TWI375122B - Positive resist compositions and patterning process - Google Patents

Description

1375122 IX. INSTRUCTIONS OF THE INVENTION [Technical Field to Be Invented by the Invention] The present invention relates to (1) suitable for microfabrication technology, and can provide a pattern of excellent resolution, density dependence, mask faithfulness, and uneven line sidewall unevenness. A positive photoresist material, and (2) a method of forming a pattern using the photoresist material.

In recent years, with the increase in the integration and speed of LSIs, the development of microfabrication techniques using far ultraviolet lithography and vacuum ultraviolet lithography has been intensively pursued in the miniaturization of pattern lines. At present, the use of KrF excimer laser light with a wavelength of 248 ηηι as the light source lithography etching is a central task in the actual production of semiconductor devices. At present, in order to achieve further miniaturization, the use of ArF quasi-wavelength at 193 nm is begun. Molecular laser light was used in some of the experimental production processes. However, φ is that ArF excimer laser lithography is still an immature technology, and there are still various problems when it is intended to be basically used for actual production. Corresponding to the characteristics required for the ArF excimer laser lithography photoresist, which has transparency to a wavelength of 193 nm and dry etching resistance, both of which are resins, such as the proposed 2-ethyl-2 -Adamantane group, 2-methyl-2-adamantyl group is a photoresist material having a high bulk density poly(meth)acrylic acid derivative as a base resin (Patent Document 1: JP-A-9-73 1) Japanese Laid-Open Patent Publication No. Hei 9-90637. There are also various proposals for materials, but almost all of them are used in the viewpoint of using a highly transparent main chain of -6-1375122 and a carboxylic acid moiety protected by a high-density tertiary alkyl group. In the case, they are all common people. Among the problems in the past materials, particularly those with deep problems are uneven size of the fine wiring (uneven side wall), which is highly affected by the performance of the manufactured semiconductor device.

The method. If only for the purpose of smoothing the pattern, etc., it is only necessary to set the molecular weight of the resin used to be lower, so that the acid generated by the photoacid generator can be easily moved and can reach a certain degree, but at this time, in addition to exposure. In addition to extreme deterioration of characteristics such as quantity dependence, density dependence, and mask faithfulness, when the fine movement of the mask is enlarged, 'there will be unevenness in the line size itself, and it is impossible to reduce the unevenness of the line side wall. link. In the process of pursuing the miniaturization of the pattern line, in addition to the excellent performance in sensitivity, substrate adhesion, and etching resistance, there is still a need for deterioration without analyticity, and Uneven countermeasures. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 9-9063 No. Hei. No. 9-9063. In the photolithography etching using a high-energy line such as a light source as a light source, it is also intended to have a positive-type photoresist material which improves the resolution and reduces the unevenness of the line sidewall, and a pattern forming method using the photoresist material. In order to achieve the above object, the present inventors have carried out intensive investigations and obtained 1375122 to know that a polymer compound composed of a specific repeating unit is used as a base resin and an antimony salt compound having a specific structure is used as an acid generator. The obtained positive-type photoresist material has extremely high analytical performance and can reduce the unevenness of the sidewall of the line, and is a photoresist material which is extremely useful for precision micro-machining. That is, the present invention provides a photoresist material and a pattern forming method thereof.

Claim 1 : A positive-type photoresist material which is a compound containing (A) a resin component which is soluble in an alkali developer based on an acid action, and an acid which generates an active light or radiation by (B), wherein The resin component (A) is a polymer compound having a repeating unit represented by the following formula (1), and the compound (B) in which the acid is generated is a positive electrode compound represented by the following formula (2). Type photoresist material,

【化1】

(R1 is independently a hydrogen atom, a methyl group, or a trifluoromethyl group; R2 is an acid labile group; R3 is a hydrogen atom or C02R4; and R4 is a linear or branched carbon having a carbon number of 1 to 20 which may contain a hetero atom. Or a cyclic monovalent hydrocarbon group; X is 〇, S, CH2, or CH2CH2; m is 1 or 2; n is 1 or 2; a, b, c (S)· -8 - 1375122, and d are repeats The ratio of the existence of the unit, a, b, c, and d are respectively above 0·01, and the number is less than 1, a+b+c+d=l). [Chemical 2]

(R5, R6, and R7 are each independently a hydrogen atom, or a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms of a hetero atom; and R8 is a carbon number 7 to 30 which may contain a hetero atom. a linear, branched or cyclic monovalent hydrocarbon group). Item 2: The positive-type photoresist material of claim 1, wherein the acid-labile group of the resin component (A) is one selected from the following formula (a-〇> (a_5) or 2 or more types.

[化3]

(a·)) (a-2) (a.3) (a-4) (a-5) (wherein the dotted line is the bonding key; R9, R1 0, R1 1 , RI 2, R, 3 respectively A linear or branched alkyl group independently having a carbon number of 1 to 4;] is 7. Γ is 1 or 2). Request item 3 = -9- <S>

1375122 A method for forming a pattern, comprising the steps of: coating a photoresist material of a request item on a substrate, and exposing the high energy line or the electron line to a heat treatment mask, and heating The step of developing using a developing solution. Claim 4: A method for forming a pattern, comprising the steps of applying the request item 1 or the resist material to the substrate, and the step of exposing the high energy line or the electron line after the heat treatment, and heating A pattern forming process for the step of developing the developer after the treatment, characterized in that the liquid having a refractive index of 1 or more is interposed by the immersion exposure of the photoresist coating film and the projection lens. The item 5 is a method for forming a pattern, comprising the steps of applying the request item 1 or the resist material to the substrate, and the step of exposing the high energy line or the electron line after the heat treatment, and heat treatment The pattern forming process of the step of developing the φ developer is characterized in that the protective film is coated on the resist film, and the immersion exposure is performed between the protective film and the projection lens using a refractive index of 1 or more. The photoresist material of the invention has a very high resolution in the microfabrication technology 'especially the shadow etching technology', and can provide a pattern of uneven sidewalls of small lines, and is extremely suitable for precision microfabrication, The photoresist material of the present invention will be described in detail. In the following description, the structure represented by the chemical formula has an enantiomer or a non-mirrored image due to the presence of asymmetric carbon: 1 or 2, after the treatment 2, the light is used by the mask, and the use is performed 2 The light is used by the reticle, and the light liquid is inferior to the ArF micro, so it will be the case of the cockroach (-10-1375122 diastereomer), in which case the isomer will be represented by a structural formula. . These isomers may be used singly or as a mixture. The photoresist material of the present invention is a compound (B) containing a resin component (A) which is soluble in an alkali developer based on an acid action, and an acid which can generate an acid by inducing active light or radiation, wherein the resin component (A) ) is a polymer compound having a repeating unit represented by the following formula (1), and the compound (B) in which the acid of φ is generated is a positive resist material of the onium salt compound represented by the following formula (2) . 【化1】

Wherein R1 is independently a hydrogen atom, a methyl group, or a trifluoromethyl group. R2 is an acid labile group, and specific examples thereof will be described later. R3 is a hydrogen atom or C02R4. ! ^4 is a monovalent hydrocarbon group which may contain a linear, branched or cyclic alkyl group having a carbon number i'so of a hetero atom, specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, or the like. η — butyl, sec — butyl, tert — butyl, tert —pentyl, η —pentyl, η—hexyl, cyclopentyl, cyclohexyl, ethylcyclopentyl, butylcyclopentyl, ethyl Cyclohexyl, butylcyclohexyl, adamantyl, ethyladamantyl, butanyl, and any carbon-carbon bonds of such groups are interspersed with -0-, -S-, -SO- , -S02-, -ΝΗ-, <s> -11 -

A hetero atomic group such as 1375122 -C( = 0)-, -C( = 0)0-, -C( = 0)NH-, etc., such as any hydrogen atom, is replaced by -OH, -NH2, -CHO, -CO base. X is 〇, S, CH2, or CH2CH2. β n is 1 or 2. a, b, c, and d indicate the existence ratio of each repeating unit, which is 0.01 or more and less than 1, and a+b+c+d=l. A preferred range is as shown below. 0.05^0.6 > more preferably 0.IS a$0.5 0.01SbS0.5, more preferably O.OlgbSO.4 O.OlScSO.6, more preferably 0.05Sc$0.5 0.01S dS 0.6, more preferably 0.05S 0.5 , a+b+c+d=l means a group of repeating units a, b, c, d in a polymer compound containing a repeating unit, or a functional group m such as 2 2 is 1 or 2 a, b, c, d each has a relative ratio of a, b, c, d

The total amount of the total repeating unit is 100% by mole. [Chemical 2]

(2) wherein 'in the formula', R5, R6 and R7 are each independently a linear, branched or hydrocarbyl group having 1 to 20 carbon atoms and a hetero atom; and a hydrocarbon group containing a hetero atom, such as a methyl group or a Propyl, η-butyl, sec-butyl 'tert_butyl, η-pentyl, π-hexyl, cyclopentyl, cyclohexyl, ethyl atom, or cyclic monovalent ethyl, propyl tert _Pentylcyclopentyl, butyl-12-1375122-cyclopentyl, ethylcyclohexyl, butylcyclohexyl, adamantyl, ethyladamantyl, butyl-hydroxyalkyl, and any carbon of such groups ·-0-'-S-, .SO-, -S〇2-, -NH-, -C( = 0)-, -C( = 0)0-, -C( =) are inserted between the carbon bonds. 0) A group of a hetero atomic group such as NH- or a hydrogen atom is exemplified by a group substituted with a functional group such as -H, -NH2'-CH0 or -C02H. R8 is a linear "branched or cyclic monovalent hydrocarbon group having 7 to 30 carbon atoms which may contain a hetero atom. Specific examples thereof are exemplified below, but are not limited thereto. [化3]

h y

(In the formula, the dotted line is the bonding key). The acid-labile group of R2 in the resin component (A) is preferably one or more selected from the following formulas (a-Ι) to (a-5). -13- 1375122 【化4】

(4°) (a-2) (a-3) (a-4) (a-5) where the dotted line is the bond key. R9, R1(), R11, R12 and R13 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, specifically, φ such as methyl group, ethyl 'propyl group, isopropyl group, and η. — butyl, sec-butyl, tert-butyl, etc. 〇 is 1 or 2. p is 1 or 2. The acid labile group of R2 is specifically exemplified below, but is not limited thereto.化I Φ kiss # ^ ^ ^ b ^ ^ <>b In the above formula (1), it has a high alkali developer affinity in units of C and d, and can be stably dissolved in In the developer, the occurrence of the swelling layer can be suppressed, and the unevenness of the side wall of the line can be reduced. However, these units have low acid diffusion inhibition ability, which causes acid diffusion during post-exposure heat treatment (Post*Exposure*Back; PEB), which causes exposure dependency and density dependence. The shortcomings of performance deterioration such as photomask fidelity. The inventors of the present invention have made intensive efforts to solve this problem -14 - 1375122', and it has been found that a derivative of a 5,3,3,3-pentafluoropropanesulfonic acid derivative having a high bulk density partial structure or a functional group can be obtained. a diffusing acid which is highly suitable for use as an acid generator as represented by the above formula (2) in which an acid is generated, and a repeating compound represented by the above formula (1) As a result of the combination of the polymer compounds of the unit, a photoresist material having excellent line sidewall uniformity and analytical performance can be obtained, and thus the present invention has been completed.

Specific examples of the preferred composition of the resin component (A) are exemplified below

But it is not limited to this. 【化6】

(S> -15- 1375122 [Chem. 7]

<s> -16- 1375122

The weight average molecular weight of the resin component (A) of the present invention is preferably from 0.001 to 30,000, particularly preferably from 2,0 Å to 30,000, in terms of polystyrene conversion by osmotic chromatography analysis (GPC). Further, the resin component (A) can be obtained by copolymerizing each repeating unit (month) (meth) acrylate derivative monomer by a radical polymerization method or the like, and any of the polymer compounds of the examples described later can be used. The (meth) acrylate derivative which can be used is polymerized and synthesized by a general method such as radical polymerization. In the case of a compound which induces an active light or a radiation to generate an acid ( -17 - according to the knowledge of the gel 1,000, regardless of the body), 1375122 is preferably a specific example of the composition, for example, but is not limited thereto. this.化化9]

< S > -18 - 1375122 [Chemical 1 ο]

In the photoresist of the present invention, in addition to the resin component (A) formed by the high molecular compound represented by the above formula (1), another resin component may be further added. The other resin component different from the resin component (A), for example, the weight average molecular weight represented by the following formula (R1) and/or the following formula (R2) is 〇〇〇~1〇0,000, It is preferably a polymer compound of 3,000 to 30,000, etc., but is not limited thereto. Further, the above weight average molecule <S> -19-1375122

The amount refers to the polystyrene conversion obtained by gel permeation chromatography (GPC)値

(R2) wherein rG()1 is a hydrogen atom, a methyl group or a ch2co2rQ()3. RQQ2 is a hydrogen atom, a methyl group or a C02RM3. RQQ3 is a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. Specifically, for example, methyl, ethyl, propyl, isopropyl, η-butyl, sec-butyl, tert-butyl, tert-pentyl, η-pentyl, n-hexyl, cyclopentyl, Cyclohexyl, ethylcyclopentyl, butylcyclopentyl, ethylcyclohexyl, -20-1375122 butylcyclohexyl, adamantyl, ethyladamantyl, butylhydroxyalkyl, etc.

RM4 is a hydrogen atom or a monovalent hydrocarbon group having a carbon number of 1 to 15, which is selected from a fluorine-containing substituent, a carboxyl group and a hydroxyl group, and specifically, for example, a hydrogen atom, a carboxyethyl group, a carboxybutyl group, or a carboxycyclopentane group. Carboxylcyclohexyl, carboxynorbornyl, carboxyadamantyl, hydroxyethyl, hydroxybutyl, hydroxycyclopentyl, hydroxycyclohexyl, hydroxynorbornyl, hydroxyadamantyl, [2,2, 2 _Trifluoro_ 1 _hydroxy-l-(trifluoromethyl)ethyl]cyclohexyl, bis[2,2,2-trifluoro-l-hydroxy-l-(trifluoromethyl)ethyl]cyclo Heji and so on. At least one of R〇〇5 to Ro〇8 is a carboxyl group, or a monovalent hydrocarbon group having a carbon number of 1 to 15 and having at least one selected from a fluorine-containing substituent 'carboxyl group and a hydroxyl group, and the other are independent hydrogen atoms. Or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, and a specific number of monovalent hydrocarbon groups having 1 to 15 carbon atoms selected from a fluorine-containing substituent, a carboxyl group and a hydroxyl group, for example, a carboxyl group. Methyl, carboxyethyl, carboxybutyl, hydroxymethyl, hydroxyethyl, hydroxybutyl, 2-carboxycarbonylcarbonyl, 4-carboxybutoxycarbonyl, 2-hydroxyethoxycarbonyl, 4-hydroxybutoxycarbonyl Carboxycyclopentyloxycarbonyl, carboxycyclohexyloxycarbonyl, carboxynorbornyloxycarbonyl, carboxyadamantyloxycarbonyl, hydroxycyclopentyloxycarbonyl, hydroxycyclohexyloxycarbonyl, hydroxynorbornyloxy Carbonyl, hydroxyadamantyloxycarbonyl, [2,2,2-trifluoro_1-hydroxy-1-(trifluoromethyl)ethyl]cyclohexyloxycarbonyl 'bis[2,2,2-trifluoro-1 —Hydroxy-l-(trifluoromethyl)ethyl]cyclohexyloxycarbonyl and the like. Specific examples of the linear, branched or cyclic alkyl group having 1 to 15 carbon atoms are the same as those shown in RM3. -21 - 1375122 R005 to R008 (two of which, for example, R0.5 and R006, R006 and R0()7, Ro〇7 and R〇〇8, etc.) may be bonded to each other and form a carbon atom bonded thereto. Ring, at this time, at least one of RflQ8 is a divalent hydrocarbon group having a carbon number of 1 to 15 containing at least a fluorene group selected from a fluorine-containing substituent, a carboxyl group, and a hydroxyl group, and the other portions are independent single bonds, A hydrogen atom,

Or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms. a divalent hydrocarbon group having at least one selected from the group consisting of a fluorine-containing substituent, a carboxyl group and a hydroxyl group, and having, for example, a group having at least one selected from a fluorine-containing substituent, a carboxyl group and a hydroxyl group; The one exemplified in the case of the monovalent hydrocarbon group is one hydrogen atom removed; the specific one of the linear, branched or cyclic alkyl group having 1 to 15 carbon atoms is exemplified by R^3. RQQ9 is a monovalent hydrocarbon group having a C02-partial structure having a carbon number of 3 to 15, specifically, for example, 2-ketooxaoxapenta-3-yl, 4,4-dimethyl-2-ketooxyl Heteroquinone- 3-yl, 4-methyl-2-keto-oxo-4-yl, 2-keto-1,3-dioxapentacyclyl 4-yl, 5-methyl-2-di Oxygen quinone ring 5-base and the like. At least one of R〇" to R013 is a monovalent hydrocarbon group having a carbon number of 2 to 15 containing a -C02-partial structure, and each of the other independently is a hydrogen atom or a linear, branched or cyclic carbon number of 1 to 15. An alkyl group; a carbon number of 2 to 15 containing a -C02-partially structured monovalent hydrocarbon group, which is specifically, for example, 2-ketooxaoxapenta-3-yloxycarbonyl, 4,4-dimethyl-2-( Ketoyloxapenta-3-yloxycarbonyl, 4-methyl-2-keto-oxo-cyclo-4-yloxycarbonyl, 2-carbonyl-1,3-dioxapenta-4-ylmethyl Oxycarbonyl, 5-methyl-2-oxooxaoxapenta-5-yloxycarbonyl, and the like. The linear form of -22 to 1375122 having a carbon number of 1 to 15, a branched or cyclic alkyl group, and specific examples thereof are the same as those shown.

