TW201250381A - Photoresist composition - Google Patents

Abstract

The purpose of the present invention is to provide a photoresist composition that fully satisfies basic properties such as sensitivity, and has excellent lithographic performance including MEEF, DOF, and LWR. This photoresist composition includes: [A] one or more types of a polymer constituent having, in identical or differing polymers, a structural unit (I) represented by formula (1), and a structural unit (II) that is a structural unit other than the structural unit (I) and includes at least one type of structure selected from the group consisting of cyclic carbonate structures, sultone structures, and lactone structures; and [B] an acid generator.

Description

201250381 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a photoresist composition. [Prior Art] In the field of microfabrication for manufacturing integrated circuit components and the like, in order to obtain a higher degree of integration, a KrF excimer laser (wavelength 248 nm) or an ArF excimer laser (wavelength 193 nm) is used. Development of lithography techniques for short-wavelength radiation. As a photoresist material suitable for such radiation, a chemically amplified photoresist composition containing a component having an acid dissociable group and an acid generator which generates an acid by radiation is widely used from the viewpoints of high sensitivity and high resolution. (Japanese Laid-Open Patent Publication No. 59-4 543-9). In such a photoresist composition, as a composition for applying an ArF excimer laser having a shorter wavelength, for example, a composition containing a polymer having an alicyclic group having no large absorption in the field of 193 nm in the skeleton is known. . In addition, the above-mentioned polymer is proposed to have a spironolactone structure (Japanese Laid-Open Patent Publication No. 2002-82441, Japanese Patent Application Laid-Open No. Hei. Such a polymer having a spirolactone structure can improve the development contrast of the photoresist composition containing the same.

However, in recent years, in order to further reduce the size of the device, the photoresist composition requires a higher level of performance and pursues superior lithography characteristics. Therefore, even if a conventional photoresist composition is used, the high level requirement cannot be satisfied. . For example, the current state of the photoresist composition cannot sufficiently satisfy the MEEF (Mask Error Enha IIcemnt Factor) indicating the mask error tolerance, and the DOF (Depth Of Focus) indicating the depth of focus indicates the line width distribution LWR 201250381 (Line Width Roughness) is the lithography feature of the indicator. In view of such a situation, in the formation of a photoresist composition for a finer resist pattern, not only the basic characteristics such as sensitivity and resolution, but also the improvement of the performance of micro-images using MEEF, DOF, LWR, etc. as indicators. Wait. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-2002-82441 (Patent Document No. JP-A-2002-82441) SUMMARY OF THE INVENTION [Problem to be Solved by the Invention] The present invention has been made based on the above circumstances, and an object thereof is to provide not only basic characteristics such as sensitivity but also microscopy performance using MEEF, DOF, LWR, etc. as indicators. Photoresist composition. [Means for Solving the Problem] The invention comprising the same or different polymer of [A] has the structural unit (I) represented by the following formula (1) and the structural unit (1) a structural component other than (I) and a polymer component of the structural unit (II) having at least one structure selected from the group consisting of a cyclic carbonate structure, a sultone structure, and a lactone structure (hereinafter) , also known as "[A] polymer component J), and

S -6- 201250381 [B] Photoresist composition of acid generator. [1] R1

(In the formula (1), R1 is a hydrogen atom, a fluorine atom, a hydroxyl group or a monovalent organic group having 1 to 20 carbon atoms. R2 and R3 each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group or a monovalent number of carbon atoms of 1 to 20. The organic group or R2 and R3 are bonded to each other to form a ring structure having a carbon number of 3 to 10, and a is an integer of 1 to 6. However, when a is 2 or more, the plural R2 and R3 are each R4 and R5 are each independently a hydrogen atom, a fluorine atom, a hydroxyl group or a monovalent organic group having a carbon number of 1 to 20 or R4 and R5 are bonded to each other to form a carbon number with the carbon atoms bonded thereto. A ring structure of 3 to 10. However, some or all of the hydrogen atoms of the above ring structure may be substituted). The photoresist composition contains a [Α] polymer component having a structural unit (I) having a lactone structure represented by the above formula (1) and a structural unit (II) having a cyclic structure such as a cyclic carbonate. The performance of lithography with MEEF, LWR, DOF, etc. is excellent. The structural unit (II) is preferably a structural unit represented by the following formula (2) (2) 201250381 [Chemical 2]

(In the formula (2), R6 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R7 is a hydrocarbon group having a carbon number of 1 to 10. X is -〇-, -COO-, -OCO· or -NH- n is an integer of 0 to 10. When η is 2 or more, each of R 6 and X may be the same or different. R 8 is a single bond or a hydrocarbon group having a carbon number of 1 to 5 is a structure having a cyclic carbonate structure. At least one structural cyclic organic group selected from the group consisting of a sultone structure and a lactone structure. However, some or all of the hydrogen atoms of R7 to R9 may be substituted. By the above-described structural unit (Π) being a specific structure represented by the above formula (2), the photo-resist composition has an improved lithography performance using MEEF, LWR, DOF or the like as an index. The polymer component of [A] is preferably a structural unit (III) represented by the following formula (3). 【化3】 R10

R11 — C —— R13 I R12 (3)

S -8- 201250381 (in the formula (3), R10 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R11 to R13 are each independently an alkyl group having 1 to 4 carbon atoms or a carbon number of 4 to 20 carbon atoms. An alicyclic group. However, R11 and R12 may bond each other to the carbon atom to which they are bonded to form an alicyclic structure. Further, some or all of the hydrogen atoms of the above alkyl group and the alicyclic group may be Was replaced). The structural unit (III) represented by the above formula (3) has an acid dissociable group which is easily dissociated by the action of an acid generated from the [B] acid generator upon exposure, and the photoresist composition is in [A] The polymer component further contains a structural unit (III), which satisfies the basic characteristics such as sensitivity. The cyclic organic group having a lactone structure represented by the above R9 is a norbornane lactone group or a butyrolactone group, and the cyclic organic group having a cyclic carbonate structure is an ethylene carbonate group, and the above has a sultone structure. The cyclic organic group is preferably a norbornane sultone group. The cyclic organic group possessed by the above structural unit (II) is the above-mentioned specific group, and the photoresist composition can improve the performance of the lithography with MEEF, LWR, DOF and the like as an index. [A] The content of the structural unit (I) in the polymer component is 5 mol% or more and 60 mol% or less, and the total content of the structural unit (I) and the structural unit (III) is 10 mol% or more. 80% or less is preferred. By setting the content ratio of the structural units (1) and (ΠΙ) in the [A] polymer component to the above specific range, the photoresist composition can be made of MEEF, LWR, DOF, etc. in addition to basic properties such as sensitivity. The lithography performance of the indicator is improved. [A] The content ratio of the structural unit in the polymer component is determined from the 13C-NMR spectrum of the [A] polymer component, and the peak area ratio of the wave of the corresponding structural unit in the spectrum is obtained in the [A] polymer component. The average 値 is found. [Effect of the Invention] As described above, the photoresist composition of the present invention contains the structural unit (I) having a lactone structure and the structural unit (II) having a cyclic structure such as a cyclic carbonate. In addition to the basic characteristics such as sensitivity, the polymer component is excellent in lithography performance using MEEF, LWR, and DOF as indicators. Therefore, by using the photoresist composition, the fine pattern can be formed with high precision. [Best Mode for Carrying Out the Invention] <Photoresist Composition> The photoresist composition contains [A] a polymer component and a [B] acid generator. Further, other components may be contained without impairing the effects of the present invention. The components are detailed below. <[A] Polymer component> [A] The polymer component is a structural unit (I) represented by the above formula (1) in the same or different polymer, and other than the structural unit (I) The structural unit further contains one or more polymer components of at least one structural unit (Π) selected from the group consisting of a cyclic carbonate structure, a sultone structure, and a lactone structure. The photoresist composition is excellent in MEEF, DOF and LWR by containing the [A] polymer component' in addition to the basic characteristics such as sensitivity. Further, the [A] polymer component may be a monomer compound such as a monomer compound constituting a structural unit (丨) and a monomer compound constituting a structural unit (Π), and the like.

S -10- 201250381 The copolymer of the substance may be a polymer containing a polymer in which a monomer compound constituting the structural unit (I) is mixed, and a polymer of a monomer compound constituting the structural unit (II). A component of two or more kinds of polymers. Further, it is preferable that the structural unit (I) and the structural unit (II) have the structural unit (III) represented by the above formula (3). Further, other structural units may be provided without damaging the effects of the present invention. Hereinafter, each structural unit will be described in detail. [Structural unit (I)] The structural unit (I) is represented by the above formula (1). [A] The polymer component is excellent in the MEEF performance, DOF and LWR because it has a structural unit (I) having a specific lactone structure directly bonded to the polymer main chain. In the above formula (1), R1 is a hydrogen atom, a fluorine atom, a hydroxyl group or a monovalent organic group having 1 to 20 carbon atoms, and R2 and R3 each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group or a monovalent number of carbon atoms of 1 to 20. The organic group, or R2 and R3, are bonded to each other to form a ring structure having a carbon number of 3 to 10 together with the carbon atoms bonded thereto. a is an integer from 1 to 6. However, when a is 2 or more, the plural R2 and R3 may be the same or different. R4 and R5 are each independently a hydrogen atom, a fluorine atom, a hydroxyl group or a monovalent organic group having 1 to 20 carbon atoms, or R4 and R5 are bonded to each other and a carbon atom bonded thereto to form a ring structure having a carbon number of 3 to 10. . However, part or all of one of the hydrogen atoms of the above ring structure may be substituted. The monovalent organic group having 1 to 20 carbon atoms represented by the above R1 to R5 may, for example, be a chain hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms. a hydrocarbon group, a heterocyclic group having a nuclear atom number of 3 to 10, an epoxy group, a cyano group, a carboxyl group, a group represented by -R'-QR", etc. However, R' -11 - 201250381 is a single bond or a carbon number of 1 a hydrocarbon group of -20. R" is a hydrocarbyl group having a carbon number of 20 which may be substituted. Q is -〇-, -CO-, -NH-, -S02-, -SO- or a combination of these. Part or all of one or more of the hydrogen atoms of the chain hydrocarbon group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted by a halogen atom such as a fluorine atom, a cyano group, a carboxyl group, a hydroxyl group or a sulfhydryl group. The chain hydrocarbon group having 1 to 20 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group or a decyl group. Among these, a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group are preferred, and a methyl group and an ethyl group are more preferred. Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include a monocyclic alicyclic hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, a cyclooctyl group or a cyclodecyl group; a norbornyl group, an adamantyl group, or the like. A polycyclic alicyclic hydrocarbon group or the like. Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group. The heterocyclic group having 3 to 10 core atoms may, for example, be a lactone group, a cyclic carbonate group, a sultone group, a furyl group, a thienyl group, a benzofuranyl group, a benzothienyl group or a dibenzofuran. Base, dibenzothiophenyl, pyridyl and the like. Among these, a lactone group, a cyclic carbonate group and a sultone group are preferred, and a lactone group is more preferred. The hydrocarbon group having 1 to 20 carbon atoms represented by R and R in the above -R'-QR" may, for example, be a chain hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, or carbon. A number of 6 to 20 aromatic hydrocarbon groups and the like. The same groups as those exemplified in the monovalent organic group having 1 to 20 carbon atoms represented by the above R1 to R5 are exemplified. R2 and R3 and R4 and R5 are bonded to each other and bonded to each other

