TW201033733A - Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same - Google Patents

Abstract

An actinic ray-sensitive or radiation-sensitive resin composition, includes: (A) a resin capable of increasing the solubility of the resin (A) in an alkali developer by the action of an acid; and (C) a resin having at least either a fluorine atom or a silicon atom and containing (c) a repeating unit having at least two or more polarity conversion groups.

Description

201033733 VI. Description of the Invention: [Technical Field] The present invention relates to a sensitized ray or radiation sensitive resin composition which is used in a manufacturing method of a semiconductor (such as 1C) or used in a circuit board for liquid crystal, heat In the manufacture of inductive heads and the like, or in other photolithographic etching methods; and pattern forming methods using the same. More specifically, the present invention relates to a positive photoresist composition suitable for exposure by a light source emitting a wavelength of 300 nm or shorter far-ultraviolet rays by an immersion projection exposure apparatus; and using the same Pattern forming method. [Prior Art] Along with the miniaturization of semiconductor components, the trend is moving toward a shorter wavelength exposure source and a higher number of aperture (higher NA) projection lenses' and it is known that the projection lens and the sample are mounted high. The refractive index liquid (hereafter referred to as the "immersion liquid") is called "immersion method" in an attempt to improve the resolution by shortening the wavelength. The immersion method is effective for all pattern shapes, and further, it can be In combination with the current super-analytical techniques (such as 'phase shifting method and modified lighting method). Because of the appearance of photoresist for KrF excimer laser (248 nm), it has been called chemical amplification. The image forming method is used as a photoresist image forming method to compensate for the sensitivity reduction caused by light absorption. For example, an image forming method by positive chemical amplification is an acid generator decomposition in an exposed region after exposure. The acid is generated, and the generated acid is used as a reaction catalyst. In the post-exposure baking (PEB: post-exposure baking), the alkali-insoluble group is converted into an alkali. The group's image formation method by removing the exposed area 201033733 by alkaline development. The photoresist used for the ArF excimer laser (193 nm) currently accounts for the vast majority of the use of this chemical amplification mechanism, but when the light When immersed in immersion exposure, it may include a pattern collapse that causes the formed line pattern to collapse to cause defects during component fabrication, or a performance that is less than the roughness of the line edge of the pattern sidewall being roughened. It has been pointed out that when the chemically amplified photoresist is applied to an immersion exposure, the photoresist layer contacts the immersion liquid upon exposure, and as a result, the photoresist layer may be damaged or the components adversely affected by the immersion liquid may In the photoresist layer ©. In order to solve this problem, in 1?-八-2006-309245 (as used in this article, the name "JP-A" means "unexamined announcement of Japanese patent application· , by JP-A-2007-3045 37, JP-A-2 0 0 7 -1 8 2 4 8 8 and JP-A-2007-153982, by adding a resin containing a halogen atom or a fluorine atom To prevent the outflow of the embodiment" In the immersion exposure method, when the scanning type immersion exposure machine is used for exposure, unless the immersion liquid moves as the lens moves, the exposure speed is lowered and this may affect productivity. The immersion liquid is water. In the examples, the photoresist film is preferably hydrophobic because of good water flow. In JP-A-2008-111103, it has been indicated that the photoresist pattern profile is improved using a specific norbornane lactone derivative. However, even when immersion exposure is performed using the techniques described above, there is a further need to further reduce development defects or scum, particle or bubble defect formation and improved pattern profile known as BLOB defects. -4-201033733 SUMMARY OF THE INVENTION An object of the present invention is to provide a sensitized ray or a radiation-sensitive resin composition capable of forming an improved line edge roughness and scum generation, reducing development defects, and ensuring only a slight acid dissolution. In the immersion liquid, good fluidity to the immersion liquid, and various patterns of properties in terms of particle suppression, pattern shape and bubble defect prevention; and a pattern forming method using the same. The present inventors have reached the present invention described below in order to achieve the intensive study of the objectives described above. The present invention has the following constitutions. (1) A photosensitive ray or radiation sensitive resin composition comprising: (A) a resin capable of increasing the solubility of the resin (A) in an alkali developer by an acid action; and (C) a resin having Any one of at least a fluorine atom or a ruthenium atom and including - at least two or more of a polarity-converting group represented by -COO- in a structure represented by formula (KA-1) or (KB-1) Repeat unit (c):

Wherein Zka represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, a guanamine group, an aryl group, a lactone ring group or an electron withdrawing group; and when a plurality of Zka are present, the plurality of zkas may be the same Or different; each zka can be combined with each other Zka to form a ring; 201033733 nka represents an integer 0 to 10;

Each of Xkbl and Xkb2 independently represents an electron withdrawing group; each of nkb and nkb' independently represents 0 or 1; and each of Rkbi to Rfcb4 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group. Or an electron withdrawing group; at least two members of Rkbl, Rkb2 and Xkbi may be bonded to each other to form a ring; and at least two members of Rkb3, Rkw and Xkb2 may be bonded to each other to form a ring. (2) The sensitized ray or radiation sensitive resin composition as described in the above (1), wherein the repeating unit (c) has at least two or more polar switching groups on one side chain and a repetitive unit of at least one of a fluorine atom or a ruthenium atom (C, (3) is a sensitized ray or a radiation-sensitive resin composition as described in the above (1), wherein the repetitive unit (c) has a repeating unit (C*) having at least two or more polar converting groups and having no fluorine atom or germanium atom; and the resin (C) further comprising a repeating unit having at least one of fluorine atoms or germanium atoms (4) The sensitized ray or radiation sensitive resin composition as described in the above (1), wherein the repeating unit (c) is a repeating unit (c") having at least two on one side chain Or more than one polarity-switching group, while having at least one of a fluorine atom or a ruthenium atom on a side chain different from the side chain in the same repeating unit. -6- 201033733 (5) as in the above (1) The sensitized ray or radiation sensitive resin described in any one of (4) Into the composition, wherein the repeating unit (c) having a junction (KY-1) represented by the following formula

Wherein each of Rkyl and Rky4 independently represents a hydrogen atom, a halogen pronator, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, a guanamine group or an aromatic group. a group; Rkyl and Rky4 may be bonded to the same atom to form a double bond;

Each of Rky2 and Rky3 independently represents an electron withdrawing group; or Rkyl combines with Rky2 to form a lactone ring, while Rky3 is an electron withdrawing group;

At least two members of Rkyl, Rky2 and Rky4 may be bonded to each other to form a monocyclic or polycyclic structure;

Rkbi to Rkb4, nkb, and nkb' have the same (6) as in the formula (KB-1), the sensitized ray or radiation-sensitive resin composition as described in any one of the above (1) to (5) Wherein the repeating unit (c) has a knot represented by the following formula (KY-2)

201033733 wherein each of Rky6 to RkylO independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, a guanamine group or an aryl group. ;

Two or more members of Rky6 to RlcylO may be bonded to each other to form a monocyclic or polycyclic structure;

Rky5 represents an electron withdrawing group: and

Rkbi, Rkb2, and nkb have the same meanings as in the formula (KB-1). (7) The sensitized ray or radiation sensitive resin composition as described in any one of the above (1) to (6), wherein the resin (C) has at least one of the formulae (F2) to (F4) And a group represented by any one of the formulae (CS-1) to (CS-3): R

Wherein each of R „ to KM independently represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group or an aryl group, and the limitation is at least one of R57 to R61, at least one of R62 to R64, and Re 5 to R68. At least one each independently represents a fluorine atom or an alkyl group containing at least one hydrogen atom replaced by a fluorine atom; and R62 and R63 may be bonded to each other to form a ring: 201033733

I, Ό Rie-S.〇^Sf-R19

(CS-3) (CS-2) (CS-1) wherein each of Rl2 to R26 independently represents a linear or branched alkyl group or a cycloalkyl group; each of L3 to L5 represents a single bond or a divalent linking group; And η represents an integer of 1 to 5. (8) The sensitized ray or radiation sensitive resin composition as described in the above (7), wherein the resin (C) includes at least one of the formula (F2) to (F4) and the formula (CS-1) to An acrylate or methacrylate repeating unit of the group represented by any of (CS-3). (9) The sensitized ray or radiation sensitive resin composition as described in any one of the above (1) to (8), wherein the content of the resin (C) is from 0.01 to 10% by mass in the sensitization The total solid content in the ray or radiation sensitive resin composition is correct. (10) The sensitized ray or radiation sensitive resin composition as described in any one of the above (1) to (9), further comprising: (Β) capable of generating an acid after irradiation with actinic rays or radiation compound of. (11) A sensitized ray or radiation sensitive resin composition as described in any one of the above (1) to (1), wherein the resin (A) comprises a repeating unit having a lactone structure. (12) A photosensitive ray or radiation sensitive resin composition as described in any one of the above (1) to (11), wherein the resin (A) has a monocyclic or polycyclic acid-decomposable group . (13) A photoresist film formed from the sensitized ray or radiation sensitive resin composition as described in any one of the above (1) to (12). (14) A pattern forming method comprising: immersing exposure and developing a photoresist film as described in the above (13). [Embodiment] Description of Specific Embodiments The present invention is described in detail below. Incidentally, in the present invention, when a group (atomic group) represented does not specifically indicate whether it is substituted or unsubstituted, the group includes a group having no substituent and a group having a substituent. both. For example, "hospital based" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present invention, the name " Actinic ray " or "radiation" refers to, for example, a bright line spectrum of a mercury lamp, a typical far ultraviolet ray, an extreme ultraviolet light, an X-ray, or an electron beam that is a quasi-molecular laser. Similarly, in the present invention, "light" means actinic radiation or radiation. Further, 'in the present invention, unless otherwise indicated, the "exposure" includes not only a mercury lamp, a typical far ultraviolet ray, a X-ray, an EUV light or the like which is excimer laser light, but also exposure. It also includes lithographic etching with a particle beam such as an electron beam and an ion beam. 201033733 The sensitized ray or radiation sensitive resin composition of the present invention comprises (A) an increase in solubility in an alkaline developer by an acid action. a resin, and (C) a resin having at least one of a fluorine atom or a ruthenium atom and comprising a repeating unit having at least two or more polar conversion groups, and further comprising (B) capable of actinic ray or radiation A compound which generates an acid after irradiation is preferred. [1] A resin which can increase the solubility in an alkaline developer by an acid action (A) The resin of the component (A) is an alkali which can be increased by an acid action. a solubility resin in the developer, and thus has a group capable of decomposing by an acid to produce an alkali-soluble group in the main chain and the side chain of the resin. Sometimes referred to as " The resin of the acid-decomposable group "). Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a fluorenyl group Imine group, (alkylalkyl)(alkylcarbonyl)methylene, (alkylalkyl)(alkylcarbonyl)indolide group, bis(alkylcarbonyl)methylene group, bis(alkane) a carbonyl iodide group, a bis(alkylindenyl)methylene group, a bis(alkyl fluorenyl) fluorenylene group, a tris(alkylcarbonyl)methylene group, and a tris(alkyl fluorenyl group) Methylene. © — The preferred embodiment of the alkali-soluble group includes a carboxyl group, a fluorinated alcohol group (preferably hexafluoroisopropanol), and a sulfonic acid group. The group of the group is a group in which the hydrogen atom of the above-mentioned alkali-soluble group is replaced by a group which can be removed by an acid action. Examples of the group which can be removed by an acid include - C(R36)(R37)(R38) and -C(R〇i)(R〇2)(〇R39). In the formula, each of R3 6 to R3 9 independently represents an alkyl group or a cycloalkyl group. , aryl, aralkyl or alkenyl; and R3 6 and R3 7 This combination to form 201033733 R〇1 and R〇2 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkenyl group. The acid-decomposable group is a mercapto ester group. Preferably, the group, the enol ester group, the acetal ester group, the tertiary alkyl ester group or the like is preferably a 'trialkyl ester group. The resin of the component (A) has a single The acid-decomposable group of the ring or polycyclic ring is preferred. As for the monocyclic or polycyclic acid-decomposable group 'Ru to r39', any one of them is a cycloalkyl group or R36 is bonded to R37 to form a ring. Preferably, the resin of the component (A) comprises a repeating unit having an acid-decomposable group. The repeating unit having an acid-decomposable group is a repeat represented by the following formula (AI) The unit is better:

Rx, (rushing cr^o--rx2 In the formula (AI), Xai represents a hydrogen atom, a methyl group which may have a substituent or a group represented by -CHz-R9. R9 represents a hydroxyl group or a monovalent organic group. And examples of the monovalent organic group include a group having a carbon number of 5 or less and a fluorenyl group having a carbon number of 5 or less. The monovalent organic group is an alkyl group having a carbon number of 3 or less Preferably, the methyl group is more preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. Τ represents a single bond or a divalent linking group.

Each of Rxi to RX3 independently represents an alkyl group (linear or branched) or a ring -12-201033733 alkyl (monocyclic or polycyclic). Two members from Ru to RX3 may be combined to form a cycloalkyl group (monocyclic or polycyclic). Examples of the divalent linking group of T include an alkylene group, a -CO〇-Rt- group, and a -Ο-Rt- group, wherein Rt represents an alkylene group or a cycloalkyl group. It is preferred that T is a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH2_ group or a -(CH2)3- group. The alkyl group of the ruthenium to Rx3 is preferably an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. The cycloalkyl group of 1^! to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclic fluorenyl group or a tetracyclic ring. Dodecyl and adamantyl. The cycloalkyl group formed by combining two members derived from Rxi to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or a polycyclic cycloalkyl group such as a decyl group. , tetracyclic fluorenyl, tetracyclododecyl and φ adamantyl. A cycloalkyl group having a single ring having 5 to 6 carbon atoms is more preferable.

Particular embodiments in which Rxi is a methyl or ethyl group and Rx2 is combined with Rx3 to form a cycloalkyl group as described above are preferred. Each of the above groups may have a substituent; and examples of the substituent include a group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group, and an alkoxy group. A carbonyl group (having a carbon number of 2 to 6). The carbon number is 8 or less. The total content of the repeating unit containing the acid-decomposable group is preferably from 20 to 70 -13 to 201033733, and more preferably from 30 to 50 mol%, so that all the repeating units in the resin are quasi. A specific preferred embodiment of the repeating unit having the acid-decomposable group is proposed below, but the invention is not limited thereto. In a particular embodiment, each of Rx and Xai represents a hydrogen atom, CH3, CF3 or CH2OH' and each of Rxa and Rxb represents a carbon number! Alkyl group up to 4. z represents (when there are a plurality of Z, each of them independently represents a polar group or a substituent containing a polar group). Specifically, Z includes the same ones as R1G of the formula (2-1) described later, and p represents 〇 or a positive integer. ©

-14 - 201033733 v=oBxa, fc丨CICIO έ -?)-μο 2 o.

Bxt |5丨-0|=0丨0' CH20=

RXIITIC ~0- ch,-l

Ibca

o :, XHst< BXl-cl=clo « llBX CH2Qchjq 0 Rx

2财—€€=(:丨0 o p Φ I^ 如R· ·' CH2 CH2o p (z) I—rr

H-

J-r丨Y

Foo.tl CIO X—)=: 0=0520 slave—°丄= P (2)

CICIO Η ο ο

, ±|. | 8 1* 20 CH2

-15- 201033733

201033733 ❹

CZ)p

Repeated unit resin is better

Ri R3

In the formulae (1) and (2), each of Ri and R3 independently represents a hydrogen atom, a methyl group which may have a substituent or a group represented by -ch2-r9. R9 represents a hydroxyl group or a monovalent organic group. Each of R2, R4, R5 and R6 independently represents an alkyl group or a cycloalkyl group. R represents an atomic group required to form an alicyclic structure together with the carbon atom. 1 is a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. -17. 201033733 The alkyl group in R2 may be linear or branched and may have a substituent. The cycloalkyl group in r2 may be monocyclic or polycyclic and may have a substituent. R2 is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group. R represents an atomic group required to form an alicyclic structure together with the carbon atom. The alicyclic structure formed by R is preferably a monocyclic alicyclic structure, and its carbon number is preferably from 3 to 7, more preferably 5 or 6. R3 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group. The alkyl group in R4, R5 and R6 may be linear or branched and may have a substituent. The alkyl group is preferably an alkyl group having a carbon number of 1 to 4, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a tertiary butyl group. The cycloalkyl group in R4, 115 and R6 may be monocyclic or polycyclic and may have a substituent. The cycloalkyl group is preferably the following: a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclononyl group, a tetracyclododecyl group, and a diamond. alkyl. Specific examples and preferred embodiments of the organic group or R9 are the same as those described for R9 of formula ® (AI). The embodiment of the repetitive unit represented by the formula (1) includes a repetitive unit represented by the following formula (1-1). In the formula, Ri has the same meaning as those in the formula (1).

-18- 201033733 The repeating unit represented by the formula (2) is preferably a repeating unit represented by the following formula (2-1): R3 person (2-1) R5 p in the formula (2-1) R3 to Rs have the same meanings as those in the formula (2). R1() represents a polar group or a substituent containing a polar group. In the case where there are; several Rios, each R1() may be the same or different from every other R1(). The polar group is, for example, a hydroxyl group, a cyano group, an amine group, an alkylguanamine group or a sulfonamide group. The polar group-containing substituent is preferably a linear or branched alkyl group or a cycloalkyl group having such a polar group, an alkyl group having a hydroxyl group is more preferable, a branched alkyl group having a hydroxyl group is more preferable, and the branched alkyl group is more preferable. It is preferably an isopropyl group. ^ P represents an integer 〇 to 15 op is an integer 0 to 2 is preferable, and 0 or 1 is more preferable. ❹ The resin (A) may comprise a plurality of repeating units containing acid-decomposable groups. As described above, the resin (A) is at least one of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) as the weight represented by the AI. The resin of the covering unit is preferred. In another specific embodiment, the resin (A) is a repeating unit comprising at least two types represented by the formula or a repeating unit represented by the formula (1) and a repeat represented by the formula (2) Both of the units are preferably used as the resin of the repeating unit represented by the formula (AI). -19- 201033733 Similarly, the photoresist composition of the present invention may comprise a plurality of resins (A), and the repeating units containing the acid-decomposable groups contained in the plurality of resins (A) may be different from each other. For example, a resin (A) comprising a repeating unit represented by the formula (1) and a resin (A) containing a repeating unit represented by the formula (2) can be used in combination.