R〇丨〇 to R013 (two of them, for example, R0丨0 and R0丨丨, R01 1 and Rfll2, R()l2 and RG13, etc.) may be bonded to each other and form a ring together with the carbon atoms bonded thereto. At least one of RQ1Q to R°13 is a divalent hydrocarbon group having a carbon number of 1 to 15 containing a -C02-partial structure, and the others are each a single bond, a hydrogen atom or a linear chain having a carbon number of 1 to 15, a branched or cyclic alkyl group; a carbon number of 1 to 15 containing a -C02-partially structured divalent hydrocarbon group, which is specifically, for example, a monoketo-2-oxopropane-1,3-diyl group, 3-diketo-2-oxapropane-l,3-diyl, 1-keto-2-oxobutane-1,4-diyl, 1,3-dione- 2-oxo In addition to the butane-1, 4-diyl group and the like, for example, a substituent obtained by removing one hydrogen atom from the substituent exemplified in the above-mentioned monovalent hydrocarbon group having a -C02-part structure: carbon number 1 to 15 A specific example of the linear, branched or cyclic alkyl group as shown in R^3 is a content in which one hydrogen atom is removed. R014 is a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group having a polycyclic hydrocarbon group, and specifically, for example, norbornyl group, bicyclo[3.3.1]fluorenyl group, tricyclo[5.2.1.02'6]癸Alkyl, adamantyl, ethyladamantyl, butyl myristyl, norbornylmethylmethyl, adamantylmethyl, and the like. RG15 is an acid labile group, and specific examples thereof will be described later. RQ 16 is a hydrogen atom or a methyl group. RG 17 is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, specifically, 'for example, methyl group, ethyl group, propyl group, isopropyl group, η-butyl group, sec-butyl group, Tert — butyl, tert-pentyl, η-pentyl, η-hexyl

<S -23- 1375122, cyclopentyl, cyclohexyl and the like. X is -ch2 or an oxygen atom. k is 0 or 1. The acid labile group of R 5 can be variously selected, for example, a group which can be deprotected by an acid generated by an acid generator described later, and a conventional photoresist material can be used, in particular, an enhanced chemical type light. Any of the well-known acid-labile groups used in the resist material, specifically, for example, a group represented by the following formulae (L1) to (L4 φ), a tetraalkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms. The alkyl group is a trialkylsulfonyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, and the like. [1 2]

In the above formula, the broken line is a link key. In the formula (L1), Rlgi and RL()2 are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10, specifically, for example, a hydrogen atom, a methyl group or a methyl group. Base, propyl, isopropyl 'n-butyl, sec-butyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, η-octyl, adamantyl, etc.; R1^3 a monovalent hydrocarbon group, a linear, branched or cyclic alkyl group having a carbon number of 1 to 18, preferably 1 to 10, which may contain a hetero atom such as an oxygen atom, or a part of a hydrogen atom thereof <S> -24- 1375122 may be substituted by a hydroxyl group, an alkoxy group, an oxo group, an amine group, an alkylamine group, a linear, branched or cyclic alkyl group, for example, with the above rL01, Rm For the same content, a substituted alkyl group such as the following group or the like is used. 【化1 3】

OH

-OH ---

RL01 and RL02, RLG1 and RLG3, and RLG2 and RL03 may be bonded to each other and form a ring together with the carbon or oxygen atom to which they are bonded. In the case of forming a ring, 'RLQ1, RLQ2, and RLG3 are carbon numbers 1 to 18, respectively. Preferably, it is a linear or branched alkyl group having a carbon number of 1 to 10. In the formula (L2), RLQ4 is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15, and each alkyl group is a trialkylsulfanyl group having 1 to 6 carbon atoms, carbon.

a oxoalkyl group of 4 to 20 or a group represented by the above formula (L1); specific examples of the tertiary alkyl group such as tert_butyl, tert-pentyl, 1,1-diethylpropyl, 2-cyclopentyl基丙院一2_基, 2-cyclohexylpropyl propyl 2-base, 2 - (bicyclo[2.2.1] Gengyuanyi 2-base) 丙院一二_基, 2—(金刚院-1 _ base) propane-2-yl, 2-(tricyclo[5_2.1.02,6]decyl-8-yl)propane_2_yl, 2_(tetracyclo[4.4.0.12,5.17'|()]12 Cyclo-3-yl)propane-2-yl, 1-ethylcyclopentyl, 1-butylcyclopentyl, 1-ethylcyclohexyl, 1-butylcyclohexyl, 1-ethyl-2-cyclohexyl Sodium, 1-ethyl-2-cyclohexenyl, 2-methyl-2-alantayl, 2 —

< S Ethyl-2-Adamantyl, 8-methyl-8-tricyclo[5.2.1_〇2>6]decyl-25- 1375122, 8-ethyl-8-tricyclic [5· 2_1·02,6] fluorenyl, 3-methyl- 3 -tetracyclo[4.4.0·12'5·17'|()] dodecyl, 3-ethyl- 3 -tetracyclic [HO. L2'5. 〗 7'1" dodecyl group and the like, a trialkylsulfanyl group, specifically exemplified by a trimethyl decyl group, a triethyl decyl group, a dimethyl _ tert - butyl fluorenyl group, etc. Specific examples of the oxoalkyl group are, for example, 3-oxocyclohexyl, 4-methyl-2-oxooxane-4-yl, 5-methyl-2-oxocyclopentane-5-yl, etc. It is an integer of 〇~6.

In the formula (L3), RLG5 is a linear, branched or cyclic alkyl group which may be substituted with a carbon number of 1 to 1 Å or an aryl group which may be substituted with a carbon number of 6 to 20, which may be substituted. Base, for example, methyl, ethyl, propyl, isopropyl, η-butyl, sec-butyl, tert-butyl, tert-pentyl, η-pentyl, η-hexyl, cyclopentyl, ring a linear, branched or cyclic alkyl group such as a hexyl or bicyclo[2.2.1]heptyl group, a part of which may be a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an oxo group or an amine group. a group substituted with an alkyl group, an alkylamino group, a cyano group, a thiol group, an alkylthio group, a sulfo group, or the like, or a part of a methyl group thereof may be substituted by an oxygen atom or a sulfur atom; an aryl group which may be substituted Specific examples thereof include a phenyl group, a methylphenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, an anthryl group and the like m is 0 or 1, and η is any one of 〇, 1, 2, 3, and is a number satisfying 2m + n = 2 or 3. In the formula (L4), RU6 is a linear, branched or cyclic alkyl group which may be substituted with a carbon number of 1 to 1 Å or an aryl group which may be substituted with a carbon number of 6 to 20, which is specifically, for example,妒05 the same content. RLQ7 to R1·16 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 15 carbon atoms, specifically, for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an η-butyl group, and a sec group.

< S -26-

1375122 butyl tert-butyl 'tert — pentyl, η-pentyl, η--hexyl 3 octyl η-fluorenyl, η fluorenyl, cyclopentyl, cyclohexyl, cyclopentacyclopentyl, ring a linear, branched or cyclic alkyl group of pentylbutyl, cyclohexylmethyl, cyclohexylcyclohexyl, a hydrogen atom thereof, a partial alkoxy group, a carboxyl group, an alkoxycarbonyl group, an oxo group 'Amine', substituted by cyano, thiol, alkylthio, sulfo, etc. 1 rL07 Two of them can be bonded to each other and form a carbon atom with their bond, for example, 9 RL07 and RL08, rL07 and RL09 , rlo 8 and R1 -1 〇% Rl 10 > rL11 and RL1 2, rL13 and rl, 14 etc.) > At this time, the base associated with the formation is a divalent hydrocarbon group having a carbon number of 1 to 15, specific example In the case where the monovalent hydrocarbon group is exemplified, the one obtained by removing one hydrogen atom, rUW to Ru6, can be bonded to the adjacent carbon to form a double bond without forming a bond (for example, RLQ7 and rl(), rL()9 and RL13 and RL15, etc.). In the acid labile group represented by the above formula (L1), specific examples of the linear or substituent are, for example, the following groups. Methyl, butyl, etc. may be hydroxyamino group to Rl" ring (RL 〇 9 and ring form as above: again, other original RL15, branched [Chemical 1 4]

<S > -27- 1375122 Specific examples of the cyclic substituent in the acid labile group represented by the above formula (L1), for example, tetrahydrofuran-2-yl, 2-methyltetrahydrofuran-2-yl, tetrahydropyran 2_yl, 2-methyltetrahydropyran-2-yl and the like.

Specific examples of the acid labile group represented by the above formula (L2) include, for example, tert_y oxycarbonyl, tert-butoxycarbonylmethyl, tert-pentyloxycarbonyl, tert-pentyloxycarbonylmethyl, 1,1-diethylpropoxy Carbonyl, 1;1-diethylpropoxycarbonylmethyl, 1-ethylcyclopentyloxycarbonyl, 1-ethylcyclopentyloxycarbonylmethyl, 1-ethyl-2-cyclopentenyloxycarbonyl丨-ethyl-2_cyclopenteneoxycarbonylmethyl, 1-ethoxyethoxycarbonylmethyl ' 2 -tetrahydropyranyloxycarbonylmethyl, 2-tetrahydrofuranoxycarbonylmethyl and the like. Specific examples of the acid labile group represented by the formula (L3) are, for example, 1-methylcyclopentyl, oxime-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 丨-sec-butylcyclopentyl, 1-cyclohexylcyclopentyl, 1-(4-methoxybutyl)cyclopentyl, 1-(bicyclo[2.2. 1] heptane-2-yl)cyclopentyl, 1-(7-oxabicyclo[2.2.1]heptane-2-yl)cyclopentyl, 1-methylcyclohexyl, 1-ethylcyclo Hexyl, 1-methyl-2-cyclopentenyl, indenyl-2-cyclopentenyl, 1-methyl-2-cyclohexenyl, 1-ethyl-2-cyclohexenyl, and the like. Specific examples of the acid labile group represented by the above formula (L4) are preferably those represented by the following formulas (L4·1) to (L4-4). [化1 5]

(U->) (L4-2) (L4-3) (L44) -28 1375122 In the above formula (L4-1) to (L4-4), the broken line is a bond. The bonding direction. RL41 each independently represents a monovalent hydrocarbon group such as a linear branched or cyclic alkyl group having a carbon number of 1 to 1 Å, and specific examples thereof include methyl 'ethyl, isopropyl, η-butyl, sec-butyl, tert- Butyl, tert, η-pentyl, η-hexyl, cyclopentyl, cyclohexyl and the like. The above formula (L4-1)~(L4-4) may be mirrored as an isoenomer or a diastereomer exists. φ The above formula (L4-l)~(L4-4) represents the stereoisomer The stereoisomers of the materials may be used singly or in the form of a mixture. For example, the above formula (L4-3) represents a formula selected from the group consisting of the following formulas (position and form, fraction, propyl-pentyl carbene (but all. L4-3-1)

And a mixture of one or two of the groups represented by (L4-3-2). 【化1 6】

(W-3-» (L4-3-2) The above formula (L4_4) represents one or a mixture of two or more selected from the group represented by the following formula (L4-4 L4-4_4). 1 7]

(L4-4-1)

(L4-4-4) The above formula (L4-1) (L4-4) L4-3-1) (L4-3- 2) and formula (L4-4-1) L4-4-4 1375122 enantiomer) Or mirror image isomer mixture. The above general formulae (L4-1) to (L4-4), (L4-3-1), (L4-3·

2) The bonding direction of the formula (L4-4-1)~(L4-4-4) is the exo side for the bicyclo[2.2.1] heptane ring, which can achieve high reaction of the acid catalyst desorption reaction. (Ref. JP-A-2000-336121). When a monomer containing a tertiary exo-alkyl group having the above-mentioned bicyclo[2 _2·1]heptane skeleton as a substituent is produced, it sometimes contains the following formula (L4-l-endo)~(L4-4- Endo ) The monomer substituted by the end 〇-alkyl group shown, but in order to achieve good reactivity, the exo ratio is preferably 50% or more, and the exo ratio is preferably 80% to ± (1)

(L4-l-cndo) (L4-2-endo) (L4-3-endo) (L44-endo)

The acid labile group of the above formula (L4) has, for example, the following group.

, Lu, households

Further, the tertiary alkyl group having 4 to 20 carbon atoms and each alkyl group each represent a trialkylsulfanyl group having 1 to 6 carbon atoms and an oxyalkyl group having 4 to 20 carbon atoms, for example, the same as those exemplified for RU4. . -30- 1375122 R〇16 is a hydrogen atom or a methyl group. 17 is a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Al, a2, ' a3, bl, b2', b3', cl', c2', c3', dl', d2', d3, and e' are 0 or more and less than 1, and are satisfied Al'+a2' + a3,+ bl,+ b2,+ b3,+ cl,+ c2,+ c3'+ dl'+ d2'+ d3' +

e, = l. f, g, h, i, j, 〇,, P, is the number less than 1 above 〇, and satisfies f'+g'+h'+i' + j, + 〇' + P'=l. X', y, and Z are integers of 〜 〜3 and satisfy l$x'+y'+z'S5, lSy'+z'$3. Each of the repeating units (R1) and (R2) can be simultaneously introduced into two or more types. Each repeating unit can adjust its performance when used as a photoresist material when using a complex unit. Further, when the sum of the above units is 1, it means that the total amount of the repeating units in the polymer compound containing each repeating unit is 100% by mole based on the total of the repeating units. An example of a specific example in which the composition ratio al is introduced in the above formula (R1) and the repeating unit in which the composition ratio f' is introduced in the formula (r2) is as follows, but is not limited thereto. [化2 0]

< S > -31 - 1375122 [Chem. 2 1]

(V4> (V|) (V-^ (V^ H )=0 H >=0 H )=0 H )=0 HO 0 0 0 H (10 H(+ p ) >-cf3 ) f3C f3c Hf2c cf2 f2c-cf2 h corpse <:s >-CF3

F2C

c rVCF2H F3C 〇H

Ho p3C 〇HF3

H

H

0 F

In the above formula (R1), a specific example of the introduction of the repeating unit of the composition ratio bl' is as follows, but is not limited thereto.

