. 2005-026266 is a priority claim, and the content of the present invention is based on the foregoing. [Prior Art] In recent years, in the manufacture of semiconductor elements or liquid crystal display elements, with the advancement of the lithography lithography technology, the gradual progress toward miniaturization has been made. The method of miniaturization generally involves a method of shortening the wavelength of the exposure light source. Specifically, in the past, ultraviolet rays represented by g-line and i-line were used. However, KrF excimer lasers and ArF excimer lasers have been introduced to start mass production of semiconductor devices. Furthermore, it has begun to investigate the shorter wavelength F2 excimer laser, electron beam, EUV (extreme ultraviolet) or X-ray. Further, it is one of the pattern forming materials which can be made into a fine-sized pattern, and is known as a substrate-containing composition containing a film forming ability and an enhanced chemical type resist which generates an acid generator by exposure. The above-mentioned enhanced chemical type resist has, for example, a negative type which is reduced in alkali solubility by exposure, a positive type which increases alkali solubility via exposure, and the like. Conventionally, a polymer is generally used as a substrate component for enhancing a chemical resist, for example, a resin obtained by protecting an acid dissociable dissolution inhibiting group using polyhydroxystyrene (PHS) or a part thereof (2) 1294557 A resin which is a PHS-based resin, a (meth)acrylic acid-derived copolymer or a part of a carboxyl group thereof which is protected by an acid dissociable dissolution inhibiting group. For example, in a negative-type enhanced chemical type photoresist, an alkali-soluble resin such as PHS and an acid generator and a crosslinking agent are generally used. The above-mentioned photoresist can cause cross-linking between the resin and the crosslinking agent based on the action of an acid which causes the acid generator component to be exposed by exposure, and the alkali solubility becomes alkali-insoluble. However, when the photoresist pattern is formed using the above-mentioned photoresist forming material, there is a problem that the upper surface of the pattern or the surface of the side wall has roughness. For example, the unevenness of the sidewall surface of the photoresist pattern, that is, the line edge irregularity (LER), etc., may cause deformation around the through hole in the through hole pattern, or uneven line width in the line and space pattern, etc., The influence of defects on the formation of fine semiconductor elements is caused. The above problem is more serious as the size of the pattern is smaller. Therefore, for example, in the lithography etching by electron beam or EUV, when a fine pattern of several 10 nm is formed, there is an urgent need to cross the current pattern. A material with extremely low unevenness in the uneven state. However, a polymer generally used as a substrate has a molecular size (average self-radiating radius per molecule) of about several nm. In the development process of the pattern formation, the dissolution action of the developed photoresist is generally performed in the form of each molecular unit substrate component, and the substrate component in the use of the polymer will make the reduction of the unevenness state more difficult. . In view of the foregoing problems, proposals have been made for materials having extremely low unevenness, that is, using a low molecular material as a resist of a substrate component. -6 - (3) 1294557 For example, Patent Documents 1 and 2 propose a proposal of a low molecular material having an alkali-soluble group such as a hydroxyl group and partially or wholly protected by an acid dissociable dissolution inhibiting group. [Patent Document 1] JP-A-2002-099088 [Patent Document 2] JP-A-2002-099089 SUMMARY OF THE INVENTION [At present, in the process of gradually miniaturizing the pattern, the short-wavelength of the exposure light source is obtained. Light source resistance has gradually sought higher sensitivity, such as the reduction of the intensity of the light source, or the improvement of productivity. Especially in the electronic wire or EUV line process, the sensitivity is a very important factor. However, in the prior art, it is extremely difficult to obtain high sensitivity and high-resolution at the same time. For example, in a method of achieving high sensitivity of photoresist, for example, a method of increasing the concentration of an acid generator in an enhanced chemi-type resist is generally sought. However, in the conventional enhanced chemical resist, when a high concentration of an acid generator is added, there is a tendency to lower the resolution. Therefore, it is difficult to add a high concentration of the acid generator, so there is still a high sensitivity. Its boundaries. The present invention has been made in view of the above circumstances, and has been proposed to form a photoresist composition having a high-sensitivity and high-resolution photoresist pattern and a method of forming a photoresist pattern. The inventors of the present invention have found out that the above problems can be solved by using a negative resist composition containing a polyhydric phenol compound having a specific structure and molecular weight, and the present invention has been completed. 1294557 ^ (4) ~ That is, the first aspect of the present invention is a negative-type photoresist composition which comprises (A) an alkali-soluble substrate component, and (B) an acid generated by exposure. a negative-type photoresist composition of the acid generator component and (C) a crosslinking agent component, wherein the substrate component (A) has the following formula (I), and has two or more A phenolic hydroxyl group, a polyhydric phenol compound (A 1 ) having a molecular weight of 300 to 2,500. • [Chemical 1]

[In the formula (I), R11 to R17 are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group, and the structure may contain a hetero atom; g and j are each independently an integer of 1 or more, and k and q are 〇 or an integer of 1 or more, and g+j+k + q is 5 or less, h is an integer of 1 or more, and 1, m is an independent 〇 or an integer of 1 or more, and h + 1 + m is 4 or less ' i is an integer of 1 or more 'η, 〇 is an integer of 0 or more, respectively, and i + n + 0 is 4 or less, Ρ is 〇 or 1, and X is a formula (la) or (lb) Show base] -8 - (5) 1294557 [Chemical 2] (〇H)r