S 12-201250381 The ring structure having a carbon number of 3 to 10, which is formed in common, may be a hetero atom such as an alicyclic ring such as cyclopropane, cyclohexane, norbornane or adamantane, an oxygen atom, a sulfur atom or a nitrogen atom. Heterocyclic and the like. In the above, the alicyclic ring is preferably cyclopentane, cyclohexane or adamantane, and the heterocyclic ring is preferably a cyclic ether, a lactone or a sultone, or a part of a hydrogen atom of the above ring structure or Examples of the substituent which may be substituted include a fluorine atom, a hydroxyl group 'carboxy group, a cyano group, a sulfonyl group, a chain hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a carbon number of 6 to 18. An aromatic hydrocarbon group of 20, a heterocyclic group having 3 to 10 nuclear atoms, a group in which these groups are combined, or any of these groups is combined with an ester group, a decyl group, a fluorene group, a -C0- group or the like. Base and so on. Among these, a hydroxyl group, a hydroxyl group-containing group, and a chain hydrocarbon group having 1 to 3 carbon atoms are preferred. The above R2 and R3 are preferably a hydrogen atom. Further, the above a is preferably 1. The structural unit (I) may be, for example, a structural unit represented by the following formulas (1-1) to (1-71). -13- 201250381 【化4】

s -14- 201250381 【化5】

(1-12)

-15- 201250381 【化6】

(1 - 32 ) R1

OH "1-37" R1

O (1-42) R1

(1-47)

S -16- 201250381 【化7】

In the above, at least one of R4 and R5 is a structural unit containing an oxygen atom, and at least one of R4 and R5 is a structural unit of a cyclic organic group, and R4-17-201250381 and R5 are bonded to each other. The bonded carbon atoms together form a structural unit of a ring structure, preferably a structural unit containing a hydroxyl group or the like. Wherein the above formulas (1_υ~(1-9), (1-12)~(1-21), (1-25)~(1-47), (1-55)~(1-67), ( 1-69) The structural unit represented by ~(1-71), etc. is better, represented by (丨-丨), (1·17), (1-19), (1-70), and (1-71) Further, the structural unit is more preferable. [Α] The content of the structural unit (I) in the polymer component is 1 mol% or more with respect to the total amount of the structural unit (1) of the entire structural unit constituting the [Α] polymer component. Mohr. /. The following is better, 5 mol% or more and 60 mol% or less is better. The content of the structural unit (I) is in the above range, while maintaining other properties, and exhibiting excellent lithography performance. Further, the [Α] polymer component may have one or two or more structural units (I). The monomer constituting the structural unit (I) may, for example, be a compound represented by the following formula.

-18- S 201250381 【化8】

-19- 201250381 【化9】 Ο

ο

ο 201250381 【化1 ο】

-21 201250381

Util)

The monomer constituting the structural unit (I) can be produced, for example, by the following method. In a tetrahydrofuran (THF) solvent to which zinc powder was added, 2-methyltetrahydrofuran-3.one (compound a) dissolved in THF and ethyl (2_bromomethyl)acrylate (compound b) were each dropped. By reacting at room temperature, compound a is reacted with compound b to synthesize 6-methyl-3-methylene-1,7-dioxaspiro[4,4]nonan-2-one ( a compound represented by the above formula (1-1)). Further, an active agent such as chlorotrimethyldecane may be added to the THF solvent to which the zinc powder is added before the addition of the compounds a and b. Further, among the compounds other than the compound represented by the formula (1-1), it can be synthesized by an equivalent substitution of the compound a. -22- 201250381 [Structural unit (II)] The structural unit (II) is a structural unit other than the structural unit (I) and is selected from the group consisting of a cyclic carbonate structure, a sultone structure, and a lactone structure. A structural unit of at least one configuration. The photoresist composition contains the [A] polymer component having the structural unit (II), and the MEEF performance, DOF and LWR can be improved. The structural unit (II) is preferably the structural unit (II-1) represented by the above formula (2). The photoresist composition can further improve MEEF performance, DOF and LWR by containing the [A] polymer component of the structural unit (II-1) having the above specific configuration. In the above formula (2), R6 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. The ruler 7 is a hydrocarbon group having a carbon number of 1 to 1 Torr. Also, -0-, -(:00-, -0(:0- or ->;^-.1! is an integer of 0 to 10. When η is 2 or more, the plural R7 and X may each be the same or R8 is a single bond or a hydrocarbon group having 1 to 5 carbon atoms. R9 is a cyclic organic group having at least one structure selected from the group consisting of a cyclic carbonate structure, a sultone structure, and a lactone structure. However, some or all of the hydrogen atoms of R7 to R9 may be substituted. The hydrocarbon group having 1 to 10 carbon atoms represented by the above R7 may, for example, be a chain hydrocarbon group having 1 to 10 carbon atoms and a carbon number of 3~ An alicyclic hydrocarbon group of 10, an aromatic ruthenyl group having a carbon number of 6 to 10, etc. The chain hydrocarbon group having 1 to 10 carbon atoms may, for example, be a methylene group, an ethyl group, a propyl group or the like. The methylene group and the ethylidene group are preferred. The alicyclic hydrocarbon group having 3 to 10 carbon atoms may, for example, be a cyclic propyl group, a -23-201250381 cyclohexyl group, an adenantyl group or the like. The adamantyl group is preferably an alkyl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. The above X is preferably -0- and -COO-. The above η is 0 to 5 The integer is better, 0 and 1 are better. The above R8 represents The hydrocarbon group having a number of 1 to 5 may, for example, be a chain hydrocarbon group having 1 to 5 carbon atoms or an alicyclic hydrocarbon group having 3 to 5 carbon atoms. The chain hydrocarbon group having 1 to 5 carbon atoms may, for example, be a methylene group. Ethyl group, propyl group, etc.. Among them, a methylene group is preferred. The alicyclic hydrocarbon group having 3 to 5 carbon atoms may, for example, be a cyclic propyl group, a cyclobutyl group or the like. The bond and the methylene group are preferable. The cyclic organic group having a cyclic carbonate structure represented by the above R9 may, for example, be an ethylene carbonate group, a 1,3-propylene carbonate group, a cyclopentene carbonate group or a ring. a hexene carbonate group, a norbornene carbonate group, etc. The above cyclic organic group having a sultone structure may, for example, be a propyl sultone group, a butyrolactone group, a pentosul a lactone group or an adamantane sulfonate. The lactone oxime or the like. The cyclic organic group having a lactone structure may, for example, be a propiolactone group, a butyrolactone group, a valerolactone group or an adamantyl lactone group. The cyclic organic group is preferably an ethylene carbonate group, and the cyclic organic group having a sultone structure is preferably a norbornane sultone group and having a lactone. The cyclic organic group is preferably a norbornane lactone group and a butyrolactone group. Some or all of the hydrogen atoms of the above R7 to R9 may be substituted.

The substituent of S-24-201250381 may, for example, be a dentate atom, a thiol group, a sulfhydryl group, a pendant oxy group, a fluorenylamino group, an amine group, a decylamino group, a cyano group or an ethyl fluorenyl group. The structural unit (II) is preferably a structural unit represented by the following formulas (2-1) to (2-17). [1 2] R6

(2-5) (2-6) (2-7) (2-8) 25-201250381 [Chem. 1 3]

(2-9) (2-10) (2-11)

In the above formula, R6 is synonymous with the above formula (2).

-26- 201250381 In the above, the viewpoint of improving the lithography performance of the photoresist composition is expressed by the above formulas (2-1), (2-4), (2-8), (2-12), ( The structural units represented by 2-13), (2_14) and (2·17) are better. [A] The content of the monoterpene (Π) in the polymer component is not more than 80% by mole based on the total amount of the structural unit (II) constituting the total structural unit of the [A] polymer component. Preferably, it is more preferably 5 mol% or more and 60 mol% or less. The content of the structural unit (II), while being in the above range, maintains other performance while exhibiting excellent lithography performance. Further, the [A] polymer component may have one or two or more structural units (II). The monomer compound constituting the structural unit (II) may, for example, be a compound represented by the following formula. -27- 201250381 【化1 4】

[Structural unit (III)] [A] The polymer component is preferably a structural unit (III). [A] The polymer component has the structural unit (III) having an acid-dissociable group, and the photoresist composition can sufficiently satisfy basic characteristics such as sensitivity, and can form a resist pattern having superior MEEF, DOF, and LWR. .

S -28- 201250381 The structural unit (III) is represented by the above formula (3). In the above formula (3), a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. Each of R11 to R13 is an alkyl group having 1 to 4 carbon atoms or an alicyclic group having 4 to 20 carbon atoms. However, R12 may bond to each other and form a divalent structure together with the carbon atoms to which they are bonded. Further, all or all of the hydrogen atoms of the above alkyl group and the alicyclic group may be substituted. The alkyl group having 1 to 4 carbon atoms represented by the above R11 to R13 may, for example, be an ethyl group, an ethyl group, an η-propyl group, an i-propyl 'η-butyl group, an i-butyl group or a tert-2-methylpropyl group. 1-methylpropyl and the like. The alicyclic group having 4 to 20 carbon atoms represented by the above R11 to R13 is an alicyclic group having a bridged skeleton such as an adamantane skeleton or a norbornane skeleton; and has a cycloalkane skeleton such as cyclopentane or cyclohexane. Single-ring base. Further, these groups may be substituted by, for example, one or more kinds of linear or cyclic alkyl groups having 1 to 10 carbon atoms. The aromatic hydrocarbon group having 6 to 20 carbon atoms represented by the above R11 to R13 is, for example, benzene, naphthalene'phenanthrene, anthracene, tetracene, pentacycline, anthracene, oxime, xylene, ethylbenzene, trimethylbenzene, cumene. A group such as an aromatic hydrocarbon group and a hydrogen atom. R11 and R12 may bond each other to an alicyclic structure common to the carbon atoms to which they are bonded, and may, for example, be a polycyclic alicyclic structure having a skeleton such as adamantane or norbornane, or have a cyclopentane or a cyclohexane. A monocyclic alicyclic structure of a skeleton such as an alkane. The structural unit (III) is preferably a structural unit represented by the following formula: R10 is a lipid and a branch independently of R11 and an alicyclic moiety such as a methyl butyl group, and a polycyclic ring can be exemplified, and the toluene can be removed. Formation of bridged naphthenes-29- 201250381 [Chem. 1 5]

In the above formula, R1Q is synonymous with the above formula (3). Rn is an alkyl group having 1 to 4 carbon atoms. m is an integer of 1 to 6. Among these, a structural unit represented by the following formulas (3-1) to (3-22) can be mentioned as a preferable structural unit.