(S -32- 1375122 [Chem. 2 2]

c. S> -33- 1375122

[Chem. 2 4]

An example of a specific example in which the composition ratio d1' is introduced in the above formula (R1) and the repeating unit in which the composition ratio g' is introduced in the formula (R2) is as follows, but is not limited thereto. (S > -34- 1375122

[化2 6] Η / Η / bamboo ο (^〇 。; 〇 °ρ

< S > -35- 1375122 [Chem. 2 7]

[化2 8]

1375122 [Chemical 2 9]

In the above formula (R1), the polymer compound composed of the repeating units of the composition ratios of al', bl', cl', and dl' is specifically exemplified below, but is not limited thereto. (5 > -37- 1375122 [Chemical 3 Ο]

-38- 1375122 [Chem. 3 1]

(S > -39- 1375122 [Chem. 3 2]

<s> -40 - 1375122 [Chemical 3 3]

In the above formula (R1), the polymer compound composed of the repeating units of the composition ratios a2', b2', c2', d2', and e' is specifically, for example, the following

For example, it is not limited thereto. [Chemical 3 4 I

-41 - 1375122 [Chem. 3 5]

<S > -42- 1375122 In the above formula (R1), the polymer compound composed of the repeating units of the composition ratios a3', b3', c3', and d3' is specifically exemplified below, but not Limited to this. [化3 7]

< S > -43- 1375122

[化3 8]

The polymer compound of the above formula (R2) is specifically exemplified below, but is not limited thereto. -44- 1375122 [Chem. 3 9]

The amount of addition of the other polymer compound different from the above (A) is preferably from 〇 to 80 parts by mass, more preferably from 0 to 80 parts by mass, based on 100 parts by mass of the total of the resin component (A) of the present invention. ~60 parts by mass, preferably 0 to 50 parts by mass. In the case of addition, it is preferably 20 parts by mass or more, particularly preferably 30 parts by mass or more. When the amount of the other polymer compound added is too large, the resin component (A) of the present invention may not exhibit the characteristics of -45 to 1375122, which may cause problems such as lowering the resolution or deteriorating the shape of the pattern. In addition, the other polymer compound is not limited to one type, and two or more types may be added. When a large number of polymer compounds are used, the properties of the photoresist material can be adjusted. In the photoresist of the present invention, the compound (B) which can induce active light or radiation to generate an acid, for example, may contain a component (B') other than the oxime compound represented by the above formula (2). The (B') component may be any compound which can generate an acid by irradiation with a high-energy line, and may use a conventional photoresist φ material, in particular, any known photoacid generator used for the reinforced chemical resist material. Can be. Preferred photoacid generators are, for example, phosphonium salts, iodine salts, sulfonyldiazomethane, N-sulfonyloxyimide, anthracene-sulfonate type acid generator, and the like. It will be described in detail below, and it may be used alone or in combination of two or more. The phosphonium salt is a salt of a phosphonium cation and a sulfonate or a bis(substituted alkylsulfonyl) quinone imine, a tri(substituted alkylsulfonyl)methyl metal, and the phosphonium cation is, for example, triphenylsulfonium (4 tert). Butoxyphenyl)diphenylhydrazine 'bis(4_tert φ-butoxyphenyl)phenylhydrazine, tris(4-tert-butoxyphenyl)fluorene, (3_tert-butoxyphenyl)diphenylhydrazine, bis( 3-tert-butoxyphenyl)phenylhydrazine, bis(3-tert-butoxyphenyl)anthracene, (3,4-di-tert-butoxyphenyl)diphenylhydrazine, bis(3,4_ditert- Butyloxyphenyl)benzoquinone, tris(3,4-ditert-butoxyphenyl)anthracene diphenyl (4-thiophenoxyphenyl) • fluorene, (4_tert — butoxycarbonyl methoxyphenyl Diphenyl hydrazine, tris(4_tert. monobutoxycarbonylmethoxyphenyl) fluorene' (4-tert-butoxyphenyl) bis(4-dimethylaminophenyl) fluorene, tris(4-dimethylamine) Phenyl) fluorene, 2_naphthyl-this mirror'-methyl (2-Caiji) vegetable, 4-Zhao phenyl dimethyl hydrazine, 4 -46-

1375122 monomethoxyphenyl dimethyl hydrazine, trimethyl hydrazine, 2-oxocyclohexylmethyl hydrazine, trinaphthyl fluorene, trityl hydrazine, diphenylmethyl mirror, phenyl hydrazine , 2-oxo-2-phenylethylthiolane, 4-oxynaphthyl-1-thione, 2-n-butoxynaphthyl-1, cyclopentyl, etc., sulfonate The acid esters are, for example, trifluoromethanesulfonate, pentafluoroethane ester, nonafluorobutanesulfonate, dodecafluorohexanesulfonate, pentafluoro perhexanesulfonate, heptadecafluorooctanesulfonic acid. Ester, 2,2,2-trifluoroethane ester, pentafluorobenzenesulfonate, 4-(trifluoromethyl)benzenesulfonate, 4-sulfonate, mesityl mesylate, 2, 4,6-triisopropylbenzenesulfonate, tosylate, benzenesulfonate, 4_(4'-toluenesulfonate sulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate , dodecyl sulfonate, butane sulfonate, methane sulfonate, 2-benzylidene oxide 1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3, 3 - pentafluoro-2-phenylphenyl fluorenyloxypropane sulfonate, 1,1,3,3,3-pentafluoro-2methylethoxypropane sulfonate, 2-cyclohexyl Alkyl carbonyl 1,1,1,pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furanyl propane sulfonate, 2-naphthyloxyl-1,1,3, 3,3 -pentafluoropropane sulfonate, 2 - ( 4 - tert - butyl benzhydryloxy)-1,1,3,3,3_ pentadecane sulfonate, 2-adamantanecarbonyloxy-1 1,3,3,3-pentafluoropropane ester, 2_acetamoxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,-pentafluoro-2-hydroxypropane sulfonic acid Ester, 1,1,3,3,3-pentafluoro-2,sulfonyloxypropanesulfonate, 1,1-difluoro-2-phenylnaphthalene-ethanesulfone, 1,1,2,2_ Four gas _2—(Ice film institute 2-2 base) B hospital to open acid 1,1,2,2-tetrafluoro- 2_(four-ring [4.4.0.12'5.17'1()] twelve one 3 - ring Hexyl dimethyl n-butyl sulfonate fluorocyclo sulfonate fluorobenzoate phenylalkyl one: 4- 3.3.3 oxyester fluoropropane sulfonic acid 3.3.3 toluate ester, ene _ -47- 1375122 8-alkyl)ethanesulfonate, etc., bis(substituted alkylsulfonyl) quinone imide, for example, bistrifluoromethyl fluorinated imine, bis(pentafluoroethylsulfonyl) fluorene Amine, bis(heptafluoropropylsulfonyl) quinone imine, perfluoro(U-propylene Sulfo acyl) (PEI) and the like, tris (substituted alkylsulfonyl) methyl embodiment, if the metal base acyl methyl trifluoromethane metal, sulfonium salts of the combination.

The iodine salt is a salt of an iodine cation with a sulfonate or a bis(substituted alkylsulfonyl) quinone imine or a tri(substituted alkylsulfonyl)methyl metal, and the aryl iodine gun cation has, for example, a diphenyl group. Iodine gun, bis(4-tert-butylphenyl) iodine gun, 4-tert-butoxyphenyl phenyl iodide, 4-methoxyphenyl phenyl iodide, etc. Acid esters such as trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, dodecafluorohexanesulfonate, pentafluoroethyl perfluorocyclohexanesulfonate, ten Heptafluorooctane sulfonate, 2,2,2-trifluorobenzate, acid ester, pentafluorobenzene, vinegar, 4-(trifluoromethyl)benzene, acid ester, 4-fluorobenzenesulfonate, Mesitylene sulfonate, 2,4,6-triisopropylbenzenesulfonate, tosylate, benzenesulfonate, 4_(4-toluenesulfonyloxy)benzenesulfonate, naphthalene Acid ester, camphor sulfonate, Xinyuan vinegar, dodecyl benzene sulfonate, butane sulfonate, methane sulfonate, 2_benzhydryloxy 1, 1, 3, 3, 3 —Pentafluoropropane sulfonate, im] — pentoxide — 2 — (4-phenylbenzyl methoxy) propane sulfonate 1,1,1,15,5,5,5,3-trifluoroethoxypropane sulfonate, 2 -cyclohexane methoxy _ 1,1,3,3,3 - pentafluoropropane vinegar , 丨, 1,3,3,3—five gas _2—furanyl methoxypropane sulfonate, 2-naphthyloxyl-1,3_pentafluoropropane sulfonate' 2- ( 4 — tert _ Butylbenzhydryloxy)-pentafluoropropane sulfonate, 2-adamantanecarbonyloxy_1, m3-penta-48-

1375122 Propane sulfonate, 2-ethoxycarbonyl-1,1,3,3,3-pentafluoropropane 1,1,3,3,3—five gas—2 — Tosyloxypropane sulfonate, 1,1 difluoro-2-ethane sulfonate ' 1,1,2,2-tetrafluoro-2-(norbornane-2 alkane sulfonate, 1, 1,2,2-tetrafluoro- 2 - (tetracyclo [4.4.0.l2: di- 3 - ene-8-yl)ethanesulfonate, etc. 'bis(substituted alkane) quinone imide, for example, double three Fluoromethylsulfonyl quinone imine, bis(sulfonyl) quinone imine 'bis(heptafluoropropylsulfonyl) quinone imine 1,3 - propylene bissulfonyl) quinone imine, etc., three ( Substituted alkylmethyl metal such as iodine salt of tris(trifluoromethylsulfonyl)methyl metal. Sulfhydryl diazomethane, for example, bis(ethyl fluorenyl) heavy double (1-methylpropyl) Sulfhydryl)diazomethane, bis(2-methylindenyl)diazomethane, bis(1,1-dimethylethylxanane, bis(cyclohexylsulfonyl)diazomethane, bis ( Perfluoroiso-yl)diazomethane, bis(phenylsulfonyl)diazide, phenylsulfonyl)diazomethane, double (2,4-12) Diphenylmethane, bis(2-naphthylsulfonyl)diazomethane, quinomethoxyphenylsulfonyl)diazomethane, bis(4-(methane)phenylsulfonyl)diazo Methane, bis(4-(4-toluene.phenylsulfonyl)diazomethane, bis(4-n-hexyloxy)benzene)diazomethane, bis(2-methyl-tetra-n-hexyloxyphenyl) Sulfomethane, bis(2,5-dimethyl-4-n-hexyloxyphenylsulfanyl methane, bis(3,5-dimethyl-4-cyclohexyloxyphenylsulfonate, ί, 3 —pentafluoro-naphthyl —yl”ethyl 5.17,10]decylsulfonylpentafluoroethyl, perfluoro(sulfonyl), the combined nitrogen methane, propyl sulfonyl)diazopropylsulfonate ( 4-Methylsulfonyl f (4-ethylsulfonyloxyoxy) sulfonyl fluorenyl) hydrazino) hydrazino) -49- 1375122 Nitrogen methane, double (2-A 5-A-5-isopropyl-4-yl-n-hexyloxyphenylsulfonyl)diazomethane, 4-methylphenylsulfonylbenzoyldiazomethane, tert-butylcarbonyl-4-methylbenzene Sulfonamide diazomethane, 2_naphthylsulfonylphenylhydrazinyl diazomethane, 4 - Bisulphonyl sulfonyl 2,naphthyl fluorenyl diazomethane, methylsulfonyl phenyl hydrazinyl diazomethane, tert-butoxy fluorenyl 4-methylphenyl fluorenyl diazomethane Diazomethane and sulfonylcarbonyl diazomethane.

N-sulfonyloxydicarboxy quinone imine type photoacid generator, for example, yttrium succinimide, naphthalene dicarboxy quinone imine, phthalimide phthalimide, cyclohexyl dicarboxy quinone imine, 5-nor Borneene- 2,3-dicarboxyarsenine, 7-oxabicyclo[2.2.1]-5-heptene-2,3-dicarboxyarmine, etc. Acid ester, pentafluoroethane sulfonate, nonafluorobutane sulfonate, dodecafluorohexane sulfonate, pentafluoroethyl perfluorocyclohexane sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-(trifluoromethyl)benzenesulfonate, 4-fluorobenzenesulfonate, mesitylene sulfonate, 2 , 4,6-triisopropylbenzenesulfonate, tosylate 'benzenesulfonate, naphthalenesulfonate, camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, D Alkane sulfonate, methane sulfonate, 2-benzoquinone-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2 — 4-phenylphenoxyoxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-pentane oxypropane sulfonate, 2-cyclohexanecarbonyloxy-1 1,3,3,3 - pentafluoropropane compound, 1,1,3,3,3-pentafluoro-2-furanyloxypropane sulfonate, 2-naphthyloxy-1,1 ,3,3,3-pentafluoropropane sulfonate, 2-(4-tert-butylphthalideoxy)-1,1,3,3,3-pentafluoropropane sulfonate, 2-adamantane ore oxygen

(S -50-1375122 base_1,1,3,3,3-pentafluoropropane sulfonate, 2-ethoxycarbonyl-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro- 2_ mercaptopropane sulfonate, 1,1,3,3,3-pentafluoro-2-methyloxypropane sulfonate, 1,1 Difluoro-2-naphthyl-ethanesulfonate, 1,1,2,2-tetrafluoro-2-(norbornane-2-yl)ethanesulfonate, 1,1,2,2- A compound such as tetrafluoro-2-(tetracycline [4.4.0_12'5.17'1()]dodecane-3-ene-8-yl)ethanesulfonate or the like.

The benzoin sulfonate type photoacid generator may, for example, be benzoin tosylate, benzoin mesylate or benzoin butanesulfonate. The pyrogallol trisulfonate photoacid generator is, for example, pyrophenol, fluoroaminoethane alcohol, catechol, resorcinol, hydroquinone, all of the hydroxyl groups are trifluoromethanesulfonate, Pentafluoroethane sulfonate, nonafluorobutane sulfonate, dodecafluorohexane sulfonate, pentafluoroethyl perfluorocyclohexane sulfonate, heptadecafluorooctane sulfonate, 2,2 , 2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4_(trifluoromethyl)benzenesulfonate, 4-fluorobenzenesulfonate, tosylate, benzenesulfonate, naphthalene Acid ester, camphor sulfonate, octane sulfonate, dodecylbenzene sulfonate, butane sulfonate, methane sulfonate, 2-benzoyloxy-1, 1, 3, 3, 3 - pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-(4-phenylphenoxy)propane sulfonate, 1,1,3,3,3-pentafluoro —2—pentamethoxypropane sulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro- 2 -furanoxypropane sulfonate, 2-naphthyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 2-(4-tert-butylphthalideoxy)-1 1,3,3 , 3 - pentafluoropropane sulfonate, 2-(1_adamantanecarbonyloxy)-1,1,3,3,3-pentafluoropropane sulfonate, 2-ethyloxy group

-51 - 1375122 1,1,3,3,3 - pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3, 3_pentafluoro-2-pyridyloxypropane sulfonate, 1,1 difluoro-2-naphthyl-ethanesulfonate, 1,1,2,2-tetrafluoro-2 (norborn) Alkan-2-yl)ethanesulfonate, 1,1,2,2-tetrafluoro-2-(tetracycline [4.4.0.12, 5.17'1Q]dodecane-3-ene-8-yl) a compound substituted with an alkanesulfonate or the like. A nitrobenzyl sulfonate type photoacid generator such as 2,4-dinitrobenzyl

Specific examples of sulfonate, 2-nitrobenzyl sulfonate, 2,6-dinitrobenzyl sulfonate, sulfonate are trifluoromethane sulfonate, pentafluoroethane sulfonate, and nine Fluorane sulfonate, dodecafluorohexane sulfonate, dodecafluorohexane sulfonate, pentafluoroethyl perfluorocyclohexane sulfonate 'heptadecafluorooctane sulfonate, 2, 2 , 2_trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4_(trifluoromethyl)benzene acid vinegar, 4 fluorobenzene sulfonate, tosylate 'benzene sulfonate, naphthalene sulfonate Acid ester, camphor sulfonate, octane sulfonate, dodecyl benzene sulfonate 'butane sulfonate, methane sulfonate, 2 phenyl hydrazine pentafluoropropyl k sulfonate, 1,1 ,3,3,3~~pentafluoro-2_(4-phenylphenoxy)propane sulfonate, 1,1,3,3,3~pentafluoro-2-pentopenoxime. , 2 - Cyclohexain oxime - nns pentafluoropropane sulfonate, 1,1,3'3,3 -pentafluoro-2-furanyloxypropane sulfonate, 2_naphthyloxyl-1 , 1,3,3,3 - pentafluoropropane sulfonate, 2_(4_tert-butylphthalideoxy)-1,1,3,3'3-pentafluoropropane sulfonate, 2-adamantanecarbonyloxy a 1,1,3,3,3-pentafluoro Alkane sulfonate, 2_acetoxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3~pentafluoro-2-hydroxypropane sulfonate 1, 1,3,3,3 -pentafluoro-2-methoxypropane sulfonate < S) -52- 1375122 -2 -naphthyl-ethanesulfonate, 1,1,2,2_4 Fluorine-2~(norbornium垸2-yl)ethanesulfonate, 1,1,2,2-tetrafluoro-2-(tetracycline[4,4.0.12,5.1^]dodecane-3 A dilute 8-octyl)ethanesulfonate or the like. Further, it is also possible to use a nitro group on the benzyl group side as a trifluoromethyl group. The sulfonic acid type photoacid generator may, for example, be bis(phenylsulfonyl)methine or bis(4-methylphenylsulfonyl)methane 'bis(2-naphthylsulfonyl)).