H2 (I b) φ [In the formula (la), R18 and R19 are each independently an alkyl group or an aromatic hydrocarbon group having 1 to 10 carbon atoms, and the structure may contain a hetero atom; r, y, and z are independently independent 0 or an integer of 1 or more, and r + y + z is 4 or less]. According to a second aspect of the invention, there is provided a method for forming a photoresist pattern, comprising the step of forming a photoresist film on a substrate by using the negative photoresist composition of the first embodiment; The step of exposing the resist film to the step of developing the photoresist film to form a photoresist pattern. Further, in the present invention, "exposure" refers to the omnipotence of radiation such as excimer laser, electron beam, φ ultraviolet ray, and X-ray. The method for forming a negative-type photoresist composition and a photoresist pattern of the present invention can form a high-sensitivity and high-resolution photoresist pattern. [Negative Photoresist Composition] The negative resist composition of the present invention is an alkali-soluble substrate component (hereinafter also referred to as (A) component) and (B) an acid which generates an acid by exposure. a negative photoresist composition of a generator component (hereinafter also referred to as component (B)) and (C) a crosslinking agent (hereinafter also referred to as component (C)) - 9 - (6) 1294557 In the composition, when the photoresist pattern is formed, the (B) component generates an acid due to exposure (radiation), and based on the action of the acid, cross-linking between the component (A) and (C) is formed. Alkali is insoluble. Therefore, in the stroke of the photoresist pattern, when the photoresist film formed of the negative photoresist composition is selectively exposed, or after exposure and then heated after exposure, the exposed portion can be converted into The alkali is insoluble, while the unexposed portion is still under alkali solubility, and a negative resist pattern is formed after alkali development. <(A) Component> The negative resist composition of the present invention contains (A), and has two or more phenolic hydroxyl groups represented by the above formula (I), and has a molecular weight of from 300 to 2500. Polyphenol compound (A1). The polyphenol compound (A1) preferably has three or more phenolic hydroxyl groups, and more preferably has 4 to 10 phenolic hydroxyl groups. Thus, good alkali solubility can be obtained. In the formula (I), R11 to R17 are each independently a linear, branched or cyclic group or an aromatic hydrocarbon group having 1 to 10 carbon atoms. The alkyl group is preferably a linear or branched lower alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 5 to 6 carbon atoms. The lower alkyl group such as methyl, ethyl, propyl, isopropyl, η-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl or the like is linear or branched. Alkyl and the like. The cyclic alkyl group is, for example, a cyclohexyl group, a cyclopentyl group or the like. The aromatic hydrocarbon group is preferably a carbon number of 6 to 15, and examples thereof include a phenyl group, a methyl-10-(7) 1294557 phenyl group, a xylyl group, a trimethylphenyl group, a phenethyl group, a naphthyl group and the like. Further, the k-group or the aromatic hydrocarbon group may have a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom in its structure. In the case of R11 to R17, the effect of the present invention is enhanced, and it is preferred to use a methyl group or a cyclohexyl group. g and j are each independently 1 or more, preferably an integer of 1 or 2, and k and q are independently 〇 or 1 or more, preferably not more than 2, and g+j + k + q is 5 or less. h is 1 or more, preferably an integer of 1 or 2, and 1, m is independently 0 or 1 or more, preferably not more than 2, and h + 1 + m is 4 or less. 1 is 1 or more, preferably an integer of 1 or 2, and n and 〇 are each independently 0 or 1 or more, preferably not more than 2, and i + n + 0 is 4 or less. P is 0 or 1, preferably 1. X is a group represented by the above formula (la) or (lb). In the formula ( la ), the substituent group of the R18 or R19 or the aromatic hydrocarbon group 9 is, for example, the same as the alkyl group or the aromatic hydrocarbon group described above to R17. In the case of R1 8 R19, the effect of the present invention is enhanced, and the methyl group is preferably Ο, r, yz is an integer of 0 or more, and r + y + z is 4 or less, wherein r is 1 And: y + : B is " [In the case of good c #, it is possible to form a high-resolution pattern with low irregularities and to have a P of 1, and R11 is a lower alkyl or cycloalkyl group. And j is 1, -11 - (8) 1294557 R12 is a lower alkyl group and k is 1, and g is a compound of 1 (Al-1). Particularly, in the compound (A1-1), a compound in which q and 1 and m and η and 〇 are 0, and h and i are 1 are more preferable. The polyphenol compound (A1) is, for example, a compound represented by the following formula (1-11), (1-1 2 ), (I _ 1 3 ) or (I -1 4 ).

-12- (9) 1294557

(I-14) In the present invention, the polyhydric phenol compound (A1) has a molecular weight of from 3 Å to 25 Å, preferably from 1,500 Å to 500 1200 in terms of the effect of the improvement. Further, the molecular weight above the above can form a pattern having a low unevenness, and the photoresist pattern is good. The polyhydric phenol compound (A 1 ) is a material which can spin-coat a crystal film. Among them, the spin coating method is a method for discriminating whether a film which is generally used to form an amorphous film is a crystallized optically transparent polyphenol compound, which is a material which can be formed by a spin coating method, for example, Specifically, it can be determined by the method described below whether or not the coating film formed by the 8-inch wafer coating method is completely transparent. First, the compound is dissolved in a solvent generally used as a resist solvent, and an ester/propylene glycol monoethyl ether acetate = 40/60 (mass ratio) agent (hereinafter, also referred to as EM) is dissolved. The concentration is i 4 and ultrasonic treatment is applied by ultrasonic cleaning (dissolution treatment, and the solution is applied to the wafer by applying a rotation of 1 500 rpm to the range of I 45 0 to the range of the present invention. One of the non-methods is a film. The amorphous film is discriminated by spin coating. More phenolated, such as the mixed mass of lactic acid B, is dissolved, -13- 1294557 - (10) • 1 In the state of 10 ° C and 90 seconds, any dry baking (pab, Post Applied Bake) was applied, and in this state, whether or not a transparent film was obtained was visually recognized to confirm whether or not an amorphous film was formed. Further, the non-transparent mist film is not an amorphous film. Further, the polyphenol compound (A1) is preferably one having a good stability in the amorphous film formed as described above, for example, after the above PAB, it is also transparent after being left at room temperature for 2 weeks. It is better to maintain the amorphous φ state. The polyphenol compound (A1) in the component (A) may be used singly or in combination of two or more kinds thereof, for example, a plurality of compounds having different numbers of hydroxyl groups, substituents or amounts. When the polyhydric phenol compound (A1) contains two or more kinds of compounds, the structure (the number of hydroxyl groups, the kind or the number of substituents, etc.) of a plurality of different polyhydric phenol compounds is preferably as close as possible. Thus, the effects of the present invention can be exerted, and the unevenness can be reduced. • In the component (A), the proportion of the polyphenol compound (A1) is preferably more than 40% by mass, more preferably more than 50% by mass, more preferably more than 80% by mass, and most preferably 1% by mass. good. The polyhydric phenol compound (A 1 ) can be produced by a generally known method, and can be produced, for example, by the method described in JP-A No. Hei. The component (A) may contain any resin component which has been proposed as a component of the substrate of the reinforced chemical resist layer so far, within the range which does not impair the effects of the present invention. -14- 1294557 The resin component is conventionally proposed as a base resin for use in a negative-type photoresist composition for reinforcing chemical KrF, a negative-type photoresist composition for ArF, etc., and can be used in combination with a photoresist pattern. The type of light source used is an appropriate choice. • In the negative resist composition of the present invention, the content of the component (A) can be appropriately adjusted in accordance with the thickness of the photoresist film to be formed. • < (B) Ingredient> (B) The composition is not specified. It can be used as an acid generator for enhancing chemical resist, the above acid generator, and so far, for example, a key salt such as iron iodide or barium salt. An acid generator, an oxime sulfonate acid generator, a dialkyl or bisarylsulfonyldiazomethane, a poly(disulfonyl)diazomethane or the like, a diazomethane acid generator, and a nitrate A variety of known compounds such as a benzyl sulfonate-based acid generator, an imidosulfonate-based acid generator, and a di-based acid generator. # Key Salt acid generator, for example, a compound represented by the following formula (b-Ι) or (b-2). [Chemical 4]