S -30- 201250381 【化1 6】

-31 201250381 In the above formula, R1Q is synonymous with the above formula (3). In the above, the above formulas (3-2), (3-3), (3-4) ' (3-7), (3-9), (3-11) to (3-14), (3) The structural units represented by -18), (3-19), (3-21) and (3-22) are even better. [A] The content ratio of the 'structural unit (Ιπ) in the polymer component, relative to the total structural unit of the [Α] polymer component, is 1 〇 mol. /. ~80 mole% is better, 1 5 mole% ~ 8 0 mole% better, 2 0 mole% ~ 7 0 mole % and even better. The content of the structural unit (I11) is improved in the lithography performance of the obtained resist pattern by the above range. Further, the [A] polymer component may have one or more structural units (III). The monomer constituting the structural unit (ΠΙ) may, for example, be a monomer represented by the following formula.

S -32- 201250381 [Chem. 1 7]

[Other structural unit] [A] The polymer component may contain a structural unit having a hydrophilic functional group (hereinafter also referred to as "structural unit (IV)"). [A] The polymer component can further improve the lithography performance of the resist pattern by further containing -33-201250381 with the structural unit (IV)'. The structural unit (IV) may, for example, be a structural unit represented by the following formula. [化1 8]

Ch3

HO

HO

0 0 h3c

OH

In the above formula, R14 is a content of a structural unit (IV) in a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl hydrazine [A] polymer component, and is a total structural unit of the [A] constituent component.言0摩尔%~30mol% is -34-

S 201250381 Good, 5 moles %~20旲%% better. [a] The polymer component may have a hydrazine species or two or more structural units (IV). In addition, the content of the structural unit (1) in the polymer component is set to be 1 mol% or more and 70 mol% or less, and the content of the structural unit (1) in the polymer component is determined by using the MEEF or the like as an index. The total content of the structural unit (1) and the structural unit (ΙΠ) is preferably 10 mol% or more and 80 mol% or less, and the content of the structural unit (I) is 5 mol% or more and 60 mol% or less. The total content of the structure monoterpene (I) and the structural monoterpene (III) is 20 mol% or more and 7 mol%. The following is better. The content of the structural unit (I) is 1% by mole or more and 50% by mole or less, and the total content of the structural unit (1) and the structural unit (ΙΠ) is 30% by mole or more and 60% by mole%. The following is even better. [A] When the polymer component contains the structural unit (1) and the structural unit (II) in the dissimilar polymer, the weight average molecular weight of the polymer (i) having the structural unit (I) has a structural unit (II) The weight average molecular weight of the polymer (Π) is preferably large. The photoresist composition in the case where the [A] polymer component is a mixture of the polymer (1) having the structural unit (I) and the polymer (ii) having the structural unit (II), the weight average molecular weight of the polymer (i) When the weight average molecular weight of the polymer (Π) is larger, MEEF, LWR, and the like are more excellent in the lithography performance of the index. <[A] Method for synthesizing polymer component> [A] The polymer component can be produced, for example, by polymerizing a monomer corresponding to each specific structural unit using a radical polymerization initiator in a suitable solvent. . For example, a solution containing a monomer and a radical initiator is dropped to a solution containing a reaction solvent or a monomer of -35 to 201250381 to carry out a polymerization reaction, a solution containing a monomer, and a solution containing a radical initiator a method in which a solution containing a reaction solvent or a monomer is dropped, followed by a polymerization reaction, and a solution containing a plurality of solutions of each monomer and a solution containing a radical initiator are respectively dropped to a solution containing a reaction solvent or a monomer. It is preferred to synthesize a method such as a polymerization method. The reaction temperature in these methods is appropriately determined depending on the kind of the initiator. It is usually 30 ° C to 180 ° C, preferably 4 〇 t to 160 ° C, and 5 (TC 〜 1 40 ° C is preferred. The dropping time is due to reaction temperature, type of initiator, reaction monomer, etc. However, it is usually 30 minutes to 8 hours, preferably 45 minutes to 6 hours, and more preferably 1 hour to 5 hours. Moreover, the total reaction time including the dropping time is also different depending on the conditions of the dropping time. However, it is usually 30 minutes to 8 hours, preferably 45 minutes to 7 hours, more preferably 1 hour to 6 hours. The radical initiator used in the above polymerization may, for example, be azobisisobutyronitrile, 2, 2 '·Azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis ( 2,4-Dimethylvaleronitrile), 2,2'-azobis(2-methylpropionitrile), etc. These initiators can be dissolved in two or more kinds of mixed agents. The effect of the ntsn shifting chain of the polymerized ruthenium has a 'phenyl group and the like. 1 (I combines the effect of the body with the chlorination, the concentration of the hydrazine is limited, and the solution is limited to the solvent. , , agent dissolved Poly outside to example such as an alcohol-based solvent, a ketone-based solvent, an amine-based solvent acyl, ester lactone-based solvents, nitrile based solvents, and mixed solvents and the like. These solvents may be used alone or two or more kinds

S -36- 201250381 Uploaded. The resin obtained by the polymerization reaction is preferably recovered by a reprecipitation method. Namely, after the completion of the polymerization reaction, the target resin is recovered as a powder by putting the polymerization liquid into a re-precipitation solvent. The solvent may be a mixture of alcohols or alkanes, or may be used alone or in combination of two or more. In addition to the reprecipitation method, the monomers and oligomers may also be subjected to a liquid separation operation, a column operation, an ultrafiltration operation, or the like. The resin is recovered by removing the low molecular component. Further, when the polymer component of [A] is one polymer component having the structural unit (I) and the structural unit (II) in the same polymer, the monomer and constituent structure constituting the structural unit (I) can be used. The monomer of the unit (II) is produced by copolymerization in the above manner. Further, when the polymer component [A] is a polymer component having two or more kinds of the structural unit (I) and the structural unit (II) in the dissimilar polymer, the structural unit (I) can be formed. The monomer is polymerized in the above manner to produce a polymer having the structural unit (I), and the monomer constituting the structural unit (II) is polymerized in the above manner to produce a polymer having the structural unit (11) and the two are mixed. And adjust [A] polymer composition. [A] The polystyrene-equivalent weight average molecular weight (Mw) of the colloidal permeation chromatography (GPC) of the polymer component is not particularly limited, but is preferably 〇〇〇 or more and 500,000 or less, 2, 〇〇 〇 Above 400,000 is better. Further, when the Mw of the [A] polymer is less than the looo, the heat resistance tends to decrease when the resist is formed. On the other hand, when the M v / of the polymer [A] exceeds 500,000, the developability tends to decrease when the resist is formed. Further, the Mw ratio (Mw/Mn) of the polymer component to the polystyrene-equivalent number average molecular weight (?η) of GPC is usually 1 or more and 5 or less, preferably 1 to 37 to 201250381 or more and 3 or less, or 1 or more. 2 is better. The photoresist film is excellent in resolution. Further, [A] Mw and Mw/Mn in two or more polymerized polymers in which the polymer component is a different polymer element (I) and a structural unit (II) are preferably in a strong state, and Mw of the present specification Μη is a ruthenium which is determined by monodisperse polystyrene as a standard (GPC) under the conditions of a flow rate of 1.0 ml/min and a solvent of tetrahydrofuran in the form of G2000HXL 2 and G3000HXL. <[Β]acid generator> [Β] acid production system In the step of forming a resist pattern, the form of the [Β] acid generator in the acid-producing product by the light passing through the mask The following may also be referred to as the "[Β]acid generator_ part of the group, or the two aspects. The acid generator may, for example, be a phosphonium salt compound, a halogen-containing compound or a diazoketone compound excipient, and a key salt compound is preferred. The onium salt compound may, for example, be a phosphonium salt (including an onium salt, a scale salt, a diazo salt, a pyridyl salt, etc.) a phosphonium salt, for example, triphenylsulfonium trifluoromethane nonafluoro-η-butanesulfonic acid Ester, triphenylsulfonium perfluoro-η·