2,2-bis(phenylsulfonyl)propane, 2,2-bis(4-methylphenylpropionic acid)propane, 2,2-bis(2-naphthalenesulfonyl)propane, 2_A Base-2((Ρ-toluenesulfonyl)propiophenone, 2_(cyclohexylcarbonyl)_2_(Ρ-toluenesulfonyl)propane, 2,4-dimethyl-2-(ρ-toluene acid extension) Wuyuan - 3-ketone and so on. The photo-acid generator of the bismuth-derivative type is, for example, a compound described in the Japanese Patent Publication No. 2 9 〇 6 9 9 9 or 曰 特 特 9 9 9 9 9 9 9 9 9 9 , , , , , 9 9 9 9 9 9 9 9 9 9 9 9 9 9 〇_(p-toluenesulfonyl)-a-dimethylglyoxime and octadecyl-p-(p-toluenesulfonyl)-diphenylethene, bis-o-p-toluene Sulfhydryl)-dicyclohexylethylenediazine, bis-indole-(p-toluenesulfonyl)- 2,3-pentanedione ethanedioxime, bis-indole-(n-butanesulfonyl)_α_ Dimethylglyoxime, bis-〇_ (Zheng Dingyuan expansion base)-α-diphenylethylenediguanidine, bis-indenyl (n-butanesulfonate)-dicyclohexylethylenedifluoride, double a 0-(methanesulfonyl) a hydrazine: — _methyl ethane oxime, bis 〇 〇 ((trifluoromethanesulfonyl)-α-monomethyl hydrazine, double _ 〇 one (2, 2j_ _Trifluoroethane sulfonyl) — a —methyl 乙一陌,双一〇 _ (丨〇-樟脑醯)

<S-53- 1375122 肟1 2 乙 I 基 、 、 、 苯 氟 双 双 双 双 双 双 双 双 双 双ο p-Methyl sulfonate di C A-fluoro octyl α 醯 I sulfonate} Phenyl sulfonium fluorobenzene trimethylhexyl fluorene - (二双-乙, ο 肟 肟 I 甲二二二乙, I base肟α-di-di-dione C-based I 醯ο sulfo-benzene bis-C, βο-di-keto bis-bis, hexamethylene ketone ketone hexyl sulfonate sulfonate sulfonate 2 : 2' 樟ο I double ' ketone diketone dihexyl} methyl fluoro sulfonium trisulfonate benzene (methyl bis- (-- double ο ' I 肟 diketone oxime dihexanone ring di I hex > gt ; ring base | 醯> sulfobenzoquinone fluorosulfonate to benzene and other 0 dioxin ring

The oxime sulfonate described in the specification of U.S. Patent No. 6,004,724, especially, for example, (5-(4-toluenesulfonyl)indolyl-5H-thiophen-2-ylphenyl)phenylacetonitrile, (5-(10) - camphorsulfonyl) fluorenyl-5H-thiophene-2-ylphenyl)phenylacetonitrile, (5-n-octanesulfonylhydrazino-5H-thiophen-2-inyl)phenylacetonitrile, 5_(4_Toluenesulfonyl fluorenyl) fluorenyl _5H-thiophen-2-ylinyl) (2-methylphenyl) acetonitrile, (5-(10-camphorsulfonyl)fluorenyl-5H-thiophene —2-(2-phenylene)(2-methylphenyl)acetonitrile, (5-n-octanesulfonylhydrazinyl-5H-thiophen-2-inyl)-(2-tolyl)acetonitrile, etc., US patent No. 69 1 659 No. 1 (5-(4-(4-toluenesulfonyloxy)phenylsulfonyl)indolyl-5H-thiophen-2-inyl)phenylacetonitrile, (5-( 2,5-Bis(4-toluenesulfonyloxy)benzenesulfonyl)indenyl-5H-thiophene-2-ylphenyl)phenylacetonitrile. US Patent No. 626 1 73 8 specification, Japanese Special Opening -54- 1375122

The oxime sulfonate described in JP-A No. 2000-3 1 4956, in particular, for example, 2,2,2-trifluoro-1-phenyl-ethanone oxime-methylsulfonate, 2, 2, 2 -trifluoro- 1-phenyl-ethanone oxime-0-(10-camphoryl sulfonate), 2,2,2-trifluoro- 1 phenyl-ethanone oxime_0—(4-methoxy Phenyl sulfonate), 2,2,2-trifluoro-l-phenyl-ethanone oxime-0-(1-naphthyl sulfonate), 2,2,2-trifluoro-1-phenyl Ethyl ketone oxime_0_(2_naphthyl sulfonate), 2,2,2 _trifluoro-1 phenyl-ketone oxime-(2,4,6-trimethylphenyl sulfonate ), 2,2,2_trifluoro-1-(4-tolyl)-ethanone oxime-〇-(10-camphorsulfonate), 2,2,2-trifluoro-oxime-(4_ Methylphenyl)-ethanone oxime_0_(methanesulfonate), 2,2,2-trifluoro-1-(2-methylphenyl)-ethanone oxime-0-(10-樟-brain Sulfonate), 2,2,2-trifluoro-l-(2,4-xylphenyl)-ethanone oxime-one (10-camphorsulfonate), 2,2,2-trifluoro _1 —(2,4-dimethylphenyl)-ethyl ketone hired _0_ (1-naphthyl acid vinegar), 2,2,2_trifluoro-1—(2,4-xylphenyl) Ethyl ketone oxime 0_ (2-naphthalene Sulfonate), 2,2,2-trifluoro-1 - (2,4,6-trimethylphenyl)-ethanone oxime-oxime (10-camphorsulfonate), 2,2, 2-Trifluoro- 1 _ (2,4,6-trimethylphenyl)-ethanone oxime-indole — (1 _naphthyl sulfonate), 2,2,2-trifluoro- 1—(2 , 4,6-trimethylphenyl)-Ethyl ketone moon bow - (2-naphthyl acid vinegar), 2,2,2-dione- 1_(4-methoxyphenyl)-ethanone oxime -〇_Methanesulfonate, 2,2,2-trifluoro- 1 -(4-methylphenylthio)-ethanone oxime-methyl sulfonate, 2,2,2-trifluoro _1_(3,4-dimethoxyphenyl)-ethanone oxime_0-methanesulfonate, 2,2,3,3,4,4,4-heptafluoro-phenyl-butyl Ketone 肟-0—( -55- 1375122 10 — rod brain sulfonate), 2,2,2-difluoro-1-(phenyl)-ethoxime_0_methanesulfonate, 2, 2,2-trifluoro_1_(phenyl)-ethanone oxime-0-10-camphorsulfonate, 2,2,2-trifluoro-1-(phenyl)-ethanone oxime_〇_ ( 4-methoxyphenyl)sulfonate, 2,2,2-trifluoro

_1_(phenyl)-ethanone oxime-Ο-(1-naphthyl)sulfonate, 2,2,2-trifluoro_1_(phenyl)-ethanone oxime-0-(2-naphthyl)sulfonic acid Ester, 2,2,2-trifluoro-1-(phenyl)-ethanone oxime_0_(2,4,6-trimethylphenyl)sulfonate, 2,2,2-trifluoro-1 (4 monomethylphenyl) _ethanone oxime 〇 〇 ( (10 — camphoryl) sulfonate, 2,2,2-trifluoro_1 _ (4-tolyl)-ethanone oxime ___ Sulfonate, 2,2,2-trifluoro-1-(2-methylphenyl)-ethanone ketone- 0-(10-camphoryl) sulfonate, 2,2,2-trifluoro 1_(2,4-dimethylphenyl)-ethanone oxime-indole-(1-naphthyl)sulfonate, 2,2,2-trifluoro-1—(2,4-dimethylphenyl) )_e-ketone oxime 〇 (2-naphthyl) sulfonate, 2,2,2-trifluoro- 1 _ ( 2,4,6-trimethylphenyl)-ethanone oxime _ 0— ( 10 — camphoryl)sulfonate, 2,2,2-trifluoro-1-(2,4,6-trimethylphenyl)-ethanone oxime-(1-naphthyl)sulfonate, 2,2,2_trifluoro_1_(2,4,6-trimethylphenyl)-ethanone ketone-0-(2-naphthyl)sulfonate, 2,2,2_trifluoro-1_ (4-methoxyphenyl)-ethanone oxime_0_methanesulfonate, 2,2,2-trifluoro_1 (4_Methylthiophenyl)-ethanone oxime 〇 甲基 methanesulfonate, 2,2,2_trifluoro_1_(3,4-dimethoxyphenyl)-ethanone ketone oxime -methanesulfonate, 2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime_0-(4-tolyl)sulfonate, 2,2,2 — Trifluoro-1_(4-methoxyphenyl)-ethanone oxime-0-(

<S -56 - 1375122 4_Methoxyphenyl)sulfonate, 2,2,2-trifluoro-1-(4-methoxyphenyl)-ethanone oxime-〇- (4 ten Dialkylphenyl)sulfonate, 2,2,2-trifluoro-1,4-(4-methoxyphenyl)-ethanone oxime-octyl sulfonate, 2,2,2_3 Fluoryl-1_(4-methylthiophenyl)-ethanone oxime_〇_(4-methoxyphenyl)sulfonate, 2,2,2-trifluoro-1—(4

-Methylthiophenyl)-Ethylketoxime-〇-(4-dodecylphenyl)sulfonate, 2,2,2-trifluoro-1-(4-methylthiophenyl)-B Ketooxime- 0 octyl sulfonate, 2,2,2-trifluoro_1-(4-methylthiophenyl)-ethyl ketone oxime 〇 (2-naphthyl) sulfonate, 2, 2,2_Trifluoro-1-(2-methylphenyl)-ethanone oxime_0_methanesulfonate, 2,2,2-trifluoro-1_(4-methylphenyl)-B Ketooxime- 0-phenylsulfonate, 2,2,2-trifluoro-l-(4-chlorophenyl)-ethanone oxime-0-phenylsulfonate, 2,2,3,3,4 ,4,4—seven gas-1_(phenyl)_ butyl stalk-0_(10 — camphoryl) sulfonate, 2,2,2-trifluoro-1-naphthyl-ethanone oxime-0- Sulfonate, 2,2,2-trifluoro-2-n-naphthyl-ethanone oxime_0_methanesulfonate, 2,2,2-trifluoro_1_[4-phenylmethylphenyl] 1-Ethyl oxime-0-methylsulfonate, 2,2,2-trifluoro- 1_[4-(phenyl-1,4-tyanoxanthrene-1-yl)phenyl]-ethanone肟_〇_Methanesulfonate, 2,2,2-trifluoro_1-naphthyl-ethanone oxime- 0-propyl sulfonate, 2,2,2-trifluoro-2-naphthyl- Ethyl ketone oxime - 0 - propyl sulfonate, 2, 2, 2 _ Fluoryl 1-[4-phenylylphenyl]-ethanone oxime-o-propyl sulfonate ' 2,2,2_trifluoro-indole _ [4-methylsulfonylphenyl]-B Ketooxime-propylsulfonate, 1,3-bis[1-(4-phenoxyphenyl)_2,2,2-trifluoroethanone oxime-sulfonyl]phenyl, 2 ,2,2_trifluoro_1—[4_methylsulfonyloxybenzene-57- 1375122

Ethyl ketone oxime-propyl sulfonate ' 2,2,2-trifluoro-l-[4-methylcarbonyloxyphenyl]-ethanone oxime-indole propyl sulfonate, 2,2,2_trifluoro-1_[6H,7H-5,8-dioxo-branched 2-yl]-acetone employs a 0-propyl sulfonate, 2,2,2-trifluoro 1-1[4-methoxycarbonylmethoxyphenyl]-ethanone oxime-indole propyl sulfonate, 2,2,2-trifluoro_1-[4_(methoxycarbonyl)_ ( 4_Amino-1_oxa-pentan-1-yl)phenyl]-ethanone oxime-indole-propyl sulfonate, 2,2,2-trifluorodimethyl- 4-ethoxy Phenyl]-ethanone oxime-O-propyl sulfonate, 2,2,2-trifluoro_1_[4-phenyloxyphenyl]-ethanone oxime-carboxylate, 2 , 2,2_trifluoro_1_[2_phenylthio]-ethanone oxime-0-propyl sulfonate and 2,2,2-trifluoro-1-[1-dioxathiophene-2- Base] — Ethyl ketone 肟 〇 丙基 propyl sulfonate, 2, 2, 2 - trifluoro_1 _ (4_ (3 - (4_ (2, 2, 2 _ 2 gas _1 1 Styrene base _ethyl)-phenoxy)-propoxy)-phenyl)ethanone oxime (trifluoromethanesulfonate), 2,2,2-trifluoro-1-(4_(3_ (4—(2,2,2_trifluoro-1 one ( 1-propanesulfonyl fluorenyl)-ethyl)-phenoxy)-propoxy)-phenyl)ethanone oxime (1-propane sulfonate), 2,2,2-trifluoro_1_ ( 4-(4-(2,2,2-difluoro-l-(1_丁丁醯基基基)_ethyl)-phenoxy)-propoxy)-phenyl)ethanone肟(1 -butane sulfonate), etc., 2,2,2-difluoro- 1 - (4 - (3 - (4 - (2, 2), as described in the specification of US Pat. No. 69 1 6 5 9 1 ,2-difluoro-indenyl (4-(4-methylphenylsulfonyloxy)phenylsulfonyl)-ethyl)-phenoxy)-propoxy)-phenyl) Ketone oxime (4-(4-methylphenylsulfonyloxy)phenylsulfonate), 2,2,2-trifluoro--58- 1375122 1 one (4- (3- (4- (2) ,2,2-trifluoro-1-(2,5-bis(4-methylphenylsulfonyloxy)-propoxy)-phenyl)ethanone oxime (2,5 — double (4 A Phenyl sulfonyloxy)phenylsulfonyloxy)phenylsulfonate), etc. Japanese Patent Publication No. 9-95479, JP-A-9-23 05 8 8

Or a prior art sulfonate, α-(p-toluenesulfonylhydrazino)phenylacetonitrile, α-(p-chlorophenylsulfonylhydrazino)phenylacetonitrile, (4-nitro) Phenylsulfonyl fluorenyl)phenylacetonitrile, α-(4-nitro- 2 -trifluoromethylbenzenesulfonylfluorenyl)phenylacetonitrile, α-(phenylsulfonylfluorenyl)-4-chloro Phenylacetonitrile, ct-(phenylsulfonylhydrazinyl)-2,4-dichlorophenylacetonitrile, (phenylsulfonylhydrazino)-2,6-dichlorophenylacetonitrile, α-(phenylsulfonate)肟 ) ) _ ) _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 、 、 、 、 、 、 、 、 、 、 、 — — (4 — dodecylbenzenesulfonyl fluorenyl)-phenylacetonitrile, α-[(4-toluenesulfonylfluorenyl)-4-methoxyphenyl]acetonitrile, α — [(10 Dialkyl benzene sulfonyl fluorenyl) 4-tetramethoxyphenyl] acetonitrile, α-(toluenesulfonyl fluorenyl)-3-thiol acetonitrile, α-(methylsulfonyl fluorenyl) 1 cyclopentenylacetonitrile, α-(ethylsulfonylhydrazinyl)-1-cyclopentenylacetonitrile, α—( Propylsulfonyl fluorenyl)-1 monocyclopentenylacetonitrile, α-(η-butylsulfonylhydrazino)-1-cyclopentenylacetonitrile, α-(ethylsulfonylfluorenyl)_1- Cyclohexenylacetonitrile, α-(isopropylsulfonylhydrazinyl)-1-cyclohexenylacetonitrile, α-(η-butylsulfonylhydrazino)-1-cyclohexenylacetonitrile, and the like. <S > -59 - 1375122 An oxime sulfonate represented by the following formula (for example, as described in WO 200 4/0 74 242). [化4 0] ORs,

I

N

Ai^1—C-RS2

(In the above formula, RS1 is a substituted or unsubstituted haloalkylsulfonyl group having 1 to 1 carbon atom; halophenylsulfonyl group; and RS2 is a haloalkyl group having 1 to 11 carbon atoms. Arsl is substituted or unsubstituted An aromatic group or a heteroaromatic group). Specifically, for example, 2 - [2, 2, 3, 3, 4, 4, 5, 5 - octafluoro-1 - (nonafluorobutylsulfonyl fluorenyl) - pentyl] hydrazine, 2 - [ 2,2,3,3,4,4_pentafluoro-1-(nonafluorobutylsulfonylhydrazino)-butyl]-anthracene, 2-[2,2,3,3,4,4, 5,5,6,6_decafluoro-l-(nonafluorobutylsulfonylhydrazino)-hexyl]-芴, 2 - [2,2,3,3,4,4,5,5-eight Fluorine-1 (nonafluorobutene fluorenyl)-pentyl]-4-phenylene, 2 - [2,2,3,3,4,4 - five gas -1_ (nonafluorobutylsulfonate)醯 肟 ))-butyl]-4_biphenyl, 2 — [2,2,3,3,4,4,5,5,6,6-decafluoro-1-1 (nonafluorobutyl) Base base) A hexyl] a 4~ biphenyl and so on. Further, the 'biguanide sulfonate is, for example, a compound of JP-A-9-208554, especially bis(α-(4-toluenesulfonyloxy)imino)-p-phenylenediacetonitrile, bis(α-( Phenylsulfonyloxy)imino)_p-phenylenediacetonitrile, bis(α-(methanesulfonyloxy)imino)-p-phenylacetonitrile, bis(α-(butanesulfonyloxy) Amino) a pair of benzenediacetonitrile, bis((10_camphorsulfonyloxy)imino)-p-phenylene-60- 1375122