The following is a summary of the combination when the resin (A) comprises a plurality of repeating units containing acid-decomposable groups, and when the plurality of resins (A) comprise different repeating units containing acid-decomposable groups. A good example. In the following formula, each R independently represents a hydrogen atom or a methyl group.

_ 编_ ^ «« _ 1 Winter 1 , • *. CTO 0^0 C Ancient • _ -e4* On 1 a _ . Cold work >· • · _ ΰ^τη-m — _ — _ _ • Peak · • «, • Life Ice 13⁄43⁄4] • Saki · . <^1* -20- 201033733 The resin of the component (A) further comprises at least one selected from the group consisting of a lactone group, a hydroxyl group, a cyano group and A repeating unit of a group soluble in a base group is preferred. The repeating unit containing the lactone group which may be contained in the resin of the component (A) is described below. As the lactone group, any group 'may be used as long as it has a lactone structure, but the lactone structure is preferably a lactone structure of 5 to 7 membered rings, and the other ring structure is formed to form a bicyclic or spiro structure. The structure is fused to a structure of 5 to 7 membered cyclic lactone structures. The resin preferably comprises a repeating unit having a lactone structure represented by any one of the following formulae (LC 1-1) to (LC 1-17). The lactone structure can be directly bonded to the backbone. Among these lactone structures, '(LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17) are preferred. . Pattern shape, isolated/dense deviation, line edge roughness, and development defects are improved by selecting the most desirable lactone group.

-21- 201033733 The lactone moiety may or may not have a substituent (Rb2). Preferred examples of the substituent (Rbz) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and having 2 to 8 carbon atoms. Alkoxycarbonyl group, carboxyl group, halogen atom, hydroxyl group, cyano group and acid-decomposable group. Among these, the alkyl group having a carbon number of 1 to 4, a cyano group and an acid-decomposable group are more preferable. Μ represents an integer 〇 to 4. When „2 is an integer of 2 or more, each substituent (Rb〇 may be the same as or different from each other substituent (Rb2); likewise 'each substituent (RbO may be associated with each other substituent (Rb2) Combining to form a ring. The repeating unit having a lactone structure represented by any one of the formulae (LC 1-1) to (LC1-17) includes a repeating unit represented by the following formula (ΑΠ):

COOAb-V In the formula (All) 'Rb 〇 represents a hydrogen atom 'halogen atom or an alkyl group having a carbon number of 1 to 4 which may have a substituent. Preferred examples of the alkyl group of the RbQ which may have a substituted fluorenyl group include a hydroxyl group and a halogen atom. The halogen atom of Rbo includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As for Rbo, a hydrogen atom 'methyl group, a methylol group or a trifluoromethyl group is preferred, and a hydrogen atom or a methyl group is more preferred.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group or a divalent linking group including a combination thereof, and a single bond or The divalent linking group represented by -Ah-CO2- is preferred. -22- 201033733

Ah represents a linear or branched alkyl group or a monocyclic or polycyclic cycloalkyl group and a methylene group, an ethyl group, a cyclohexylene group, an adamantyl group or a stretched fluorenyl group is preferred. V represents a group having a structure represented by any one of the formulae (LC1-1) to (LC1-17). The repeating unit having a lactone group usually has an optical isomer' but any optical isomer can be used. One optical isomer may be used alone or a mixture of a plurality of optical isomers may be used. In the case of mainly using an optical heterostructure, the optical purity (ee) is preferably 90% or more, more preferably 95% or more. The repeating unit having a lactone group is represented by the following formula: (3) The repeated unit containing the internal vinegar structure is preferably:

In the formula (3), A represents an ester bond (-COO-) or a guanamine bond (-CONH-). R 〇 represents (when a plurality of R 存在 are present, each independently represents) an alkyl group, a cycloalkyl group or a combination thereof. Z represents (when there are a plurality of Z, each of them independently represents an ether bond, an ester bond, a guanamine bond, a urethane bond or a urea bond). R8 represents a monovalent organic group having a lactone structure. η is the number of overlaps of the structure represented by -R〇-Z- in the repeating unit of the formula (3) and represents the integers 1 to 5. h represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent. -23- 201033733 The alkylene and cycloalkyl groups of the R〇 may have a substituent. Z is preferably an ether bond or an ester bond, and the ester bond is more preferred. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and more preferably a methyl group. The alkyl group in R7 may be substituted, and examples of the substituent include a halogen atom (such as a fluorine atom, a chlorine atom, and a bromine atom), a hydrazine group, a hydroxyl group, an alkoxy group (such as a methoxy group, an ethoxy group). 'Isopropoxy, tert-butoxy and benzyloxy), and anthraceneoxy (such as ethoxylated and propyloxy). The ruler 7 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. The alkyl group in R 为 is preferably a chain alkyl group having 1 to 10 carbon atoms, more preferably a chain alkyl group having 1 to 5 carbon atoms, and examples thereof include methylene group and ethyl group. And stretch propyl. The cycloalkyl group is preferably a cycloalkyl group having 4 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, an extended fluorenyl group and an adamantyl group. In order for the effect of the present invention to occur, the alkylene group is more preferred and the methylene group is still better. The lactone-containing structural substituent represented by Rs is not limited as long as it has a lactone structure. Specific examples thereof include the lactone structure represented by the formulae (LC1-1) to (LC1-17) and among these, the structure represented by (LC1-4) is preferred. The structure in which n2 in (LC1-1) to (LC1-17) is an integer of 2 or less is more preferable.

The monovalent organic group having a monovalent organic group having an unsubstituted lactone structure or a lactone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent preferably contains a fluorine group as a substituent. The monovalent organic group of the lactone structure (cyanolactone) is more preferred. The repeating unit having a lactone structure is preferably a repeating unit represented by the following formula (3_υ: 201033733

In the formula (3-1), 'R7, a, R〇, Z and η have the same meanings as in the formula (3). Represented (when there are a plurality of 119, each of which is independently represented by each), a cycloalkyl, alkoxycarbonyl, cyano, hydroxy or alkoxy group; and when a plurality of R9 are present, Two members can combine to form a ring. X represents an alkyl group, an oxygen atom or a sulfur atom. m is the number of substituents and represents an integer 〇 to 5. It is preferred that m is 0 or 1. The alkyl group of R9 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group. The cycloalkyl group includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a n-butoxycarbonyl group, and a tertiary butoxycarbonyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. These groups 〇 may have a substituent, and the substituent includes a hydroxyl group, an alkoxy group such as a methoxy group and an ethoxy group, a cyano group, and a halogen atom such as a fluorine atom. R9 is preferably a methyl group, an alkoxycarbonyl group or a cyano group, and a cyano group is more preferred. Examples of the alkylene group of X include a methylene group and an ethyl group. X is preferably an oxygen atom or a methylene group, and a methylene group is more preferred. When m is an integer of 1 or more, at least one R9 substitution is preferably at the α-position or the A-position of the carbonyl group of the lactone, and more preferably at the a-position. A particularly preferred embodiment of the repeating unit having a lactone group is set forth below. In these particular embodiments, Rx represents h, ch3, ch2oh or cf3. -25- 201033733 R represents a hydrogen atom, an alkyl group or a halogen atom which may have a substituent, and a hydrogen atom, a methyl group or an alkyl group having a substituent (that is, a trifluoromethyl group, a hydroxymethyl group or an ethyl fluorenyl group) Oxymethyl group is preferred.

-26- 201033733 The content of the repeating unit having a lactone group is preferably from 15 to 60 mol%, more preferably from 20 to 50 mol%, even more preferably from 30 to 50 mol%. All repeating units in the resin shall prevail. The resin (A) may comprise a repeating unit containing a lactone group or a plurality of repeating units containing a lactone group. It is also possible to use two or more lactone repeating units selected from the formula (3) in combination to enhance the effect of the present invention. When used in combination, it is preferred to use two or more in combination with a repeating unit selected from a lactone repeating unit of the formula (3). It is also preferred to use a lactone repeating unit in which Ab in the formula (All) is a single bond, and a lactone repeating unit derived from the formula (3). The resin of the component (Α) preferably comprises a repeating unit having a hydroxyl group or a cyano group, which is separate from the repeating unit represented by the formula (ΑΙ) and the repeating unit containing a lactone group (when these repeats are repeated) When the unit contains a hydroxyl group or a cyano group). Due to this overlapping unit, the adhesion to the substrate and the affinity for the developer are improved. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably does not contain an acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group is preferably an adamantyl group, a bisadamantyl group or a norbornyl group. Preferred examples of the alicyclic hydrocarbon structure substituted by a hydroxy group or a cyano group include monohydroxyadamantyl, dihydroxyadamantyl, monohydroxydiadamantyl, dihydroxydiadamantyl and cyano substituted萡基. The alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group is preferably a partial structure represented by the following formulas (Vila) to (Vlld): -27- 201033733

In the formulae (VIIa) to (Vlie), each of R2C to R4C independently represents a hydrogen atom, a sulfhydryl group or a cyano group, with the limitation that at least one of R2c to R4c represents a hydroxyl group or a cyano group. A structure derived from one or two of R2C to R4c is a hydroxyl group and the remainder is a hydrogen atom. In the formula (VIIa), two members derived from R2c to R4c are a hydroxyl group and the remainder is preferably a hydrogen atom. The repeating unit having a partial structure represented by the formulae (VI la ) to (VI Id) includes a repeating unit represented by the following formulas (Alla) to (Alld):

In the formulae (Alla) to (Alld), R1C represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. R2c to R4c have the same meanings as R2c to R4c in the formulas (Vila) to (Vile). The content of the repeating unit having a hydroxyl group or a cyano group is from 5 to 40 moles. /. Preferably, it is more preferably from 5 to 30 mol%, more preferably from 10 to 25 mol%, and all of the repeating units in the resin (A) are taken as the standard. -28-201033733 A specific embodiment of the repeating unit having a hydroxyl group or a cyano group is proposed below, but the invention is not limited thereto.

The resin of the component (A) preferably comprises a repeating unit having a group soluble in a base. The alkali-soluble group includes a carboxyl group, a sulfonamide group, a mercaptoquinone group, a bis-indenylene imine group, and an aliphatic alcohol (such as hexafluorofluoride) substituted at an electron withdrawing group. Isopropyl alcohol group). It is more preferable to include a repeating unit having a carboxyl group. The resolution in the use of forming contact holes is increased by including a re-fraction unit having a group soluble in a base. As for the repeating unit having a base which is soluble in a base, the alkali-soluble group is directly bonded to the repeating unit of the resin main chain (such as a repeating unit by acrylic acid or methacrylic acid), The alkali-soluble group is bonded to the repeating unit of the resin main chain via a linking group, and the base is soluble in the polymerization using a polymerization initiator or a chain transfer agent containing a hydrazine-soluble group. It is preferred that the group introduces repeating units in the polymer chain terminal. The linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. In particular, a repeating unit made of acrylic acid or methacrylic acid is preferred. The content of the repeating unit having an alkali-soluble group is preferably from 〇 to 20 mol%, more preferably from 3 to 15 mol%, still more preferably from 5 to 10 mol%, and more preferably in the resin. All repeating units in (A) shall prevail. -29-201033733 The following is a specific embodiment of the repeating unit having the alkali-soluble group, but the present invention is not limited thereto. Rx represents a hydrogen atom, CH3, CF3 or ch2oh.

The repeating unit having at least one group selected from the group consisting of a lactone group, a hydroxyl group, a cyano group and a base soluble group has at least two selected from the group consisting of a lactone group, a hydroxyl group, a cyano group, and The repeating unit of the member of the alkali-soluble group is preferably more preferably a repeating unit having a cyano group and a lactone group. In particular, a repeating unit having a structure in which a cyano group is substituted with a lactone structure of (LC1-4) is preferred. The resin of the component (A) further preferably comprises a repeating unit represented by the formula (1) having no hydroxyl group or cyano group.

In the formula (I), R5 represents a hydrocarbon group having at least one cyclic structure and having no hydroxyl group or cyano group.

Ra represents a hydrogen atom, an alkyl group or a _CIl2-〇_Ra2 group, wherein Ra2 represents -30-201033733 an alkyl group or a fluorenyl group. Examples of Ra include H, CH3, and CF3. The cyclic structure possessed by R5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having a carbon number of 3 to 12, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and a cycloalkenyl group having a carbon number of 3 to 12, such as a ring. Hexenyl. The monocyclic hydrocarbon group is preferably a monocyclic hydrocarbon group having 3 to 7 carbon atoms, more preferably a cyclopentyl group or a cyclohexyl group. The polycyclic hydrocarbon group includes a cyclic hydrocarbon group and a crosslinked cyclic hydrocarbon group. Examples of the hydrocarbon group accumulated in the ring include a dicyclohexyl group and a perhydronaphthalenyl group. Examples of the crosslinked hydrocarbon ring include bicyclic hydrocarbon rings such as a decane ring, a decane ring, a norbornane ring, a norbornane ring, and a bicyclooctane ring (for example, a bicyclo[2.2.2]octane ring. , bicyclo[3_2.1]octane ring); tricyclic hydrocarbon ring, such as homobredane ring, adamantane ring, tricyclo[5.2.1.02,6]nonane ring and tricyclic ring [4.3.1. I2'5] undecane ring; and tetracyclic hydrocarbon ring, such as tetracyclo[4.4.0.12'5.17,1()]dodecane ring and perhydro-1,4-methylalkyl-5,8-methane Naphthalene ring. The crosslinked cyclic hydrocarbon ring also includes a condensed cyclic hydrocarbon ring, for example, a fused ring formed by condensing a plurality of 5 to 8 membered cycloalkane rings, such as a perhydronaphthalene (decalin) ring, Hydroquinone ring, perhydrophenanthrene ring, perhydroethane naphthalene ring, perhydroindene ring, perhydroindole ring and perhydroindole ring. Preferred examples of the crosslinked cyclic hydrocarbon ring include a descending group, a diamond base, a bicyclooctyl group, and a tricyclo[5.2.1.02>6]decyl group, and a thiol group and an adamantyl group. Better. The alicyclic hydrocarbon group may have a substituent, and preferred examples of the substituent include a halogen atom, an alkyl group, a trans group protected by a protecting group, and an amine group protected by a protecting group. The halogen atom is preferably a bromine atom, a chlorine atom or a fluorine atom -31 to 201033733; and the alkyl group is preferably a methyl group, an ethyl group, a butyl group or a tertiary butyl group. The alkyl group may further have a substituent, and the substituent which the alkyl group may further have includes a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amine group protected by a protecting group. Examples of such protecting groups include alkyl groups, cycloalkyl groups, aralkyl groups, substituted methyl groups, substituted ethyl groups, alkoxycarbonyl groups, and aralkyloxycarbonyl groups. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms; the substituted methyl group is a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, a tertiary butoxymethyl group or 2-methoxyethoxymethyl is preferred; the substituted ethyl group is 1-ethoxyanthoylethyl or 1-methyl-1.methoxyethyl; the fluorenyl group has carbon The aliphatic sulfhydryl groups of 1 to 6 are preferably, such as a methyl fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl group, an isobutyl fluorenyl group, a pentamidine group and a pentamidine group; and the alkoxycarbonyl group has carbon Alkoxycarbonyl groups of 2 to 4 are preferred. The content of the repeating unit represented by the formula (I) having no hydroxyl group or cyano group is preferably from 0 to 40 mol%, more preferably from 〇 to 20 mol%, in the resin (A). All repeating units shall prevail.特定 A specific embodiment of the repeating unit represented by the formula (I) is proposed below, but w is not limited thereto. In the equation, Ra represents H, CH3 or CF3.