Mw/Mn has the same range in the case where the above-described structural component is present in this embodiment. The compound was exposed by a GPC column (Tosoh G4000HXL 1), one step of colloidal permeation chromatography at a column temperature of 40 °C. The photoresist group of the manganese compound (j) is poorly compounded by one of the polymers and the sulfonium imine. These [B] acids produce 3 hydroxythiophene salt), iodine sulfonate, triphenyl octyl octane sulfonate, triphenyl-38-201250381 quinone 2-bicyclo[2.2.1]heptan-2-yl · 1,1,2,2-tetrafluoroethane sulfonate, triphenylsulfonium 1,1-difluoro-2-(1-adamantyl)ethanesulfonate, triphenylsulfonium 1,1 , 2,2-tetrafluoro-6-(1-adamantylcarbonyloxy)hexane-1-sulfonate, triphenylsulfonium 3-(2-oxa-3-oxo-l,7, 7-trimethylbicyclo[2,2,1]heptan-1-ylcarbonyloxy-1,1,2-trifluoropropane-1-sulfonate, triphenylphosphonium 5-(norbornane) Lactoneyloxycarbonyl-i,2-cyclohexanediylcarbonyloxy-1,1,2,2-tetrafluoropentane-1-sulfonate, 4-cyclohexylphenyl Phenyl fluorene trifluoromethane sulfonate, 4-cyclohexyl phenyl diphenyl sulfonium hexafluoro-n-butane sulfonate, 4-cyclohexyl phenyl diphenyl fluorene perfluoro-η-octane sulfonic acid Ester, 4-cyclohexylphenyldiphenylfluorene 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-methanesulfonylphenyl Diphenylsulfonium trifluoromethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium hexafluoro-η-butanesulfonate, 4-methanesulfonylphenyl diphenyl Base perfluoro-η-octane sulfonate, 4-methanesulfonylphenyldiphenylfluorene 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethyl Alkanesulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-6-(1-adamantanecarbonyloxy)-hexane-1-sulfonate, and the like. Among these, 'triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n. butanesulfonate, triphenylsulfonium 1,1-difluoro-2-(1-adamantyl) Ethane sulfonate, triphenylsulfonium 1,1,2,2-tetrafluoro-6-(1-adamantylcarbonyloxy)hexane-hydrazine-sulfonate, triphenylsulfonium 3-(() 2-oxa-3-oxo-oxime, 7,7·. trimethylbicyclo[2,2,1]heptan-1-yl-oxyl-1,1,2-difluoropropene- 1-expanded vinegar, triphenylsulfonium 5-(lactonyloxycarbonyl._ 1,2-cyclohexanediylcarbonyloxy)-1,1,2,2-tetra Fluoropentane-1-sulfonate is preferred. The tetrahydrothiophene sulfonium salt may, for example, be 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate or 1-(4-η-butoxynaphthalene-1- Tetrahydrothiophene-39- 201250381 噏9-fluoro-η-butyl basal acid ester, i-(4-n-butoxynaphthalen-1-yl) tetraqithiophene, perfluoro-η-octane sulfonate, 1-(4-n-Butoxynaphthalen-1-yl)tetrahydrothiophene 2-(bicyclo[2_2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonic acid Ester, i-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene 1,1,2-trifluoro-4-(1-adamantylcarbonyloxy)butane-1-sulfonic acid Ester, l-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-(6·η-butoxynaphthalen-2-yl)tetrahydrothiophene quinone Fluorine-n-butanesulfonate, 1·(6-η·butoxynaphthalen-2-yl)tetrahydrothiophene perfluoro-η-octanesulfonate, 1-(6-η-butoxy Naphthyl-2-yl)tetrahydrothiophene 2-cyclobi[2·2·1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1-(3,5- Dimethyl 4-hydroxyphenyl) tetrahydrosaporin trifluoromethanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene nonafluoro-η-butane Sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl) Hydrothiophene fluorene perfluoro-η-octane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene 2-cyclobi[2.2.1]hept-2-yl-1 1,2,2-tetrafluoroethane sulfonate, and the like. Among these tetrahydrothiophene sulfonium salts, 1-(4-η-butoxynaphthalen-1-yl)tetrahydrothiophene nonafluoro-η-butane sulfonate, 1-(4·η-butoxy Naphthyl-1-yl)tetrahydrothiophene perfluoro-η-octane sulfonate and 1-(3,5·dimethyl-4·ylphenyl)tetrahydrothiophene nonafluoro- η-butyl Sauerkraut, 1-(4·η-butoxynaphthalen-1-yl)tetrahydrothiophene 2-(bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetra Fluoroethanesulfonate, 1-(4-η-butoxynaphthalen-1-yl)tetrahydrothiophene 1,1,2-trifluoro-4-(1-adamantylcarbonyloxy)butane - 丨-sulfonate is preferred. The iodonium salt may, for example, be diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate or diphenyliodonium perfluoro-n-octanesulfonate. , diphenyliodonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis(4-t-butylphenyl)iodonium Fluoromethanesulfonate, bis(4-t-butyl

S -40- 201250381 phenyl)iodoquinone nonafluoro-η-butane sulfonate, bis(4-t-butylphenyl)iodonium perfluoro-η-xinyuan vinegar, double (4- T-butylphenyl) iodonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane vinegar and the like. Among these dangerous salts, bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate is preferred. The sulfonimide compound may, for example, be Ν-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, Ν-(nonafluoro-η · Butanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, fluorene-(perfluoro-η-octanesulfonyloxy)bicyclo[2.2 .1]hept-5-ene-2,3-dicarboxy quinone imine, Ν-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate Bisyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, and the like. Among these sulfonimide compounds, fluorene-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarenimine is preferred. These [Β] acid generators may be used singly or in combination of two or more kinds of "[Β] acid generators as "agents", and the resist coating film formed by the photoresist composition is ensured. From the viewpoint of sensitivity and lithography performance, it is preferably 〇. 〇 1 part by mass or more and 25 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, relative to [Α] polymer component 1 〇〇 by mass. Other optional components> Other optional components which may be contained in the photoresist composition include, for example, [C] acid diffusion controlling agent, [D] fluorine atom-containing polymer, [Ε] additive, solvent, and alicyclic ring. a skeleton compound, a surfactant, a sensitizer, and the like. The components are detailed below. -41 - 201250381 <[C] Acid Diffusion Control Agent> The photoresist composition preferably further contains a [C] acid diffusion controlling agent. The [c] acid diffusion controlling agent controls the diffusion of an acid generated from the [B] acid generator by exposure in the resist film, and suppresses an undesired chemical reaction in the non-exposed field. By combining such a [C] acid diffusion controlling agent, the obtained photoresist composition has improved storage stability, and the resolution as a resist is further improved, and baking from exposure to post-exposure heat treatment can be suppressed. The change in the line width of the resist pattern caused by the change in the post-time delay (PED) gives a composition excellent in process stability. [C] The acid diffusion controlling agent, for example, a nitrogen-containing compound having an N-t-alkoxycarbonyl group is preferably used. Specifically, for example, Nt-butoxycarbonyldi-η-octylamine, Nt-pentyloxycarbonyldi-η-octylamine, Nt-butoxycarbonyldi-η-decylamine, Nt-pentyloxy Carbonyl di-n-decylamine 'Nt-butoxycarbonyldi-η-decylamine, Nt-pentyloxycarbonyldi-η-decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt -pentyloxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-pentyloxycarbonyl-1-adamantylamine, Nt-butoxydecyl-2-golden Alkylamine, Nt-pentyloxyindenyl-2-Dragonylamine, N-t-butoxycarbonyl-N-methyl-1.adamantylamine, Nt.pentyloxycarbonyl-N-methyl- 1-adamantylamine, (S)-(-)-l-(t-butoxycarbonyl)-2-pyrrolidinemethanol, (S)-(-)-l-(t-pentyloxycarbonyl) -2-pyrrolidinemethanol, (R)-( + )-l-(t-butoxycarbonyl)-2·pyrrolidinemethanol, (R)-( + )-l-(t-pentyloxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonylcarbonyl-4-hydroxypiperidine, Nt-pentyloxycarbonyl-4-hydroxypiperidine 'Nt-butoxycarbonylpyrrolidine, Nt-pentyloxycarbonylpyrrolidine , N,N'-di-t-butoxycarbonylpiperazine, N,N'-di-t-pentyl Oxycarbonyl

S-42- 201250381 piperazine, N,N-di-t-butoxycarbonyl-1-adamantylamine, N,N-di-t-pentyloxycarbonyl-1-adamantylamine, Nt -butoxycarbonyl-4,4'-diaminediphenylmethane, Nt-pentyloxycarbonyl-4,4'diaminediphenylmethane, N,N'-di-t-butoxycarbonyl Hexamethylenediamine, N,N'-di-t-pentyloxycarbonylhexamethylenediamine, N,N,N',N'-tetra-t-butoxycarbonylhexamethylene Amine, N,N,N',N'-tetra-t-pentyloxycarbonylhexamethylenediamine, N,N'-di-t-butoxycarbonyl-1,7-diamineheptane, N,N'-di-t-pentyloxycarbonyl-1,7-diamineheptane, N,N'-di-t-butoxycarbonyl-1,8-diamine octane, N,N' -di-t-pentyloxycarbonyl-1,8-diamine octane, N,N'-di-t-butoxycarbonyl-1,9.diamine decane, hydrazine, Ν'-di-t -Pentyloxycarbonyl-1,9-diamine decane, hydrazine, Ν'-di-t-butoxycarbonyl-1,10-diamine decane, N,N'-di-t-pentyloxy Carbonyl-1,10-diamine decane, N,N'-di-t-butoxycarbonyl-1,12-diaminedodecane, N,N'-di-t-pentyloxycarbonyl-1 , 12-diamine dodecane, N, N'- Di-t-butoxycarbonyl-4,4'-diamine diphenylmethane, N,N'-di-t-pentyloxycarbonyl-4,4,-diamine diphenylmethane, Nt-butyl Oxycarbonylbenzimidazole, Nt-butoxycarbonylbenzimidazole, Nt-pentyloxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole, Nt-pentyloxycarbonyl- A compound such as 2-phenylbenzimidazole or 2-phenylimidazole. Among these, N-t-butoxycarbonyl-4-hydroxypiperidine, N-t-pentyloxycarbonyl-4-hydroxypiperidine and 2-phenylimidazole are preferred. Further, the [C] acid diffusion controlling agent may be a nitrogen-containing compound such as a tertiary amine compound, a fourth-order ammonium hydroxide compound or another nitrogen-containing heterocyclic compound, in addition to the above compounds. The tertiary amine compound may, for example, be triethylamine, tri-n-propylamine, di-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptyl Amine, -43- 201250381 tris(octyl)alkylamines such as tris-octylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, tricyclohexylamine; aniline, anthracene-methylaniline, Ν, Ν-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 2,6-dimethylaniline, 2,6-diisopropyl Aromatic amines such as aniline; alkanolamines such as triethanolamine, hydrazine, hydrazine-bis(hydroxyethyl)aniline; hydrazine, hydrazine, hydrazine, Ν'-tetramethylethylenediamine, hydrazine, hydrazine, Ν',Ν'-肆(2-hydroxypropyl)-extended ethyldiamine, 1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzenetetramethylenediamine , bis(2-dimethylaminoethyl)ether, bis(2-diethylaminoethyl)ether, and the like. The fourth-order ammonium hydroxide compound may, for example, be tetra-n-propylammonium hydroxide or tetra-n-butylammonium hydroxide. Further, the [C] acid diffusion controlling agent may also be a key salt compound which is decomposed by exposure and which loses alkalinity as an acid diffusion controlling property. Specific examples of such a key salt compound include an onium salt compound represented by the following formula (5-1) and an iodonium salt compound represented by the following formula (5-2). [化1 9]

S 44- 201250381 Rl5 to R丨9 in the above formula (5-1) and formula (5-2) are each independently a hydrogen atom, a siloxane group, an alkoxy group, a hydroxyl group or a halogen atom. Further, Anb· is OH·, R2()_c〇0_, R2()-S〇3_ (however, R2 is independently a group, an aryl group or an alkanol group), or the following formula (6) The anion indicated. [化2 0]