Nitrile, bis(α_(4-toluenesulfonyloxy)imino)p-phenylenediacetonitrile 'bis(α-(trifluoromethanesulfonyloxy)imino)-p-phenylenediacetonitrile, bis(α —(4-methoxyphenylsulfonyloxy)imino)-p-phenylenediacetonitrile, bis(α-(4-tosyloxy)imino)-p-phenylenediacetonitrile, bis(α- (phenylsulfonyloxy)imino)-m-phenylenediacetonitrile, bis(α-(methanesulfonyloxy)imino)-m-phenylenediacetonitrile, bis(α-(butanesulfonyloxy) Imino) a benzenediacetonitrile, bis-(10-camphorsulfonyloxy)imino)-p-phenylenediacetonitrile, bis(4-toluenesulfonyloxy)imide)benzene Diacetonitrile, bis(α-(trifluoromethanesulfonyloxy)imido)-m-phenylenediacetonitrile, bis(α-(4-methoxy-4-sulfonyloxy)imino)-m-phenylene Diacetonitrile and the like. Among them, preferred photoacid generators are sulfonium salts, bis-sulfonyldiazomethane, hydrazine sulfonyloxy quinone imine, quinone sulfonate, and ethylene quinone derivatives. More preferred photoacid generators are sulfonium salts, disulfonyl diazomethane, hydrazine-sulfonium φ oxy quinone imine, hydrazine-hydrazine sulfonate. Specific examples are triphenylsulfonium p-toluenesulfonate, triphenyl camphorsulfonate triphenylsulfonium pentafluorobenzenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium 4-(4'-toluene Sulfomethoxy)benzenesulfonate, triphenylsulfonium-2,4,6-triisopropylbenzenesulfonate, 4-tert-butoxyphenyldiphenylphosphonium p-toluenesulfonate, 4- Tert —butoxyphenyldi-phenyl camphole sulfonate, 4-tert-butoxyphenyldiphenylphosphonium 4_( 4′-toluenesulfonyloxy)benzenesulfonate, three (4 Methylphenyl) camphorsulfonate, tris(4-tert-butylphenyl) camphosulfonate, 4-tert_butylphenyldiphenyl sulfonium vinegar, 4 tert-butyl Phenylphenyl group (S > -61 - 1375122 diphenyl sulfonium hexafluoro- 1-butane sulfonate ' 4 - tert - butyl phenyl diphenyl quinone pentafluoroethyl perfluorocyclohexane sulfonate 4-tert-butylphenyldiphenylphosphonium perfluoro- 1-octanesulfonate 'triphenylsulfonium 1,1-difluoro-2-phenylnaphthalene monoethanesulfonate, triphenylsulfonate, Bismuth, 2,2-tetrafluoro-2((norbornane-2-yl)ethanesulfonate' bis (tert-butylsulfonate) ) Diazomethane,

Bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, bis(4-n-hexyloxy)phenylsulfonyl)diazomethane, double (2-methyl-4(n-hexyloxy)phenylsulfonyl)diazomethane, bis(2,5-dimethyl-4(n-hexyloxy)phenylsulfonyl)diazomethane, Bis(3,5-dimethyl-4-yl(n-hexyloxy)phenylsulfonyl)diazomethane, bis(2-methyl-5-isopropyl-4-(n-hexyloxy)phenylsulfonate Diazomethane, bis(4-tert-butylphenylsulfonyl)diazomethane 'N-camphorsulfonyloxy-5-norbornene- 2,3-dicarboxylic acid quinone imine, N - p-toluenesulfonyloxy-5-norbornene- 2,3-dicarboxylic acid quinone imine, 2-[2,2,3,3,4,4,5,5-octafluoro-1 ( Nonafluoro φ butyl sulfonyl fluorenyl) pentyl] hydrazine, 2-[2,2,3,3,4,4-pentafluoro- 1 -(nonafluorobutylsulfonyl fluorenyl)- Butyl]-芴, 2_ [2,2,3,3,4,4,5,5,6,6-decafluoro-1 (nonafluorobutyrylsulfonyl)-hexyl]-medicine . In the photoresist material of the present invention, the photoacid generators (B) and (B,) may be added in any amount "generally relative to the base polymer in the photoresist material (the above resin component of the present invention (A) And 100 parts by mass of the other resin component to be added, if necessary, is 0.1 to 40 parts by mass, preferably 〇" to 20 parts by mass. When the proportion of photoacid generator is too large, it may cause -62-1375122

There is a problem that the analytic property is deteriorated, or foreign matter is generated during development/resistance peeling. The ratio of addition of (B) to (B') is preferably 0.1S [B] / ([B] + [B']) in the case where the respective addition amounts are [B] and [B,] Each 1 is more preferably 0.3S [B]/ ( [B]+ [B,]) $ 1, preferably 0.5$ [B]/ ( [B] + [B'] ) S 1. When the addition ratio of the photoacid generator (B) is too low, the exposure amount dependency, the density dependence, the mask faith, and the like may be deteriorated. Further, the photoacid generators (B) and (B') may be used singly or in combination of two or more kinds. Further, when a photoacid generator having a low transmittance is used in the exposure wavelength, the amount of addition can control the transmittance in the photoresist film. A compound (acid-proliferating compound) which generates an acid by acid decomposition can be added to the photoresist material of the present invention. This compound is described in J. Photopolym. Sci. and Tech., 8.43-44, 45-46 (1 9 9 5 ), J. P ho t ο ρ ο 1 y m. Sci .and

Tech·, 9.29- 3 0 (1 996). The acid-proliferating compound is, for example, tert-butyl-2-methyl-2-toluenesulfonyloxymethylacetate acetate 2-2-phenyl-2-(2-toluenesulfonyloxy)-ylethyl}. 3_dioxolane, etc., but not limited to this. Among the known photoacid generators, most of the compounds having poor stability, particularly thermal stability, have the characteristics of an acid-proliferating compound. The amount of the acid-proliferating compound to be added to the photoresist of the present invention is 〇 to 2 parts by mass, preferably 〇 to 1 part by mass, based on 100 parts by mass of the base polymer in the photoresist. When the amount of addition is too large, it is difficult to control the diffusion, and the resolution is deteriorated, and the shape of the pattern is deteriorated. The photoresist of the present invention may be other than the above (A) and (B).

(S-63-1375122 further contains (C) an organic solvent, and if necessary, further contains (D) a nitrogen-containing organic compound, (E) a surfactant, and (F) other components.

The organic solvent (C) used in the present invention can be used as long as it is an organic solvent which can dissolve the basic resin 'acid generator, other additives and the like. Such organic solvents such as ketones such as cyclohexanone and methylpentanone; 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, Alcohols such as 1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl hydrazine Class: propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, Esters such as tert-butyl acetate, tert-butyl propionate, and tert-butyl ether acetate such as propylene glycol: lactones such as r-butyrolactone, which may be used alone or in combination of two or more. It is not limited to the above solvent. In the present invention, it is preferred to use diethylene glycol dimethyl ether or 1-ethoxy-2-propanol or propylene glycol monomethyl ether B which is most excellent in solubility in an acid generator in a photoresist component. Acid esters and their mixed solvents. The organic solvent is used in an amount of from 200 to 3,000 parts by mass, particularly preferably from 400 to 2,500 parts by mass, per 100 parts by mass of the base polymer. Further, the photoresist material of the present invention may contain one or two or more kinds of nitrogen-containing organic compounds of the component (D). The nitrogen-containing organic compound inhibits a compound which diffuses into the photoresist film by the acid generated by the acid generator. Addition of nitrogen-containing organic compounds can inhibit the diffusion rate of acid in the photoresist film of -64-1375122, improve the resolution, suppress the sensitivity change after exposure, or reduce the dependence of the substrate or the environment, and improve the exposure tolerance or pattern. Shape and so on.

The nitrogen-containing organic compound may be any conventional nitrogen-containing organic compound used as a photoresist material, particularly a reinforced chemical resist material, for example, there are first, second, and third stages. Aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group Alcoholic nitrogen-containing compounds, guanamines, quinones, urethanes, and the like. Specifically, the aliphatic amines of the first stage are, for example, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert _ Pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, decylamine, decylamine, laurylamine, hexadecylamine, methyldiamine, ethylenediamine 'tetraethylene pentylamine, etc.; Class 2 fatty amines such as dimethylamine, φ diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, diamylamine, dicyclopentane Amine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, diamine, diamine, dilaurylamine, dihexadecylamine, hydrazine, hydrazine-dimethylmethylenediamine, N,N-dimethylethylenediamine, N,N-dimethyltetraethylenepentamine, etc.; the aliphatic amines of the third stage are, for example, trimethylamine, triethylamine tri-n-propylamine, triisopropylamine , tri-n-butylamine, triisobutylamine., tris sec — butylamine, triamylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, tridecylamine Guanamine, trilaurylamine, tri-hexadecaneamine, N, N, N' , N'-tetramethylmethyldiamine, N,N,N',N'-tetramethyl-65- 1375122-based ethylenediamine, N,N,N',N'~tetramethyltetraethylenepentylamine Wait.

Further, the mixed amines are, for example, dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine or benzyldimethylamine. Specific examples of the aromatic amines and heterocyclic amines are aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline 'N-propylaniline, N N-dimethylaniline, 2-methyl) Aniline, 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, dimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-2 Nitroaniline, 2,6-dinitroaniline, 35-dinitroaniline, N,N-dimethyltoluidine, etc.), diphenyl (p-tolyl)amine, methyldiphenylamine, triphenylamine, Phenylenediamine 'naphthylamine, diaminonaphthalene, pyrrole derivatives (eg, bismuth, 2 Η - 卩 哈, 1 - methyl υ 哈, 2, 4 _ dimethyl mascara, 2, 5 - Dimethylpyrrole, hydrazine-methylpyrrole, etc.), oxazole derivatives (eg, anthraquinone, iso-D-oxime, etc.), thiazide derivatives (eg, thiazide, isothiazide, etc.), imidazole derivatives (eg Imidazole, 4-methylimidazole, 4-monomethyl-2-phenylimidazole, etc., pyrazole derivatives, furazan derivatives, pyrroline derivatives (for example, pyrroline, 2-methyl-1-pyrroline, etc.) ), pyrrolidine derivatives (for example) Pyrrolidine, fluorene-methylpyrrolidine, pyrrolidone, ν-methylpyrrolidone, etc.), imidazoline derivatives, imidazopyridine derivatives, pyridine derivatives (eg pyridine, picoline, ethylpyridine, propylpyridine, Butylpyrrole, 4-(1-butylpentyl)pyridine, dimethylpyrrolidine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4 — Tert — butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridinidine, butoxypyridinium, dimethoxypyridine, 4-pyrrolidinylpyridine, 2 (1-ethyl) Propyl)pyridine, aminopyridine, dimethylaminopyridine, etc.)

-66 - 1375122

, pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, anthracene derivatives, isoindole a derivative, a hydrazine-carbazole derivative, a porphyrin derivative, a porphyrin derivative (for example, quinoline, 3-quinolinonitrile, etc.), an isoquinoline derivative, a porphyrin derivative, a quinazoline derivative , quinoxaline derivative, pyridazine derivative, anthracene derivative, pteridine derivative, carbazole derivative, phenanthroline derivative, acridine derivative, phenazine derivative, 1,1 〇-phenanthrene Derivatives, adenine derivatives, adenosine derivatives, guanine derivatives 'guanosine derivatives, uracil derivatives, ureaazine derivatives, and the like. And 'a nitrogen-containing compound having a carboxyl group, such as an aminobenzoic acid, an anthracene carboxylic acid, an amino acid derivative (for example, nicotine, alanine, arginine, aspartic acid, decanoic acid, glycine, group Amino acid, isolysine, glycine leucine, leucine, methionine, phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxy Alanine), etc.; nitrogen-containing compounds having a sulfonyl group such as 3-pyridine sulfonic acid, p-toluenesulfonic acid pyridine gun, etc.; nitrogen-containing compound having a hydroxyl group, nitrogen-containing compound having a hydroxyphenyl group, and an alcoholic nitrogen-containing compound For example, there are 2-hydroxypyridine, aminocresol' 2,4 quinacridol, 3-hydrazine methanol hydride 'monoethanolamine, diethanolamine, triethanolamine, hydrazine-ethyldiethanolamine, ν, Ν-II Ethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-propanol, 4-amino-1-butanol, 4 (2) Hydroxyethyl)morpholine 2 2-(2-hydroxyethyl)pyridine, (2-hydroxyethyl)piperazine, ι_[2~(2-hydroxyethoxy)ethyl]piperazine, piperazine ethanol 1- (2_ hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidone 3 '- piperidin Steep

<S-67- 1375122 keto-1,2-propanediol, 3-pyrrolidinyl-1,2-propanediol, 8-hydroxy jiuronis, 3-dark alcohol, 3-terpineol, 1-methyl Base-2 - Abdominal ethanol, 1-azacyclopropaneethanol, N-(2-hydroxyethyl) quinone imine, N-(2-hydroxyethyl) isonicotamine and the like. Indoleamine derivatives such as formamide, N-methylamine, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, Propylamine, benzoguanamine, 1-cyclohexylpyrrolidone, and the like. a quinone imine derivative such as a quinone imine,

Amber succinimide, maleimide, and the like. The urethanes are, for example, N-tert-butoxycarbonyl-N,N-dicyclohexylamine, N-ten-butoxycarbonylbenzimidazole, oxazolone. For example, a nitrogen-containing organic compound represented by the following formula (B)-1. (B)-l N(X) „(Y)3. (wherein η is 1, 2 or 3. The side chains X may be the same or different and may be represented by the following general formulae (XI) to (Χ3). The side chain γ may be the same or different φ hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may have an ether group or a hydroxyl group. X may be bonded to each other to form a ring). 4 1] _J_r30(L_q_R301 j (XI) --R302—Ο—R303—C—R304 (X2) --R305—C—0—R306 (X3) where R3QQ, R3Q2, and R3Q5 are carbon numbers 1 to 4 Straight chain or minute

< S -68-1375122 Branched alkyl group: 113 () 1, 1 ^ 3 <) 4 is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain One or more of a hydroxyl group, an ether group, an ester group, and a lactone ring. R3<)3 is a single bond, a linear or branched alkyl group having 1 to 4 carbon atoms, and R3G0 is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain 1 Or a plurality of hydroxyl, ether, ester, lactone rings.

The compound represented by the above formula (B)-1, specifically, for example, tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, three {2—( 2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine , three {2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethyloxy)ethoxy}ethyl]amine, 4,7,]3 ,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexadecane, 4,7,13,18-tetraoxa-1,10-diaza Ring [8.5.5] 20th courtyard, 1,4,1〇, 13-tetraoxa-7,16-azepine-cyclohexadecane, 1-aza- 12-crown-4, 1-aza a 15-crown _5, 1_aza-18-crown-6, tris(2-methyloxyethyl)amine, tris(2-acetoxyethyl)amine, tris(2-propaneoxy) Amine, tris(2-butyloxyethyl)amine, tris(2-isobutyloxyethyl)amine, tris(2-pentenyloxyethyl)amine, tris(2-hexyloxyethyl) Amine, N,N-bis(2-ethoxyethyl)2-(acetyloxyethoxy)ethylamine, (2-methoxycarbonyloxyethyl)amine 'tris(2-tert-butoxy oxyethyl)amine, tris[2-(2-oxopropoxy)ethyl]amine, three [2_ (a Oxygen methyl)oxyethyl]female, bis[2-(tert-butoxymethyloxy)ethyl]amine, tris[2-(cyclohexyloxycarbonylmethyloxy)ethyl]amine , three (S > -69-1375122 (2-methoxycarbonylethyl)amine, tris(2-ethoxycarbonylethyl)amine, hydrazine, hydrazine, a pair of (2-hydroxyethyl) 2 - (A Oxycarbonyl)ethylamine, hydrazine, hydrazine-bis(2-ethoxycarbonylethyl) 2-(methoxycarbonyl)ethylamine, hydrazine, hydrazine-bis(2-hydroxyethyl)2-(ethoxycarbonyl) Ethylamine, hydrazine, hydrazine - bis(2-ethoxycarbonylethyl) 2-(ethoxycarbonyl)ethylamine, hydrazine, hydrazine-bis(2-hydroxyethyl)2-(2-methoxyethoxycarbonyl) Ethylamine, hydrazine, hydrazine-bis(2-ethoxycarbonylethyl) 2-(2-methoxyethoxycarbonyl)ethylamine, hydrazine, hydrazine-bis(2-hydroxyethyl)2

-(2-hydroxyethoxycarbonyl)ethylamine, hydrazine, hydrazine-bis(2-ethoxycarbonylethyl)2-(2-ethoxycarbonylethoxycarbonyl)ethylamine, hydrazine, hydrazine-bis(2-hydroxyl Ethyl) 2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, hydrazine, hydrazine-bis(2-ethoxyethyl)2-[(methoxycarbonyl)methoxycarbonyl]ethylamine, hydrazine, hydrazine - bis(2-hydroxyethyl)2-(2-oxopropoxycarbonyl)ethylamine, hydrazine, hydrazine-bis(2-ethoxypropoxyethyl)2-(2-oxopropoxycarbonyl)ethylamine ,Ν,Ν-bis(2-hydroxyethyl)2-(tetrahydrofuranyloxycarbonyl)ethylamine, anthracene, fluorene-bis(2-ethoxycarbonylethyl)2-(tetrahydroindolyloxycarbonyl) Ethylamine, hydrazine, hydrazine-bis(2-hydroxyethyl)2-[2-(oxotetrahydrofuran-3-yl)oxycarbonyl]ethylamine, hydrazine, hydrazine-bis(2-ethoxyethyl)2 —[(2-oxotetrahydrofuran_3_yl)oxycarbonyl]ethylamine, hydrazine, hydrazine-bis(2-hydroxyethyl)2-(4-hydroxybutoxycarbonyl)ethylamine, hydrazine, hydrazine-bis (2 -Methoxyethyl)2 - (4-methyloxybutoxycarbonyl)ethylamine, hydrazine, hydrazine - bis(2-methyloxyethyl) 2_(2-methoxycarbonylethoxycarbonyl) Amine, hydrazine, hydrazine - double (2 - methoxy (2-(methoxycarbonyl)ethylamine, hydrazine-(2-hydroxyethyl) bis[2-(methoxycarbonyl)ethyl]amine' Ν-(2 - ethoxylated ethyl) bis[2 — (methoxycarbonyl)ethyl]amine, Ν-(2-hydroxyethyl) bis[2-(B-70- 1375122