Wherein R1'' to R3'', R5" to R6" are each independently an aryl or alkyl group; R4" is a linear, branched or cyclic alkyl or fluorinated alkyl group; To 15- 1294557 * (12) • At least one of R3" is an aryl group, and at least one of R5'' to R6" is an aryl group. In the formula (), R1" to R3" are independent Or an alkyl group; at least one of R1" to R3 is an aryl group, and two or more of R1" to R3" are preferably an aryl group, and those having Ri" to R3'' are all aryl groups are preferred. . The aryl group of R1' to R3" is not particularly limited, and is, for example, an aryl group having a carbon number of 6 to 20. And a part or all of a hydrogen atom of the aryl group may be an alkyl group, a decyloxy group, The halogen atom or the like may be substituted, and the unsubstituted one may also be an aryl group having a carbon number of 6 to 1 Å from the viewpoint of being inexpensive and easy to synthesize. Specifically, for example, a phenyl group. , naphthyl, etc. The alkyl group which may be substituted for the hydrogen atom of the above aryl group, preferably an alkyl group having 1 to 5 carbon atoms, and a methyl group, an ethyl group, a propyl group, an n-butyl group, a tert-butyl group. The alkoxy group which may be substituted for the hydrogen atom of the above aryl group is preferably an alkoxy group having 1 to 5 carbon atoms, and most preferably a methoxy group or an ethoxy group. The halogen atom of the atom is preferably the fluorine atom. The alkyl group of R1'' to R3'' is not particularly limited, and may be, for example, a linear, branched or cyclic group having a carbon number of 1 to 1 G. The alkyl group or the like is preferably one having a carbon number of from 1 to 5 in view of improving the resolution, and specifically, for example, a methyl group, an ethyl group, an η-propyl group, an isopropyl group, an n-butyl group, or the like. A butyl group, an η-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a fluorenyl group, a fluorenyl group, etc., are excellent in resolvability and can be synthesized inexpensively, and for example, a methyl group or the like can be used. It is preferred that all of ''to R3'' are phenyl. R4'' is a linear, branched or cyclic alkyl group, or a fluorinated alkyl group. -16 - 1294557 * (13) ^ The linear alkyl group is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 4. The above cyclic alkyl group is as described above for R1''. The ring group shown is preferably a carbon number of 4 to 15, preferably a carbon number of 4 to 10, and a carbon number of 6 to 10. Preferably, the fluorinated alkyl group has a carbon number of 1 Preferably, it is preferably from 1 to 8. The carbon number is from 1 to 4. The fluorination rate of the fluorinated alkyl group (the ratio of fluorine atoms in the alkyl group) is preferred. Preferably, it is 10 to 100 mol% φ, more preferably 50 to 100 mol%, and especially if the hydrogen atom is completely replaced by a fluorine atom, it is more preferable because the acid strength is stronger. R4'', straight Chain or cyclic alkyl, or fluorinated alkyl is the best In the formula (b-2), R5" to R6'' are each independently an aryl group or an alkyl group; at least one of R5" to R6" is an aryl group, and all of R5" to r6" are aryl groups. optimal. The aryl group of R5'' to R6'' is, for example, the same as the aryl group of R1" to R3". • The base of R5'' to R6" is, for example, the same as the alkyl group of R1" to R3". It is preferred that all of R5" to R6'' are phenyl groups. R4" in the above formula (b-2) is the same as R4" in (bu). Specific examples of the iron salt acid generator include, for example, diphenyl iodine trifluoromethanesulfonate or nonafluorobutane sulfonate, bis(4-tert-butylphenyl)iron iodide trifluoromethanesulfonic acid Ester or nonafluorobutane sulfonate, triphenylmethane trifluoromethane sulfonate, heptafluoropropane sulfonate or its nonafluorobutane sulfonate, three ( -17- (14) 1294557 ' 4- Triphenylmethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, dimethyl(4-hydroxynaphthyl)phosphonium trifluoromethanesulfonate, and heptafluoropropane sulfonate An acid ester thereof or a nonafluorobutane sulfonate thereof, a triphenylmethanesulfonate of monophenyldimethylhydrazine, a heptafluoropropane sulfonate thereof or its *nonafluorobutane sulfonate, diphenylmonomethyl hydrazine a trifluoromethanesulfonate, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof, a (4-methylphenyl)diphenylphosphonium trifluoromethanesulfonate, a heptafluoropropane sulfonate or Its nonafluoro φ butane sulfonate, (4-methoxyphenyl) diphenyl sulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, three (4 - Tert - Ding Phenylhydrazine trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, diphenyl (1 - (4-methoxy)naphthyl) fluorene trifluoromethanesulfonate An acid ester, a heptafluoropropane sulfonate or a nonafluorobutane sulfonate thereof. Further, the anion portion of the above-mentioned key salt may be a key salt substituted with a methanesulfonate, η-propanesulfonate, η-butanesulfonate or η-octanesulfonate. In addition, in the above formula (b-1) or (b-2), the anion moiety may be substituted with an anion moiety represented by the following formula (b-3) or (b-4) (cation moiety and Formula (b-Ι) or (b-2) the same). [化5] /S〇2, 〇2S—Y"