Specific examples of the above sulfonium salt compound and iodonium salt compound, such as triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonyl salicylate, diphenyl-4-hydroxyphenylhydrazine hydrogen Oxide, diphenyl-4-hydroxyphenylhydrazine acetate, diphenyl-4-hydroxyphenylhydrazine salicylate, bis(4-t-butylphenyl)iodonium hydroxide, double (4-t-butylphenyl)iodonium acetate 'bis(4-t-butylphenyl)iodonium hydroxide, bis(4-t-butylphenyl)iodonium acetate, Bis(4-t-butylphenyl)iodonium salicylate, 4-t-butylphenyl-4-hydroxyphenyliodonium hydroxide, 4-t-butylphenyl-4-hydroxyl Phenyl iodonium acetate, 4-t-butylphenyl-4-hydroxyphenyliodonium salicylate, bis(4-t-butylphenyl)iodonium 10-camphorsulfonate, two Phenyl iodide 10_ camphor vinegar, triphenyl vegetable 10-camphor sulfonate, 4-t-butoxyphenyl. diphenyl vegetable 1 〇 - camphor acid expansion, 4-(cyclohexyl sulfonate Nonylphenyldiphenylphosphonium 5,6-bis(2,2,2-trifluoroethoxy-45-201250381 carbonyl)bicyclo[2,2,1]heptane-2-sulfonate, etc. Triphenylsulfonyl salicylate Triphenylphosphonium 10-camphorsulfonate and 4_(cyclohexylsulfonylphenyldiphenylphosphonium 5,6-bis(2,2,2-trifluoroethoxycarbonyl)bicyclo[2,2,1 The heptane-2-sulfonate is preferably used. [C] The acid diffusion controlling agent may be used singly or in combination of two or more kinds. The content ratio of the acid diffusion controlling agent is 100 parts by mass relative to the [A] polymer component. It is more preferably 10 parts by mass or less, more preferably 0.1 parts by mass or more and 8 parts by mass or less. When the amount exceeds 10 parts by mass, the sensitivity tends to decrease as a resist. [D] Polymer of fluorine atom> The photoresist composition further contains a polymer of [D] fluorine-containing atom (hereinafter also referred to as "[D] polymer"). [D] The polymer is a fluorine atom-containing polymer in a ratio [A] polymer It is preferable that the fluorine atom content of the component is high. The photoresist composition contains a [D] polymer, and when the hydrophobicity of the resist film is increased and the liquid immersion exposure is performed, the substance elution inhibition property is excellent and the resistance can be made. The etching film and the liquid immersion liquid have a high back contact angle, and the effect of not leaving water droplets is achieved in the case of high-speed scanning exposure, and the utility of the photoresist composition in liquid immersion exposure is increased. The aspect of the [D] polymer may, for example, be a structure in which a main chain is bonded with a fluorinated alkyl group; a side chain is bonded with a fluorinated alkyl group; and a main chain and a side chain are bonded with a fluorinated alkyl group; A monomer constituting a structure in which a main chain is bonded with a fluorinated alkyl group, for example,

S 201250381 A trifluoromethacrylate compound, a trifluoromethacrylate compound, an α,β-trifluoromethacrylate compound, and hydrogen of one or more kinds of ethylene sites are substituted by a fluorinated alkyl group such as a trifluoromethyl group. Compounds, etc. The monomer constituting the structure in which the side chain is bonded with a fluorinated alkyl group, for example, the side chain of the alicyclic olefin compound such as norbornene is a fluorinated alkyl group or a derivative thereof, for example, the side of acrylic acid or methacrylic acid The ester compound in which the chain is a fluorinated alkyl group or a derivative thereof is a side chain of a olefin having 1 or more types (a portion not containing a double bond), and is a fluorinated alkyl group or a derivative thereof. The monomer constituting the structure in which the main chain and the side chain are bonded with a fluorinated alkyl group may, for example, be a side chain such as α-trifluoromethacrylic acid, β-trifluoromethacrylic acid or α,β-trifluoromethacrylic acid. An ester compound of a fluorinated alkyl group or a derivative thereof, or a side chain of a compound in which one or more types of hydrogen of an ethylene moiety is substituted with a fluorinated alkyl group such as a trifluoromethyl group, is substituted by a fluorinated alkyl group or a derivative thereof, The hydrogen bonded to the double bond of the alicyclic olefin compound of the type or more is substituted by a fluorinated alkyl group such as a trifluoromethyl group, and the side chain is a fluorinated alkyl group or a derivative thereof. Further, the alicyclic olefin compound means a compound in which a part of the ring is a double bond. The [D] polymer is preferably a structural unit (d1) represented by the following formula (?) and/or a structural unit (d2) represented by the formula (8), and may have a structural unit (dl) and a structure. "Other structural units" other than unit (d2). The details of each structural unit are detailed below. [Structural unit (dl)] The structural unit (dl) is a structural unit represented by the following formula (7). -47- 201250381

In the above formula (7), R21 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R22 is an alkyl group having 1 to 6 carbon atoms having a fluorine atom or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms having a fluorine atom. However, in the above alkyl group and alicyclic hydrocarbon group, part or all of a hydrogen atom may be substituted. The monomer constituting the structural unit (dl) may, for example, be trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate or perfluoroethyl (meth) acrylate. Ester, perfluoro η-propyl (meth) acrylate, perfluoro i-propyl (meth) acrylate, perfluoro η-butyl (meth) acrylate, perfluoro i-butyl (methyl Acrylate, perfluoro-t-butyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2-(1,1,1,3,3,3-hexafluoro)propyl (A) Acrylate, 1-(2,2,3,3,4,4,5,5-octafluoro)pentyl (meth) acrylate, 1-(2,2,3,3,4,4 ,5,5-octafluoro)hexyl (meth) acrylate, perfluorocyclohexylmethyl (meth) acrylate, 1-(2,2,3,3,3-pentafluoro)propyl (methyl Acrylate, 1-(2,2,3,3,4,4,4-heptafluoro)penta(meth)acrylate, 1-(3,3,4,4,5,5,6,6 ,7,7,8,8,9,9,10,10,10-heptadecafluoro)fluorenyl (meth) acrylate, 1-(5-trifluoromethyl-3,3,4,4, 5,6,6,6-octafluoro)hexyl (meth) acrylate, and the like. The structural unit (dl) can be represented, for example, by the following formulas (7-1) and (7-2).

S -48- 201250381 Construction unit. [Chemical 2 2]

(7-2) In the above formulae (7-1) and (7-2), R21 has the same meaning as the above formula (7). In the [D] polymer, the content of the structural unit (dl) is preferably from 10 mol% to 70 mol%, more preferably from 20 mol% to 50 mol%, based on the constituent [D] polymer total structural unit. Further, the [D] polymer may contain one type or two or more types of structural units (dl). [Structural unit (d2)] The structural unit (d2) is a structural unit represented by the following formula (8). [化2 3] R23

-49- 201250381 In the above formula (8), R23 is a hydrogen atom, a fluorine atom, a methyl group or a tri-methyl group. R24 is a (k+Ι) valency linkage. Y is a divalent linking group having a fluorine atom. 1125 is a hydrogen atom or a monovalent organic group. k is an integer of 1 to 3. However, where k is 2 or 3, the plural γ and R25 may each be the same or different. The structural unit (d2) may be, for example, a structural unit represented by the following formulas (8-1) and (8.2). 【化24】

In the above formula (8-1), R24 is a divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. R23, Y and R2 5 are synonymous with the above formula (8). In the above formula (8-2), R23, Y, R25 and k are synonymous with the above formula (8). However, where k is 2 or 3, the plural γ and R25 may each be the same or different. The structural unit represented by the above formula (8-1) and formula (8-2) is represented by, for example, the following formula (8-1-1), formula (8-1-2), and formula (8-2-丨). Construction unit.

S -50- .201250381

In the above formulae (8-1-1), (8-1-2), and (8-2-1), R23 has the same meaning as the above formula (8). The monomer constituting the structural unit (d2) may, for example, be a (meth)acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-3-propyl) ester or a (methyl) group. (1,1,1-Trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) acrylate, (meth)acrylic acid (1,1,1-trifluoro-2-trifluoromethyl) -2-hydroxy-5-pentyl)ester, (1,1,1·trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl), (meth)acrylic acid 2-{[5-(1',1',1'-trifluoro-2'-trifluoromethyl-2'-hydroxy)propyl]bicyclo[2.2.1]heptyl} ester and the like. In the [D] polymer, the content of the structural unit (d2) is preferably 20 mol% to 80 mol%, and 3 mol% to 70% of the total structural unit of the [D] polymer. good. Further, the [D] polymer may contain one type or two or more types of structural units (d2). -51 - 201250381 [Other structural unit] [D] The polymer may contain one or more "other structural units" having a lactone structure, a cyclic carbonate structure or a sultone structure in order to improve the solubility to the developer. Structural unit, structural unit containing an alicyclic structure for improving etching resistance, and the like. The structural unit having a lactone structure, a cyclic carbonate structure or a sultone structure may be, for example, the same structural unit as the structural unit exemplified in the structural unit (II) of the above [A] polymer component. The structural unit having an alicyclic structure is, for example, a structural unit represented by the following formula (9). [Chem. 2 6] R26

In the formula (9), R26 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. Y2 is an alicyclic hydrocarbon group having 4 to 20 carbon atoms. The monomer constituting the structural unit containing the alicyclic compound may, for example, be a (meth)acrylic acid-bicyclo[2.2.1]hept-2-yl ester (meth)acrylic acid-bicyclo[2.2.2]octane-2 -yl ester, (meth)acrylic acid-tricyclo[5.2.1.02'6]non-7-yl ester, (meth)acrylic acid-tricyclo[3.3.1.13'7]non-1-yl ester, (a Acetyl-tricyclo[3.3.1.I3,7]non-2-yl ester and the like.