Oxycarbonyl)ethyl]amine, N-(2-ethyloxyethyl)bis[2-(ethoxycarbonyl)ethyl]amine, N-(3-hydroxyl-propyl) bis[2-( Methoxycarbonyl)ethyl]amine, N-(3-acetoxy-l-propyl)bis[2-(methoxycarbonyl)ethyl]amine, N-(2-methoxyethyl) bis[ 2-(methoxycarbonyl)ethyl]amine, N-butylbis[2-(methoxycarbonyl)ethyl]amine, N-butylbis[2 _(2-methoxyethoxycarbonyl)ethyl] Amine, N-methylbis(2-ethoxyethyl)amine, N-ethylbis(2-acetoxyethyl)amine, N-methylbis(2-trimethylacetoxyethyl) Amine, N_ethylbis[2-(methoxycarbonyloxy)ethyl]amine, N-ethylbis[2_(tert-butoxycarbonyloxy)ethyl]amine, tris(methoxycarbonyl) Methyl)amine, tris(ethoxycarbonylmethyl)amine, N-butylbis(methoxycarbonylmethyl)amine, N-hexylbis(methoxycarbonylmethyl)amine, none (diethylamino) A 6-pentalinamide. For example, a nitrogen-containing organic compound having a cyclic structure represented by the following formula (B)-2. [化4 2]

(In the above formula, X is as described above, R3t) 7 is a linear or branched alkyl group having 2 to 20 carbon atoms, and may contain one or a plurality of carbonyl groups, ether groups, ester groups or thioethers) . Specific examples of the above formula (B)-2 are 1-[2-(methoxymethoxy)ethyl]pyrrolidine, 1-[2-(methoxymethoxy)ethyl]piperidine, 4 — [ 2-(methoxymethoxy)ethyl]morpholine, 1_ [2- [2 - (methoxyethoxy) CS) -71 - 1375122

Methoxy]ethyl]pyrrolidine, 1-[2 _[2 _(methoxyethoxy)methoxy]ethyl]piperazine, 4-mono[2-[2-(methoxyethoxy) Methoxy]ethyl]morpholine, 2-(1-pyrrolyl)ethyl acetate, 2-piperidinylethyl acetate, 2-morpholinium acetate, 2-(ι-pyrrolyl)carboxylate, Propionic acid 2 峨 峨 乙酯 ethyl ester, acetoxyacetic acid 2 morpholine ethyl ester 'methoxy acetic acid 2 - (1 - pyrrolyl) ethyl ester, 4 - [2 _ (methoxycarbonyloxy) ethyl ]morpholine, 1 — [2-(tert-butoxypropoxy)ethyl]piperidine, 4_[2_(2-methoxyethoxycarbonyloxy)ethyl]morpholine, 3_pyrrolyl)propionic acid Methyl ester, methyl 3-piperidinylpropionate, methyl 3-morpholinylpropionate, methyl 3-(thiomorpholinyl)propionate, 2-methyl-3-(1-pyrrolyl)propene Methyl ester, ethyl 3-morpholinylpropionate, methoxycarbonyl methyl 3-piperidinylpropionate, 2-hydroxyethyl 3-(1-pyrrolyl)propanoate, 3-morpholinylpropionic acid 2-Ethyloxyethyl ester, 3-(1-pyrrolyl)propionic acid 2-oxotetrahydrofuran-3-ester, 3-morpholinylpropionic acid tetrahydrofurfuryl ester, 3-piperidylpropionic acid glycidol Ester, 2-methoxyethyl 3-morpholinylpropionic acid, 2-(2-methoxyethoxy)ethyl 3-(1-pyrrolyl)propanoate, butyl 3-morpholinylpropionate , 3-piperidyl propionic acid cyclohexyl ester, α-(1_pyrrolyl)methyl-butyrolactone, stone-piperidinyl-r-butyrolactone, morpholinyl-<5-valerolactone, 1-methylpyrrolylacetate, methyl piperidinylacetate, methyl morpholinylacetate, methyl thiomorpholinylacetate, ethyl 1-pyrrolylacetate, 2-methoxyethyl morpholinylacetate , 2-methoxyacetic acid 2-morpholinoethyl ester, 2-(2-methoxyethoxy)acetic acid 2-morpholinoethyl ester, 2-[2-(2-methoxyethoxy)ethyl Oxy]acetic acid 2-morpholinoethyl ester, 2-morpholinylethyl hexanoate, 2-morpholinylethyl octanoate, 2-morpholinyl phthalate

-72- 1375122 vinegar, lauric acid 2~morpholinylethyl ester, myristyl 2-morpholinylethyl ester, hexyl acid 2-cyanoethyl ester, octadecanoic acid 2-morpholinylethyl ester. Example 1 is a nitrogen-containing organic compound having a cyano group represented by the following formula (B)-3 to (B)-6.

[化4 3]

(B)-3 Π

(B)-4

R3C)S-l-〇-R3.9-CN (B)-6

(In the above formula, X, R307, and n are the same as those described above, and R3G8 and R3 are the same or different linear or branched alkyl groups having 1 to 4 carbon atoms.) The above formula (B)-3 Specific examples of the nitrogen-containing organic compound containing a cyano group as shown in (B)-6 are, for example, 3-(diethylamino)propionitrile, hydrazine, hydrazine-bis(2-hydroxyethyl)-3-aminopropionitrile, Ν,Ν-bis(2-acetoxyethyl)-3-aminopropionitrile, hydrazine, hydrazine-bis(2-methyloxyethyl)-3-aminopropionitrile' Ν, Ν-double ( 2-methoxyethyl)-3-aminopropionitrile, hydrazine, hydrazine-double [2 - -73- 1375122

(methoxymethoxy)ethyl]_3_aminopropionitrile, N-(2-cyanoethyl)-N-(2-methoxyethyl)-3-aminopropionic acid methyl ester, N— ( 2-cyanoethyl)-N-(2-hydroxyethyl)-3-aminopropionic acid methyl ester, N-(2-ethoxyethyl)-N-(2-cyanoethyl)-3_ Methyl aminopropionate, N-(2-cyanoethyl)-N-ethyl-3-imidopropionitrile, N-(2-cyanoethyl)-N-(2-hydroxyethyl)- 3-Aminopropionitrile, N-(2-ethoxyethyl)-N-(2-cyanoethyl)_3-aminopropionitrile, N _ (2-cyanoethyl)-N- (2- Methoxyethyl)_3_aminopropionitrile, N-(2-cyanoethyl)-N-(2-methoxyethyl)-3-aminopropionitrile, N-(2-cyanoethyl) N-[2 _(methoxymethoxy)ethyl]-3-aminopropionitrile, N-(2-cyanoethyl)-N-(3-hydroxy-1-propyl)-3-amine Propionitrile, N-(3_acetamido-1-propyl)-N-(2-cyanoethyl)-3-aminopropionitrile, N-(2-cyanoethyl)_N- (3-A Awoxy-1-propyl)-3-aminopropionitrile, N-(2-cyanoethyl)-N-tetrahydroindenyl-3-aminopropionitrile, hydrazine, hydrazine — Bis(2-cyanoethyl)-3-aminopropionitrile, diethylaminoacetonitrile, hydrazine, hydrazine-bis(2-hydroxyethyl)aminoacetonitrile, hydrazine, hydrazine-bis(2-ethoxylated) Aminoacetonitrile, hydrazine, hydrazine-bis(2-methyloxyethyl)aminoacetonitrile, hydrazine, hydrazine-bis(2-methoxyethyl)aminoacetonitrile, hydrazine, hydrazine-bis[2-( Methoxymethoxy)ethyl]aminoacetonitrile, methyl cyanomethyl-hydrazine-(2-methoxyethyl)-3-aminopropionic acid methyl ester, hydrazine-cyanomethyl-hydrazine _ (2-hydroxyl Base)_3 - methyl aminopropionate, Ν-(2_acetoxyethyl)- hydrazine-methyl cyanomethyl-3-aminopropanoate, Ν-cyanomethyl Ν- (2-hydroxyl Ethyl)aminoacetonitrile, Ν-(2_acetoxyethyl)-indole-(cyanomethyl)aminoacetonitrile, hydrazine-

(S-74- 1375122 cyanomethyl-N-(2-carbomethoxyethyl)aminoacetonitrile, N-cyanomethyl-N-(2-methoxyethyl)aminoacetonitrile, N-cyanomethyl N-[2-(methoxymethoxy)ethyl]aminoacetonitrile, N_(cyanomethyl)-N-(3-hydroxy-1-propyl)aminoacetonitrile, N-(3-acetamidine) Oxyl-1 monopropyl)-N-(cyanomethyl)aminoacetonitrile, N-cyanomethyl-N-(3-methyloxy-l-propyl)aminoacetonitrile, N,N-double (cyanomethyl) Aminoacetonitrile, 1-pyrrolidinylpropionitrile, 1-piperidinylpropionitrile, 4-morpholine

Propionitrile, 1-pyrrolidine acetonitrile, 1-piperidinyl acetonitrile, 4-morpholine acetonitrile, cyanomethyl 3-diethylaminopropionate, hydrazine, hydrazine-bis(2-hydroxyethyl)-3-amine Methyl cyanopropionate, hydrazine, hydrazine - bis(2-acetoxyethyl)-3-cyanopropionate cyanomethyl, hydrazine, hydrazine - bis(2-methyl methoxyethyl)-3-amine Methyl cyanopropionate, hydrazine, hydrazine - cyanomethyl bis(2-methoxyethyl)-3-aminopropanoate, hydrazine, hydrazine-bis[2-(methoxymethoxy)ethyl]- 3-Aminopropyl propionate, 2-diethylaminopropionic acid (2-cyanoethyl) ester, hydrazine, hydrazine-bis(2-hydroxyethyl)-3-aminopropionic acid (2-cyanide) Ethyl)ester, anthracene, fluorene-bis(2-acetoxyethyl)-3-aminopropionic acid (2-cyanoethyl) ester, hydrazine, hydrazine-bis(2-methyl methoxyethyl) 3_Aminopropionic acid (2-cyanoethyl) ester, hydrazine, hydrazine-bis(2-methoxyethyl)-3-aminopropionic acid (2-cyanoethyl) ester, hydrazine, hydrazine-double [ 2-(Methoxymethoxy)ethyl]-3-aminopropionic acid (2-cyanoethyl) ester, 1-pyrrolidine propionate cyanamide, 1 piperidine propionic acid cyanate, 4 Methyl morpholine propionate, iota-pyrrolidonic acid (2-cyanoethyl) ) vinegar, 1-piperidinyl propionic acid (2-cyanoethyl) ester, 4-morpholine propionic acid (2-cyanoethyl) vinegar. Χ ', for example, a nitrogen-containing organic compound having an imidazole skeleton represented by the following formula (Β)-7 and a polar group -75-1375122. (B)-7 (In the above formula, R3IG is a linear, branched or cyclic ring having a carbon number of 2 to 20.

[4 4]

The polar functional group of the alkyl group, the polar functional group contains one or a plurality of hydroxy 'carbonyl' ester groups, ether groups, thioether groups, carbonate groups, cyano groups, acetal groups. R311, R312 and R313 are a hydrogen atom, a linear one having a carbon number of 1 to 10, a branched or cyclic alkyl group, an aryl group or an aralkyl group). Further, for example, a nitrogen-containing organic compound having a benzimidazole skeleton represented by the following formula (B)-8 and a polar functional group.

[化 4 5]

(B)-8 (In the above formula, R314 is a hydrogen atom, a linear, branched or cyclic alkyl, aryl or aralkyl group having 1 to 10 carbon atoms, and R315 has a carbon number of 1 to 20 An alkyl group having a linear, branched or cyclic polar functional group, which contains one or more ester groups, an acetal group, a cyano group as a polar functional group, and may further contain at least one or more hydroxyl group, carbonyl group, ether group, Thioether group, carbonate group). Further, for example, a nitrogen-containing ring compound having the following formula (B)-9. And the polarity officer shown in (B)-l〇 [Chem. 4 6]

ΒΒ)-9

(In the above formula, A is a nitrogen atom or a tri-C-R3 eC-R 3 2 3 ; R316 is an alkyl group having a polar functional group having a carbon number of 2 to 20, a polar functional group, a carbonyl 'ester group, an ether group, Thioether group, group, R317, R3I8, R319, R32. Hydrogen [ φ chain, branched or cyclic alkyl or aryl group and R32 () respectively bond to form benzene ring, naphthalene atom, carbon number 1 a straight chain or a branch of ～10. R3 2 2, R3 2 3 is a hydrogen atom, a C 1 to a cyclic alkyl group or an aryl group. R321 and R323 - ) 0 Further, for example, have the following general formula (B) -ll Nitrogen-containing organic compounds of the acid ester structure. (Β)-ΐ〇22; B is a nitrogen atom or a linear, branched or cyclic group containing more than one hydroxycarbonate group, a cyano group or an acetal oxygen, a carbon number of 1 to 1 〇, Or R317 with R318, R319 ring or pyridine ring. R321 is a hydrogen or a cyclic alkyl group or an aryl group 10 which is linear, branched or bonded to form a benzene ring or a naphthalene ring - (B)-14 aromatic carboxyl group <S> -77-1375122 [化 4 7]

324 Ο (8)-13

(Β)-14

(wherein R3 24 is an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 4 to 20 carbon atoms, and a part or all of a hydrogen atom may be a linear or branched group of a halogen atom or a carbon number of 1 to 20; a cyclic or cyclic alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a decyloxy group having 1 to 10 carbon atoms, or a carbon number 1 to 10 alkylthio substituted. R3 25 is C02R3 26, OR 3 2 7 or cyano. R3 2 6 - part of the methyl group which may be substituted by an oxygen atom and has a carbon number of 1 to 10. R3 2 7 is a part of an alkyl group or a fluorenyl group having a carbon number of 1 to 10 which may be substituted by an oxygen atom. R3 2 8 is a single bond, a methyl group, a methyl group -78-1375122, a sulfur atom or 〇(CH2CH20)n-yl.n = 〇, ], 2, 3 or 4. R329 is a hydrogen atom 'methyl, ethyl or phenyl. X is a nitrogen atom or CR330. Υ is a nitrogen atom or C R3 31. Ζ is a nitrogen atom or c R3 3 2 . R 3 3 〇, R 3 31 , R 3 3 2 are each independently a hydrogen atom, a methyl group or a phenyl group, or R 33. Bonding with R331 or R331 and R 3 3 2 can form a carbon number. 6 to 20 aromatic rings or carbon number 2 to 20 heteroaromatic rings). Further, for example, it has a 7-oxo-norbornene sheet represented by the following formula (Β)-15.

- 2 -Carboxylic acid-containing organic compounds of the carboxylate structure [Chem. 4 8]

(Β)-15 (In the above formula, R333 is hydrogen or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. R 3 3 4 and R 3 3 5 may each independently contain one or a plurality of alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and carbons of a polar functional group such as an ether group, a carbonyl group, an ester group, an alcohol, a thioether, a nitrile, an amine, an imine or a guanamine φ. A part of the 7 to 20 aralkyl 'hydrogen atom may be substituted by a halogen atom. R334 and R3 3 5 are bonded to each other to form a heterocyclic or heteroaromatic ring having 2 to 20 carbon atoms). The amount of the nitrogen-containing organic compound to be added is 0.001 to 4 parts by mass per 100 parts by mass of the total base polymer, and particularly preferably 1 to 2 parts by mass. When the amount is less than 0.001 part by mass, a sufficient effect of addition cannot be obtained. When the amount is more than 4 parts by mass, the sensitivity may be lowered. In the photoresist material of the present invention, in addition to the above components, any surfactant (S>-79-1375122 parts which is commonly used for improving coatability may be added. The addition amount of any component does not affect the range of the effect of the present invention. The general amount of addition in the surfactant. The surfactant is preferably a nonionic surfactant, such as perfluoroalkyl polyethylene oxide ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkyl E0 plus For example, Florade "FC-430", "FC-43 1" (Sumitomo 3M (share) system), and Surfuron "S-14 1"' "S-145" , "KH-10"' "KH-20

"KH-30", "KH-40" (Asahi Glass Co., Ltd.), Unidye "DS-401", "DS-403", "DS-451" (Daikin Industries Co., Ltd.), Megafac "F-8151" (Daily Ink Industry Co., Ltd.), "X-70-092", "X-70-093" (Shin-Etsu Chemical Industry Co., Ltd.). It is preferably Florade "FC-430" (Sumitomo 3M (share) system), "KH-20", "KH-30" (Asahi Glass Co., Ltd.), "X-70-093" (Shin-Etsu Chemical Industry Co., Ltd. In the photoresist material of the present invention, in order to adjust the balance of hydrophilicity and hydrophobicity φ of the surface, or to improve water repellency, or when the coating film is in contact with water or other liquid, it has a hindrance to low molecular components. When flowing out or flowing into the function, any component other than the above components may be added, and the mergon compound which is partially occupied by the coating film may be added. Further, the amount of the polymer compound added is a normal amount within a range that does not impair the effects of the present invention. - Among them, a polymer compound which is a part of the polymer film in the upper part of the coating film, and a copolymer obtained by using one or two or more kinds of fluorine-containing units, and a copolymer obtained from a fluorine-containing unit and other units are preferred. Specific contents of the fluorine-containing unit and other units are exemplified below, but are not limited thereto. -80- 1375122

[化4 9]

Η Η Η Η Η HO

Η Η (+

Vcf3 〇 f2c ρ- f3c\SF2H 0-cf, cf3

Η

Ο

The weight average molecular weight of the polymer compound in the upper portion of the coating film is preferably from 1,000 to 50,000, more preferably from 2,000 to 20,00. (When the temperature exceeds the range, the surface is not sufficiently obtained. The effect of the modification may cause a development defect or the like. Further, the above weight average molecular weight is <S> -81 - 1375122. The light of the present invention is represented by polystyrene-converted 凝胶 using gel permeation chromatography (GPC). The resist material may be added with other components such as a dissolution inhibitor, a carboxylic acid compound or an acetylene alcohol derivative, if necessary. Further, the addition amount of any component does not affect the general addition amount within the range of the effect of the present invention.