Xn ---(bS) ---(b-4) s〇2^ o〉s—Z" -18- (15) 1294557 [wherein X" is a carbon in which at least one hydrogen atom is replaced by a fluorine atom a number of 2 to 6 alkyl groups; Y", Z" are independently an alkyl group having at least one hydrogen atom substituted by a fluorine atom and having a carbon number of 1 to 1 Å] X" is at least one hydrogen atom substituted by a fluorine atom A linear or branched alkylene group having a carbon number of 2 to 6, preferably 3 to 5 carbon atoms, most preferably 3 carbon atoms. Y", Z" are each independently a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the alkyl group has a carbon number of 1 to 1 Torr, preferably a carbon number of 1 to 7, most Good for carbon numbers 1 to 3. When the carbon number of the alkyl group of X" or the alkyl group of Y" and the alkyl group is in the above range, it is preferably as small as possible because of the excellent solubility to the resist solvent. Further, in the carbon number of the alkyl group of X" or the alkyl group of Y" or Z", the greater the number of hydrogen atoms substituted by fluorine atoms, the stronger the strength of the acid and the higher the density of 200 nm or less. When the energy light or the electron beam is used, it is preferable to improve the transparency. The ratio of the fluorine atom in the alkyl group or the alkyl group, that is, the fluorination rate is preferably from 70 to 100%, more preferably from 90 to 100%, preferably a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are replaced by a fluorine atom. In the present invention, the oxime sulfonate-based acid generator has, for example, at least one of the following formula (B-1) The compound of the group shown has the property of generating an acid by radiation irradiation. The above-mentioned sulfonate-based acid generator is often used for enhancing the chemical-type resist composition, and the present invention can be arbitrarily selected and used. 1294557 - Czz: N - Ο - S 〇 2 - R22 (B - l) (In the formula (Bl), R21 and R22 are each independently an organic group) In the present invention, the organic group is a carbon atom. a base, but it may also contain atoms other than carbon atoms (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom) The chlorine atom, etc.), etc. The organic group of R21 is preferably a linear, branched or cyclic alkyl or arylalkyl group. The above alkyl group and aryl group may have a substituent. The substituent is not limited. For example, it may be a fluorine atom, a linear one having a carbon number of 1 to 6, a branched or a cyclic alkyl group, etc., wherein "having a substituent" means a part or all of a hydrogen atom of an alkyl group or an aryl group. Replaced by the substituents. The base of the hospital preferably has a carbon number of 1 to 20, preferably a carbon number of 1 to 10, a carbon number of 1 to 8, preferably a carbon number of 1 to 6, and a carbon number of 4 to 4. . The alkyl group is particularly preferably an alkyl group partially or wholly halogenated (hereinafter also referred to as a halogenated alkyl group). Further, a partially halogenated alkyl group means an alkyl group in which one hydrogen atom is partially substituted by a halogen atom, and a completely halogenated alkyl group means an alkyl group in which a hydrogen atom is entirely substituted by a halogen atom. A halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, is preferably a fluorine atom. That is, the halogenated hospital base is preferably a fluoride hospital base. The aryl group is preferably a carbon number of 4 to 20, more preferably a carbon number of 4 to 10, and -20-(17) 1294557 ' is more preferably a carbon number of 6 to 10. The aryl group is particularly preferably a partially or fully halogenated square group. Further, a partially halogenated aryl group means an aryl group substituted with a halogen atom as a part of a hydrogen atom, and a completely halogenated aryl group means an aryl group obtained by completely replacing a hydrogen atom with a halogen atom. R21 is particularly preferably an alkyl group having 1 to 4 carbon atoms which has no substituent, or a fluorinated alkyl group having 1 to 4 carbon atoms. The organic group of R22 is preferably a linear, branched or cyclic alkyl group, an aryl group or a cyano group. The alkyl group or the aryl group of R22 is, for example, the same as the alkyl group or the aryl group exemplified in the above R21. R22 is particularly preferably a cyano group, an unsubstituted alkyl group having 1 to 8 carbon atoms, or a fluorinated group having 1 to 8 carbon atoms. The oxime sulfonate-based acid generator is more preferably a compound represented by the following formula (Β-2) or (Β-3). (B-2) R32—C=N~〇—S02-R33 [In the formula (B-2), R31 is a cyano group, an unsubstituted alkyl group or a halogenated alkyl group; and R32 is an aryl group. R33 is an alkyl group having a substituent or a halogenated alkyl group] [Chemical Formula 8] * · · "B-3" R35-C=N-0-S02-R36 R34 LJ p -21 - (18) 1294557 In (B_3), R34 is a cyano group, an unsubstituted alkyl group or a halogenated alkyl group; R35 is a 2 or 3 valent aromatic hydrocarbon group; R36 is an unsubstituted alkyl group or a halogenated alkyl group, and P is 2 Or 3] in the above formula (B-2), the unsubstituted alkyl group or the halogenated alkyl group of R31 is preferably a carbon number of 1 to 1 Torr, more preferably a carbon number of 1 to 8, and a carbon number of 1 To 6 is the best. R31 is preferably a halogenated alkyl group, and more preferably a fluorinated alkyl group. The fluorinated alkyl group in R31 is preferably one in which the hydrogen atom in the alkyl group is fluorinated by 50% or more, more preferably 70% or more, and more preferably 90% or more of the fluorinated one. An aryl group of R32, for example, a ring of an aromatic hydrocarbon such as a phenyl group or a biphenylyl group, a fluorenyl group, a naphthyl group, an anthracyl group or a phenanthroline group, and one hydrogen atom group is removed. And a heteroaryl group obtained by substituting a part of a carbon atom of the ring of the above-mentioned group with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. Among them, the base is better. The aryl group of R32 may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group or an alkoxy group. The alkyl group or the halogenated alkyl group in the substituent is preferably a carbon number of 1 to 8, more preferably a carbon number of 1 to 4. Further, the halogenated alkyl group is more preferably a fluorinated alkyl group. The alkyl group or the halogenated alkyl group having no substituent of R33 is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 6. R33 is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group, and most preferably a partially fluorinated alkyl group. -22- (19) 1294557 A fluorinated alkyl group in R33, wherein a hydrogen atom in the alkyl group is preferably fluorinated by 50% or more, more preferably 70% or more, and more than 90% is fluorinated. It is better to increase the acid produced. The most preferred is a perfluorinated alkyl group in which the hydrogen atom is 100% replaced by fluorine. In the above formula (B-3), the alkyl group or the halogenated alkyl group having no substituent of R34 is, for example, the same as the alkyl group or the halogenated alkyl group having no substituent represented by the above R31. The 2 or 3 valent aromatic hydrocarbon group of R35 is, for example, a group obtained by further removing 1 or 2 hydrogen atoms from the aryl group of the above R32. The unsubstituted alkyl group or the halogenated alkyl group of R36 is, for example, the same as the unsubstituted alkyl group or the halogenated alkyl group represented by the above R33, and ρ is preferably 2. Specific examples of the sulfonate-based acid generator, such as α-(p-toluenesulfonyloxyimido)-benzyl cyanide (cyanide), α-(ρ-chlorophenylsulfonyloxyimino) -benzyl cyanide, α-(4-nitrophenylsulfonyloxyimido)-benzyl cyanide, α-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimido)- Benzyl cyanide, α-(phenylsulfonyloxyimido)-4-methylchlorobenzyl cyanide, α-(phenylsulfonyloxyimino)-2,4-dichlorobenzyl cyanide, —-(phenylsulfonyloxyimino)- 2,6-dichlorobenzyl cyanide, α-(phenylsulfonyloxyimino)-1,4-methoxybenzyl cyanide, α-(2) -Chlorobenzenesulfonyloxyimino)-1,4-methoxybenzyl cyanide, ^(phenylsulfonyloxyimino)-thiazol-2-ylacetonitrile, α-(4-dodecane Benzosulfonyloxyimido)monobenzyl cyanamide-23 (20) 1294557 compound, α-[(p-toluenesulfonyloxyimino)-4-methoxyphenyl]acetonitrile, α — [ (dodecylbenzenesulfonyloxyimino)-1,4-methoxyphenyl]acetonitrile, α-(p-toluenesulfonyloxy) Amino)-4-ylthiocyanate, α-(methylsulfonyloxyimino)-1,4-cyclopentenylacetonitrile, α-(methylsulfonyloxyimino)-1-cyclohexenyl Acetonitrile, α-(methylsulfonyloxyimido)-1-cycloheptenylacetonitrile, α-(methylsulfonyloxyimido)-1-cyclooctenylacetonitrile, α-(trifluoromethyl Sulfonoxyimino)-1-cyclopentenylacetonitrile, α-(trifluoromethylsulfonyloxyimido)-cyclohexylacetonitrile, α-(ethylsulfonyloxyimino)-ethylacetonitrile, --(propylsulfonyloxyimido)-propyl acetonitrile, α·(cyclohexylsulfonyloxyimino)-cyclopentylacetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclohexyl Acetonitrile, α-(cyclohexylsulfonyloxyimido)-1-cyclopentanylate, α-(ethyl expanded oxyimido)-1-cyclopentenylacetonitrile, α-(isopropylsulfonate醯 oxyimino)-1-cyclopentenylacetonitrile, α-(η-butylsulfonyloxyimido)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1 —cyclohexenylacetonitrile, α — (isopropylsulfonyloxy) Amino)-1-cyclohexenylacetonitrile, α-(η-butylsulfonyloxyimido)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-phenylacetonitrile, —-(methylsulfonyloxyimino)-fluorenyl-methoxyphenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-phenylacetonitrile, α-(trifluoromethylsulfonate) Oxyimine)-ρ-methoxyphenylacetonitrile, α_(ethylsulfonyloxyimido)-ρ-methoxyphenylacetonitrile, α-(propylsulfonyloxyimino)-ρ —methylphenylacetonitrile, α-(methylsulfonyloxyimido)-ρ-bromophenylacetonitrile, and the like. Further, for example, a compound represented by the following chemical formula (compound groups (i) to (iii)) and the like.