S -52- 201250381 [D] In the polymer, the structural unit (dl), the structural unit (d2), and other structural units may have only one type or two or more types of structural units, but the [D] polymer It is preferred that the unit has no aromatic group. In particular, when an ArF light source is used, there is a case where the sensitivity is lowered. Further, when development is carried out using a negative developing solution, the shape is deteriorated. The content ratio of the [D] polymer is preferably 1 part by mass to 15 parts by mass, more preferably 2 parts by mass to 1 part by mass, based on 1 part by mass of the [A] polymer component. <[D] Polymer Synthesis Method> The [D] polymer can be produced, for example, by polymerizing a monomer corresponding to each specific structural unit using a radical polymerization initiator in a suitable solvent. Further, the polymerization initiator, the solvent, and the like used for the synthesis of the [D] polymer may, for example, be the same as those exemplified in the method for synthesizing the above [A] polymer component. The reaction temperature of the above polymerization is usually 40 ° C to 15 (TC, preferably 50 ° C to 120 ° C. The reaction time is usually 1 hour to 48 hours, preferably 1 hour to 24 hours. [D] The polystyrene-equivalent weight average molecular weight (Mw) of the colloidal permeation chromatography (GPC) method of the polymer is preferably 1,000 to 50,00 Å, more preferably 1,000 to 30,000, and 1,000 to 10 Å. In the case where the Mw of the polymer [D] is less than 1, the sufficient advancing contact angle cannot be obtained. On the other hand, when Mw exceeds 50,000, the developability tends to be lowered as a resist. [D] The Mw of the polymer and the polystyrene equivalent number of the GPC method are -53 - 201250381, and the ratio (Mw/Mn) is usually 1 to 3, preferably 1 to 2. [ E] Additive> The photoresist composition may be combined with the [E] additive in the case of forming a resist pattern by a liquid immersion exposure method, etc. The [E] additive which may be contained in the photoresist composition may, for example, be γ- Butyrolactone, propylene carbonate, etc. Among these, γ-butyrolactone is preferred. <Solvent> The photoresist composition usually contains a solvent. The solvent is at least soluble [Α] polymer The solvent of the acid generator and other components is not particularly limited, and an alcohol solvent, an ether solvent, a ketone organic solvent, a guanamine solvent, an ester organic solvent, or a hydrocarbon system can be used as the solvent. Solvent, etc. The alcohol solvent may, for example, be methanol, ethanol, η-propanol, i-propanol, η-butanol, i-butanol, sec-butanol, tert-butanol, η-pentanol, i -pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, η-hexanol, 2-methylpentanol, sec-hexanol, 2-ethyl Butanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, η-mercaptool, 2,6-dimethyl-4-heptanol, η - sterol, sec-decahydrol, trimethyldecyl alcohol, sec-tetradecyl alcohol, sec-heptadecanol, mercapto alcohol, phenol, cyclohexanol, methylcyclohexanol, 3, Monoalcoholic solvent such as 3,5-trimethylcyclohexanol, benzyl alcohol or diacetone; ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol , 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2·B

S-54- 201250381 base_polyol solvent such as 1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol or dipropylene glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-based acid, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol Monomethyl acid, monoethyl alcohol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl acid, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl An oxime ether solvent such as a glycol partial acid solvent such as a diethylene glycol monopropyl ether, a propylene glycol monobutyl ether, a dipropylene glycol monomethyl acid, a dipropylene glycol monoethyl ether or a dipropylene glycol monopropyl ether. For example, diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether and the like. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl η-propyl ketone, methyl-η-butyl ketone, diethyl ketone, formazan-i-butyl ketone, and methyl group. Η-amyl ketone, ethyl-η-butyl ketone, methyl-η-hexyl ketone, di-i-butyl ketone, trimethyl fluorenone 'cyclopentanone, cyclohexanone, cycloheptanone, ring A ketone solvent such as octanone's methylcyclohexanone, 2,4-pentanedione, acetonylacetone or acetophenone. The amide-based solvent 'for example, N,N,-dimethylimidazolidinone' N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, Acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone, and the like. The ester solvent may, for example, be diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, or ethyl 13⁄4 i-propyl vinegar. Η-butyl acetate, i-butyl vinegar acetate, sec-butyl acetate, -55- 201250381 η-amyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, acetic acid 2-ethylbutyl ester, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, η-decyl acetate, methyl acetate, ethyl acetate, acetic acid Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-η-butyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diacetic acid glycol, acetic acid Methoxy tridiol, ethyl propionate, η-butyl propionate, i-pentyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, lactate B , Η-, butyl lactate, amyl lactate η-, diethyl malonate, dimethyl terephthalate, diethyl phthalate and the like. Examples of the hydrocarbon-based solvent include η-Autumn, i-Autumn' η-Academy, i-Hospital, η-Gengyuan, i-Gengyuan, 2,2,4-trimethylpentane, η - an aliphatic hydrocarbon solvent such as octane, i-octane, cyclohexane or methylcyclohexane; benzene, toluene, xylene, trimethylbenzene, ethylbenzene, trimethylbenzene, methylethylbenzene, An aromatic hydrocarbon solvent such as η-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene or η-pentylnaphthalene. Among these, an ester solvent and a ketone solvent are preferred, and propylene glycol monomethyl ether and cyclohexanone are more preferred. These organic solvents may be used singly or in combination of two or more. [Monthly ring-shaped skeleton compound]

S-56-201250381 The alicyclic skeleton compound is a component having an effect of improving dry etching resistance, pattern shape, and substrate adhesion. Examples of the alicyclic skeleton compound include adamantane derivatives such as 1-adamantanecarboxylic acid, 2·adamantanone, and 1-adamantanecarboxylic acid t-butyl ester; t-butyl deoxycholate, deoxygenated Deoxycholate esters such as t-butoxycarbonyl methyl cholate and 2-ethoxyethyl deoxycholate; t-butyl lithic acid, butyl oxycarbonyl methyl lithate , lithocholic acid esters such as 2-ethoxyethyl lithic acid; 3-[2-hydroxy-2,2-bis(trifluoromethyl)ethyl]tetracyclo[4.4.0.12, 5.17' 10] Dodecane, 2-hydroxy-9.methoxycarbonyl-5-oxo-4-oxa-tricyclo[4.2.1.〇3,7]decane, and the like. [Surfactant] The surfactant is a component having an effect of improving coatability, scratches, developability, and the like. The surfactant may, for example, be polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene η-octyl phenyl ether, polyoxyethylene η-nonylphenyl ether In addition to the nonionic surfactant such as polyethylene glycol dilaurate or polyethylene glycol distearate, ΚΡ341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, and the same Ν · 95 of the following trade names are exemplified. (above, Kyoeisha Chemical Co., Ltd.), EFTOPEF301, EF3 03, EF3 52 (above, Thochem Products), MEG AF ACEF 177, F173 (above, Dainippon Ink Chemical Industry), FluoraclFC430, Same as FC431 (above, Sumitomo 3M system), AsahiGuardAG710, Surflson S-3 82, same SC-101, same SC-102 'same SC-103, same SC-104, same SC-105, same SC-106 (above, Asahi Glass) System) and so on. -57- 201250381 [Sensitizer] A sensitizer is an sensitizing agent that absorbs radiation energy and transmits this energy to [CJ acid generator, thereby increasing the amount of acid generated, and improving the apparent sensitivity of the photoresist composition. effect. The sensitizer may, for example, be azoles, acetophenones, benzophenones, naphthalenes, phenols, diacetyl esters, eosin, bengal rose, quinones, anthraquinones, thiodiphenylamines. Classes, etc. <Preparation method of photoresist composition> The photoresist composition can be prepared, for example, by mixing [A] polymer component, [B] acid generator, and other optional components in a specific ratio in the above solvent. The photoresist composition is usually dissolved in a solvent at a total solid content of 1% by mass to 30% by mass, preferably 1.5% by mass to 25% by mass, for example, at a pore diameter of about 0.2 μm. The filter is filtered to prepare. <Formation Method of Resistivity Pattern> The formation method of the resist pattern using the photoresist composition of the present invention is as follows. The method for forming a resist pattern of the photoresist composition of the present invention may be, for example, a step of forming (1) a coating film of the photoresist composition on a substrate (hereinafter, also referred to as "step (1)" (2) a step of irradiating at least a part of the above-mentioned coating film with radiation (hereinafter, also referred to as "step (2)"), and -58-

S 201250381 (3) A method of forming a step of developing a coating film that irradiates the radiation (hereinafter, also referred to as "step (3)"). Hereinafter, each step will be described in detail. According to the above formation method, the photoresist composition can be used to form an excellent resist pattern of MEEF, LWR and DOF. Therefore, even if it is a radiation such as a KrF quasi-molecular laser, an ArF excimer laser, or an EUV, the photoresist composition can be formed into a fine pattern with high precision and stability, and can be applied to a semiconductor device which is more refined in the future. [Step (1)] In this step, the photoresist composition obtained by dissolving the photoresist composition or dissolving the solvent is applied by a coating means such as spin coating, cast coating, or roll coating. A substrate such as a germanium wafer, a germanium dioxide, or a wafer coated with an antireflection film is applied with a specific film thickness, and is usually soft baked at a temperature of about 70 ° C to 160 ° C depending on the case. (SB), the solvent in the coating film is volatilized to form an anti-contact film. [Step (2)] In this step, the resist film formed in the step (1) (different from the case, permeated medium such as water) is irradiated with radiation to expose it. Further, at this time, the radiation is irradiated through the mask having a specific pattern. The radiation can be irradiated by suitable choices such as visible light, ultraviolet light, far ultraviolet light, X-ray, charged particle beam, EUV, etc. depending on the line width of the target image. In this case, far ultraviolet rays represented by ArF excimer laser (wavelength 193 nm) and KrF excimer laser (wavelength 248 nm) are preferred, and EUV (extreme ultraviolet ray, wavelength Ι3.5 ηηι) -59-201250381 may also be used. A light source that forms a finer pattern. Next, it is preferable to perform post-exposure baking (PEB). Through the PEB, the acid-dissociable group of the [A] polymer component can be made to proceed smoothly. The heating condition of PEB can be suitably selected depending on the composition of the photoresist composition, but it is usually about 50 ° C to 180 ° C. [Step (3)] In this step, a resist pattern is formed by developing the exposed resist film with a developing solution. After development, it is generally washed with water and dried. Developing solution, for example, to dissolve sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, η-propylamine, diethylamine, di-n-propylamine , triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, pyrrole, piperidine, choline, 1,8-di Preferably, at least one aqueous alkali solution of a basic compound such as azabicyclo-[5.4.0]-7-undecene or 1,5-diazabicyclo-[4.3.0]-5-decene is preferred. Further, in the case of performing immersion exposure, in order to protect the liquid immersion liquid from direct contact with the resist film before the step (2), a liquid immersion liquid-insoluble protective film for liquid immersion may be provided on the resist film. As the protective film for liquid immersion, a solvent-peelable protective film which is peeled off with a solvent before the step (3) (for example, JP-A-2006-227632, etc.), and a developer which is peeled off simultaneously with the development of the step (3) can be used. Any of the peeling type protective films (for example, International Publication No. 2005-069076, International Publication No. 2006-03 5 790, etc.). [Embodiment] [Embodiment]