-32- 201033733 In addition to the properties required for resistance to dry etching, compatibility with standard developers, adhesion to substrates, photoresist shapes, and photoresist properties such as resolution, heat resistance and sensitivity, In addition to the above-described repetitive structural unit, the resin of the component (A) may include a plurality of repetitive structural units. Embodiments of this repetitive structural unit include, but are not limited to, repetitive structural units corresponding to the monomers described below. Due to this repetitive structural unit, in particular, the properties required for the resin of the component (A) can be skillfully controlled: (1) solubility in a coating solvent; (2) film forming properties (glass transition point); (3) Alkaline developing ability; (4) Film loss (selection of hydrophilic, hydrophobic or alkali-soluble groups); (5) Adhesion of unexposed areas to the substrate; (6) Dry etching resistance: Its similar nature. Examples of the monomer include compounds selected from the group consisting of an addition polymerizable unsaturated bond: acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds , vinyl ethers and vinyl esters. In addition to these, an addition polymerizable unsaturated compound copolymerizable with a monomer corresponding to the various rectifying unit units described above may be copolymerized. In the resin of the component (A), the molar ratio of the respective repetitive structural units included is appropriately determined to control the dry etching resistance of the photoresist, the compatibility with the standard -33-201033733 developer, The adhesion to the substrate, the shape of the photoresist, and the properties normally required for the photoresist (such as resolution, heat resistance, and sensitivity). In the example in which the sensitized ray or radiation sensitive resin composition of the present invention is used for ArF exposure, the resin of the component (A) is preferably free of aromatic groups in consideration of the transmittance to ArF light (especially In the resin, the ratio of the aromatic group-containing repeating unit is 5 mol% or less, 3 mol% or less is better and ideally 〇 mol%, that is, no aromatic group The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure. Similarly, the resin of the component (A) of the present invention is preferably a resin different from the resin (C), and in view of compatibility with the resin (C), it is preferred that the fluorine atom and the sand atom are not contained. The resin of the component (A) is preferably a resin composed of a repeating unit based on (meth) acrylate. In this example, all of the repeating units may be methacrylate-based repeating units, all of the repeating units may be acrylate-based repeating units, or all of the repeating units may be methacrylated The base-based repeating unit is composed of a repeating unit based on acrylic vinegar, but the content of the acrylate-based repeating unit is 50% by mole or less preferably 'to all of the repeating units Prevail. The resin is more preferably a copolymerized polymer, which comprises from 2 to 50 mol% of a (meth) acrylate based on the (meth) acrylate represented by the formula (AI) containing an acid-decomposable group. a unit, from 20 to 50 mol% of a repeating unit based on a (meth)acrylic acid vinegar containing an internal vinegar group, from 5 to 30 mol% of an alicyclic ring substituted with a hydroxyl group or a gas group A repeating unit based on (meth) succinic acid vinegar of a hydrocarbon structure, and a repeating unit based on (meth)-34-201033733 acrylate from 0 to 20 mol%. In the example of irradiating the sensitized ray or radiation sensitive resin composition of the present invention with KrF excimer laser light, electron beam, X-ray or wavelength nanometer or a shorter high energy beam (for example, EUV), in addition to the formula ( In addition to the repeating unit represented by AI), the resin of the component (A) further comprises a repeating unit based on hydroxyphenylene, and the hydroxystyrene-based repeating unit is decomposed by acid The group is protected by a hydroxystyrene-based repeating unit and an acid-decomposable repeating unit such as a tertiary alkyl (meth)acrylate. A preferred embodiment of the repeating unit having an acid-decomposable group includes three stages of tertiary butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene or (meth)acrylic acid A repeating unit consisting of a mixture of esters. A repeating unit consisting of (meth)acrylic acid 2-homoyl-2-adamantyl ester or dialkyl (1-adamantyl)methyl methacrylate, preferably 〃 (A) The resin can be synthesized by an ordinary method (for example, radical polymerization). Examples of the synthesis method generally include a batch polymerization method in which a hydrazine monomer species and an initiator are dissolved in a solvent and heating the solution, thereby achieving polymerization; and a dropping polymerization method in 1 to 10 hours, A solution containing the monomer species and the starter is added dropwise to the hot solvent. The dropping polymerization method is preferred. Examples of the reaction solvent include ethers such as diisopropyl acid, tetrahydrofuran, 1,4-dioxane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate An ester; a guanamine solvent such as dimethylformamide and dimethylacetamide; and a solvent which is capable of dissolving the composition of the present invention, such as propylene glycol monomethyl ether acetate (PGMEA, also known as - 35-201033733 1-methoxy-2-ethenyloxypropane), propylene glycol monomethyl ether (pgme, also known as 1-methoxy-2-propanol) and cyclohexanone. It is more preferable to carry out polymerization using the same solvent as that used in the photosensitive ray or radiation sensitive resin composition of the present invention. By using this solvent, generation of particles during storage can be suppressed. The polymerization is preferably carried out in an inert gas atmosphere such as nitrogen or argon. As the polymerization initiator, polymerization is started using a commercially available radical initiator (e.g., an azo-based initiator, a peroxide). The free radical initiator is preferably an azo-based initiator, and an azo-based initiator having an ester group, a cyano group or a carboxyl group is preferred. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile and dimethyl 2,2'-azobis(2-methylpropionate). The starter is added additionally or in part, if necessary. After the reaction is completed, the reaction product is charged into a solvent, and the desired polymer is recovered by a method such as powder or solid recovery. The reaction concentration is from 5 to 50% by mass, and preferably from 10 to 30% by mass, and the reaction temperature is usually from 10 to 150 ° C, and preferably from 30 to 120 ° C, from 60 to 100 °. C is better. (In this patent specification, the mass ratio is equal to the weight® ratio.) The weight average molecular weight of the resin of this component (A) is preferably from 1, 200 to 200,000, more preferably from 2,000 to 20,000, and from 3,000 to 15,000. More preferably, from 5,000 to 13,000 is better, in terms of polystyrene by the GPC method. When the weight average molecular weight is from 1, 〇〇〇 to 200,000, heat resistance, dry etching resistance, and developing ability can be prevented from being lowered; and since the viscosity is increased, the film formation property can be prevented from being lowered. -36- 201033733 The polydispersity (molecular weight distribution) is usually from 1 to 3, and preferably from 1 to 2.6, more preferably from 1 to 2, still more preferably from 1.4 to 1.7. When the molecular weight distribution is small, the resolution and the resistive shape are better, the sidewalls of the photoresist pattern are smoother, and the good roughness is changed. In the sensitized ray or radiation sensitive resin composition of the present invention, the amount of the resin of the blended component (A) is preferably from 50 to 99% by mass, more preferably from 70 to 98% by mass, based on the total composition. From 70 to 95% by mass, more preferably, based on the total solids content. In the present invention, as the resin of the component (A), one kind or a plurality of kinds (polymer blend) may be used in combination. [2] A compound capable of generating an acid after irradiation with actinic rays or radiation (B) The sensitized ray or radiation-sensitive resin composition of the present invention includes a compound capable of generating an acid after irradiation with actinic rays or radiation (here) It is sometimes referred to as "acid generator". It is preferable to use an acid generator which can be suitably selected from the following: a photoinitiator for cationic photopolymerization, a photoinitiator for radical photopolymerization Agents, photodegraders for dyes, photodecolorizers, compounds known to produce acids upon irradiation with actinic radiation or radiation, and compounds useful for micro-resistance or the like, and mixtures thereof. Examples of such compounds Including diazonium salt, strontium salt, strontium salt, strontium salt, sulfhydrazine sulfonate, sulfonium sulfonate, diazo bismuth, diflavonoid and o-nitrobenzyl sulfonate. A group or compound capable of generating an acid upon irradiation with actinic radiation or radiation is introduced into the main or side chain of the polymer - 37-201033733, for example, as described in U.S. Patent 3,849,137, German Patent 3,9. 1 4,407, JP-A-63-26653, JP-A-55-1 64824, JP-A - 62-69263, JP-A-63- 1 4603 8 , JP-A-63 - 1 63452 , JP-A-62- 1 5 3 8 5 3 and compounds in JP-A-63-146029. Compounds which are capable of generating an acid by photoeffects, such as those described in U.S. Patent No. 3,7,7,7,7,8, and European Patent No. 126,7,12, can also be used. From the acid generator, by the following formula (ZI), The compounds represented by ZII) and (ZIII) are preferred. 0 II • s—R207 0 0 II ^206-S· 0 • ^201 R202~S+ z~ R204—R205 R203 z

Z1II

ZI ZII In the formula (ZI), each of R2Q1, R2 02 and R2Q3 independently represents an organic group. The carbon number in the organic group as R2〇1, R202 and R2 0 3 is usually from 1 to 30, and preferably from 1 to 20. Two members from R201 to R2Q3 may be bonded to form a ring structure ' and ◎ The ring may include an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group. Examples of groups formed by combining two members derived from R2Q1 to R2Q3 include an alkylene group (e.g., butyl group, pentyl group). Represents a non-nucleophilic anion. Examples of the non-nucleophilic anion as z include a sulfonate anion, a carboxylate anion, a mercaptoquinone anion, a bis(alkylindenyl)quinone anion, and a tris(alkylfluorenyl) group. Methyl anion. The non-nucleophilic anion is an -38 to 201033733 anion having a very low nucleophilic reactivity, and the anion inhibits decomposition with age due to intramolecular nucleophilic reaction. Due to this anion, the aging stability of the photoresist is improved. Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphorsulfonate anion. Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkyl carboxylate anion. The aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group, but an alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms is preferred, and its implementation Examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary butyl, pentyl, neopentyl, hexyl, heptyl, octyl, decyl, decyl, ten Monoalkyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, decyl, cyclopropane Base, cyclopentyl, cyclohexyl, adamantyl, norbornyl and fluorenyl. The aromatic group in the aromatic sulfonate anion is preferably an aryl group having from 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group and a naphthyl group. ^ Each of the alkyl group, the cycloalkyl group and the aryl group in the aliphatic sulfonate anion and the aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, the cycloalkyl group and the aryl group in the aliphatic sulfonate anion and the aromatic sulfonate anion include a nitro group, a halogen atom (for example, fluorine, chlorine, bromine, iodine), A carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), a cycloalkyl group (having preferably a carbon number of 3 to 15), and an aryl group (having a carbon number of 6 to 14 are preferred). Alkoxycarbonyl (preferably having 2 to 7 carbon atoms), mercapto (preferably having 2 to 12 carbon atoms), alkoxycarbonyloxy group (having a carbon number of 2 to 7 and preferably -39 to 201033733), An alkylthio group (having preferably a carbon number of 1 to 15), an alkyl maple group (having preferably a carbon number of 1 to 15), an alkyl imino fluorenyl group (having a carbon number of preferably 15), an aryl oxygen group Base mill base (having a carbon number of 6 to 20 is preferred), alkylaryloxy maple group (having a carbon number of 7 to 20 is preferred), cycloalkylaryloxy running base (having a carbon number of 10 to 20) Further, an alkyloxyalkyloxy group (having preferably 5 to 20 carbon atoms) and a cycloalkylalkyloxyalkyloxy group (having preferably 8 to 20 carbon atoms). As for the aryl or ring structure in each group, the embodiment of the substituent further includes an alkyl group (having preferably a carbon number of 1 to 15). Examples of the aliphatic moiety in the aliphatic carboxylate anion include the same alkyl groups and cycloalkyl groups in the aliphatic sulfonate anion. Examples of the aromatic group in the aromatic carboxylate anion include the same as those in the aromatic sulfonate anion. The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and Naphthylbutyl. Each of the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group in the aliphatic carboxylate anion, the aromatic carboxylate anion and the aryl © alkyl carboxylate anion may have a substituent. Examples of substituents of alkyl, cycloalkyl, aryl and aralkyl groups in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkyl carboxylate anion include and Examples of the sulfonate anion having the same halogen atom, alkyl group, cycloalkyl group, alkoxy group and alkylthio group as the anthracene quinone anion include saccharin anions. -40-201033733 Preferably, the alkyl group in the bis(alkylindenyl) quinone anion and the tri(alkyl i anion is an alkyl group having a carbon number of 1 to 5, and examples include methyl, ethyl, and propyl groups. Base, isopropyl, n-butyl, isobutyl, pentyl and neopentyl. The substituent atom of this alkyl group, the alkyl group substituted by a halogen atom, the alkoxy group, the alkylthio group The alkyl group substituted with a aryloxy group and a cycloalkylaryloxyfluorenyl group is preferred. Other examples of the non-nucleophilic anion include fluorinated bismuth boron and fluorinated ruthenium. The non-nucleophilic anion is an aliphatic sulfonate anion substituted at the α-position of the sulfonic acid, an aromatic sulfonate anion substituted by a fluorine atom or fluorine, and having an alkyl group derived from a fluorine atom (alkyl sulfhydryl group) The quinone imine anion, or having an alkyl group derived from a fluorine atom (alkyl group) methyl anion. The non-nucleophilic anion having a number of 4 to 8 perfluoroaliphatic sulfonate anions or having a fluoroorthoester anion Good, nonafluorobutane sulfonate anion, perfluoroanthracene anion, pentafluorobenzene sulfonate anion or 3,5- (Trifluoromethyl anions and better.

The compound (ZI-1) to (ZI-4) described later as the solid of the organic group of R2〇1, R2 0 2 and R2 0 3 may have a plurality of compounds The compound represented by (ZI), for example, has at least one bond of R 2 〇 3 in the compound represented by the formula (ZI) to 另 201 to R 2 G 3 in the other - represented by the formula (ZI) At least one structure of the compound. Methyl group and its butyl group, two cases including a halogen group, a hospital group, and a disubstituted three substituted by a fluorine atom in the fluorine atom and a fluorinated atom is a benzenesulfonane having a carbon: The sulfonic acid methyl)benzenesulfonate i is included in the g 〇 structure of β·2 0 1 to • the compound -41- 201033733 In the formulas (ZII) and (ZIII), each of R2〇4 to R2 07 Independently represents an aryl group, an alkyl group or a cycloalkyl group. The aryl group of R204 to R2G7 is preferably a phenyl group or a naphthyl group, and the phenyl group is more preferred. The aryl group of R2〇4 to R2G7 may be an aryl group having a heterocyclic structure and containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by removing a hydrogen atom from a pyrrole), a furan residue (a group formed by removing a hydrogen atom from a furan) , a thiophene residue (a group formed by removing a hydrogen atom from thiophene), a hydrazine residue (a group formed by removing a hydrogen atom from hydrazine), a benzofuran residue (a group formed by removing one hydrogen atom from benzofuran) and a benzothiophene residue (a group formed by removing one hydrogen atom from benzothiophene). The alkyl group and the cycloalkyl group in R204 to R207 are a linear or branched alkyl group having a carbon number of 1 to 10 (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group) and having a carbon number of 3 to 10 A cycloalkyl group (e.g., cyclopentyl, cyclohexyl, norbornyl) is preferred. Each of the aryl group, the alkyl group and the cycloalkyl group of R2G4 to R2Q7 may have a substituted group. Examples of the substituent which the aryl group, the alkyl group and the cycloalkyl group of R204 to R207 may have include an alkyl group (for example, having a carbon number of 1 to 15) and a cycloalkyl group (for example, having a carbon number of 3 to 15). An aryl group (for example, having a carbon number of 6 to 15), an alkoxy group (for example, having a carbon number of 1 to 15), a halogen atom, a hydroxyl group, and a phenylthio group. Z_ represents a non-nucleophilic anion, and the examples thereof are the same as those of the non-nucleophilic anion Z_ in the formula (ZI). As for the component (ZI), it is described in the following compounds (ZI-1) to (ZI-4) -42 - 201033733. The compound (ΖΙ-1) is R2()1 in the formula (zi) At least one aryl fluorene compound which is an aryl group to R2Q3, that is, a compound having an aryl hydrazine as a cation. In the arylsulfonium compound, R2G1 to R2G3 may all be an aryl group, or R2 (a part of M to r2Q3 may be an aryl group and the remainder is an alkyl group or a cycloalkyl group. Examples of the arylsulfonium compound include a triaryl group An anthracene compound, a diarylalkylhydrazine compound, an aryldialkylfluorene compound, a diarylcycloalkylfluorene compound, and an arylbicycloalkylsulfonium compound. The aryl group in the arylsulfonium compound is benzene The phenyl group is preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure and containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the aryl group having a heterocyclic structure Including a pyrrole residue (a group formed by removing a hydrogen atom from a pyrrole), a furan residue (a group formed by removing a hydrogen atom from a furan), a thiophene residue (by sputum) Removal of a group formed by a hydrogen atom), a residue of hydrazine (a group formed by removing a hydrogen atom from hydrazine), a benzofuran residue (by removing one from benzofuran) a group formed by a hydrogen atom) and a benzothiophene residue (by benzothiazide) a group formed by removing a hydrogen atom. In the case where the aryl fluorene compound has two or more aryl groups, the two or more aryl groups may be the same or different. If necessary, present in The alkyl or cycloalkyl group in the arylsulfonium compound is preferably a linear or branched alkyl group having 1 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a methyl group and an ethyl group. , propyl, n-butyl, secondary butyl, tert-butyl, cyclopropyl, cyclobutyl and cyclohexyl. -43- 201033733 aryl, alkyl and naphthenic groups of R2〇1 to R2〇3 The group may have the following substituents: an alkyl group (for example, having a carbon number of 1 to 丨5), a cycloalkyl group (for example, having a carbon number of 3 to I5), and an aryl group (for example, having a carbon number of 6 to 14). Alkoxy (for example, 'having a carbon number of 1 to 15), a halogen atom, a hydroxyl group or a phenylthio group. The substituent is a linear or branched alkyl group having a carbon number of 1 to 12 and a cycloalkane having a carbon number of 3 to 12. The base, or a linear, branched or cyclic alkoxy group having a carbon number of 1 to 12 is preferably 'having an alkyl group having 1 to 4 carbon atoms, or a group having a carbon number of 1 to 4, more preferably. It may be substituted to any one of the three members r2()i to r2()3, or may be substituted for all three members. In the case where r2()1 to r2Q3 © is an aryl group, the substituent is substituted in the The p-position of the aryl group is preferred. The compound (ZI-2) is described below. The compound (ZI-2) is R2 in the formula (ZI) (n to R2〇3 each independently represents no fragrance) a compound of an organic group of a ring. As used herein, the aromatic ring includes an aromatic ring containing a hetero atom. The aromatic ring-free organic group as a core to R2〇3 has a carbon number of usually from 1 to 30, And preferably from 1 to 20. © R201 to R2 03 each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, a linear or branched 2-side oxyalkyl group, a 2-side oxygen group. A cycloalkyl or alkoxycarbonylmethyl group is more preferred, and a linear or branched 2-sided oxyalkyl group is more preferred. The alkyl group and the cycloalkyl group of R2 (n to R2D3 are a linear or branched alkyl group having a carbon number of 1 to 10 (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group) and having a carbon number of 3 to A cycloalkyl group of 10 (e.g., a cyclopentyl group, a cyclohexyl group, a -44 - 201033733 fluorenyl group) is preferred. The alkyl group is preferably a 2-sided oxyalkyl group or an alkoxycarbonylmethyl group. More preferably, it is a 2-oxocycloalkyl group. The 2-sided oxyalkyl group may be linear or branched, and a group having > C = 〇 at the 2-position of the alkyl group described above is preferred. The -oxycycloalkyl group is preferably a group having >C = 0 at the 2-position of the cycloalkyl group described above. The alkoxy group in the alkoxycarbonylmethyl group has a carbon number of 1 to 5. Alkoxy groups (e.g., 'methoxy, ethoxy, propoxy, butoxy, pentyloxy) are preferred. R2 (n to R2G3 each may further be a halogen atom, an alkoxy group (for example, having The compound (ZI-3) is a compound represented by the following formula (ZI-3), and is a compound having a benzoguanidine salt structure.