-25 - (22) 1294557 (Compound group (i)) [Chemical 9]

c—N 一Ο——S〇2——CH3 CN

CH3—02s——Ο—N=C NC

C=N—O—S02—C2H5 C4H9—O2S—〇-

C4H3—O2S—O N=C CN

-N=C—\ 7~C=N I I CN CN

CF3—〇aS—0_

NC

C=N'~—0—S〇2—CF3 CN

CF3-0, S-〇-N=C CN

NC ^ CM CH3-C=N-0S〇2-(CH2}3CH3 CH3-C=N-〇S〇2-(CH2)3CH3 -26- (23) 1294557 Further, the above formula (B-2) or Among the compounds shown in B-3), preferred compounds are shown below.

-27- (24) 1294557 (compound group (Π)) [化 ίο] ch3 <y C —N Ο—S〇2—CF3 (CF2)6—Η C^N—〇—S02—CF3 c2f5

Ch3〇 乂)- C —N—0—S〇2—CF3 c3f7

C~N—0—S〇2—CF3 (CF2)6-H

C-=N—〇一〇2_CF3 C3F7 o

C3F7-C^N—O—S〇2—CF3

%—C=N—O—S02—CF3 C3F7

(CH2)3 o

C—N—0—S〇2—CF3 C3F7 CF3 d—O—S02—C4F9 -28- (25) 1294557 (Compound Group (iii)) [Chem. 11]

C=N_0—S〇2—CF3 (CF2)6—Η C=NΟ—S〇2—C4F9 (CF2)6—Η

C*=N_0一S〇2—CF3 (CF2)6-H C=M—O—S02—C4F9 {cf2)6-h ^C=N—Ο—S02—CF3

(CF^e-Η

C=N—0—S02—CF3 (CF2)6-H 0~〇'HOh· C=NΟ—S〇2—C4F9

(CFJe—Η C=N—0—S〇2—C4F9 C3F7

C=N—Ο—S〇2—CF3

(CF2)6-H

^—C=N—0—S〇2—CeFi3 (CF2)6-H ^~- 0-S02-C4F9

(CF2)6-H

-29- (26) 1294557 Among the above exemplified compounds, the following three compounds (iv), (V), and (v i ) are more preferable. [化 12]

C=N——0—S02—C4H9 CN (iv) φ [Chemical 13] Strictly 2 sides 3% %OHSOr_CH3 (V)

Specific examples of the dialkyl or bisarylsulfonyldiazomethane in the diazomethane acid generator, such as bis(isopropylsulfonyl)diazomethane or bis(P-toluenesulfonyl) Diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl) Diazomethane, etc. Further, poly(disulfonyl)diazomethanes have, for example, 1,3-bis(phenylsulfonyldiazomethylsulfonyl- 30-(27) having the structure (vii) or (viii) shown below. 1294557 ^) Propane (in the case of A=3), 1,4-bis(phenylsulfonyldiazomethylsulfonyl)butane (in the case of 4), 1,6-bis(phenylsulfonyl) Diazomethanesulfonyl)hexane (in the case of A = 6), 1,1 0-bis(phenylsulfonyldiazomethylsulfonyl)decane (in the case of A = 1 0), 1 , 2 -^ bis(cyclohexylsulfonyldiazomethylsulfonyl)ethane (in the case of B = 2), 1,3-bis(cyclohexylsulfonyldiazomethylsulfonyl)propane (in the case of B = 3), 1,6-bis(cyclohexylsulfonyldiazomethylsulfonyl)hexane (in the case of B = 6), 1,1 0 - bis(cyclohexylsulfonyl) Diazomethanesulfonyl) decane (in the case of B = 1 0), etc. [Chem. 15] 〇〇Ο 0 Ν2 οU II II , —c—·; —c—{

(νϋ)