A dissolution inhibitor which may be added to the photoresist of the present invention, for example, a compound having a weight average molecular weight of 100 to 1,000, preferably 150 to 800, and having two or more phenolic hydroxyl groups in the molecule, and the phenol may be added. The hydrogen atom of the hydroxyl group is substituted with the acid labile group at a ratio of the average of 〇100 mol%, or a compound having a carboxyl group in the molecule, and the hydrogen atom of the carboxyl group is averaged by the acid labile group. The compound obtained is substituted with a ratio of 50 to 100 mol%. Further, the substitution ratio of the hydrogen atom in the phenolic hydroxyl group substituted by the acid labile group is, on average, more than 〇 mol% of the total phenolic hydroxyl group, preferably 30 mol% or more, and the upper limit is 100 mol%. More preferably, it is 80% by mole. The substitution ratio of the hydrogen atom in the carboxyl group substituted by the acid labile group is, on average, 50 mol% or more, preferably 70 mol% or more, and the upper limit is 100 mol%. In this case, the compound having two or more phenolic hydroxyl groups or the compound having a carboxyl group, for example, those represented by the following formulas (D 1 ) to (D 1 4 ) are preferably -82-1375122. 0 CH CH (Dl)

OH

(D2)

(D7)

(OH), · R201, (D4) (:: heart 'from (D6)

(D8)

(OH)r R201s, 03

COOH (D12)

(CH2)hCOOH

(D13)

R

COOH ( -83-

1375122 In the above formula, R2QI and R2Q2 are each a hydrogen atom or a linear or branched alkyl or alkenyl group of carbon, for example, a hydrogen atom, an ethyl group, a butyl group, a propyl group, an ethynyl group or a cyclohexyl group. R2Q3, which is a hydrogen atom, or a linear or alternative alkyl or alkenyl group having a carbon number of 1 to 8, or -(R2fl7)hCOOH (wherein R2Q7 is a linear or branched alkyl group of a carbon wife) For example, the same content as R2G1, R, or -COOH, -CH2COOH. R20 is -(CH2)i~(i=2~10), carbon number 6~10, carbonyl, sulfonyl, oxygen or sulfur atom, for example, phenyl, carbonyl, sulfonyl, oxygen, sulfur Atoms, etc. R205 is an alkylene group having 1 to 10 carbon atoms, a carbonyl group having 6 to 10 carbon atoms, a sulfonyl group 'oxygen atom or a sulfur atom. For example, R2 () 4 is the same. R2<)6 is a hydrogen atom, a linear or branched carbon group of 1 to 8, an alkenyl group, or at least one of each hydrogen atom thereof is taken from a hydroxyl group or a naphthyl group, for example, a hydrogen atom, a methyl group, or an ethyl group. Further, at least one of each of the hydrogen atoms of the butyl group, the propyl group and the cyclohexyl group is a hydroxyl group or a naphthyl group. R2()8 is a hydrogen atom or a hydroxyl group. j is an integer from 0 to 5. U, h is 〇 or ieS, t's', and t" respectively satisfy s+t=8, s'+t, =5, s, and +t"=4, and the i skeleton has at least one hydroxyl group. The weight average molecular weight of the compound in which α is a formula (D8) is! 〇〇~〗, the number of 〇〇〇. The acid labile group of the dissolution inhibitor may be used in various types of 1 to 8 methyl groups, and the branched [1 to 1 0 2 <) 2 is a phase: an exoaryl group, a aryl group, an exoaryl group, or Alkyl: phenyl; acetylene [substituted benzene, t, s'. For each phenol (D9) specific (S> -84-

1375122, for example, a group represented by the above formulas (L1) to (L4), a tertiary alkyl group of carbon, a decyl group having a carbon number of 1 to 6 and a ketone group having a carbon number of 4 to 20, respectively. Base. Also, the individual bases are as identical as the previous description. The amount of the above-mentioned dissolution inhibitor added is 〇 50 parts by mass, preferably 0 to 40 parts by mass, preferably 0 to 30 parts by mass, based on 100 parts by mass of the photoresist material resin, and may be added singly or in combination of two or more kinds. When the amount is 50 parts by mass or less, the film of the pattern can be reduced, and the resolution is lowered. Further, the above-mentioned dissolution inhibitor can be synthesized by introducing an acid-labile compound with respect to a phenolic hydroxy compound by using an organic chemical formulation. The carboxylic acid compound which can be added to the photoresist of the present invention is one or two selected from the following [Group I] and [Group], but is not limited by the above examples. When this component is added, the PED (Post Exposure Delay) stability is hindered, and the edge unevenness on the substrate is changed. [I group] In the compound represented by the following general formulae (A1) to (A10), one or all of the hydrogen atoms are partially or wholly by -R4()1-cooh (R4〇·10 linear or branched) A compound in which a phenolic hydroxyl group (C) is substituted with a phenolic hydroxyl group (C) and a group (D) represented by ΞC-COOH/(C+D) = 0.1 to 1.0. Number 4~20 Base sand yard base system, the basic part of the sample, used together. The side which produces a reduction or a base of a carboxyl group, for example, can be combined to improve the optically good nitride film.

The phenolic hydroxyl group is a carbon number of 1 molecule, and the ear ratio is C <S> -85-1375122 [Group II] a compound represented by the following formula (All) to (A15)

[5 1 (0H),, ,402

(A2)

(OH). 〇402 jQ>-(R4O5)UIH0r (A4)

(〇H), 2 p402 K S2

(A10) 1375122 [OH 5j R (OH), 5 (OHXj R402,

r4I,-cooh COOH (All)

COOH (A 12)

(A13)

In the above formula, R402 and R4Q3 are each a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms. R4M is a hydrogen atom or a linear or branched alkyl or alkenyl group having 1 to 8 carbon atoms, or a -(R4°9)hl-COOR' group (R' is a hydrogen atom or -R4Q9-C〇OH) . R4Q5 is -(CH2)i- (i = 2 to 10), a aryl group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R4()6 is an alkylene group having 1 to 10 carbon atoms, an extended aryl group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom. R4()7 is a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a phenyl group or a naphthyl group each substituted with a hydroxyl group. R4<)8 is a hydrogen atom or a methyl group. R4()9 is a linear or branched alkyl group having a carbon number of 1 to 10. R41() is a hydrogen atom or a linear or branched alkyl group having a carbon number of 1 to 8 -87- <5> 1375122 or an alkenyl group or a -R4n-COOH group (wherein R411 is a carbon number of 1 to 10) a linear or branched alkyl group). R412 is a hydrogen atom or a hydroxyl group. j is a number from 0 to 3, si, tl, s2, t2, s3, t3, s4, t4, respectively satisfying sl+tl=8, s2+t2=5, s3+t3=4, s4+t4=6, And each phenyl skeleton has at least one hydroxyl group.

S5 and t5 are the numbers satisfying s520, t520, and s5+t5=5. Ul is a number satisfying l$ulS4, hi is a number satisfying lghl$4, and c is a compound of the formula (A6) having a weight average molecular weight of 1,000 to 5,000. The compound of the formula (A7) is a weight average molecular weight of 1,000 to 1 Torr, and the number of ruthenium. The present component is specifically, for example, a compound represented by the following formulas (ΑΙ-1) to (ΑΙ-14) and (ΑΙΙ-1) to (ΑΙΙ-10), but is not limited by the above φ exemplification. < S > -88 1375122 [Chemical 5 3 OR"

Οό (AM) Gan

RO

Rw. _ /=\

RO OR" ch2 COOR" (AI-3) (AI-2) CH-R°°-^y9-Q^〇Rn ch2 I l CH2-COORn (AM) O~0R"R"°^〇-°-〇-0R" (AI-5) ch2-^~^— or” (AI-7)

(AI-9)

λ OR" (AMI) OR"

•OR" (AI-6) h3c

OR" (AI-10)

Ο, OR" RO—(\ />-CH9COORn (AI-14) < S > -89- 1375122

[5 4

Or ch2cooh

COOH (AII-5)

(AII-7)

(ΑΠ-2)

Ch2cooh

(AII-6) COOH j〇 (AII-8)

COOH (wherein 'R' in the above formula is a hydrogen atom or a CH2COOH group, and in each compound, 10 to 100 mol% of R" is a CH2COOH group. /c and λ have the same meanings as described above). Further, the amount of the compound having a group represented by sC-COOH in the molecule is 0 to 5 parts by mass, preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass based on 100 parts by mass of the base resin. The mass fraction is preferably 0.1 to 2 parts by mass. When it is 5 parts by mass or less, the resolution of the photoresist material < S > -90-1375122 can be lowered. The acetylenic derivative ** which can be added to the photoresist of the present invention is preferably used, for example, as shown by the following general formulae (SI) and (S2). [5 5] R5〇2 r5M r502 R501—C=C-C-R503 R505-C-C=C-C-R503

I I I

0—(CH2CH20)YH H(0CH2CH2)x-0 〇—(CH2CH2〇)yH (SI) (S2) (In the above formula, R5(n, R5°2, R5°3, R5°4, R5°5 They are each a hydrogen atom, or a linear, branched or cyclic alkyl group having a carbon number of 1 to 8, and X and Y are 〇 or a positive number, and satisfy the following number: 0SXS30, 0SYS30, 0 ^ X + Υ ^ 40) Among the acetylenic alcohol derivatives, preferred are, for example, Surfynol® 61, Surfynol® 82, Sur y f y 1® 104, Surfy η o 1® 104E,

S urfy η o 1 ® 1 0 4 H, S urfy η o 1 ® 1 0 4 A, Surfynol® TG, Surfynol® PC 'S ur fy η ο 1 ® 4 4 0, Sur yfy η ο 1 ® 4 6 5 Surfynol® 485 (SUrfyn〇l® E 1 004 manufactured by Air Products and Chemicals Inc.), etc. The amount of the above-mentioned alkynol derivative is added to the base polymer 100 of the photoresist material. The mass part is 〇2 parts by mass, more preferably 0.01 to 2 parts by mass, most preferably 0.02 to 1 part by mass. When it exceeds 2 parts by mass, there is a case where the resolution of the photoresist material is lowered. The pattern forming method of the photoresist material can be carried out by using a known lithography etching technique, by coating, heat treatment (pre-baking) -91 - 1375122, exposure, heat treatment (Post*Exposure*Back; PEB) It is achieved by various steps such as development, and if necessary, several additional steps can be added.

When forming a pattern, first, the photoresist material of the present invention is spin-coated on a substrate for manufacturing an integrated circuit (Si, SiO 2 , SiN, SiON, TiN, WSi, BPSG, SOG, organic anti-reflection film, Cr, On the CrO, CrON, Mo Si, etc., the coating film thickness is applied to the coating film by a coating method such as roll coating, flow coating, dip coating, spray coating or blade coating as appropriate. /zm, on a hot plate, at 60 to 150 ° C for 1 to 10 minutes, preferably at 80 to 140 ° C for 1 to 5 minutes of pre-baking. Compared with the photoresist thin film formation and the etching selectivity of the substrate to be processed, the processing is more severe. At present, the germanium containing interlayer film is laminated under the photoresist, and the layer is laminated under the high carbon density. The three-layer process obtained by etching the underlying film under the etch resistance and laminating the substrate to be processed is investigated. The etching of the ruthenium containing interlayer film and the underlayer film using oxygen gas, hydrogen gas, ammonia gas or the like is relatively high, and the ruthenium containing interlayer film can also be thinned. The single-layer photoresist and the tantalum-containing intermediate layer have a higher etching selectivity ratio, so that the single-layer photoresist can also be formed into a thin film. In this case, the method for forming the underlayer film includes, for example, a method of forming a coating and baking, a method of forming a CVD, and the like. In the case of a coating type, a resin obtained by polymerizing an olefin having a novolac resin or a condensed ring or the like can be used, and in the case of producing a CVD film, a gas such as butane, ethane, propane, ethylene or acetylene can be used. Examples of the ruthenium-containing intermediate layer include a coating type and a CVD type, and the coating type is, for example, a sesquiterpene oxide or a caged sesquioxaxane (POSS). For CVD, for example, various decane gases are used. Raw materials, etc. The antimony-containing intermediate layer may have an anti-reflection function of light absorption, and may have a light-absorbing group such as C S>-92-1375122 phenyl or an SiON film. An organic film may be formed between the ruthenium containing interlayer film and the photoresist, and the organic film in this case may be an organic antireflection film. After the formation of the photoresist film, pure water washing (post soak) may be carried out to extract the acid generator or the like from the surface of the film, or to wash the particles, or to apply a protective film.

Next, a light source selected from ultraviolet light, far ultraviolet light, electron beam, X-ray, excimer laser, r-line, isotope radiation, or the like is used, and exposure is performed by a specific mask to form a target pattern. The exposure amount is preferably from about 1 to 200 mJ/cm 2 , particularly preferably from about 10 to about 1 μM/cm 2 . Next, it is baked on a hot plate at 60 to 150 ° C for 1 to 5 minutes, more preferably at 80 to 120 ° C for 1 to 3 minutes (Post· Exposure* Back; PEB). Subsequently, 0.1 to 5% by mass, preferably 2 to 3% by mass of a developing solution of an aqueous alkali solution such as tetramethylammonium hydroxide (TMAH) is used, for 0.1 to 3 minutes, preferably 0.5 to 2 minutes. The development is carried out by a usual method such as a dip method, a puddle method, or a spray method, and a desired pattern can be formed on the substrate. Further, the photoresist material of the present invention preferably uses ultraviolet rays having a wavelength of 254 to 193 nm, vacuum ultraviolet rays having a wavelength of I57 nm, electron lines, soft X-rays, X-rays, excimer laser 'r-line, isotope radiation'. In order to use a high-energy line in the range of 180 to 200 nm, the micro-pattern is best described. Further, the photoresist of the present invention can be applied to immersion lithography etching in ArF immersion lithography, immersion solvent Pure water, or a liquid having a refractive index of 1 or more and having less absorption of exposure light can be used. Immersion micro-etching <S> -93-

In 1375122, a liquid or other liquid can be inserted between the pre-baked photoresist film and the projection lens. In this way, a lens having an NA of 1.0 or more can be formed to form a finer pattern. Immersion lithography is an important technique for extending ArF to 45nm node, and it is urgent to accelerate the exposure of the immersion exposure. In order to remove the residual water droplets on the photoresist film, pure water is washed after exposure (post-soak In addition, in order to prevent the hindered substance from being blocked by light and to improve the water slidability of the film surface, a protective film may be formed on the prosthetic photoresist film. a resistive protective film for immersion liquid lithography, for example, a molecular compound which is insoluble in water and soluble in the 1,1,1,3,3,3-hexa-2-2-propanol residue of the alkali developing solution Further, it is preferably an alcohol solvent having a carbon number of 4 or more, a solvent having a carbon number of 8 to 12, and a material of the mixed solvent. In addition, the ArF lithography is extended to a 32 nm extension technique such as a repeated pattern drawing method. The repeating pattern drawing method is performed, for example, under the first light, by etching the bottom of the 1:3 trench pattern, and then moving the position by performing the second exposure to form a 1: groove pattern formation 1 : 1 pattern groove method 'by the first exposure, the first bottom of the 1:3 independent residual pattern is etched and then the position is moved by performing the second exposure 'to form a pair 1: The second bottom below the first bottom of the residual pattern is processed to form a 1:1 line method with a half pitch. [Embodiment] [Examples] Pure water meter, micro-shadow. The solvent which can be calcined in the fire can be used as a base ether, and the third exposure is carried out by a single exposure, and the work is carried out, and the three processes are carried out, and the following examples are given to the present invention by way of examples and comparative examples. It should be noted that the present invention is not limited by the following embodiments. Preparation of Photoresist Material [Examples] The polymer compound, the acid generator, the basic compound, and the solvent were mixed and dissolved according to the composition shown in Table 1 below, and then Teflon (φ registered trademark) was used. The filter (aperture 〇. 2 vm) was filtered to serve as a photoresist material. Further, all of the solvents were used in an amount of 0.005 mass% of KH-20 (manufactured by Asahi Glass Co., Ltd.) containing a surfactant. < S >