In the formula (ZI-3), Ri. Each of R5e independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a hydroxyl group, a nitrate Base or halogen atom. Each of the ruthenium and R7c independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. Each of 1^ and Ry independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group. -45- 201033733 Any two or more members from the Rlc to R5e, R6e and R7c pairs and the core and Ry pairs may be combined to form a ring structure. This ring structure may contain an oxygen atom, a sulfur atom, an ester bond or a guanamine bond. The above ring structure includes an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic fused ring formed by combining two or more of these rings. The ring structure is a 3 to 10 membered ring, and a 4 to 8 membered ring is preferred, and a 5 or 6 membered ring is preferred by combining any two or more of Ric to R5c, R6c and R7c pairs, and Ry pairs. Examples of groups formed by members include butyl and pentyl groups. Representative of non-nucleophilic anions, and examples thereof, are the same as those of the non-nucleophilic anion Z. in formula (ZI). This is as Rle to R7. The alkyl group may be linear or branched, and is, for example, an alkyl group having a carbon number of 1 to 20 and having a linear or branched alkyl group having 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a linear or branched propyl group, Linear or branched butyl, linear or branched pentyl groups are preferred. The cycloalkyl group is, for example, a cycloalkyl group having a carbon number of 3 to ( 8 (e.g., a cyclopentyl group, a cyclohexyl group). The aryl group as Rle to R5e is preferably an aryl group having 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. The alkoxy group as Rle to R5e may be linear, branched or cyclic 'and is, for example, a linear or branched alkoxy group having a carbon number of 1 to 10 and having a carbon number of 1 to 5 (for example, A) An oxy group, an ethoxy group, a linear or branched propoxy group, a linear or branched butoxy group, a linear or branched pentyloxy group) or a cyclic alkoxy group having a carbon number of 3 to 8 (for example, a cyclopentyloxy group, a ring) Hexyloxy) is preferred. -46 - 201033733 In the case of Ri. A specific embodiment of the alkoxy group in the alkoxycarbonyl group to R5e is the same as the specific embodiment of the above alkoxy group of Rlc to R5e. In that as R!. To R5. Specific examples of the alkyl group in the alkylcarbonyloxy group are the above Rle to R5. The specific embodiment of the alkyl group is the same. In that as R!. To R5. Specific examples of the cycloalkyl group in the cycloalkylcarbonyloxy group are the same as the specific examples of the above cycloalkyl group of Rle to R5e. In this as Ri. Specific examples of the aryl group in the aryloxy group of R5e are as described above with Rle to R5. The specific embodiment of the aryl group is the same. ® •. To R5. Any one of linear or branched alkyl, cycloalkyl or linear, branched or cyclic alkoxy groups is preferred, and Rle to R5. The sum of carbon numbers is preferably from 2 to 15 compounds. Due to this compound, solvent solubility is further improved and generation of particles during storage can be suppressed. Can be combined with R!. To R5. The ring structure formed by any two or more members is preferably a 5 or 6 membered ring, and a 6 membered ring (e.g., a phenyl ring) is more preferred. Examples of the alkyl group and the cycloalkyl group as 1 and Ry are the same as those in Ric to R7c. Among these, a 2-oxoalkyl group, a 2-sided oxocycloalkyl group and an alkoxycarbonylmethyl group are preferred. Examples of the 2' side oxyalkyl group and the 2-sided oxocycloalkyl group include a group having > C = 0 at the 2-position of the alkyl group or the cycloalkyl group as Rlc to R7e. The examples of the alkoxy group in the alkoxycarbonylmethyl group are the same as those in Ric to R5c. Each of 1^ and Ry is preferably an alkyl group or a cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, still more preferably 8 or more. The allyl group is not particularly limited, but an unsubstituted allyl group or an allyl group substituted by a mono-47-201033733 ring or a polycyclic cycloalkyl group (having preferably a cycloalkyl group having 3 to 10 carbon atoms). Preferably. The vinyl group is not particularly limited, but an unsubstituted vinyl group or a vinyl group substituted by a monocyclic or polycyclic cycloalkyl group (having preferably a cycloalkyl group having 3 to 10 carbon atoms) is preferred. This compound (ZI-4) is a compound represented by the following formula (ZI-4):

Z 0 (ZI-4) ❹ In the formula (ZI-4), R13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group or an alkoxycarbonyl group.

Rm represents (when a plurality of R14 are present, each independently represents) a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl maple group or a cycloalkyl group. Each r15 independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two Ris can be combined to form a loop. 1 represents an integer of 0 to 2. Γ represents an integer from 0 to 1 0. L represents a non-nucleophilic anion, and the examples thereof are the same as those of the non-nucleophilic anion in the formula (ΖΙ). In the formula (ΖΙ-4), the alkyl group as R13, R14 and R15 is preferably a linear or branched alkyl group having a carbon number of from 1 to 10, and examples thereof include a methyl group, an ethyl group, and a n-propyl group. , isopropyl, n-butyl, 2-methylpropyl, 1-methylpropanyl-48 - 201033733, tributyl, n-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl , 2-ethylhexyl, n-decyl and n-decyl. Among these alkyl groups, a methyl group, an ethyl group, a n-butyl group and a tertiary butyl group are preferred. Examples of the cycloalkyl group of Rl3, R14 and R15 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, cyclopentenyl, cyclohexyl Alkenyl, cyclooctadienyl, norbornyl, tricyclodecyl, tetracyclodecyl and adamantyl. In particular, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group are preferred. The alkoxy group of R13 and R14 is preferably a linear or branched alkoxy group having a carbon number of 1 to 10, and examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, and a positive electrode. Butoxy, 2-methylpropoxy, 1-methylpropoxy, tert-butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-Ethylhexyloxy, n-decyloxy and n-decyloxy. Among these alkoxy groups, a methoxy group, an ethoxy group, a n-propoxy group and a n-butoxy group are preferred. The alkoxycarbonyl group of R13 is preferably a linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, and an isopropoxy group. Carbocarbonyl, n-butoxycarbonyl, 2-methylpropoxycarbonyl, 1-methylpropoxycarbonyl, tert-butoxycarbonyl, n-pentyloxycarbonyl, neopentyloxycarbonyl, n-hexyloxycarbonyl , n-heptyloxycarbonyl, n-octyloxycarbonyl, 2-ethylhexyloxycarbonyl, n-decyloxycarbonyl and n-decyloxycarbonyl. Among these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group and a n-butoxycarbonyl group are preferred. The alkyl selenyl group and the cycloalkyl group of the Rm are linear, branched or cyclic -49-201033733 and have a carbon number of 1 to 10, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, and a positive Propisulfonyl, n-butylsulfonyl, tert-butylsulfonyl, n-pentylsulfonyl, neopentylsulfonyl, n-hexylsulfonyl, n-heptylsulfonyl, n-octylsulfonyl, 2-B A hexyl sulfonyl group, a sulfonium sulfonyl group, a sulfonium sulfonyl group, a cyclopentyl sulfhydryl group, and a cyclohexylsulfonyl group. Among these alkylthio groups, a methylsulfonyl group, an ethylsulfonyl group, a n-propylsulfonyl group, a n-butylsulfonyl group, a cyclopentylsulfonyl group and a cyclohexylsulfonyl group are preferred. 1 is 〇 or 1 is preferred, 1 is more preferred; and r is preferably 0 to 2 in number. Examples of substituents which each of the groups of R13, Rm and R15 may have include a halogen atom (e.g., fluorine), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, and an alkane group. Oxycarbonyl and alkoxycarbonyloxy. Examples of the alkoxy group include linear, branched or cyclic alkoxy groups having a carbon number of 1 to 20, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2 -methylpropoxy, 1-methylpropoxy, tert-butoxy, cyclopentyloxy and cyclohexyloxy. Examples of the alkoxyalkyl group include a linear, branched or cyclic alkoxyalkyl group having a carbon number of 2 to 21, such as methoxymethyl, ethoxymethyl, oxime 1-methoxyethyl. , 2-methoxyethyl, 1-ethoxyethyl and 2-ethoxyethyl. Examples of the alkoxycarbonyl group include a linear, branched or cyclic alkoxycarbonyl group having a carbon number of 2 to 21, such as a methoxycarbonyl group, an ethoxycarbonyl group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, n-Butoxycarbonyl, 2-methylpropoxycarbonyl, 1-methylpropoxycarbonyl, tert-butoxycarbonyl, cyclopentyloxycarbonyl and cyclohexyloxycarbonyl" -50- 201033733 The alkoxy Examples of the carbonyloxy group include a linear, branched or cyclic alkoxycarbonyloxy group having a carbon number of 2 to 21, such as a methoxy pseudoyloxy group, an ethoxycarbonyloxy group, a n-propoxycarbonyloxy group. Base, isopropoxyloxy, n-butoxycarbonyloxy, tert-butoxycarbonyloxy, cyclopentyloxy, and cyclohexyloxycarbonyl. As for the ring structure formed by combining two R15, a group capable of forming a 5- or 6-membered ring together with a sulfur atom in the formula (ZI-4) is preferable, and a group capable of forming a 5-membered ring. (That is, the tetrahydrothiophene ring) is better. Examples of the substituent on the ring structure include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. There may be a plurality of substituents on the ring structure, and these substituents may be combined to form a ring (aromatic or non-aromatic hydrocarbon ring, aromatic or non-aromatic heterocyclic ring, or two or more by combining these rings) A plurality of formed polycyclic fused rings) R15 is preferably a methyl group, an ethyl group, a naphthyl group, or a divalent group in which two Ri5 groups are bonded together to form a tetrahydrothiophene ring structure together with a sulfur atom. As described above, the alkyl group, the cycloalkyl group, the alkoxy group and the alkoxy fluorenylcarbonyl group of Ri 3 and the alkyl group, the cycloalkyl group, the alkoxy group, the alkyl fluorenyl group and the cycloalkyl fluorenyl group of the Rm are each The substituent may be substituted, and the substituent is preferably a hydroxyl group, an alkoxy group, an alkoxy group or a halogen atom (particularly a fluorine atom). Specific preferred embodiments of the cations in the compounds represented by the formula (ZI-4) are set forth below. -51 - 201033733

-52-201033733 Other examples of the acid generator include compounds represented by the following formulae (ZIV), (zv) and (ZVI): ϊ

Ar3*S〇2~S〇2~Ar4 ZIV Ο R208"S〇2*〇*~N, ζν

ZVI In the formulae (ZIV) to (ZVI), each of Ar3 and Ar4 independently represents an anthracene group. Each of the ruthenium 2, 8, R2, and R210 independently represents an alkyl group, a cycloalkyl group or an aryl group. A represents an alkyl group, an alkenyl group or an aryl group. Specific examples of the aryl groups of Ar3, Ar4, R2G8, R2Q9 and R21Q are the same as the specific examples of the aryl groups of Rm, r2Q2 and R2Q3 in the formula (ZI-.1). Specific examples of the base and ring base of the Κ·2〇8, R2〇9 and R^o and ❹ in the formula (ZI-2) as the alkyl group and cycloalkyl group of Rm, Rm and r2Q3 The specific embodiments are the same. The alkylene group of the A includes an alkylene group having a carbon number of 丨 to 12 (for example, a methylene group, an exoethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group); The alkenyl group includes an alkenyl group having 2 to 12 carbon atoms (for example, an ethynyl group, a propenyl group, a butenyl group); and the exoaryl group of the A includes an exoaryl group having a carbon number of 6 to 1 Å. (for example, phenyl, tolyl, and naphthyl). Among the acid generators, the compound -53-201033733 represented by the formula (ZI) to (ZIII) is more preferable. Specific preferred embodiments of the cation produced from the acid generator include cations indicated by the following formula.

-54 201033733

-55- 201033733 -〇作[分- CeHl3H0^-I C8H17^Q X;k X>0 〇 丄o 0.0 丄cc >X;s〇 ^X;s〇 >^C° Ο^8. 〇^+〇 〇r^〇.0^

9 +r"

-56- 201033733

-57- 201033733

-58- 201033733

Ο

The acid generator is preferably a compound capable of producing an acid having a sulfonic acid group or a quinone imine group, a compound capable of producing a monovalent perfluoroalkanesulfonic acid, and capable of being substituted by a fluorine atom or a fluorine atom-containing group. a compound of a monovalent aromatic sulfonic acid or a compound capable of producing a monovalent imidic acid substituted by a fluorine atom or a fluorine atom-containing group, a fluorine-substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid, a fluorine Substituted quinucin or fluorinated methic acid bismuth salt - 59 - 201033733 is even better. In particular, an acid generator which can be used is preferably a compound which can produce a fluorine-substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid or a fluorine-substituted sulfimine, wherein the acid produced has a PKa of -1 or Less, and in this case, the sensitivity can be improved. The compound which produces the acid described above is preferably a compound capable of producing an acid represented by the following formula (I): ho3s

-or9 m5 (1)

In the formula (1), each of 1 to R8 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a hydroxyl group. R9 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, -CORx or -S02Rs. A represents a divalent linking group or a single bond containing a hetero atom. Rx represents an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group. Rs represents an alkyl group, a cycloalkyl group or an aryl group. Each of ml to m4 independently represents an integer 〇 to 12 with a constraint of m3 + m4g 1. M5 represents an integer of 1 to 3. When any of ml to m5 is an integer of 2 or more, each of the plurality of 1^ to R8 and A members may be the same or different. Here, the alkyl group, the cycloalkyl group and the alkenyl group may have a fluorine atom as a substituent. Similarly, Rs may further have one or more substituents ' and examples of the substituent include an alkyl group (a linear or branched alkyl group having a carbon number of 1 to 4 is preferred) and an alkoxy group (having a carbon number of 1 to A linear or branched alkoxy group of 4 is preferred). The hetero atom-containing divalent linking group of A includes an oxygen atom, -CO-, -CONR-, -S02NR-, -CONRCO-, -S02NRC0-, -S02NRS02_-60-201033733 and -OCONR-, wherein R represents A hydrogen atom, an alkyl group or a cycloalkyl group.

Each of Ri to Rjt is independently a hydrogen atom, a perfluoroalkyl group or a fluorine atom, and a perfluoroalkyl group or a fluorine atom is more preferred. A is preferably a single bond or an oxygen atom. R9 is preferably a fluorenyl group represented by -CORx. Rx is preferably a cycloalkyl group or an aryl group. In the formula (1), a carbon atom adjacent to S03H is preferably substituted by a fluorine atom or a trifluoromethyl group. The compound capable of producing an acid having a structure represented by the formula (1) is preferably a structure represented by the following formula (1-A): 〇 .

In the formula (1-A), ^ to r9, A and ml to m5 each have the same meaning as Ri to R?, A and ml to m5 in the formula (1); and M + represents an organic counter cation . The organic counter ion represented by M + is preferably ruthenium or osmium ion, and the ruthenium ion is more preferable. Examples of the organic counter ion represented by M + include a cation in the formulae (ZI) and (ZII) and a cation represented by the formula (Hd) described later. The iron cation M+ is more preferably a cation in the compound represented by the formula (ZI-4). The acid represented by the formula (1) is more preferably represented by the following formulas (1-B) to (1_D): -61 - 201033733 F cf3 ffhhff / ff\ f HO3S—I—j—0R9 HO3S—( —|—I_L〇r9 HO3S—I~|4〇—f~|4-0—FH FF Η HFF \ CFS F/m6 (1-B) (1-C) (1-D) In Equation (1- In B) to (1-D), r9 has the same meaning as R9 in the formula (1); and m6 represents an integer of 0 to 2. The compound which can produce the acid represented by the formula (1) is as follows The structure represented by formula (1-E) to UG) is better: —J~(-03⁄4 can 3S—~|~I~[―j-ORg MOjS—I~[i〇-J~lX〇—l= =CF2 ." FFHH ^ ^ ^ l Approx. (1_E) (1-F) (1-G) 〇 In the formula (1-E) to (1-G), m6 has the above formula (1-D) M6 has the same meaning; and Han 9 and m + have the same meaning as M + in the above formula (1_in). The following is proposed to produce acid production of acid represented by formula (1) Particular embodiments of the agent 'but the invention is not limited thereto. In a particular embodiment, M + represents the organic counter cation described above. ❹ -62- 201033733 o ©

Onsno

-63- 201033733

-64- 201033733

. -〇4-. -!卄. cut

A compound represented by the following formula (I) is also preferable as the acid generator.

In the formula (I), X + represents an organic counter ion and R represents a hydrogen atom or an organic group. -65- 201033733 R represents a hydrogen atom or an organic group and is preferably an organic group having a carbon number of 1 to 40, more preferably an organic group having 3 to 20 carbon atoms, and is represented by the following formula (Π). The organic group is the best. The organic group of R is sufficient if it has one or more carbon atoms. The organic group is preferably an organic group in which the atom bonded to the oxygen atom in the ester bond of the formula (I) is a carbon atom, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, and an aromatic group. Alkyl group and group having a lactone structure. The organic group may contain a hetero atom such as an oxygen atom and a sulfur atom in the chain. Likewise, these groups may have another substituent as a substituent; or the organic group may have a substituent such as a hydroxyl group, a decyl group, a decyloxy group, a pendant oxygen group (= 0) or a halogen atom. -(CH2)n-Rc-(Y)m (II) In the formula (II), Rc represents a monocyclic or polycyclic organic group (having preferably having a carbon number of 3 to 30), which may include a cyclic ether, Cyclic thioether, cyclic ketone, cyclic carbonate, lactone or indoleamine structure. Y represents a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a hydrocarbon group (having preferably having a carbon number of 1 to 10), a hydroxyalkyl group (having preferably 1 to 10 carbon atoms), and an alkoxy group (having a carbon number of 1 to 10). Preferably, a mercapto group (having preferably a carbon number of 2 to 10), an alkoxycarbonylcarbonyl group (having preferably a carbon number of 2 to 10), a decyloxy group (having preferably a carbon number of 2 to 10), an alkoxyalkyl group The base (having preferably a carbon number of 2 to 10) or a haloalkyl group (having preferably a carbon number of 1 to 8). m represents an integer of 0 to 6; and when there are a plurality of Ys, each Y may be the same or different from each other Y. η represents an integer of 0 to 1 〇〇 The total number of carbon atoms constituting the organic group represented by the formula (II) is 40 or -66 to 201033733, which is less preferred. Preferably, η is an integer of 0 to 3 and Rc is a monocyclic or polycyclic organic group having a carbon number of 7 to 16. The molecular weight of the compound represented by the formula (I) is usually from 300 to 1,000 - preferably from 400 to 800, more preferably from 500 to 700. Examples of the organic counterion X+ include phosphonium cations and iodine cations. Preferable specific examples of the compound represented by the formula (I) include compounds represented by the formulae ® (ZSC1) and (ZIC1).