(ym) In the present invention, the (Β) component is preferably a key salt using a fluorinated alkylsulfonic acid ion or an alkylsulfonic acid ion as an anion. (B) The above-mentioned acid generator may be used singly or in combination of two or more kinds. The content of the component (B) is 0.5 to 30 parts by mass, preferably 1 to 15 parts by mass, preferably 5 to 10 parts by mass, per 100 parts by mass of the component (A). In the above range, the pattern can be sufficiently formed. It is preferable to obtain a uniform solution and to have good storage stability. -31 - (28) 1294557 < (C) Component> (C) The component is not particularly limited, and may be appropriately selected from the crosslinking agents used in the currently known chemically enhanced negative-type photoresist composition. use. Specifically, for example, 2,3-dihydroxy-5-hydroxymethyl raw spinel, 2-hydroxy-5,6-bis(hydroxymethyl)prolinane, cyclohexanedimethanol, 3,4,8 (or 9) tris-trihydroxytricyclodecane, 2-methyl- 2-adamantanol, U4-dioxane-2,3-diol, 1,3,5-trihydroxycyclohexane, etc. A hydroxy group or a hydroxyalkyl group or an aliphatic cyclic hydrocarbon having two or an oxygen-containing derivative thereof. Further, for example, an amine group-containing compound such as melamine, methyl decylamine, benzoguanamine, urea, ethylene urea, propylene urea or glycoluril is reacted with formaldehyde or formaldehyde with a lower alcohol, and the hydrogen atom of the cyano group is made into a methylol group. Or a compound substituted with a lower alkoxymethyl group or the like. Among them, those who use melamine are called melamine cross-linking agents, those who use urea are called urea-based cross-linking agents, those that use ethylene urea, propylene urea, etc. are called alkylene urea-based cross-linking agents. Urea is called a glycoluril crosslinker. (C) The composition is selected from the group consisting of a melamine-based crosslinking agent, a urea-based crosslinking agent, an alkylene-based crosslinking agent, and a glycoluric crosslinking agent, and is preferably a urea-based compound. A crosslinking agent or a glycoluric crosslinking agent is more preferred, and a glycoluric crosslinking agent is preferred. A chlorine-based chelating agent, such as melamine and formaldehyde, reacts a compound obtained by substituting a hydrogen atom of amino-32-(29) 1294557 with a hydroxymethyl group, and reacting melamine with formaldehyde with a lower alcohol to give a hydrogen atom of the amine group. The obtained compound or the like is substituted by a lower alkoxymethyl group. Specifically, for example, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutyloxymethyl melamine or the like, among which hexamethoxymethyl melamine is preferred. A urea-based crosslinking agent, for example, a reaction of urea with formaldehyde, a compound obtained by substituting an argon atom of an amine group with a hydroxymethyl group, and a reaction of urea with formaldehyde and a lower alcohol, and the hydrogen atom of the amine group is substituted by a lower alkoxymethyl group. Compounds, etc. Specifically, for example, bismethoxymethyl urea, diethoxymethyl urea, bis oxymethyl urea, dibutoxymethyl urea, etc., of which bismethoxymethyl uridine is preferred. The alkylene urea-based crosslinking agent is, for example, a compound represented by the following formula (III). [Chemistry 16]

(III) (wherein R1' and R2' are each independently a hydroxyl group or a lower alkoxy group, and R3' and R4' are each independently a hydrogen atom, a hydroxyl group or a lower alkoxy group; and v is 0 or 1 or 2 In the case where R1' and R2' are lower alkoxy groups, an alkoxy-33-(30) 1294557' group having 1 to 4 carbon atoms is preferable, and it may be linear or branched. R1' and R2' may be the same or different, and the same is preferable. When R3 and R4 are a lower alkoxy group, it is preferably a hospital oxygen group having 1 to 4 carbon atoms, which may be linear or branched. R3 ′ and R4 ′ may be the same or not, and the same is preferable. And v is 〇 or an integer of 1 or 2, preferably 〇 or 1. The sputum-supporting urea-based parent-linking agent is preferably a compound in which v is ruthenium (a urea-based cross-linking agent) and/or a compound in which V is 1 (a propylene-urea-based cross-linking agent). The compound of the above formula (III) can be obtained by a condensation reaction of an alkylene urea with formic acid or a reaction of a product thereof with a lower alcohol.