-95- 1375122

[Table i] Photoresist resin acid generator Basic compound solvent 1 Solvent 2 R-01 P-01 (80) PAG-1 (101) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-02 P -02 (80) PAG-1 (10_1) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-03 P-03 (80) PAG-1 (10.1) Base-1 (1.4) PGMEA (U20) CyHO (480) R-04 P-04 (80) PAG-1 (10.1) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-05 P-05 (80.) PAG-I (iO.i Base-i (i.4) PGMEA (i, i20) CyHO (480) R-06 P-06 (80) PAG-1 (10-1) Base-1 (1-4) PGMEA (1,120) CyHO ( 480) R-07 P-07 (80) PAG-1 (10.1) Base-1 (1_4) PGMEA (1,120) CyHO (480) R-08 P-08 (80) PAG-1 (10.1) Base-1 ( 1.4) PGMEA (l,12〇) CyHO (480) R-09 P-09 (80) PAG-1 (10.1) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-10 P-10 (80 PAG-1 (101) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-11 P-11 (80) PAG-1 (10_1) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-12 P-12 (80) PAG-1 (10.1) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-13 P-13 (80) PAG-1 (IO.i) Base-1 ( 1-4) PGMEA (1,120) CyHO (480) R-14 P-14 (80) PAG-1 (10.1) Base-1 (1.4) PGMEA (1,120) Cy HO (480) R-15 P-15 (80) PAG-1 (10.1) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-16 P-16 (80) PAG-1 (10.1) Base- 1 (1_4) PGMEA 0,120) CyHO (480) R-17 P-17 (80) PAG-1 (ίο-i) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-18 P-18 (80 PAG-1 (10.1) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-19 P-19 (80) PAG-1 (10.1) Base-1 (1.4) PGMEA 0,120) CyHO (480) R -20 P-01 (80) PAG-2 (11.0) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-21 P-01 (80) PAG-3 (10.0) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-22 P-01 (80) PAG-4 (10.2) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-23 P-01 (80) PAG-5 (15.0 Base-1 (1.4) PGMEA (U20) CyHO (480) R-24 P-01 (80) PAG-6 (10.6) Base-1 (1.4) PGMEA (U20) CyHO (480) R-25 P-15 (80) PAG-2 (11.0) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-26 P-15 (80) PAG-3 (10.0) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-27 P-15 (80) PAG-4 (10.2) Base-1 (1.4) PGMEA (U20) CyHO (480) R-28 P-15 (80) PAG-5 (15.0) Base- 1 (1.4) PGMEA (U20) CyHO (480) R-29 P-15 (8〇) PAG-6 (10.6) Base-1 (1.4) PGMEA (1,120) C yHO (480) R-30 P-17 (80) PAG-2 (no) Base-1 (1.4) PGMEA (U20) CyHO (480) R-31 P-17 (80) PAG-3 (10.0) Base- 1 (1.4) PGMEA (U20) CyHO (480) R-32 P-17 (8〇) PAG-4 (10.2) Base-1 (1.4) PGMEA 0,120) CyHO (480) R-33 P-17 (80) PAG-5 (15.0) Base-1 (1.4) PGMEA (U20) CyHO (480) R-34 P-17 (80) PAG-6 (10.6) Base-1 (1.4) PGMEA (1,120) CyHO (480 ) In the brackets, the addition ratio (parts by mass).

c S -96-1375122 [Comparative Example] According to the composition shown in the following Table 2, a comparative photoresist was produced in the same order as in the examples. [Table 2] Photoresist resin acid generator Alkaline ί 匕 Compound solvent 1 Solvent 2 R-35 P-20 (80) PAG-1 (10.1) Base-1 (1.4) PGMEA (U20) CyHO (480) R -36 P-21 (80) PAG-1 (10.1) Base-1 (1-4) PGMEA (1,120) CyHO (480) R-37 P-22 (80) PAG-1 (101) Base-1 (1_4 PGMEA (1,120) CyHO (480) R-38 P-01 (80) PAG-7 (8.7) Base-1 (1.4) PGMEA (U20) CyHO (480) R-39 P-15 (80) PAG-7 (8.7) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-40 P-17 (80) PAG-7 (8.7) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-41 P -01 (8〇) PAG-8 (9-3) Base-1 (1.4) PGMEA (1,120) CyHO (480) R-42 P-15 (80) PAG-8 (9.3) Base-1 (1.4) PGMEA (U20) CyHO (480) R-43 P-17 (80) PAG-8 (9.3) Base-1 (1.4) PGMEA (1,120) CyHO (480)

In the brackets, the addition ratio (parts by mass). In Tables 1 and 2, the number 値 in parentheses is parts by mass. The base φ compound and solvent shown by the abbreviation are as follows.

Base-Ι: Tris(2-methoxymethoxyethyl)amine PGMEA: 1-methoxyisopropyl acetate

CyHO: cyclohexanone Further, the resins shown in Tables 1 and 2 are abbreviated as the polymer compounds shown in Tables 3 to 8, respectively. < £ ) -97- 1375122

[Table 3] Resin unit 1 (introduction ratio) Unit 2 (introduction ratio) Unit 3 (introduction ratio) Unit 4 (introduction ratio) Weight average molecular weight P-01 A-1M (0.30) B-1M (0.15) C-1M (0.30) D-1M(0.25) 7,100 P-02 A-2M(0.30) B-1M(0.15) C-1M(0.30) D-1M(0.25) 6,800 P-03 A-3M(0.30) B-1M (0.15) C-1M(0.30) D-1M(0.25) 6,500 P-04 A-4M(0.30) B-1M(0.15) C-1M(0.30) D-1M(0.25) 7,000 P-05 A-5M (0.30) B-1M(0.15) C-1M(0.30) D-1M(0.25) 7,200 P-06 A-1M(0.30) B-1M(0.15) C-2M(0.30) D-1M(0.25) 7,300 P-07 A-2M(0.30) B-1M(0.15) C-2M(0.30) D-1M(0.25) 6,800 P-08 A-1M(0.30) B-1M(0.15) C-3M(0.30) D -1M(0.25) 7,300 P-09 A-2M(0.30) B-1M(0.15) C-3M(0.30) D-1M(0.25) 6,900 P-10 A-1M(0.30) B-1M(0.15) C -1M(0.30) D-2M(0.25) 7,000 P-11 A-1M(0.30) B-1M(0.15) C-1M(0.30) D-3M(0.25) 6,900 P-12 A-1M(0.30) B -1M(0.15) C-2M(0.30) D-2M(0.25) 7,100 P-13 A-1M(0.30) B-1M(0.15) C-2M(0.30) D-3M(0.25) 6,900 P-14 A -2MC0.30) B-1M(0.15) C-1M(0.30) D-2M(0.25) 6,700 P-15 A-2M(0.30) B-1M(0.15) C-1M(0.30) D-3M(0.25 ) 6,600 P-16 A-2M (0.30) B-1M (0.15) C-2M (0 .30) D-2M(0.25) 6,700 P-17 A-2M(0.30) B-1M(0.15) C-2M(0.30) D-3M(0.25) 6,500 P-18 A-1M(0.30) B-2M (0.15) C-1M(0.30) D-1M(0.25) 7,000 P-19 A-1M(0.30) B-1A(0.15) C-1M(0.30) D-1M(0.25) 6,700 P-20 A-2M (0.30) B-1M(0.15) C-1M(0.55) 6,700 P-21 A-2M(0.30) B-1M(0.15) E-1M(0.55) 6,900 P-22 A-2M(0.30) B-1M (0.15) E-2M (0.55) 6,700 The introduction ratio is the molar ratio. < B > -98- 1375122 [Table 4]

• [Table 5] φ m 6]

(S > -99- 1375122 [Table 7]

[Table 8]

In Tables 1 and 2, the acid generators referred to as abbreviations are shown as the onium salt compounds shown in Table 9, respectively. -100- 1375122 [Table 9]

Analytical evaluation [Examples 1 to 34 and Comparative Examples 1 to 9]

The photoresist materials (R-01 to 34) of the present invention and the photoresist materials (R-35 to 43) for comparison are respectively spin-coated on an antireflection film (ARC29A, manufactured by Nissan Chemical Industries Co., Ltd.). On a silicon wafer of 78 nm), a photoresist film having a thickness of 120 mm was formed by heat treatment at 100 ° C for 60 seconds. It was exposed to an ArF excimer laser stepper (manufactured by Ricoh Ricoh, NA = 0.85) after being subjected to a heat treatment (PEB) for 60 seconds, and then subjected to a 2.38 mass% aqueous solution of tetramethylammonium hydroxide. A 30-second agitation development resulted in a 1:1 line and space pattern and a 1:10 independent line pattern. In PEB, the temperature most suitable for each photoresist material is used. For -101 - 1375122

The wafer with the pattern produced is observed by SEM (scanning electron microscope) from above, and the exposure amount is 1:10 when the line and space pattern of 80 nm are analyzed as the optimum exposure amount (mJ) /cm2), the minimum size of the line and space pattern of the 1:1 separation and analysis is the critical resolution (the size on the mask, 5 mm scale, the smaller the size, the better). In addition, in the optimum exposure amount, an independent circuit pattern of 1:1 is observed, and the actual size of the independent wiring pattern of the mask size of 140 nm on the wafer is measured, as the mask faith (size on the wafer, size) The bigger the better). In addition, and observe the roughness of the pattern (LER = line sidewall unevenness), judge by the evaluation of the three-stage (good 'can be, bad'). The evaluation results (critical resolution, mask fidelity, LER) of the photoresist of the present invention are shown in Table 10, and the evaluation results (critical resolution, mask fidelity, LER) of the photoresist materials for comparison are described. In Table 11. -102- 1375122

[Table 10 Example Photoresist PEB Temperature Optimal Exposure Critical Resolution Mask Faithfulness LER 1 R-01 9 5〇C 24.0mJ/cm2 65nm 79nm Good 2 R-02 9 5〇C 27.0mJ/cm2 65nm 81nm Good 3 R-03 9 5〇C 25.0mJ/cm2 65nm 80nm Good 4 R-04 r\ r 27.0mJ/'cm2 05nm 82nm 5 R-05 105°C 28.0mJ/cm2 70nm 75nm Good 6 R-06 9 5 〇C 23.0mJ/cm2 65nm 77nm Good 7 R-07 9 5〇C 25.0mJ/cm2 65nm 78nm Good 8 R-08 9 5 °C 24.0mJ/cm2 70nm 76nm Good 9 R-09 9 5〇C 26.0mJ/ Cm2 65nm 78nm Good 10 R-10 9 5 °C 23.0mJ/cm2 65nm 76nm Good 11 R-11 9 5 °C 24.0mJ/cm2 65nm 77nm Good 12 R-12 9 5 °C 23.0mJ/cm2 65nm 75ran Good 13 R-13 9 5〇C 23.0mJ/cm2 65nm 75nm Good 14 R-14 9 5〇C 26.0mJ/cm2 65nm 78nm Good 15 R-15 9 5 °C 26.0mJ/cm2 65nm 79nm Good 16 R-16 9 5 °C 24.0mJ/cm2 65nm 77nm Good 17 R-17 9 5 °C 25.0mJ/cm2 65nm 77nm Good 18 R-18 9 5 °C 26.0mJ/cm2 65nm 80nm Good 19 R-19 90°C 22.0mJ/cm2 70nm 75nm Good 20 R-20 9 5 °C 27.0mJ/cm2 65nm 81nm Good 21 R-21 9 5 °C 25.0mJ/cm2 6 5nm 82nm Good 22 R-22 9 5 °C 25.0mJ/cm2 65nm 81nm Good 23 R-23 9 5〇C 29.0mJ/cm2 65nm 84nm Good 24 R-24 9 5 °C 25.0mJ/cm2 65nm 79nm Good 25 R -25 9 5〇C 29.0mJ/cm2 65nm 81nm Good 26 R-26 9 5〇C 28.0mJ/cm2 65nm 82nm Good 27 R-27 9 5〇C 28.0mJ/cm2 65nm 82nm Good 28 R-28 9 5〇 C 33.0mJ/cm2 65nm 85nm Good 29 R-29 9 5〇C 28.0mJ/cm2 65nm 80nm Good 30 R-30 9 5 °C 28.0mJ/cm2 65nm 79nm Good 31 R-31 9 5 °C 27.0mJ/cm2 65nm 80nm Good 32 R-32 9 5〇C 28.0mJ/cm2 65nm 79nm Good 33 R-33 9 5 °C 31.0mJ/cm2 65nm 83nm Good 34 R-34 9 5 °C 27.0mJ/cm2 65nm 78nm Good< s > -103- 1375122 [Table 11] Comparative Example Photoresist PEB Temperature Optimal Exposure Critical Resolution Mask Faithfulness LER 1 R-35 9 5〇C 22.0mJ/cm2 70nm 71nm Available 2 R-36 105° C 24.0mJ/cm2 65nm 83nm Poor 3 R-37 105°C 24.0mJ/cm2 70nm 79nm Poor 4 R-38 9 5〇C 21.0mJ/cm2 75nm 65nm Good 5 R-39 9 5〇C 22.0mJ/cm2 75nm 59nm good 6 R-40 9 5〇C 20.0mJ/cm2 75nm 57nm good 7 R-41 9 5〇C 22.0mJ/c M2 75nm 67nm Good 8 R-42 9 5〇C 20.0mJ/cm2 75nm 58nm Good 9 R-43 9 5〇C 20.0mJ/cm2 75nm 59nm Good

As is apparent from the results of the table, the photoresist materials of the present invention (Examples 1 to 3 4) confirmed that the LER was sufficiently suppressed in addition to the excellent analytical performance. Further, from Comparative Examples 1 to 3 in the Table, it was found that when the conventional resin was used, the analysis performance was deteriorated, or the LER was not inhibited. Further, in Comparative Examples 4 to 9 in Table 11, it was found that even in the case where the resin of the present invention was used in combination with a conventional acid generator, it was extremely difficult to derive φ, which was particularly advantageous in analytical performance. There is no improvement over previous products. As described above, the use of a polymer compound having a specific repeating unit as a base resin, and a photoresist material of the present invention used in combination with a special acid generator having suppressed acid diffusion property is constructed in comparison with the prior art. When the materials were compared, it was confirmed that the analytical performance was improved and the LER was suppressed. -104-

Claims (1)

137-5122 Patent application No. 096,144,172 Patent application for amendment of the scope of patent application in the Republic of China, June 22, 2011, Amendment X. Patent application scope 1. A positive-type photoresist material, which is formed by containing (A) acid-based action a compound which is a soluble resin component to the alkali developer and (B) an acid which generates an acid by inducing active light or radiation, wherein the resin component (A) is a polymer having a repeating unit represented by the following formula (1) The compound 'B' and the acid-generating compound (B) is a positive-type photoresist material of the onium salt compound represented by the following formula (2), R1 is independently a hydrogen atom, a methyl group, or a trifluoromethyl group; R2 is an acid labile group; R3 is a hydrogen atom or C〇2R4; and R4 is a linear or branched group having a carbon number of 1 to 20 which may contain a hetero atom. a monovalent hydrocarbon group or a ring; X is 〇, s, CH2' or CH2CH2; m is 1 or 2; n is 1 or 2; a, b, c, and d are the ratios of the respective repeat positions, a , b, c, and d are respectively above 001, and the number is less than 1, a+b+c+d=l [Chemical 2] In the formula, R5, R6 and R7 are each independently a hydrogen atom, or may contain a hetero atom of 1375122, a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms; and R8 is a carbon which may contain a hetero atom A straight-chain, branched or cyclic monovalent hydrocarbon group of 7 to 8. 2. The positive-type photoresist material according to claim 1, wherein the acid-labile group of the resin component (Α) is one or two selected from the following formulas (al) to (a-5); More than the above, [Chemical 3] (a·)) (a-2) (a-3) (a-4) (a-5) where the dotted line is the bonding key: R9, R1G, R11, R12, and R13 are each independently carbon number 1~ a linear or branched alkyl group of 4; 0 is 1 or 2: p is 1 or 2. 3. A method of forming a pattern, comprising the steps of applying a photoresist material according to claim 1 or 2 to a substrate, and applying a high energy line or an electron beam through the mask after the heat treatment; The step of exposing, and the step of developing using a developing solution after the heat treatment. 4. A method for forming a pattern, comprising the step of applying a photoresist material according to claim 1 or 2 to a substrate, and applying a high energy line or an electron beam through the mask after the heat treatment The step of exposing, and the pattern forming process of the step of developing using a developing solution after the heat treatment, is characterized in that a liquid having a refractive index of 1 or more is used between the photoresist coating film and the projection lens to perform immersion exposure. 5. A method for forming a pattern, comprising the step of applying a photoresist material according to claim 1 or 2,375, 122 or 1 to a substrate, and applying high energy to the mask after the heat treatment a step of forming a line or an electron beam, and a pattern forming process of the step of developing with a developing solution after the heat treatment, wherein the protective film is coated on the photoresist coating film, and a refractive index of 1 or more is used. The liquid is infiltrated between the protective film and the projection lens