In the formula (zscl), the definition and preferred range of the R are the same as those in the formula (I). Each of R2 (M, R2G2 and R2G3 independently represents an organic group. Specific examples, preferred specific examples and analogs of the organic groups of R2()1, R2Q2 and R2 0 3 are in the formula (ZI) Those in R2G1, r2G2 and r203 are the same. In the formula (ZIC1), the definition and preferred range of R are the same as those defined in formula (I). R2 04 and R2 05 each independently represent aryl Specific examples and preferred embodiments of the R2G4 and R2G5 aryl, alkyl and cycloalkyl groups and the above-mentioned R2C)4 in the formulae (ZII) and (ZIII) And the same as those described for the aryl, alkyl and cycloalkyl groups of R2〇5. -67- 201033733 The compound may be a compound having a plurality of structures represented by the formula (Z sc ,). For example, the compound may be R2 (having at least one bond of H to R2〇3 in the compound represented by the formula (ZSC1) to R2()1 in another compound represented by the formula (zscl) A compound of the structure of at least one of R2G3. The compound represented by the formula (I) can be synthesized by a known method (for example, according to the method described in JP-A-2007-61 1 707).

As the acid generator, a compound which can produce an acid represented by the formula (1-A) or (1-B) after irradiation with actinic rays or radiation is also preferred.

(I-A)

(1·Β) In the formulae (1-Α) and (1-Β), each of 1 to R8 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a hydroxyl group, and the restriction condition is R1 Ο At least one of to R8 is a fluorine atom or a fluorine atom-containing group. Eight! And each of the eight and two independently represents a divalent linking group or a single bond. R represents a substituent. When there are a plurality of Rs, two or more Rs may combine to form a ring. k represents an integer of 0 to 5, η represents an integer of 0 to 5, and ml to m4 each independently represent an integer of 0 to 12, with a constraint that at least one of ml to m4 is an integer of 1 or more. -68-201033733 Examples of the divalent linking group of the oxime and A2 include -0-, -S-, carbonyl, ester group, arylene, maple, methylene, 1,1-extended ethyl 1,2-extended ethyl, propyl, 1-methylpropyl, 1-ethylpropyl, trimethylene, difluoromethylene, tetrafluoro-1,2-extended ethyl, 1 , 2-phenylene, 1,3-phenylene, 1,4-phenylene, and a group formed by combining two or more of these groups. Among these divalent groups, a carbonyl group, an ester group, a methylene group, a difluoromethylene group, and a tetrafluoro-1,2-extended ethyl group are preferred. Examples of the substituent of the R include a pendant oxygen group. (= 0), hydroxy, carboxymethyl, methylidene, alkyl (linear or branched, preferably having a carbon number of 1 to 10), vinylidene (linear or branched, preferably having a carbon number of 1 to 10), Monovalent cyclic organic group (having preferably having a carbon number of 3 to 12), aryl group (preferably having a carbon number of 6 to 20), an alkoxy group (linear or branched, preferably having a carbon number of 1 to 10), and an aryloxy group a base (having preferably a carbon number of 6 to 20), an alkylcarbonyl group (linear or branched, preferably having a carbon number of 2 to 10), an arylcarbonyl group (having preferably a carbon number of 7 to 20), an alkoxycarbonyl group (linear Or a branch having a carbon number of 2 to 10 is preferred) and an aryloxycarbonyl group (having preferably a carbon number of 7 to 20). The substituent of R is a pendant oxygen group (= 〇), an alkyl group, an alkoxy group, an alkylcarbonyl group (linear or branched, preferably having a carbon number of 2 to 10) or an alkoxycarbonyl group. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl and癸基. Examples of the vinylidene group include a carbenyl group, a vinylidene group, a propylene group, a 1-methylpropylene group, and a 1-ethylpropylene group. -69-201033733 Examples of the monovalent cyclic organic group include a cyclopentyl group, a cyclohexyl group, a diamond base, a sulphate group, and a campholoyl group. Examples of the aryl group include a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a p-hydroxyphenyl group, a 1-naphthyl group, a 1-indenyl group, and a benzyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, and a tertiary butoxy group. Examples of the aryloxy group include a phenoxy group, a p-hydroxyphenoxy group, an o-, a tolyloxy group, a m-tolyloxy group, and a p-tolyloxy group. Examples of the alkylcarbonyl group include a methylcarbonyl group, an ethylcarbonyl group, a n-propylcarbonyl group, an isopropylcarbonyl group, a n-butylcarbonyl group, and a tertiary butylcarbonyl group. Examples of the arylcarbonyl group include a phenylcarbonyl group and a benzylcarbonyl group. Examples of the oxiranyl group of the present invention include a methoxyindenyl group, an ethoxylated group, a n-propoxycarbonyl group, an isopropoxycarbonyl group, a n-butoxycarbonyl group, and a tertiary butoxycarbonyl group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a benzyloxy group. These substituents may further have any substituent, for example, - or a plurality of the above-mentioned substituents. ❹ R may be bonded to any carbon atom constituting the norbornene ring or the norbornane ring, and when there are a plurality of R's, each may be the same as or different from each other R. Similarly, when there are a plurality of Rs, two or more rs may be combined to form a ring. That is, at least two or more scales may be bonded to each other together with the carbon atoms to which these R are bonded to form a ring. k is preferably 0 and η is 〇 or 1 is preferred. The structure represented by the free-form (1-Α) and the furnace-70-201033733 represented by the formula (1_Β) have an absorption intensity at a similar wavelength, considering that at the wavelength 193 〇, the equation (1-A) The preferred embodiment of the acid represented by the g g of the crucible includes the structure shown by the following formulas (1·Α) and (1·Β).

-71- 201033733 The compound capable of producing an acid represented by the formula (1-A) or (l-Β) is more preferably a structure represented by the following formula (11-A) or (11-B).

In the formulae (II-A) and (II-B), each of 'zi and Z2' independently represents a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group. Υι stands for a single bond or a divalent linking group. R represents a substituent. When there are a plurality of Rs, two or more Rs may combine to form a ring. M + represents a monovalent gun cation. k represents an integer of 0 to 5 and η represents an integer 〇 to 5. The perfluorol base of Ζι and Ζ2 may be linear or branched, and a perfluoroalkyl group having 1 to 10 carbon atoms is preferred. The perfluorocycloalkyl group of 2! and Z2 may be monocyclic or polycyclic, and, for example, perfluorocyclohexyl or perfluorocyclopentyl is preferred. The examples of the divalent group of Yi are the same as those of the formulas (1-A) and (1_B). R, k and η are the same as those in the formulae (1-A) and (l-Β). The monovalent key cation represented by M + is preferably ruthenium or osmium ion, and the mirror ion is better. Specific examples thereof include cations in the formulae (ZI) and (ZII), and cations in the formula (ZI) are preferred. A cation represented by the following formula (Illd) is also preferred. 201033733

(llld) In the formula (Illd), each of P1G to P21 independently represents a hydrogen atom, a hydroxyl group, an alkyl group (having preferably a carbon number of 1 to 12), and a cycloalkyl group (having a carbon number of 3 Torr to 12). ), an alkoxy group (having preferably a carbon number of 1 to 12) or a halogen atom (gas, gas, bromine, bowl). Y represents a sulfur atom or an oxygen atom. m stands for 0 or 1. Examples of the alkyl, cycloalkyl and alkoxy groups to the same are those of Rlc to R5e in the formula (ZI-3). Each of these groups may further have a substituent, and the substituent which each group may further have includes an organic group (an organic sulfonium group having a carbon number of 丨 to 4 Å is preferable, and an organic group having a carbon number of 3 to 20) Better group). Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a lactone-containing structural group' and the organic group may contain a hetero atom such as an oxygen atom and a sulfur atom in the chain. A preferred specific example of the cerium ion as the m + in the formulae (II-A) and (II-B) is a cerium ion represented by the following formula (111 e): -73- 201033733

In the formula, each of P22 to P24 independently represents a hydrogen atom or an alkyl group (having preferably having a carbon number of 1 to 12). The embodiment of the hospital base of P22 to I»24 is the same as those of Ric to R5c in the formula (ZI_3). Each of these groups may further have a substituent, and the examples in which each group may have a substituent in one step are the same as the specific examples of the substituent which each group in the formula (IIId) may further have. From the acid generator, the following particularly preferred embodiments are presented.

-74- 201033733 (Q^s+CFsS〇r (0-3- (: (03- (Z1)

C"F23COO* (^S+ CAS〇J-(22) ^s^sH0

o (Z7) (z5) (z«) (Or (z3) -^^s+CeFi7S〇r (ζβΓ5^ C^Pt7S〇3> S+ CHaCOO- Qύ (Z9)

OJF^SOr 9 4F*SOr

Q (Z12) (z13) (z14) ◎ -j-Q-^^eSOa- But>O-(215) (z16) (z17) 崎. 〇4FgSOj- (z18)

F^V (219) (220) 75- 201033733 CF8S〇r (221) CF3SO3* (z24) C^gSOgr CaFnSOv (222) (z23) CJr^SOz- CsFitSOs-' (Z25) (226) os-cf3 Φ ^Ν'( (227)

MeO

9^9 SC-* (z30) ?N 0 (z28)9i^9 /~\ V y /-Λ 〇-|-c-|-〇(231) i3^n-〇tcf3 °(z29) I 9 !?* 9 I -rrc"|T" ❹ 〇"|"CF9 H3CH2CH2C-|-〇.nA^^

(z32) o ^-O-S-CHiCHiCHj (r33) (234) (z35) (236) "Ό- S+C4Ft>F&SQr(z38);--〇}r (z30) οφ o

7S03-(Z37) OBU ❹ C4pgS〇3* (240) 6s2〇, σΐ; £ (r41) (242) £ C4F,S〇r-fXs〇 (z43) -76- 201033733

(z44)

(z45)

C4.F9SO)-» Ο (247)

ο^1' C4F〇S<<zSO> C4H, "C4H* Or

(z51) (z46)

〇 u 0=S—〇2Fs S+ *M 〇—s—C2F5 0 (zS9) 〇

(a (261) [Otr 5—c4F* sS-C4Pd li o (z62) -77- 201033733

(〇)r •O3S °t C4F9SO3- (263) (z64) (〇)·, -〇3S-CF2CFaCFa O /^v f〇

(266) (^3)^ wcF2CF*CF*t0 again"'(z68>

(z65> 9 /—s, S+ -O^-CFiCFjCFa-S-N 〇 3 〇 W(z67) o o o S+ F3C-S-N-S-CF2CF2CFa^S-F 3 〇 - 〇 (269) 〇

S+ F3C-S-N-S-<^2CFiCF2-S-0-^J- 〇 II 〇=s-c3f7 (0-r 0 - 0(Z70> o -〇3S-CF2CF2CFz-S-0 (3C72) ©

(〇); 0—8—C3F7 fl(271) 〇 S+ -O3S—CF2CF2CF2·· IO (z73)

(^s+c-(|(z77>(^3)^s+CaFsS〇!r<z79)

-C2Fe Milk S£V(z»〇) CASOr(z81) ❹ -78 201033733 〇 c〇* (z82) ❹

(z83)

〇 o Μ M -S-N-S- M II O - o (z90> FjC-S-N-S-CFjCFiCFi-S-N^^ {0r

s+-oss^~VQ(z91) -79- 201033733

201033733

-81 · 201033733

-82- 201033733

~c ω 3:, , λ ) 驭 _ b ) The following examples include, but are not limited to, the following compounds. •83- 201033733

-84- 201033733

As the acid generator, one type may be used alone or in combination of two or more kinds. The content of the acid generator in the sensitized ray or radiation sensitive resin composition is preferably from 0.1 to 30% by mass, more preferably from 0.1 to 20% by mass, still more preferably from 0.5 to 15% by mass, and from 1 to More preferably, 13% by mass, based on the total solid content of the sensitized ray or the radiation-sensitive resin composition. [3] Resin (C) having at least one of a fluorine atom or a ruthenium atom and comprising a repeating unit having at least two or more polarity-switching groups 〇 The sensitized ray or radiation-sensitive resin composition of the present invention comprises ( C) a resin having at least one of a fluorine atom or a ruthenium atom and a repeating unit (c) having at least two or more polar conversion groups. The resin (C) is hydrophobic, and it is particularly preferable to add the resin (C) in view of reducing development defects. The fluorine atom may be a fluorine atom as an electron-withdrawing group in a polarity-switching group described later, or a fluorine atom different from a fluorine atom as an electron-withdrawing group. The repeating unit (C) is preferably a repeating unit (c,) having at least two or more polar converting groups and at least one of a fluorine atom or a sand atom on one side chain -85 to 201033733, That is, a repeating unit having a structure in which at least a fluorine atom or a ruthenium atom exists on a side chain having a plurality of polarity-converting groups. The repeating unit (C) is also preferably a repeating unit (C*) having at least two or more polar converting groups and having no fluorine atom or germanium atom, and the resin (C) further comprising at least A repeating unit of either a fluorine atom or a germanium atom. Furthermore, it is preferred that the repeating unit (C) is a repeating unit (C") having at least two or more polarity-switching groups on one side of the chain, while in the same repeating unit, The side chain having a different side chain has at least one of a fluorine atom or a ruthenium atom. In this example, the side chain having a polar conversion group and a side chain having at least one of a fluorine atom or a ruthenium atom are passed through The carbon atom in the main chain is preferably in a positional relationship at the α-position (that is, in a positional relationship of the following formula (4)). In the formula, Β1 represents a moiety having a polarity-switching group. The structure, and Β2, represents a partial structure having at least one of a fluorine atom or a ruthenium atom. ® Β 1 (4) Β 2 These specific examples from the resin (C) have a repetitive unit (c'). The polar conversion group is a group which can be decomposed by the action of the test developer to increase the solubility in the alkaline developer, and is in the formula (KA-1) -86 - 201033733 or (ΚΒ-l) Part of the structure represented by -COO- in the structure. As for the formula (KA-1) As the lactone structure shown, any group can be used as long as it has a lactone ring, but the group is preferably a group having a 5- to 7-membered ring lactone structure, and the other ring structure is formed to form a bicyclic or spiro structure. Preferably, the group is fused to a 5- to 7-membered ring lactone structure. Attached is an ester group directly bonded to the resin backbone in the repeating unit (for example, -COO- in an acrylate) It is poor in function as a polarity converting group and is not included in the polarity converting group of the present invention. ^ The overlapping unit (c) may not have a symbol represented by (KA-1) or (KB-1), respectively. Two complete structures, but even when the structures partially overlap (for example, in the form of an electron withdrawing group sandwiched by two ester structures or a specific example of the formula (KY-1) described later), this is inferred to be Containing two polarity-switching groups. Similarly, in the repeating unit (C*) and the repeating unit (C"), the polarity-switching group is -COO- in the structure of formula (KA-1) The part of the structure represented is better.

In the formulae (KA-1) and (KB-1), Zka represents an alkyl group, a ring-based group, an ether group, a hydroxyl group, a guanamine group, an aryl group, a lactone ring group or an electron-withdrawing group. And when there are a plurality of Zkas, the plurality of Zkas may be the same or different. Each Zka can be combined with each other Zka to form a ring. Examples of the ring formed by bonding with each other by Zka-87-201033733 include a cycloalkyl ring and a heterocyclic ring such as a cyclic ether ring or a lactone ring). Nka represents an integer of 0 to 10 and an integer of 0 to 8, preferably, an integer of 0 is more preferable, an integer of 1 to 4 is more preferably, and an integer of 1 to 3 is most preferable.

Each of Xkbl and Xkb2 independently represents an electron withdrawing group. Each of nkb and nkb' independently represents 〇 or 1. Here, when nkb' is 0, this indicates that each of Xkbl and Xkb2 is directly bonded to the group (-COO-).

Each of Rkbi to Rkb4 independently represents a hydrogen atom, an alkyl group, a aryl group or an electron withdrawing group; at least two members of Rkb丨, Rkb2 and Xkbl may be bonded to each other to form a ring; and R kb 3, R kb 4 And at least members of X kb 2 may be combined with each other to form a ring. Preferably, the ring formed by at least two members of Rkb3, Rkb4 and Xkb2 is a cycloalkyl group or a heterocyclic group, and the heterocyclic group ester ring group is preferred. Examples of the lactone ring include structures represented by (KA-1-1) to (KA-1-17) described later. Incidentally, when in the example of the structure represented by the formula (KA-1) and the structure represented by the formula (KB-1) in which Xk Xkb2 is a unit price, the (KA-1) or (KB-1) The structure represented is (when there is no bond) a monovalent or larger partial structure that removes at least one arbitrary hydrogen atom in the structure. The electron withdrawing group in Zka, Xkbl, Xkb2 and Rkbi to Rkb4 includes a halogen atom, a cyano group, an oxygen group, a carbonyl group, a carbonyloxy group, an oxycarbonylnitrile group, a nitro group, a fluorenyl group, an anthranylene group, and _C(Rfl)(Rf2)-Rf3 (example to 5 nkb ester cycloalkane in two combinations of internal formula bi and halo (cyclo)alkyl group represented by formula Or a haloaryl group, and combinations thereof. The name "halo(cyclo)alkyl" refers to at least a portion of a halogenated alkyl or cycloalkyl group. The electron withdrawing group is a divalent or larger valent group. In the examples of the group, the remaining bond forms a bond with any atom or substituent and may be bonded to the main chain of the resin (C) via a further substituent. In the above formula, Rfi represents a halogen atom, a perhaloalkyl group, A halocycloalkyl group or a perhaloaryl group, and a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group are preferred, and a fluorine atom or a trifluoromethyl group is preferred. Each of Rn and Rn independently represents a hydrogen atom, a halogen atom or an organic group; and Rf2 and Rf3 may be bonded to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group. .

At least two members of Rn to Rn may be bonded to form a ring, and examples of the ring formed include a (halo)cycloalkyl ring and a (halo)aryl ring. The (halo)alkyl group in Rn to Rn is, for example, an alkyl group in Zka or a structure formed by halogenation. The (per)halocycloalkyl or (per)haloaryl group in Rn to Rf3 or in the ring formed by bonding Rf2 and Rf3 is a structure formed, for example, by halogenation of a cycloalkyl group in zka, Further, a fluorocycloalkyl group represented by -Cu)F(2n_2)H or a perfluoroaryl group represented by -C(n)F (nu is preferable. Here, the carbon number η is not particularly limited, but from 5 Preferably, it is preferably 1 and 6 is better.

Rf2 represents the same group as Rfi or is bonded to Rf3 to form a ring. The electron withdrawing group is a halogen atom or a halogen (cyclo)alkyl group or a halogen aryl group represented by the above -C(Rfl)(Rf2)-Rf3, -C(CF3)2H or -C(CF3)2CH3. -89- 201033733 Better. In the above electron withdrawing group, a part of the fluorine atom may be replaced by another electron withdrawing group.