S - 60 - 201250381 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the embodiments. The weight average molecular weight (Mw) and the number average molecular weight (Μη) were GPC columns (G2000HXL2, G3 000HXL1, and G4000HXL1) manufactured by Tosoh Corporation, and the flow rate was 1.0 mL/min, and the solvent was eluted: tetrahydrofuran. Column temperature: The analysis conditions of 40 ° C were measured by colloidal permeation chromatography (GPC) using monodisperse polystyrene as a standard. Further, the degree of dispersion (Mw/Mn) was calculated from the measurement results of Mw and Μη. The analysis of the constituent units derived from the monomer in the polymer was carried out using a JNM-ECX400' measuring solvent manufactured by JEOL Ltd. using heavy chloroform. The content ratio of the structural unit in the polymer is determined by measuring the 13C-NMR spectrum of the polymer, and the area ratio of the peaks corresponding to the respective structural units in the spectrum is obtained, and the average enthalpy in the polymer is determined. <[A] Synthesis of polymer component> [A] The monomer used for the synthesis of the polymer component and the [D] polymer described later is as follows. 201250381 【化化2 7】

s -62- 201250381 【化2 8】

[Synthesis Example 1] Compound (M1) 18.5 g (50 mol%), compound (Ss-1) 9.3 g (25 mol%), and compound (L1) 12.2 g (25 mol%) were dissolved in 80 g. 2--63- 201250381 Butanone, AIBN 3.6g was added to prepare a monomer solution. A 200 mL three-necked flask containing 40 g of 2-butanone was added to nitrogen for 30 minutes, and then heated to 80 ° C while stirring, and the prepared monomer solution was dropped for 3 hours as a dropping funnel. The start of the dropwise addition was regarded as the start time of the polymerization reaction, and the polymerization reaction was carried out for 6 hours. After completion of the polymerization reaction, the polymerization solution was cooled to water and then cooled to 30 ° C or lower. The cooled polymerization solution was placed in 800 g of methanol, and the precipitated white powder was collected by filtration. The white powder obtained by filtration was washed twice with 160 g of methanol, filtered, and dried at 50 ° C for 17 hours to obtain a white powdery polymer component (A-1) (30 g, yield: 75%). The obtained polymer component (A-1) had Μλν of 4,000 and Mw/Mn of 1.4. Further, as a result of 13C-NMR analysis, a structural unit derived from the compound (Μ-1): a structural unit derived from the compound (Ss-Ι): the content of the structural unit derived from the compound (l^) was 46: 23: 31 ( Moer%). [Synthesis Examples 2 to 19, Comparative Synthesis Examples 1 to 9] In addition to the monomers described in the specific amount table 1, the synthesis examples were made! The polymer components (A-2) to (A-19) and (a-Ι) to (a-9) were obtained in the same manner. Further, the Mw, M w/Μη, yield (%) of each of the obtained polymers, and the content ratio of the structural unit derived from each monomer in each polymer are shown in the table [Synthesis Example 20] Compound (Ml) 20g (50 moles / /) and compound (Ss-1) 20g (50 mole %) dissolved in 80g of 2-butanone, adding azobisisobutyronitrile (AIBN) 3 9g to prepare monomer solution . Will add 40g of 2-butanone to 200mL three mouths

S-64 - .201250381 After the flask was purged with nitrogen for 30 minutes, it was heated to 80 ° C with stirring, and the monomer solution thus prepared was dropped by dropping the funnel for 3 hours. The start of the dropwise addition was regarded as the start time of the polymerization reaction, and the polymerization reaction was carried out for 6 hours. After completion of the polymerization reaction, the polymerization solution was cooled to water and then cooled to 30 ° C or lower. The cooled polymerization solution was placed in 800 g of methanol, and the precipitated white powder was collected by filtration. The white powder thus filtered was washed twice with 160 g of methanol, filtered, and dried at 5 ° C for 17 hours to obtain a white powdery polymer (3 6 g, yield 90%). Further, a polymer was obtained in the same manner as above except that the compound (38_1) 2 (^ (50 mol%) was used, and 22.8 g (50 mol%) of the compound (L1) was used. The molar composition of 1 is mixed to form a polymer component (A-20). Further, the physical properties of the above two types of polymers are shown in Table 1. [Synthesis Example 21] Except for the monomer described in the specific amount table 1, The polymer component (A · 2 1) was obtained in the same manner as in Synthesis Example 20. Further, Mw ' Mw/Mn, yield (%) of each of the obtained polymers, and a structure list derived from each monomer in each polymer The content of bismuth is shown in Table 1. -65- 201250381 [Table 1] [A] Polymer component compound i Tower amount Polymer in the structural unit Physical properties 搭配 compound collocation Mohr % Content ratio Moer % Mw Mw /Μη 1 A-1 M- 1/Ss- 1/L- 1 50/25/25 46/23/31 4,000 1.4 2 A-2 M-S/Ss- 1/L- 2 60/20/20 60 /17/23 4,200 1.4 3 A— 3 M- 5/Ss- 1/L- 3 40/30/30 48/21/31 3,900 1.4 4 A-4 Ma^Ss- l/L-4 40/30/ 30 44/21/35 5,000 1.4 5 A— 5 M— 1/M_ Skin Ss — VL — 5 10/40/20/30 7/43/15/35 4,900 1.3 6 A—6 Μ- 7/M- # Ss- V L- 6 35/10/25/30 36/11/19/34 4,700 1.4 7 A-7 M-6/Ss-3/L- 7 60/20/20 58/19/23 3,800 1.4 8 A-8 M- 7/Ss-3/L-8 60/20/20 64/20/16 4,650 1.4 in 9 A-9 M-9/Ss- 3/L-9 40/20/40 34/18/48 3,950 1.5 10 A-10 M- 3/ Ss- -V L- 1/ L- 10 40/10/20/30 42/8/18/32 5,000 1.4 to 11 A —11 Μ—2/M— 7/ S s— VL— VL— 11 25/25/30/10/10 22/28/28/11/11 4,800 1.4 Example 12 A—12 Μ- 3/M- Ss- 1/ Ss- L- 12 40/10/30/10/10 38/13/24/10/15 4J00 1.4 13 A-13 M-4/Ss- l/Ss-2/L - 13 40/20/10/30 46/14/8/32 4,400 1.4 14 A-14 M-^Ss-l/Ss-a/L-14 40/20/20/20 37/19/20/19 4,000 1.4 15 A-15 MI/IVHIO/Ss- 1/L- 14 20/10/10/60 19/10/10/59 5,000 1.4 16 A — 16 Ml/Ss- 1/L- 15 35/5/ 60 34/5/61 5,400 1.4 17 A-17 M—10/ S s— 1/ L— 15 25/15/60 26/14/60 5,300 1.4 18 A—18 Ml/Ivh S/Μ-1 (V Ss- 2/ L- 1 40/5/5/10/40 39/4/4/13/40 4,900 1.4 19 A-19 M-VSs-2/L- 1 50/10/40 48/11/51 10,500 1.6 A- 20 M— 1/ Ss~ 1 50/50 50/50 4.500 1.5 M- 1/ L- 1 50/50 43/57 3,80 0 1.5 A— 21 M— 7/ Ss— 3 60/40 51/49 8,000 1.3 M- 7/ L- 8 60/40 57/43 4,500 1.3 1 a— 1 M- 1/ L- 1 50/50 43 /57 3,800 1.5 2 a— 2 M- 7/ L- 1 40/60 43/57 4,600 1.4 to 3 a — 3. M- 1/M- 7/L- 2 35/15/50 28/18/54 4,000 1.4 4 a— 4 M- 1/Ss- 1 50/50 50/50 4,500 1.5 Compared to 5 a – 5 M~ 2/ Ss — 2 70/30 72/28 4,700 1.3 Example 6 a – 6 M- 7/ Ss- 3 50/50 52/48 5,000 1.4 7 a— 7 M— 8/ S s— 4 40/60 37/63 3,800 1.5 8 a— 8 M- lty Ss — 5 50/20/30 41/22/ 37 4,100 1.4 9 a-9 M-L- 1 50/50 48/52 11,000 1,6 <[D] Polymer Synthesis> [Synthesis Example 22] Compound (M-13) 15.8 g (50 Mo The ear %) and the compound (M-7) 14.2 g (50 mol%) were dissolved in 60 g of 2-butanone, and AIBN (2.9 g) was added to prepare a monomer solution. The 300 ml three-necked flask to which 30 g of 2-butanone was added was subjected to nitrogen purge for 30 minutes, and then heated to 80 ° C with stirring, and the prepared monomer solution was dropped by dropping the funnel for 3 hours. Think of the beginning of the drop as a polymerization

S-66-201250381 Reaction start time 'The polymerization reaction was carried out for 6 hours. After completion of the polymerization reaction, the polymerization solution was cooled to 300 ° C or lower, and the polymerization solution was added to a solution of 600 g of methanol:water = 8:2, and the precipitated white powder was collected by filtration. The white powder obtained by filtration was washed twice with 120 g of methanol, filtered, and dried at 50 ° C for 17 hours to obtain a white powdery polymer component (D1) (20 g, yield 67% p). The polymer (D-1) had Mw of 4,200 and Mw/Mn of 1.4. Further, as a result of 13C-NMR analysis, a structural unit derived from the compound (M-1): a structural unit derived from the compound (Ss-1): The content of the structural unit derived from the compound (L-1) was 48.:5 : 5 1.5 (Molar [Synthesis Examples 23 to 24] The same as the synthesis example 22 except that the monomer described in the specific amount table 2 was used. The polymer (D-2) to (D-3) were obtained, and Mw, Mw/Mn, yield (%) of each of the obtained polymers, and the content of the structural unit derived from each monomer in each polymer were obtained. The rate is shown in Table 2. [Table 2] [D] Polymer compound tower amount in the polymer. Structural unit physical property 値 compound collocation molar % % Mohr % Mw Mw / Mn Synthesis Example 22 D-1 Μ — 7/M— 12 50/50 48.5/51.5 4,200 1.4 Synthesis Example 23 D-2 M- 2/U- 13 30/70 32/78 4,100 13 Synthesis Example 24 D-3 M- 11/M- 13 40/ 60 41/59 5,000 1.4 <Tune of the photoresist composition The [B] acid generator, the [C] acid diffusion control agent, the [E] additive and the solvent used for the preparation of the photoresist composition are as follows. -67- 201250381 <[B]acid generator>; B-1 to B-7 : a compound represented by the following formula [Chemical 2 9]

(B-6) (B-7) <[C] Acid Diffusion Control Agent> C-1 to C-6 : a compound represented by the following formula

S -68- 201250381 【化3 0】

<Solvent> F-1: propylene glycol monomethyl ether F-2: cyclohexanone [Example 1] 100 parts by mass of the mixed polymer component (Al), an acid generator (B1), 1 part by mass, and an acid 2 parts by mass of the diffusion controlling agent (C-3), 3 parts by mass of (C-4), 4 parts by mass of the polymer (D-1), 30 parts by mass of γ-butyrolactone as the additive (E-1), and a solvent ( Fl) 1, 75 parts by mass, (F-2) 75 parts by mass, and the resulting mixed solution was filtered with a filter having a pore size of 0.2 μm to prepare a photoresist composition. -69-201250381 [Examples 2 to 2 and Comparative Examples 1 to 9] A photoresist composition was prepared in the same manner as in Example 1 except that each component of the type and amount shown in Table 3 was used. 【table 3】