Specific examples of the k-supported urea-based parent-linked agent, such as mono- and/or dimethylolated ethylene urea, mono- and/or dimethoxymethylated ethylene urea, mono- and/or mono-ethoxymethylated ethylene urea, Mono- and/or dipropoxymethylated ethylene urea, mono- and/or di-butoxymethylated ethylene urea; mono- and/or dimethylolated propylene urea, mono- and/or dimethoxymethylated propylene urea , propylene urea-based cross-linking agent such as mono- and/or di-ethoxymethylated propylene urea, mono- and/or dipropoxymethylated propylene urea, mono- and/or di-butoxymethylated propylene urea; 1,3 — mono(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, I”-(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone and the like. The glycoluril-based parent-linking agent is, for example, a glycoluril derivative obtained by substituting one or both of a hydroxyalkyl group and an alkoxyalkyl group having a carbon number of i to 4 at the N position. The aforementioned glycoluril derivative ' can be obtained, for example, by a condensation reaction of glycoluril with formaldehyde or a reaction thereof with a lower alcohol. -34- (31) 1294557 Specific examples of glycoluril-based cross-linking agents, such as mono-, di-, poly-glycolides, mono-, di-, tri- and/or tetramethoxymethyl, tri- and/or tetraethoxymethyl Glycoluril, mono-, di-, methylated glycoluril, mono-, di-, tri- and/or tetrabutoxy (C) components, can be used alone or in combination. (c) The amount of the component to be added is preferably 3 to 30 parts by mass for the component (a) and 15 parts by mass for 3 to 15 parts by mass. When the content of the component (C) is sufficiently cross-linked, and a good photoresist pattern is obtained, the photoresist coating liquid can have a good deterioration resistance over time. <Other optional components> In the negative resistive composition of the present invention, in order to enhance the post exposure latent image formed by the pattern-wise resist layer, any component may be added. Contains D) (hereinafter also referred to as (D) component). As the component (D), a plurality of compounds are currently used, and any known components such as η-hexylamine, octylamine, η-decylamine, η-decylamine or the like, monoalkyl-n-cis-amine, Dialkylamines such as di-h-heptylamine, di-n-hexylamine; trimethylamine, triethyl® tri- and/or tetrahydro-methylammonium, mono-, di-, and/or tetrapropoxy Glycoluril and the like. The combination of two or more types makes 100 parts by mass more preferable, and when it is 5 or more, it is acceptable. Moreover, the stability is at the upper limit, and the shape of the photoresist pattern, the stability of the exposure of the nitrogen organic compound (the proposal may also be η-heptylamine, η-amine; diethylamine, monooctyl Amine, bicyclo-, tri- η-propyl-35- 1294557 ^ (32) , amine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine, tri-n- a trialkylamine such as heptylamine, tris-n-octylamine, tri-n-decylamine, tris-n-decylamine, tris-n-dodecylamine; diethanolamine, triethanolamine, two An alkanolamine such as isopropanolamine, triisopropanolamine, di-n-octanolamine, • tris-n-octanolamine, especially a secondary aliphatic amine or a tertiary aliphatic amine. Further, trialkylamine having a carbon number of 5 to 1 Torr is more preferable, and tri-n-octylamine is preferred. φ It may be used singly or in combination of two or more kinds. (D) Ingredients 100 parts by mass of the component (A) is generally in the range of 〇·〇.1 to 5.0 parts by mass. Further, the negative photoresist composition of the present invention is used to prevent the addition of the above (D) component. Deterioration in sensitivity, or post exposure stability of the latent image formed by the pattern-wise exposure of the resist layer, etc., may add any φ parts An organic carboxylic acid or a phosphorus oxyacid or a derivative thereof (E) (hereinafter also referred to as an (E) component). Further, the component (D) may be used in combination with the component (E), or any one of them may be used alone. Organic carboxylic acids such as malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. Phosphorus oxyacids or derivatives thereof, such as phosphoric acid, di-n-butyl phosphate Derivatives such as esters and diphenyl phosphates such as phosphoric acid or esters thereof, Phosphonic acid, dimethyl phosphonate, phosphonic acid-di-n-butyl ester, phenylphosphonic acid, diphenyl phosphonate, phosphine a phosphonic acid such as dibenzyl ester and an ester thereof, such as -36- 1294557 (33), phosphinic acid (Phosphinic acid), phenylphosphinic acid, and the like, and a phosphinic acid derivative such as an ester thereof, wherein It is preferred to use phosphonic acid. (E) The composition is generally 1 part by mass of the component (A). The range of 0.01 to 5.0 parts by mass. The negative photoresist composition of the present invention may be further added with additives for increasing the compatibility, such as an additive resin added to improve the properties of the photoresist film, for the intended purpose, A coating agent for improving coatability, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, a halo preventing agent, a dye, and the like. <Organic solvent> The negative resist composition of the present invention can be obtained by dissolving the above component (A), component (B), component (C) and various optional components in an organic solvent. The organic solvent can be used as long as it can dissolve the respective components to form a uniform solution. For example, one or two or more kinds of the above-mentioned solvents which are conventionally used as the reinforced chemical resist solvent can be used. a solvent such as a lactone such as r-butyrolactone or a ketone such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone or 2-heptanone; ethylene glycol or ethylene glycol monoacetic acid; Monomethyl ether, monoethyl ether, monopropyl ether, ester, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, or dipropylene glycol monoacetate Polyols such as monobutyl ether or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, Methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate, etc. -37-(34) 1294557 Esters. These organic solvents may be used singly or in combination of two or more. Further, it is preferred to use a mixed solvent obtained from propylene glycol monomethyl ether acetate (PGME A) and a polar solvent, and the addition ratio (mass ratio) can be appropriately determined depending on the compatibility of PGMEA with a polar solvent. Preferably, it is preferably from 1:9 to 9:1, more preferably in the range of from 2:8 to 8:2. More specifically, when the polar solvent is EL (ethyl lactate), the mass of PGMEA: EL is preferably from 1:9 to 9:1, more preferably from 2:8 to 8:2. Further, among the organic solvents, for example, a mixed solvent of at least one selected from PGMEA and EL and r-butyrolactone is preferably used. In this case, the mass ratio of the former to the latter is 70:30 to 95:5. The amount of the organic solvent used is not particularly limited, and generally, the concentration applied to the substrate, the thickness of the coating film, etc. A suitable selection setting can be generally carried out in the range of 2 to 20% by mass, preferably 5 to 15% by mass, based on the solid content of the photoresist composition. [Formation Method of Photoresist Pattern] The method for forming a photoresist pattern of the present invention comprises the step of forming a photoresist film on a substrate by using the negative photoresist composition of the present invention described above, and exposing the photoresist film to The step of developing the aforementioned photoresist film to form a photoresist pattern is characterized. Further, for example, a photoresist pattern can be formed by the formation method of the photoresist pattern described below. That is, first, the negative photoresist composition is coated on a substrate such as a germanium wafer using a spin coater or the like, and any pre-bake (PAB) is applied to form a photoresist film. . For the formed photoresist film, for example, an exposure device such as an electron beam drawing device or an EUV exposure device is used for exposure by a photomask, or is directly exposed to an electron beam through a mask to perform drawing, and the like. , then apply PEB (heating after exposure). Next, after developing treatment using an alkali developing solution, a washing treatment is applied, and the developing solution on the substrate and the photoresist composition dissolved in the developing solution are washed away, and dried to obtain a photoresist pattern. The foregoing steps can be carried out in accordance with a known method. The operating conditions can be appropriately set in accordance with the composition or characteristics of the negative resist composition used. The exposure light source is not specific, for example, ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron), X-ray, soft can be used. Radiation such as X-rays. In particular, the negative photoresist composition of the present invention is effective for electronic wires or EUV, and is particularly effective for electronic wires. Further, depending on the treatment, the base may be further subjected to a post-baking step after the development of the base, or an organic or inorganic anti-reflection film may be provided between the substrate and the photoresist film. As described above, the negative-type photoresist composition of the present invention and the method for forming a photoresist pattern using the negative-type photoresist composition can provide a high-sensitivity and high-resolution photoresist pattern. The reason should be that the polyphenol compound (A 1 )-39- 1294557 (36) has high alkali solubility, so the alkali solubility is not easily affected by other components in B, and the reactivity with the polyphenol compound (parts) It is a polyphenol compound (A 1 or the like. That is, the conventional photoresist of the (A) component is affected by the component (B), etc., for example, when the amount of the component (B) is increased as described above, Reducing the photoresist> The resolution is lowered, and there is a limit to the amount of addition of the component which cannot form a photoresist pattern. In contrast, in the present invention, it is presumed that the addition amount of the component (B) is increased. It is also sufficient, and the cross-linking reactivity with the component (C) is high and the coupling property is obtained, so that the exposed portion can rapidly form an alkali-insoluble property. The sensitivity and the high-resolution photoresist pattern are. In the case of the polyphenol compound (A1 > compound, the unevenness may be expected to be reduced. [Embodiment] Hereinafter, embodiments of the present invention will be described, but the present embodiment is limited. Examples 1 to 6, Comparative Example 1 Mix and dissolve the ingredients shown in Table 1 to The solution A) and the (C) compound have a cross-linking composition, which is easy to improve the sensitivity, and makes the I-direction, so (B) alkali solubility, and That is, the high sensitivity of the analysis itself also has an intersection, so that it can be formed high in the use of low molecular weight and is not the following negative negative photoresist composition -40-(37) 1294557