Zka is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group or an electron withdrawing group, and an alkyl group, a cycloalkyl group or an electron withdrawing group is more preferable. The ether group is preferably an ether group substituted with, for example, an alkyl group or a cycloalkyl group, that is, an alkyl ether group or a group thereof is preferred. This electron withdrawing group has the same meaning as described above. The halogen atom as zka includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred. The alkyl group as zka may have a substituent and may be linear or branched. The linear alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, more preferably from 1 to 20, and examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, N-heptyl, n-octyl, n-decyl and n-decyl. The branched alkyl group is preferably an alkyl group having 3 to 30 carbon atoms, more preferably from 3 to 20, and examples thereof include isopropyl, isobutyl, secondary butyl, tert-butyl, isopentyl. , tertiary pentyl, isohexyl, tertiary hexyl, isoheptyl, tertiary heptyl, isooctyl, tertiary octyl, isodecyl and tertiary terpene fluorenyl. The alkyl group having 1 to 4 carbon atoms is preferred, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. The cycloalkyl group of Zka may be monocyclic or polycyclic. In the latter example, the cycloalkyl group can be crosslinked. That is, in this example, the cycloalkyl group may have a bridge structure. Incidentally, a part of the carbon atoms in the cycloalkyl group may be replaced by a hetero atom such as an oxygen atom. The monocyclic cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 8 and -90 to 201033733. Examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include a group having a bicyclic, tricyclic or tetracyclic structure and having a carbon number of 5 or more. A cycloalkyl group having a polycyclic number of 6 to 20 carbon atoms is preferred, and examples thereof include an adamantyl group, a decyl group, an isodecyl group, a fluorenyl group, a dicyclopentyl group, and an α-pinel. a group, a tricyclic fluorenyl group, a tetracyclododecyl group, and an androstylene group. Examples of such cycloalkyl groups include those shown by the following formulas. π> Ο 〇 w a) Pi [=〇COC〇 w (S) (f> CO CO coo ω m m

A9 66 °Q <M) (11) (10)

(15) 〇 Oc7 cx> A a«) 〇7) im

<^\ (M) Network (station) 〇!) (3«) (37) <38> (33⁄4 i6>i& ^ (40) («) (42> (43) °s> ® Λ ( 44> (4S) (46) 〇〇o〇(47) (48) (49) (50) (23⁄4 (M) (22) (») A ^ 〇b <c^ (2S) (2«) (27) Preferred alicyclic hydrocarbon moieties include adamantyl, norantantyl, naphthyl, tricyclodecyl, tetracyclododecyl, norbornyl, cedarol, cyclohexyl, ring Heptyl, cyclooctyl, cyclodecyl and cyclododecyl. adamantyl, naphthyl group, thiol group, cedar group, cyclohexyl, cycloheptyl, -91- 201033733 Cyclooctyl More preferably, cycloalkyl, cyclododecyl and tricyclodecyl. The substituent of the alicyclic structure includes an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. Preferred are lower alkyl groups such as methyl, ethyl, propyl, isopropyl and butyl, and more preferably methyl, ethyl, propyl or isopropyl. The alkoxy group has a carbon number of 1. Alkoxy groups to 4 are preferred, such as methoxy, ethoxy, propoxy and butoxy. Substituents which the alkyl and alkoxy groups may have Examples include a hydroxyl group, a halogen atom and an alkoxy group (preferably having a carbon number of 1 to 4.) Examples of the aryl group of the Zka include a phenyl group and a naphthyl group. © The alkyl group, the cycloalkyl group and the aryl group of the Zka may be used. Examples of further substituents include a hydroxyl group, a halogen atom, a nitro group, a cyano group, an alkyl group as described above, an alkoxy group (such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxy group). Oxyl, n-butoxy, isobutoxy, secondary butoxy and tertiary butoxy), alkoxycarbonyl (such as methoxycarbonyl and ethoxycarbonyl), aralkyl (such as benzyl) , phenethyl and fluorenyl), aralkyloxy, fluorenyl (such as formazan, ethyl fluorenyl, butyl fluorenyl, benzhydryl, cinnamyl and amyl), decyloxy (such as butyl oxy) Alkenyl, alkenyl, alkenyloxy (such as vinyloxy, propenyloxy, allyloxy, and butenyloxy), aryl, aryloxy (such as phenoxy) and aryl described above An oxycarbonyl group (such as benzhydryloxy group). The polar conversion group is decomposed by the action of an alkaline developer to achieve polarity conversion, thereby Reducing the receding contact angle of the resin composition film with water after alkaline development. The film of the resin composition is exposed to the smear, during exposure (usually at room temperature 23±3°c) and humidity 45±5 % lower 'receives contact with water-92-201033733 The angle is 50° or less is better, 40° or smaller is better, 35° or smaller and better and 30° or smaller is best. The contact angle is the contact angle measured when the contact line on the droplet-substrate interface is retracted, and is generally known to be useful in simulating the mobility of droplets in a dynamic state. In a simple manner, the receding contact angle can be defined as the contact angle at which the droplets are retracted at the droplet interface as they are ejected from the tip of the needle onto the substrate and then again aspirated into the needle. Generally, the receding contact angle can be measured by a contact angle measuring method called an expansion/contraction method. The hydrolysis rate of the resin (C) to the alkaline developer is preferably 0.001 nm/sec or more, more preferably 〇·〇1 nm/sec or more, and more preferably 0.1 nm/sec or more. And 1 nanometer / second or more is best. The rate of hydrolysis of the resin (C) to the alkaline developer is the thickness of the film formed by the resin (C) alone, when 23 (tetramethylammonium hydroxide hydrazine) at 23 ° C (2.38 mass) %) The rate at which it is reduced during development. Λ As for the lactone ring structure in the formula (ΚΑ-1), the group having a lactone structure represented by any one of the following formulae (ΚΑ-1-1) to (ΚΑ-1-17) is more good.. The lactone-containing structural group can be directly bonded to the main chain. Preferred lactone structures are (ΚΑ-1-1), (ΚΑ-1-4), (ΚΑ-1-5), (ΚΑ-1-6), (ΚΑ-1-13), (ΚΑ- 1-14) and (ΚΑ-1-17). The specific embodiment of the lactone-containing structural skeleton is proposed below, but the present invention is not limited thereto. -93- 201033733

The lactone moiety may or may not have a substituent. Preferred examples of the substituent include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkoxy group having 2 to 8 carbon atoms. a carbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. Among these, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a cyano group, an alkoxycarbonyl group having 2 to 4 carbon atoms, a carboxyl group, a sulfonium atom, a hydroxyl group, and an acid group The decomposed group is better. When a plurality of substituents are present, these may be the same or different, and likewise, one substituent may be bonded to another substituent to form a ring. Some lactone structures have optical isomers, but any optical difference may be used. Structure. One optical isomer may be used alone or a mixture of a plurality of optical isomers may be used. In the case of mainly using one optical isomer, the optical purity (ee) is preferably 90% or more, more preferably 95% or more, and most preferably 98% or more. The structure represented by (KB-1) has a high polarity conversion ability because the electron group of the absorption of 94-201033733 exists at a position close to the ester structure.

Xkb2 is preferably a halogen atom or a halogen (cyclo)alkyl group or a halogen aryl group represented by the above -C(Rn)(Rf2)-Rf3. As for at least two polarity-switching groups in the repeating unit (C), a partial structure having two polarity-converting groups represented by the following formula (KY-1) is more preferable. The structure represented by the formula (KY-1) is a group derived from a group having a monovalent or larger valence number obtained by removing at least one arbitrary hydrogen atom in the structure. 〇

(KY-1) In the formula (KY-1), each of Rkyi and R ky 4 represents a nitrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, or the like. An ether group, a hydroxyl group, a cyano group, a guanamine group or an aryl group. Furthermore, Rkyl and Rky4 can be bonded to the same atom to form a double bond. For example, Rkyl and Rky4 can be bonded to the same oxygen atom to form a portion of the carbonyl group (= 〇).

Each of Rky2 and Rky3 independently represents an electron withdrawing group; or Rkyl combines with Rky2 to form a lactone ring, while Rky3 is an electron withdrawing group. The lactone ring formed is preferably a structure (KA-1-1) to (KA-1-17). Examples of the electron withdrawing group are the same as those of Xkbi in the formula (KB-1), and a halogen atom and a halogen (cyclo)alkyl group or a halogen group represented by the above -C(Rfl)(Rf2)-Rf3 The base is preferred. -95- 201033733

At least two members of Rkyl, Rky2 and Rky4 may be bonded to each other to form a monocyclic or polycyclic structure.

Rkbi to Rkb4, nkb and nkb have the same meanings as in the formula (KB-1).

Rkyl and Rky4 particularly include the same groups as those of ZKA in the formula (KA-1). The lactone ring formed by combining Rkyl and Rky2 is preferably a structure of (KA-1-1) to (foot 8-1-17). The electron withdrawing group includes the same groups as those of Xkbi in the formula (1:6-1). The structure represented by the formula (KY-1) is preferably a structure represented by the following formula (KY-2). Here, the structure represented by the formula (KY-2) is a group which gives a group having a monovalent or larger valence number from at least one hydrogen atom removed in the structure.

In the formula (KY-2), each of Rky6 to RkylO represents a nitrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, and a cyanogen. a base, a guanamine group or an aryl group.

Two or more members of Rky6 to RkylO may be bonded to each other to form a monocyclic or polycyclic structure. -96- 201033733

Rky5 represents an electron withdrawing group. The electron withdrawing group includes the same groups as those of Xkbl in the formula (ΚΒ-1), and a halogen atom and a halogen (ring) group represented by the above _C:(Rfl)(Rf2)'Rf3 or Haloaryl is preferred.

Rkbl, Rkb2, and nkb have the same meanings as in the formula (KB-1).

Rky5 to Rkyl<) specifically include the same groups as those of ZKA of the formula (KA-1).

The structure represented by the formula (KY-2) is preferably a partial structure represented by the following formula (κγ_3).

In the formula (ΚΥ-3), and nka have the same meaning as in the formula (ΚΑ-1). Rkys has the same meaning as in the formula (KY-2).

Rkbl, Rkb2 and nkb have the same meanings as in the formula (Lyke represents an alkyl group, an oxygen atom or a sulfur atom. Examples of the alkyl group of the Lky include a methylene group and an ethyl group. Lky Preferably, it is an oxygen atom or a methylene group, and a methylene group is more preferable.

Rs represents a chain or a cyclic alkyl group, and when a plurality of groups are present, these may be the same or different.

Ls represents a single bond, an ugly bond, an ester bond, a urethane bond, a urethane bond or a urea bond; and when a plurality of Ls are present, these may be the same or different. Ns is the number of repeats of the linking group represented by -(Rs-Ls)- and represents an integer of 0 to 5. -97- 201033733 The repeating unit (c) has a structure represented by the formula (K0): (Κ0) - R^2 In the formula, Rkl represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a ring An alkyl group, an aryl group or a group having a polar conversion group.

Rk2 represents an alkyl group, a cycloalkyl group, an aryl group or a group having a polar conversion group, with the proviso that Rk1 and Rk2 all have two or more polar conversion groups.附 Incidentally, as described above, when used in the present invention, the ester group directly bonded to the main chain of the repeating unit represented by the formula (K0) is not contained in the polarity converting group. The repeating unit (c) is not limited as long as it is a repeating unit obtained by polymerization (such as addition polymerization, condensation polymerization, and addition condensation), but obtained by addition polymerization of a carbon-carbon double bond. The repeating unit is preferred. Examples thereof include an acrylate-based repeating unit (including a system having a substituent at a ct- or /3-position), a styrene-based repeating unit (included in an alpha- or @cold-position) a system having a substituent), a vinyl ether-based repeating unit, a decene-based repeating unit, and a maleic acid derivative (for example, maleic anhydride or a derivative thereof, maleimide) ) Repeat the unit. Acrylate-based repeating unit, styrene-based repeating unit, vinyl ether-based repeating unit, and decene-based repeating unit; acrylate-based weight The coating unit, the vinyl ether-based repeating unit and the decene-based repeating unit are more preferable; and the repeating unit based on the acrylic acid-98-201033733 ester is the best. The resin (C) contained in the sensitized ray or radiation sensitive resin composition of the present invention includes a repeating unit having at least one of a fluorine atom or a ruthenium atom. Due to the repetitive unit, the resin (C) is unevenly distributed to the surface layer of the sensitized ray or the radiation-sensitive resin film, and when the immersion medium is water, the formed sensitized ray or radiation-sensitive resin film can be formed. The water receding contact angle and the fluidity of the immersion liquid on the surface of the photoresist film are increased. The receding contact angle of the photosensitive ray or the radiation sensitive resin film is preferably from 60 to 90 °, 65 ° or more at a temperature during exposure (usually at room temperature of 23 ± 3 ° C) and a humidity of 45 ± 5%. More preferably, 70° or more is better. It can be used by appropriately adjusting the content of the resin (C) in the sensitized ray or the radiation sensitive resin composition to provide a sensitized ray or a radiation sensitive resin film having a receding contact angle within the above range, but The content thereof is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, based on the total solid content of the sensitized ray or the radiation-sensitive resin composition. As described above, the resin (C) is unevenly distributed to the interface, but unlike the surfactant, it does not need to have a necessary hydrophilic group in the molecule and may not contribute to uniform mixing of the polar/nonpolar substance. In the immersion exposure step, the immersion liquid needs to be swept with high speed. The moving and moving angles are touched by the high-crystal under the high-speed crystal. The dynamic exposure of the light is moved in the light of the thin film of the film with the head film. To be exposed. The immersion resistance-shaped luminescence and the circle, and the residual crystals are not-99-201033733. The resin (C) has at least one of a fluorine atom or a ruthenium atom, thereby enhancing the light. Hydrophobicity (water flow) on the surface and reduction of development residue (scum). When the resin (C) is a resin having a plurality of polarity-converting groups and having at least one of a fluorine atom or a ruthenium atom, the fluorine atom may be an electron-withdrawing group of XkM and Xkb2 in the formula (KB-1). group. The fluorine atom or the ruthenium atom in the resin (C) may be present in the main chain of the resin or may be substituted on the side chain. The resin (C) is preferably a resin having a fluorine atom-containing alkyl group, a fluorine atom-containing cycloalkyl β group or a fluorine atom-containing aryl group as the fluorine atom-containing partial structure resin. The fluorine atom-containing alkyl group (having preferably having a carbon number of 1 to 10, more preferably 1 to 4) is a linear or branched alkyl group having at least one hydrogen atom replaced by a fluorine atom and may further have other substituents. The fluorine atom-containing cycloalkyl group is a monocyclic or polycyclic cycloalkyl group having at least one hydrogen atom replaced by a fluorine atom and may further have other substituents. The fluorine atom-containing aryl group is an aryl group (e.g., phenyl group, naphthyl group) having at least one hydrogen atom replaced by a fluorine atom and may further have other substituents. Preferred examples of the fluorine atom-containing alkyl group, the fluorine atom-containing cycloalkyl group, and the fluorine atom-containing aryl group include groups represented by the following formulas (F2) to (F4), but the invention is not limited thereto. this.

Ree

^ ResH—«Θ7

Re3--OH

Rfi2 Ree (F3) (F4) -100- 201033733 In the formulae (F2) to (F4), each of R57 to R68 independently represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group (having a carbon number of 1 to 4) Preferably, the linear or branched alkyl group or the aryl group (the aryl group having 6 to 14 carbon atoms) is at least one of R57 to R61, at least one of R62 to R64 and at least one of R65 to R68. It is a fluorine atom or an alkyl group having at least one hydrogen atom replaced by a fluorine atom (preferably having a carbon number of 1 to 4). Preferably, all of R57 to R6I and R65 to R67 are fluorine atoms. Each of R62, R63 and R68 is preferably an alkyl group having at least one hydrogen atom substituted by a fluorine atom (having preferably a carbon number of 1 to 4), and more preferably a perfluoroalkyl group having a carbon number of 1 to 4. R62 and R63 may be bonded to each other to form a ring. Specific examples of the group represented by the formula (F2) include p-fluorophenyl, pentafluorophenyl and 3,5-bis(trifluoromethyl)phenyl. Specific examples of the group represented by the formula (F3) include trifluoromethyl, pentafluoropropyl, pentafluoroethyl, heptafluorobutyl, hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro ( 2-methyl)isopropyl, nonafluorobutyl, octafluoroisobutyl, nonafluorohexyl, nonafluorotributyl, perfluoroisopentyl, perfluorooctyl, perfluoro(trimethyl) Hexyl, 2,2,3,3-tetrafluorocyclobutyl and perfluorocyclohexyl. Among these, 'hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro(2-methyl)isopropyl, octaisobutyl, nonafluorotributyl and perfluoroisopentyl are preferred' and Hexafluoroisopropyl and heptafluoroisopropyl are preferred. Specific examples of groups to be evaluated by formula (F4) include -c(cf3)2oh, -C(C2F5)2OH, -c(cf3)(ch3)oh, and -ch(cf3)oh, and -c (cf3) 2oh is preferred. The resin (C) is preferably a resin having an alkyl fluorenyl group structure (preferably a three-compartment based sand yard base) - 101 - 201033733 or a cyclic siloxane structure as a partial structure of the ruthenium atom-containing. Specific examples of the alkyl fluorenyl structure and the cyclic siloxane structure include groups represented by the following formulae (CS-1) to (CS-3), but the invention is not limited thereto.

Sl~Rl4 (CS-1) In the formulae (CS-1) to (CS-3), each of R12 to R26 independently represents a linear or branched alkyl group (having preferably a carbon number of 1 to 20) or a naphthenic ring. Base (having a carbon number of 3 to 20 is preferred). Each of L3S L5 represents a single bond or a divalent linking group. The divalent linking group is a single group selected from the group consisting of or a combination of two or more groups: an alkyl group, a cycloalkyl group, a phenyl group, an ether group, a thioether. The group 'carbonyl, ester group, guanamine group, urethane group and ureido group. η represents an integer of 1 to 5. It is preferable that η is an integer of 2 to 4. The groups represented by the formulae (F2) to (F4) and the formulae (CS-1) to (CS-3) are preferably contained in the acrylate or methacrylate repeating unit. The specific embodiment of the repeating unit (c) is proposed below, but the invention is not limited thereto. Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. -102- 201033733

-103- 201033733

-104- 201033733 ❹

O

.Ra for 0^0

Oh,

Ra

Jr-γτT

C3F7

^l^J> 〇^C3F7 F3°Y° Ογ cf3

CeF7 JC^\) -r^r

. Seven: 'f3c-(

P3C J ^cf3

FaC 0 people.