[Α1 polymer component [B] acid to produce hip [Cl acid expansion control m P] polymer tD] additive Bake sensitivity UTR DOF coffee time ΠΑ桕 苜 苜 份 面 face lion SB (t) ΡΕΒ (·〇 (nm MEEF (nm) ) 100 100 Β - 1 10 C-VC-4 2/3 D- 1 4 E- 1 30 120 105 38 52 Z2 180 2 A- 2 100 Bl ] 〇 C-3 S D-2 3 E- 1 100 120 80 39 S3 33 200 3 A-3 100 Β- 1 10 C-4 6 D-3 5 E- 1 50 120 85 37 6.4 32 210 4 A-4 100 B_ 4 11 C- 1 3 D- 1 3 E- 1 100 120 80 38 5.4 3.4 190 5 A-5 100 Bl 11 C-2 3 D-2 4 E- 1 so 120 95 36 52 33 200 6 Α-β 100 Bl 12 C-2 3 D-3 5 E- 1 50 120 90 35 5.4 3.4 200 7 A- 7 100 B~ 4 9 C-VC-4 2/4 D- 1 2 E- 1 50 120 )00 37 5.4 35 190 8 A-8 100 Bl 9 C-3 5 D-2 5 E- 1 30 120 80 37 S3 35 180 9 A-9 100 B-2/B-3 6/5 C-4 6 D-3 4 E- 1 】 00 120 100 38 6.4 3JS 170 寅10 A- 10 100 B-2 9 C- 3/C-4 3/3 D- 1 3 E- 1 50 120 80 37 53 3.4 190 η An 100 Bl 10 C-3 & D-2 3 E- 1 SO 120 85 37 5.4 3.4 200 12 A- 12 100 Bl 11 C- 3/C-4 3/2 D-3 3 E- I 30 120 80 36 52 33 210 Example 13 A- 13 100 Bl 11 C-3 6 D- 1 2 E- 1 100 120 90 37 5.4 3.4 180 14 A- 14 100 Bl 10 C-4 7 D- 1 4 E- 1 100 120 95 36 S2 3*5 190 15 A- 15 100 Bl 12 C-2 3 D- 1 4 E— 1 30 no 90 38 S3 3.4 170 16 A- 1Θ 100 B- 1/ B- 5 10 C-2/0-6 5/2 D- 1 4 E- 1 30 100 90 38 5*2 3<3 200 17 A- 17 100 B~ 1/ B- 6 5/9 C-2/C-6 7/1 D- I 4 E- 1 30 110 90 38 S. 4 35 220 18 A- 18 100 B- l/B-5 5/5 C-yC-4 3/3 D- 1 4 E- 1 30 120 100 38 32 200 19 A- 19 100 B- 1/ B- 7 5/5 C-2 3 D-2 4 E- t 30 120 9S 36 S2 32 190 20 A-20 100 Bl 10 C-5 5 D-2 3 E- 1 SO 120 105 36 62 32 180 21 A- 21 100 8- 1 9 C-3 5 D-3 2 E- 1 30 120 80 37 S3 33 190 1 e- 1 100 Bl 10 C-^C-4 3/3 D- 1 3 El 50 120 105 36 SS 3.7 150 2 aa 100 B- I/B-3 S/6 Cl 3 D-2 3 E- 1 30 120 85 36 6 3JB 160 3 a— 3 100 B- l/B-2 5/5 C-2 9 D-3 i El too 120 95 37 BS 150 to 4 a - 4 100 B-4 9 C-3 5 D- 1 2 El 30 in 20 105 36 5fi 3.7 140 & a - 5 100 Bl 9 C-3 6 D-2 3 El 50 120 100 39 5.7 3£ 1&0 6 a- β 100 Bl 10 C-3 6 D- 1 4 El 50 120 es 38 3 .7 160 cases 7 a- 7 100 B-2/B-3 4/6 C- ί 2 D-2 4 El 30 120 80 39 S£ 3>8 ISO Θ a— 8 100 Bl U C-4 6 I&gt ;-3 3 El 50 120 80 37 Sj6 3J9 140 9 a—9 100 B- l/B-7 5/5 C-2 3 D-2 4 El 30 120 95 38 S£ 3<9 HO <Evaluation> The photoresist compositions of Examples 1 to 2 1 and Comparative Examples 1 to 9 were evaluated as follows. The results of the assessment are shown in Table 3. [Evaluation of Sensitivity] 12 layers of anti-reflection film (ARC66-70-manufactured by Seiko Chemical Co., Ltd.) were formed.

S 201250381 A film with a thickness of 75 nm is formed on the germanium wafer by a photoresist composition, and soft baked (SB) is performed for 10 seconds (TC is performed for 60 seconds). Next, the film is subjected to an ArF excimer laser immersion exposure apparatus. (NSR S610C, manufactured by NIKON Co., Ltd.), under the conditions of ΝΑ=1·3, ratio = 0.800, and Annular, the pattern is formed by a pattern of 50 nm Linel 00 nm Pitch, and the composition of each photoresist is exposed after exposure. After baking for 60 seconds, it is baked (?8). After that, it is developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide, washed with water, and dried to form a positive resist pattern. The pattern of 50 nm Linel 00 nm Pitch forms a portion of the line exposed by the mask pattern to form an exposure amount of a line having a line width of 50 nm as the optimum exposure amount (Εορ). The optimum exposure amount is used as the sensitivity (mJ/cm 2 ). Scanning electron microscope (Hitachi High-Technologies, CG4000). When the sensitivity is below 40 (mJ/cm2), it is evaluated as good [MEEF]. The positive method is formed by the same method as the above-mentioned sensitivity (mJ/cra2) evaluation method. Resistor pattern and measure Εορ The above Εορ is formed by the pattern of the mask pattern formed by the pattern of the 48 nm line 100 nm, the 49 nm line 100 nm pitch, the 50 nm line 100 nm pitch, the 5 lnm line 100 nm pitch, and the 52 nm line 100 nm pitch. When the line size (nm) of the cover is plotted on the horizontal axis and the line width (nm) formed on the resist film using each mask pattern is plotted on the vertical axis, the slope of the straight line is calculated as MEEF. MEEF (slope of the line), The better the recovery, the better the reproducibility of the mask. The results are shown in Table 2. 201250381 [LWR(nm)] The same method as the above-mentioned sensitivity (mJ/cm2) evaluation method to form a positive resist pattern Measure Εορ. 'The line width of 50 nm formed by the above Εορ is observed from the upper part of the pattern, and the line width in any one of the points is measured. The line width is measured as the standard deviation 値 (distribution) of the WR (distribution) is LWR (nm) The LWR 値 is below 5.4 nm, and the shape of the pattern formed is evaluated to be good. [DOF(nm)] The optimum exposure amount (E〇P) in the evaluation of the above sensitivity, with a line of 50 nm and an interval. The size of the pattern when the pattern is resolved by the mask is within the range of ±10% of the mask design size as the DOF (nm). As shown in Table 2, the photoresist composition of the present invention is excellent in lithography performance of sensitivity, MEEF, DOF, and LWR. [Industrial Applicability] The photoresist composition of the present invention is applied to a semiconductor device, a liquid crystal device, or the like. The formation of a resist pattern for the lithography steps of various electronic devices. -72-

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Claims (1)

201250381 VII. Patent application scope: 1 - A photoresist composition characterized by having the same or different polymer of [A], having a structural unit (I) represented by the following formula (1), and the structure One or more polymer components of the structural unit (II) having at least one structure selected from the group consisting of a cyclic carbonate structure, a sultone structure, and a lactone structure, and a structural unit other than the unit (I) And [B] acid generator, R4 R5 (In the formula (1), R1 is a hydrogen atom, a fluorine atom, a hydroxyl group or a monovalent organic group having 1 to 20 carbon atoms, and each of R2 and R3 is independently a hydrogen atom, a fluorine atom, a hydroxyl group or a carbon number of 1 to 20. a monovalent organic group, or R2 and R3 are bonded to each other and a carbon atom bonded thereto to form a ring structure having a carbon number of 3 to 10' a is an integer of 1 to 6, but when a is 2 or more, a plurality of R2 And each of R3 may be the same or different, and each of R4 and R5 is independently a hydrogen atom, a fluorine atom, a hydroxyl group or a monovalent organic group having 1 to 20 carbon atoms, or a carbon atom to which R4 and R5 are bonded to each other and bonded thereto. Together, a ring structure having a carbon number of 3 to 10 is formed 'but a part or all of one of the hydrogen atoms of the above ring structure may be substituted). 2. The photoresist composition as described in claim 1 wherein the structural unit 201250381 (Π) is a structural unit (II-1) represented by the following formula (2), lit 2] (2) (In the formula (2), R6 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, R7 is a hydrocarbon group having a carbon number of 1 to 10, and X is -0-, -COO., -OCO- or -NH-, η is an integer of 0 to 10, and when η is 2 or more, each of R 7 and X may be the same or different, R 8 is a single bond or a hydrocarbon group having 1 to 5 carbon atoms, and R 9 is a ring-shaped group. The cyclic organic group of at least one structure selected from the group consisting of a carbonate structure, a sultone structure, and a lactone structure, but some or all of the hydrogen atoms of R7 to R9 may be substituted. 3. The photoresist composition according to claim 1 or claim 2, wherein the [Α] polymer component further contains a structural unit (m) represented by the following formula (3), [Chemical 3] R10 R11—C — R13 R12 (3) s -74- 201250381 (In the formula (3), R1Q is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and each of R11 to R13 is a carbon number of 1 to 4 An alicyclic group having a carbon number of 4 to 20, but R11 and R12 may be bonded to each other to form an alicyclic structure together with the carbon atoms bonded thereto. Further, the above alkyl group and alicyclic group have Part or all of one of the hydrogen atoms may be substituted). The photoresist composition according to claim 2 or claim 3, wherein the cyclic organic group having a lactone structure represented by the above R9 is a norbornene inner acetate group or a butyrolactone group, and the above ring The cyclic organic group of the carbonate structure is an ethyl carbonate group, and the cyclic organic group having a sultone structure is a norbornane sultone group. 5. The photoresist composition according to any one of claims 1 to 4, wherein the content of the structural unit (1) in the polymer component [A] is 5 mol% or more and 60 mol. /. Hereinafter, the total content of the structural unit (]) and the structural unit (ΙΠ) is 10 moles. /〇 above 80% of the following. -75- 201250381 Four designated representatives: (1) The representative representative of the case is: None (2) The symbol of the representative figure is simple: No 201250381 If there is a chemical formula in the case, please disclose the chemical formula that best shows the characteristics of the invention: No S -4 -