[Table 1] (A) Component (B) Component (C) Component (D) Component (E) Component Organic Solvent Example 1 Compound 1 PAG1 BINDER1 Aminel ADD1 PGME 『1〇〇1 [12.61 『1〇1 『0.381 i 〇.31 Example 2 Compound 1 PAG1 BINDER2 Aminel ADD1 PGME [1001 [12.61 『1〇1 [0.38] 『0.3] [1560] Example 3 Compound 1 PAG1 BINDER3 Aminel ADD1 PGME 『1001 『12.61 ΐ〇1 『0.381 Γ0.31 [1560] Example 4 Compound 2 PAG1 BINDER1 Aminel ADD1 PGME Π001 [12.6] 『101 [0.381 [〇·31 [1560] Example 5 Compound 2 PAG1 BINDER2 Aminel ADD1 PGME 『1001 Π2.61 Π〇 1 [0.38] Γ0.31 [1560] Example 6 Compound 2 PAG1 BINDER3 Aminel ADD1 PGME 『1001 [12.61 『1〇1 [0.381 『0.31 [1560] Comparative Example 1 Resin 1 PAG1 BINDER1 Aminel ADD1 PGME 『1001 『6.01 Π 〇1 [0.75] i〇.31 [1560] Further, in Table 1, the number of enthalpy in [] is the amount of addition (parts by mass). Compound 1 (manufactured by Honshu Chemical Industry Co., Ltd.), Compound 2 (manufactured by Honshu Chemical Industry Co., Ltd.), BINDER 1 to 3 (manufactured by Sanwa Chemical Industry Co., Ltd.): a compound having the structure shown below. Resin 1: copolymer of 80 mol% of p-hydroxystyrene and 20 mol% of styrene (mass average molecular weight 3600, dispersion degree 2.0, Japan Cao-41 - (38) 1294557 Manufactured by the company) PAG1 : triphenyl Nine-nonafluorobutane sulfonate

Aminel: Sanyi η-octylamine ADD1: salicylic acid PGME: propylene glycol monomethyl ether [Chem. 17]

OH 0Η

[it 18]

BINDERI BINDER2

Next, the obtained negative-type photoresist composition solution was used for the following evaluation <analytical> The negative-type photoresist composition solution was uniformly coated on -42-(39) 1294557 8-inch treatment using a spin coater. Hitachi's and the use of 2 3 〇 C type and the shape of the sensible 矽 substrate, and then baked at 100 ° C, 90 seconds to form a photoresist film (PAB) Film thickness 125 nm). The photoresist film was subjected to drawing (exposure) at an acceleration voltage of 70 kV using an electron beam drawing machine HL-800D (VSB) (manufactured by the company), and baking was performed under conditions of 1 l ° C and 90 seconds (PEB). After that, a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) was developed for 60 seconds, and then washed with pure water for 30 seconds. As a result, in Examples 1 to 6, a 1 0 line and space (L/S) pattern of a 50 nm independent space map of 50 nm was formed. Further, in Comparative Example 1, the photoresist of the space portion was completely removed, and the 50 nm independent spatial pattern was not obtained. Degree> The exposure amount (V C/cm 2 ) which forms a 50 nm independent space pattern is obtained. The results are shown in Table 2. -43- (40) 1294557 --- Analytical (nm) sensitivity (uC/cm2) Example 1 50 17 Example 2 50 25 - Example 3 50 19 ___..---- -- Example 4 50 17 Example 5 50 27 —---------- Example 6 50 17 Comparative Example 1 - - From the above results, Examples 1 to 6 can form a high-sensitivity and high-resolution photoresist Graphic type. Among them, the sensitivity of the embodiments 1, 3, 4, and 6 using BINDER 1 or 3 is the highest. Further, the component (A) used Comparative Example 1 of Resin 1, and failed to form a pattern of 50 nm. (Industrial Applicability) The method for forming a negative-type photoresist composition and a photoresist pattern of the present invention can form a high-sensitivity and high-resolution photoresist pattern, and is therefore suitable for negative-type light. Formation of resistive composition and photoresist pattern. -44 -

Claims (1)

1294557 X. Patent Application No. 95 103 1 64 Patent Application Revision of Chinese Patent Application Scope Amendment of February 9, 1996 1 a negative-type photoresist composition which is a (A) alkali-soluble substrate component, and (B) an acid generator component which generates an acid by exposure, and (C) a negative-type photoresist of a crosslinking agent component The composition, wherein the content of the component (B) is 0.5 to 30 parts by mass for the (A) component, and the amount of the component (C) is 3 to 30 by mass for the (A) component of 100 parts by mass. And the above-mentioned base material component (A) is a polyhydric phenol compound (A 1 ) having two or more oxime-based base groups having a molecular weight of 300 to 2,500, as shown by the following formula (I). ] [In the formula (I), R11 to R17 are independently an alkyl group of 1294557 or an aromatic hydrocarbon group having a carbon number of 丨 to 1 (), and a hetero atom may be contained in the structure; and g and j are each independently an integer of 1 or more. k, q is an integer of 0 or more, and g + j+k + q is 5 or less, h is an integer of 1 or more, and l and m are independent 〇 or an integer of i or more, and h + 1 + m 4 or less, 丨 is an integer of 1 or more, and η and 〇 are independent integers of 0 or more, and i + n + o is 4 or less, ? Is 〇 or 1, and is a base represented by the following formula (1&) or (:^)] [Chemical 2] (〇H)r (la) (I b) [In the formula (la), R18 and R19 are independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group, and the structure may contain a hetero atom; r, y, and z are independently 0 or an integer of 1 or more, and r + y + z is 4 or less]. 2. The negative resist composition of claim 1 of the patent scope, wherein 尙 contains (D) a nitrogen-containing organic compound. 3. A method for forming a photoresist pattern characterized by the step of forming a photoresist film on a substrate by the negative photoresist composition of claim 1 or 2, and exposing the photoresist film 'Step of developing the aforementioned photoresist film to form a photoresist pattern. -2-