In the resin (C), the content of the M-recovering unit (c) is from 10 to 1 mol%, preferably from 2 〇 to 1 〇〇. /«Better, from 30 to 100 mol% and more preferably from 40 to l〇〇: ^-B*n _ odor % is optimal, based on all repeating units in the resin (C) . -105- 201033733 The content of the repeating unit (c,) is from 10 to 100 mol%, preferably from 2 〇 to 1 〇 0 mol%, more preferably from 30 to 100 mol%, and more preferably from 4 〇. The optimum amount to 1 mol% is based on all the repeating units in the resin (C). The content of the repeating unitary crucible (c*) is preferably from 1 90 to 90 mol%, more preferably from 15 to 85 mol%, even more preferably from 20 to 80 mol% and more preferably from 25 to 75 mol%. Most preferably, all of the repeating units in the resin (C) are taken as the standard. The content of the repeating unit having at least one of fluorine atoms or germanium atoms (used in combination with the repeating unit (c*)) is preferably from 10 to 9 mol%, from Η to 85 mol%. More preferably, from 20 to 80 %% and more preferably from 25 to 75 mol%, Q is optimally determined by all the repeating units in the resin (C). The content of the repeated single crucible (C") is preferably from 10 to 1 mol%, more preferably from 20 to 1 mol%, from 30 to 100 mol%, and more preferably from 4 to 1 mol% is optimal, which is based on all the repeating units in the resin (C). The resin (C) may further include a repeating unit (cl) having at least a fluorine atom or a halogen atom. One and different from the repeating units (c,) and (c,.) The fluorine atom or the halogen atom in the repeating unit (cl) may be present in the resin main chain or may be substituted on the side chain. The fluorine atom-containing partial structure in the repeating unit (cl) includes the same as those described above and the fluorine atom may be directly bonded to the partial structure or may be via a separate group selected from the group consisting of the following: Or a combination of two or more groups to bond: alkyl, phenyl, ether, thioether, ortho, ester, guanamine, urethane groups And a urea group. The partial structure of the fluorine atom is preferably a group represented by the formulae (F2) to (F4). The following is suitable for the fluorine as the repeating unit (cl) -106-201033733 junction structure sub-portions.

In the formula, each of Rio and Rii independently represents a hydrogen atom, a fluorine atom or an alkyl group (a linear or branched alkyl group having a carbon number of 1 to 4 is preferred; the alkyl group having a substituent of the oxime particularly includes fluorine Alkyl). Each of W3 to W6 independently represents an organic group containing at least one or more fluorine atoms. In particular, the organic group includes atomic groups of (F2) to (F4). In addition to these repetitive units, a resin having the following units may also be suitable. R4 Rg

(C-II) (ΟΙΠ) In the formula, each of R4 to R7 independently represents a hydrogen atom, a fluorine atom or an alkyl group (a linear or branched alkyl group having a carbon number of 1 to 4 is preferred; The alkyl group includes, in particular, a fluorinated alkyl group, with the proviso that at least one of R4 to R7 represents a fluorine atom. R4 and R5 or R6 and r7 form a ring. Q represents an alicyclic structure. The lipid steroid structure may be monocyclic or polycyclic and -107-201033733 may have a substituent. The monocyclic alicyclic structure is preferably a cycloalkyl group having 3 to 9 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group and a cyclooctyl group. Examples of the polycyclic alicyclic structure include a group having a bicyclic, tricyclic or tetracyclic structure and having a carbon number of 5 or more. The cycloalkyl group having 6 to 20 carbon atoms is preferred, and examples thereof include adamantyl group, norbornyl group, dicyclopentyl group, tricyclodecyl group and tetracyclododecyl group. Incidentally, a part of the carbon atoms in the cycloalkyl group may be replaced by a hetero atom such as an oxygen atom. The alicyclic structure of the Q is preferably an alicyclic structure having a carbon number of 5 to 9. W2 represents an organic group containing at least one fluorine atom. In particular, the organic group includes atomic groups of (F2) to (F4). L2 represents a single bond or a divalent linking group. The divalent linking group is a substituted or unsubstituted extended aryl group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted stretched alkyl group, -〇-, -S02-,- CO-, -N(R)- (wherein R represents a hydrogen atom or an alkyl group), -NHS02-, or a divalent linking group formed by combining a plurality of these groups. The partial structure of the ruthenium containing atom in the repeating unit (cl) includes the same as those described above, and the groups represented by the formulae (CS-1) to (CS-3) are preferred. The repeating unit (cl) is preferably a (meth) acrylate based repeating unit. A specific embodiment of the repeating unit (cl) is proposed below, but the present invention is not limited thereto. In a particular embodiment, Xi represents a hydrogen atom, -CH3, -F or -CF3; and X2 represents -F or -CF3. -108- 201033733

Fs

-109- 201033733

Ο-^Ο

ο

F3c-4-cf3 ten α=3

^c+cf3 5. Ten CF3 OH

R=CH3i C2H5. C3Hr, C4H9

-110- 201033733 The resin (c) may further comprise at least one group selected from the group consisting of the following groups (X), (y) and (Z): (X) a group soluble in a base; (y) capable a group which decomposes by the action of an alkali developer to increase the solubility in the test developer; and (z) a group which can be decomposed by an acid action. Examples of the (X) alkali-soluble group include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a maple quinone imine group, (alkyl mercapto) (alkylcarbonyl) methylene, (alkyl maple) (alkylcarbonyl) fluorenylene group, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl) fluorene An amine group, a bis(alkylindenyl)methylene group, a bis(alkylmercapto)anthracene group, a tri(alkylcarbonyl)methylene group, and a tris(alkyl-based)methylene group. Preferred base-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis(carbonyl)methylene groups. Q The repeating unit having (x) a base-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to a resin main chain (such as by repeated acid or acrylic acid) a unit), a repeating unit in which a base-soluble group is bonded to a resin primary bond via a linking group, and a polymerization initiator or a chain transfer agent containing a base which is soluble in a base to be soluble in a polymerization The groups of the base are introduced into the repeating unit in the terminal of the polymer chain, and all of these repeating units are preferred. The content of the repeating unit having (X) an alkali-soluble group is preferably from 1 to 5 mol%, more preferably from 3 to 35 mol%, and even more preferably from 5 to 3 mol%. The total repeating unit in the resin (C) shall prevail. -111-201033733 The specific embodiment of the repeating unit having the (X) alkali-soluble group is proposed below, but the invention is not limited thereto. In a particular embodiment, Rx represents H, CH3, CH2OH or CF3.

Examples of the group (y) which is contained in the resin (C) and which can be decomposed by the action of an alkali developer to increase the solubility in the alkaline developer include a group having a lactone structure, an acid anhydride group The group having a quinone imine group and having a lactone structure of -112 to 201033733 is preferred. The repeating unit having a group (y) capable of decomposing by an action of an alkali developer to increase solubility in an alkali developer is a repeating unit having at least two or more polar converting groups ( c) a repeating unit having only one polarity converting group; and a group (y) capable of decomposing by an action of an alkali developer to increase solubility in an alkali developer to the resin backbone Repeating unit (such as by repeating unit of acrylate or methacrylate), and using a polymerization initiator or chain transfer agent containing a group (y) during polymerization, can increase the alkali development It is preferred that the solubility group (y) in the agent is introduced into the repeating unit in the polymer chain terminal. The content of the repeating unit having a group (y) capable of increasing the solubility in the test developer is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, and from 5 to 20 mol. % is even better, based on all the repeating units in the resin (C). The specific embodiment of the repeating unit having the group (y) capable of increasing the solubility in the alkaline developer is the same as those having the lactone structure described for the resin of the component (A). An embodiment of the repeating unit comprising a group (z) capable of decomposing by an acid in the resin (C) and an acid-decomposable group described by the resin of the component (A) Those repeating units are the same. The acid-decomposable group is preferably a mercaptoester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like, and the tertiary alkyl ester group is more good. The repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following formula (CAI): -113- 201033733 f Rx, (_cr^o--rx2 RX3 in the formula (CAI) Xat represents a hydrogen atom, a methyl group or a group represented by -CH2-R9. R9 represents a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having a carbon number of 5 or less and a mercapto group. The organic group is preferably an alkyl group having a carbon number of 3 or less, and more preferably a methyl group. Xai is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. T represents a single bond or a divalent linking group. group.

Each of Rx! to Rx3 independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). Two members from Rm to Rx3 may be combined to form a cycloalkyl group (monocyclic or polycyclic). Examples of the divalent linking group of T include an alkylene group, a -COO-Rt- group, and -O- An Rt- group wherein Rt represents an alkylene or cycloalkyl group. It is preferred that T is a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH2- group or a -(CH2)3- group. The alkyl group of 11\1 to Rx3 is preferably an alkyl group having a carbon number of 1 to 4, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group and a tertiary butyl group. The cycloalkyl group of 11\1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclic fluorenyl group, or a tetraalkyl group. Cyclododecyl and adamantyl. -114-201033733 The cycloalkyl group formed by combining two members derived from Rxi to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or a polycyclic cycloalkyl group such as A thiol group, a tetracyclic fluorenyl group, a tetracyclododecyl group, and an adamantyl group; a cycloalkyl group having a monocyclic ring having 5 to 6 carbon atoms is more preferable.

Particular embodiments in which Rxi is a methyl or ethyl group and Rx2 is combined with Rx3 to form a cycloalkyl group as described above are preferred. Each of these groups may have a substituent, and examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (having a carbon number of 1 to 4), a carboxyl group and an alkane. Oxycarbonyl (having a carbon number of 2 to 6). The substituent has a carbon number of 8 or less. In the resin (C), the content of the repeating unit having the group (z) capable of decomposing by acid action is preferably from 1 to 80 mol%, more preferably from 10 to 80 mol%, from 2 0 to 60% of the mole % is more preferable, which is based on all the repeating units in the resin (c). The LWR can be modified by having a group (z) which can be decomposed by an acid action. The resin (C) can further comprise other resurfacing units. Preferred specific examples of the other repeating unit d ^ include the following: (cyl) a repeating unit having a fluorine atom and/or a halogen atom and which is stable to the acid and slightly soluble or insoluble in the alkaline developer; (cy2) a repeating unit having a fluorine atom and a germanium atom and which is stable to the acid and slightly soluble or insoluble in the alkaline developer; (cy3) has a fluorine atom and/or a germanium atom and has in addition to the above (x) and (z) a repeating unit of a polar group; and (cy4) a repeating unit having no fluorine atom or germanium atom and having a polar group other than the above (x) & (z) -115 - 201033733. The term "slightly soluble or insoluble in alkaline developer" in the repetitive unit of (cyl) and (cy2) means that (cyl) and (cy 2) do not contain a group soluble in hydrazine. The group may be a group capable of producing a base-soluble group (for example, an acid-decomposable group or a polar conversion group) by the action of an acid or an alkali developer. The repeating units (cyl) and (cy2) have an alicyclic hydrocarbon structure having no polar group. Preferred Embodiments of the repeating units (cyl) to (cy4) are described below. The repeating units (cyl) and (cy2) are preferably the repeating unit represented by the following formula (CIII):

U3 (cni)

In the formula (CIII), Re31 represents a hydrogen atom, an alkyl group which may be substituted by fluorine, a cyano group or a -CH2-0-Rae2 group, wherein Rae2 represents a hydrogen atom, an alkyl group or a fluorenyl group. Re31 is preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, and a hydrogen atom or a methyl group is more preferred.

Rc32 represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. Each of these groups may be substituted by a group containing a halogen atom or a fluorine atom or the like.

Lc3 represents a single bond or a divalent linking group. In the formula (CIII), the alkyl group of Re32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms. The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms. -116-201033733 The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms. The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and each of these groups may have a substituent.

Rc3 2 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom. The divalent linking group of Le3 is preferably an alkylene group (preferably having a carbon number of 1 to 5), an oxy group, a phenyl group or an ester bond (a group represented by -COO-). The repeating units (cyl) and (cy2) are preferably the repeating unit shown by the following formula (C4) or (C5):

(Rc6)n In this equation, R. 5 represents a hydrocarbon group which has at least one cyclic structure and does not have a hydroxyl group or a cyano group.

Rac represents a hydrogen atom, an alkyl group which may be substituted by fluorine, a cyano group or a -CH2_0-Rac2 group, wherein Rac2 represents a hydrogen atom, an alkyl group or a fluorenyl group. Rac is preferably a hydrogen atom, a methyl group, a methylol group or a trifluoromethyl group, and a hydrogen atom or a methyl group is more preferred. By R. The ring structure possessed by 5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms and a cycloalkenyl group having 3 to 12 carbon atoms. The monocyclic hydrocarbon group is preferably a monocyclic hydrocarbon group having 3 to 7 carbon atoms. The polycyclic hydrocarbon group includes a cyclic hydrocarbon group and a crosslinked cyclic hydrocarbon group -117-201033733. Examples of the crosslinked cyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring. The crosslinked hydrocarbon ring also includes a fused cyclic hydrocarbon ring (e.g., a fused ring formed by condensing a plurality of 5 to 8 membered cycloalkane rings). Preferred examples of the crosslinked cyclic hydrocarbon ring include a thiol group and an adamantyl group. The alicyclic hydrocarbon group may have a substituent, and preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amine group protected by a protecting group. The halogen atom is preferably a bromine atom, a chlorine atom or a fluorine atom; and the alkyl group is preferably a methyl group, an ethyl group, a butyl group or a tertiary butyl group. The alkyl group may further have a substituent, and the substituent further further possessed by the alkyl group includes a halogen atom, an alkyl group, a hydroxyl group protected by a protecting group, and an amine group protected by a protecting group. Examples of such protecting groups include alkyl groups, cycloalkyl groups, aralkyl groups, substituted methyl groups, substituted ethyl groups, alkoxycarbonyl groups, and aralkyloxycarbonyl groups. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms; the substituted methyl group is a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, a tertiary butoxymethyl group or 2-methoxyethoxymethyl is preferred; the substituted ethyl group is preferably 1-ethoxyethyl or 1-methyl-1-methoxyethyl; the fluorenyl group has a carbon number 1 W to 6 aliphatic fluorenyl groups are preferred, such as formazan, ethyl fluorenyl, propyl fluorenyl, butyl fluorenyl, isobutyl decyl, pentylene and pentylene; and the alkoxycarbonyl group has a carbon number of 1 The alkoxycarbonyl group to 4 is preferred.

Rc6 represents the base of the hospital, the base of the hospital, the suspected base, the ring base, the oxycarbyl group or the alkylcarbonyloxy group. These groups may each be substituted by a group containing a halogen atom or a fluorine atom or the like. The alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably from -118 to 201033733, and the cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms. The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms. The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. The alkoxycarbonyloxy group is preferably an alkoxycarbonyloxy group having 2 to 20 carbon atoms. η represents an integer of 0 to _ 5. When η is an integer of 2 or more, 'each Rc6 may be the same as or different from each other Re6. 〇 Re6 is preferably an unsubstituted alkyl group or an alkyl group substituted by a fluorine atom, and a trifluoromethyl group or a tertiary butyl group is more preferable. The repeating units (cyl) and (cy2) are also preferably the repeating unit represented by the following formula (CII-AB):

(C I I -AB) Ο In the formula (CII-AB), each of Rcll' and Rcl2' independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group. Zc' represents an atomic group used to form an alicyclic structure of a carbon atom (C-C) containing two bonds. The formula (CII-AB) is preferably the following formula (CII-AB1) or (CII-AB2): -119- 201033733

In the formulae (CII-AB1) and (CII-AB2), each of Rcl3' to rc16' independently represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group. At least two members from Rcl3' to Re 16' may be combined to form a ring. η represents 0 or 1. Specific embodiments of (cyl) and (cy2) are presented below, but the invention is not limited thereto. In the equation, Ra represents H, CH3, CH2〇H, CF3 or CN.

-120-201033733 As for (cy3) and (cy4), it is preferred to include a repeating unit having a hydroxyl group or a cyano group as the polar group. Due to this repetitive unit, the affinity for the developer is increased. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure which has been substituted by a hydroxyl group or a cyano group is preferably an adamantyl group, a bisadamantyl group or a norbornyl group. Preferred examples of the alicyclic hydrocarbon structure which has been substituted by a hydroxy group or a cyano group include monohydroxyadamantyl, dihydroxyadamantyl, monohydroxydiadamantyl, dihydroxydiadamantyl and substituted by a cyano group. Lowering the base.重 The repeating unit having this atomic group includes a repeating unit represented by the following formulas (CAIIa) to (CAIId):

In the formulae (CAIIa) to (CAIId), R!c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. Each of R2c to R4c independently represents a hydrogen atom, a hydroxyl group or a cyano group, with the proviso that at least one of R2c to R4c represents a hydroxyl group or a cyano group. A structure in which one or two members of R2c to R4C are a hydroxyl group and a remaining hydrogen atom is preferred. In the formula (CAIIa), two members derived from R2c to R4c are a hydroxyl group and the remainder is preferably a hydrogen atom. A specific embodiment of the repeating unit having a hydroxyl group or a cyano group is proposed below, but the invention is not limited thereto. -121 - 201033733

^ ηΡ i&OH J&OK

$ 0 oh m The content of the repeating unit represented by (cyl) to (cy4) is preferably from 5 to 4 〇 mol%, more preferably from 5 to 30 mol%, from 1 25 to 25 mol%. More preferably, the total repeating unit in the resin (C) is taken as the standard. The resin (c) may have a plurality of repeating units represented by (cyl) to (Cy4). In the example in which the resin (C) contains a fluorine atom, the fluorine atom content is preferably from 5 to 80% by mass, more preferably from 10 to 8% by mass, based on the molecular weight of the resin ((:). Preferably, the fluorine atom-containing repeating unit is preferably from 1 〇 to 1% by mass, more preferably from 30 to 1% by mass, based on all of the repeating units in the resin (c). In the example in which the resin (C) contains a halogen atom, the content of the germanium atom is preferably from 2 to 50% by mass, more preferably from 2 to 30% by mass, based on the molecular weight of the resin (〇:). The sand atom-containing repeating unit is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, based on all of the repeating units in the resin (c). The standard polyphenylene of the resin (C) The weight average molecular weight of ethylene reduction is preferably from looo to 100,000, more preferably from 1, 〇〇〇 to 50,000, more preferably from 2 000 to 15,000. A resin similar to the component (A) is in the resin (C) Of course, the amount of impurities (such as -122-201033733 metal) is preferably less, but similarly, the residual monomer or oligomer component The amount is preferably from 0 to 10% by mass, more preferably from 〇 to 5% by mass, even more preferably from 〇 to _质量%. By satisfying these conditions, it is possible to obtain no foreign substance or sensitivity and the like in the liquid. A photoresist composition that does not change with aging. In addition, considering the resolution, photoresist profile, sidewall photoresist pattern, coarse sugar content, and the like, the molecular weight distribution (Mw/Mn, also known as polydispersity) is derived from 1 to 3 is preferably 'preferably from 1 to 2, more preferably from 1 to ι·8, and most preferably from 1 to 1-5. Ο As for the resin (C)', a variety of commercially available products can be used. Or the resin can be synthesized by a conventional method (for example, radical polymerization). Examples of the synthesis method generally include a batch polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating the solution, thereby achieving polymerization; and a dropping polymerization method which takes 1 to 10 hours, A solution comprising the monomer species and the starter is added dropwise to the hot solvent. The dropping polymerization method is preferred. Examples of the reaction solvent include ethers such as diisopropyl ether, tetrahydrofuran, 1,4-dioxane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents, such as acetic acid Ethyl ester; guanamine solvent such as dimethylformamide and dimethylacetamide; and a solvent which is capable of dissolving the composition of the present invention, such as propylene glycol monomethyl ether acetate (PGME A, also known) It is 1 methoxy-2-ethoxypropane propane), propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol) and cyclohexanone. It is more preferable to carry out polymerization using the same solvent as that used in the photosensitive ray or the radiation sensitive resin composition of the present invention. By using the same solvent, generation of particles during storage can be suppressed. The polymerization is carried out in an inert gas atmosphere such as nitrogen or argon, preferably from -123 to 201033733. As for the polymerization initiator, the polymerization is started using a commercially available radical initiator (for example, an azo-based initiator, a peroxide). The radical initiator is preferably an azo-based initiator, and an azo-based initiator having an ester group, a cyano group or a carboxyl group is preferred. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl 2,2'-azobis(2-methylpropionate). The reaction concentration is usually from 5 to 50% by mass, preferably from 30 to 50% by mass, and the reaction temperature is usually from 10 to 150 ° C, from 30 to 120 ° C, from 60 to 100 ° C. Better. After the reaction was completed, the reaction solution was allowed to cool to room temperature and purified. Purification can be carried out by a normal method, for example, a liquid-liquid extraction method, which employs water washing or a suitable solvent to remove residual monomer or oligomer components; a purification method in a solution state, such as by Extracting only the ultrafiltration method having those having a molecular weight of not more than a specific hydrazine for removal; a reprecipitation method, which adds the resin solution dropwise to a poor solvent to cure the resin in the poor solvent' thus removing residual Monomers and analogs thereof, and purification methods in a solid state, such as a method in which a resin slurry separated by filtration is subjected to washing with a poor solvent. For example, the resin is obtained by allowing the reaction solution to be slightly soluble or insoluble in the resin (poor solvent, the volume of which is 10 times or less of the reaction solution, preferably from 1 to 5 times) It is precipitated and precipitated as a solid. The solvent used in the precipitation or reprecipitation from the polymer solution! ! (precipitating or reprecipitating the solvent), if it is a poor solvent for the polymer, it is sufficient and the solvent which can be used may be, for example, a hydrocarbon, a halogenated hydrocarbon, a nitro compound, an ether, a ketone, an ester, or a carbonate depending on the kind of the polymer. A salt, an alcohol, a carboxylic acid, water-124-201033733, and a mixed solvent containing the solvent are appropriately selected. Among these solvents, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferred as the precipitation or re-sinking solvent. The amount of the precipitation or reprecipitation solvent to be used may be appropriately selected in consideration of efficiency, productivity, and the like, but generally, the amount used is from 100 to 10,000 parts by mass per 100 parts by mass of the polymer solution. It is preferably from 200 to 2,000 parts by mass, more preferably from 300 to 1,000 parts by mass. The temperature at the time of precipitation or reprecipitation® may be appropriately selected in consideration of efficiency or operability, but it is usually at a level of 0 to 50 ° C, adjacent to room temperature (for example, from about 20 to 35 ° C) Preferably. This precipitation or reprecipitation operation can be carried out by a known method such as a batch system and a continuous system using a commonly used mixing vessel such as a stirring tank. The precipitated or reprecipitated polymer is typically subjected to conventionally used solids • liquid separation (such as filtration and centrifugation), followed by drying and use. The solvent-resistant filter element is preferably used, preferably under pressure. Drying is carried out at atmospheric pressure or under reduced pressure (preferably under reduced pressure) at a temperature of from about 30 to 100 ° C (preferably from 3 Torr to 50 ° C). Incidentally, once the resin is precipitated and separated, the resin may be dissolved again in a solvent and then brought into contact with a solvent in which the resin is slightly soluble or insoluble. That is, the method usable herein includes contacting the polymer with a solvent which is slightly soluble or insoluble with the polymer after completion of the radical polymerization reaction to precipitate the resin (step a); from the solution Separating the resin (step b); once again dissolving the resin in a solvent to prepare a resin solution A (step c); bringing the resin solution A to a slightly soluble or insoluble state with the resin -125-201033733 The solvent (having a volume less than 10 times (5 times or less) of the resin solution A) is contacted to precipitate a resin solid (step d); and the precipitated resin is separated (step e). Specific examples of the resin (C) are set forth below, but the invention is not limited thereto. Similarly, the repeating unit in each resin (corresponding to the repeating unit from the left side in the structural formula) The molar ratio, weight average molecular weight (Mw), and polydispersity (Mw/Mn) are shown in the following table. -126- 201033733

-127- 201033733

-128- 201033733

-CFg (C-32)

(C-36)

-129- 201033733

-130- 201033733

Ο

(C-δΟ)

131 201033733

-132- 201033733

-133- 201033733

(C-156)

-134 201033733

-135- 201033733

-136- 201033733

-137- 201033733

FaC (C-236)

138- 201033733 Table 1

Resin composition Mw Mw/Mn C-1 100 6000 1.5 C-2 100 7500 1.4 C-3 100 6000 1.4 06 50/50 6500 1.4 C-7 90/10 8000 1.4 C-8 60/40 8000 1.3 C-9 30/30/30/10 9500 1.4 C-10 70/30 7000 1.4 C-11 50/10/40 9000 1.6 C-12 80/20 6000 1.4 C-14 50/50 8000 1.4 C-16 100 6000 1.4 C -17 100 8000 1.4 C-18 40/20/40 6000 1.4 C-21 40/40/10/10 6000 1.4 C-22 100 5500 1.4 C-23 100 9500 1.5 C-24 70/30 8500 1.4 C-25 50/30/20 5000 1.4 C-26 50/20/30 5500 1.4 C-27 50/50 9000 1.5 C-28 50/40/10 9000 1.4 C-30 70/30 6500 1.4 031 70/30 9000 1.5 C -32 90/10 9000 1.5 C-33 70/20/10 7000 1.4 C-34 80/10/10 8500 1.5 C-35 60/30/10 7500 1.4 C-36 50/50 5000 1,5 C-38 50/50 4500 1.4 Resin composition Mw Mw/Mn C-39 80/20 5000 1.4 C-40 100 5000 1.4 C-43 90/10 8500 1.4 C-44 30/30/30/10 5500 1.4 C-49 60 /30/10 6000 1.4 C-50 60/40 8000 1.5 C-51 50/50 9500 1.4 C-53 100 7000 1.5 C-54 70/10/10/10 5500 1.4 C-55 80/20 6500 1.4 C- 56 30/30/40 6000 1.4 C-62 100 6500 1.4 C-63 80/10/10 7000 1,5 C-64 90/10 9000 1.5 C-67 100 6500 1.4 C-68 80/20 6500 1.4 C-69 70/20/10 7000 1.4 070 60/30/10 9000 1.5 C-71 60/20/20 8000 1.4 C-72 100 9500 1.5 C -73 40/60 8000 1.4 C-74 60/10/30 7000 1,5 C-75 100 5500 1.5 C-76 90/10 6500 1.4 C-77 90/10 7500 1.3 C-80 70/10/20 8500 1.5 C-81 80/20 5500 1.3 C-88 40/30/30 6000 1.3 C-89 70/30 6500 1.3 C-96 100 6000 1.5 -139- 201033733 Table 1 (continued) Resin composition Mw Mw/Mn resin Composition Mw Mw/Mn C-101 80/20 7000 1.3 C-201 80/20 8000 1.5 C-102 50/20/30 4500 1.3 C-205 80/20 7000 1.4 C-114 80/20 7000 1.5 C- 207 80/15/5 10000 1.4 C-115 90/10 6000 1.2 C-208 85/10/5 5000 1.5 C-117 50/50 6000 1.5 C-209 90/8/2 13000 1.5 C-118 100 9500 1.5 C-210 85/10/5 6000 1.5 C-119 50/20/20/10 8000 1.5 C-211 90/8/2 8000 1.4 C-120 75/10/10/5 7000 1.3 C-212 50/50 12000 1.5 C-121 30/30/10/30 5500 1.3 C-213 50/50 8000 1.3 C-131 60/20/20 4000 1.4 C-214 85/15 6500 1.5 0132 50/30/20 6500 1.4 C- 215 85/15 4000 1.5 C-133 70/10/20 7000 1.4 C-216 90/10 7500 1.6 C-134 80/10/10 9000 1.4 C-217 90/10 3500 1.5 C-135 60/40 8000 1.5 C-218 95/5 5500 1.4 C-136 30/70 9000 1.4 C-219 85/10/5 5000 1.5 C-143 50/40/10 7000 1.4 C-220 88/10/2 13000 1.4 C-146 50/50 9000 1.5 C-221 90/8/2 12000 1.5 C-147 48/50/2 6000 1.4 0222 90/8/2 11000 1.4 C-148 50/50 9000 1.5 0223 90/8/2 9000 1.5 C-149 50/25/25 6000 1.4 0224 50/50 6000 1.5 C-155 50/50 6000 1.5 C- 225 50/50 8000 1.5 C-156 50/50 4000 1.5 C-226 80/20 4500 1.3 C-164 25/50/25 6000 1.5 C-227 85/15 8500 1.6 C-165 40/40/10/10 6500 1.4 C-228 90/10 10000 1.4 0171 100 4500 1.4 C-229 90/10 3500 1.5 C-172 100 3500 1.4 C-230 95/5 4500 1.5 C-173 60/40 5000 1.4 C-231 50/50 4000 1.5 C-174 90/10 6000 1.4 C-232 80/18/2 6000 1.5 C-179 100 6000 1.4 C-233 90/8/2 9500 1.5 C-180 100 7000 1.3 C-234 80/20 6500 1.4 C-191 90/10 5500 1.4 C-235 90/10 8000 1.5 C-192 75/25 9000 1.4 C-236 100 8000 1.5 C-193 70/30 10000 1.5 C-237 95/5 4500 1.5 C-194 70 /30 5000 1.4 C-238 90/10 10000 1.5 C-199 100 500 0 1.4 C-239 100 6500 1.7 C-200 80/20 6000 1.4 C-240 40/20/20/20 12000 1.8 -140- 201033733 As for the resin (C), one type may be used alone or in combination. More or more types. Similarly, it is preferred to use a resin (CP) having at least one of fluorine atoms or germanium atoms and different from the resin (C). Resin (CP) having at least one of a fluorine atom or a ruthenium atom The photosensitive ray or radiation sensitive resin composition of the present invention may further comprise a resin having at least one of fluorine atoms or ruthenium atoms and having a difference from the resin (C) (CP). By including the resin (C) and the resin (CP), the resin (C) and the resin (CP) are unevenly distributed to the surface layer of the film, and when the immersion medium is water, the formed film can be The water receding contact angle and the fluidity of the immersion liquid on the surface of the photoresist film are increased. The receding contact angle of the film is preferably from 60 to 90°, more preferably 70° or more. The resin (CP) can be used by appropriately adjusting the content thereof to provide a film having a receding contact angle within the above range. However, the content is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, still more preferably from 0.1 to 4% by mass, and more preferably from 0.1 to 3% by mass, with the sensitized ray or sensation The total solid content of the radioactive resin composition is the standard. As described above, the resin (CP) is unevenly distributed to the interface, but unlike the surfactant, it does not need to have a necessary hydrophilic group in the molecule and may not contribute to uniform mixing of the polar/nonpolar substance. In the immersion exposure step, the immersion liquid needs to move on the wafer as the exposure head scans the wafer at high speed and forms an exposure pattern. Therefore, the contact angle of the immersion liquid with the film in a dynamic state is important, and the photoresist needs to have an exposure head capable of following the high-speed scanning of the liquid droplets without the residual performance of -141-201033733. Due to the combination of the resin (C) and the resin (CP), the hydrophobicity (water fluidity) on the surface of the film is improved and the development residue (scum) is reduced. The fluorine atom or the ruthenium atom in the (CP) resin having at least one of fluorine atoms or ruthenium atoms may be present in the resin main chain or may be substituted on the side chain. The resin (CP) is preferably a resin having a fluorine atom-containing alkyl group, a fluorine atom-containing cycloalkyl group or a fluorine atom-containing aryl group as a partial structure of the fluorine atom. The fluorine atom-containing alkyl group (having preferably having a carbon number of 1 to 10, more preferably 1 to 4) is a linear or branched alkyl group having at least one hydrogen atom replaced by a fluorine atom and may further have other substituents. The fluorine atom-containing cycloalkyl group is a monocyclic or polycyclic cycloalkyl group having at least one hydrogen atom replaced by a fluorine atom and may further have other substituents. The fluorine atom-containing aryl group is an aryl group (e.g., phenyl group, naphthyl group) having at least one hydrogen atom replaced by a fluorine atom and may further have other substituents. Preferred examples of the fluorine atom-containing alkyl group, the fluorine atom-containing cycloalkyl group, and the fluorine atom-containing aryl group include the groups represented by the above formulas (F2) to (F4) for the resin (C). Group, but the invention is not limited thereto. In the present invention, the groups represented by the formulae (F2) to (F 4) are preferably contained in the (meth) acrylate-based repeating unit. The specific embodiment of the repetitive unit having a fluorine atom is proposed below, but the invention is not limited thereto. In a particular embodiment, Χι represents a hydrogen atom, -ch3, -f or -cf3. X2 stands for -F or -CF3 » -142- 201033733

-143- 201033733

The resin (CP) is preferably a resin having a structure of an alkyl fluorenyl group (preferably a trialkyl decyl group) or a cyclic siloxane structure as a partial structure of the ruthenium atom. Specific examples of the alkyl fluorenyl structure and the cyclic siloxane structure include the groups represented by the above formula (CS-1) to (CS-3) described for the resin (C). Further, the resin (CP) may comprise at least one group selected from the group consisting of (X) a group soluble in a base, (y) capable of being a base The group of the developer is decomposed to increase the solubility in the alkaline developer, and (z) is a group which can be decomposed by the action of an acid. Specific examples of these groups are the same as those described above for the resin (c) -144-201033733. The content of the repeating unit having a group (y) capable of increasing the solubility in the alkaline developer is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, and from 5 to 20 mol. % is even better 'based on all repeating units in the resin (cp). The specific embodiment of the repeating unit having a group capable of increasing the solubility in the alkaline developer is the same as those having the lactone structure described for the resin of the component (A). Examples of the recoating unit contained in the resin (CP) having a group (z) capable of decomposing by an acid action and those having an acid-decomposable group described in the resin of the component (A) The repeating unit is the same. The content of the repeating unit in the resin (CP) which has a group (z) which can be decomposed by an acid action is from 1 to 80 mol. /. Preferably, it is preferably from 10 to 80 mol%, more preferably from 20 to 60 mol%, and all of the repeating units in the resin (CP) are used. The resin (CP) may further have a repeating unit represented by the above-mentioned formula (III) regarding the resin (C). In the example in which the resin (CP) contains a fluorine atom, the fluorine atom content thereof is preferably from 5 to 80% by mass, more preferably from 1 Å to 80% by mass, based on the molecular weight of the resin (CP). Similarly, the fluorine atom-containing repeating unit preferably occupies from 10 to Wo% by mass, more preferably from 30 to 100% by mass, based on all of the repeating units in the resin (CP). In the example in which the resin (CP) contains a halogen atom, the content of the germanium atom is preferably from 2 to 50% by mass, more preferably from 2 to 30% by mass, based on the molecular weight of the resin (CP). Similarly, the ruthenium-containing repeating unit occupies from 10 to -145 to 201033733, preferably 100% by mass, more preferably from 20 to 100% by mass, based on all of the repeating units in the resin (CP). The resin (CP) has a standard polystyrene equivalent average molecular weight of preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, even more preferably from 2,000 to 15,000. Similar to the resin of the component (A), in the resin (CP), a small amount of impurities such as a metal is of course preferable, but similarly, the content of the residual monomer or oligomer component is from 0 to 10% by mass is more preferable, more preferably from 〇 to 5% by mass, still more preferably from 0 to 1% by mass. By satisfying these conditions, a sensitized ray or a radiation sensitive resin composition in which no foreign matter or sensitivity and the like in the liquid do not change with aging can be obtained. Furthermore, considering the resolution, the photoresist profile, the sidewall of the photoresist pattern, the roughness, and the like, the molecular weight distribution (Mw/Mn, also referred to as polydispersity) is preferably from 1 to 3, from 1 to 2. More preferably, from 1 to 1.8 is better and from 1 to 1.5 is the best. As the resin (CP), a variety of commercially available products can be used, or the resin can be synthesized by a usual method (e.g., radical polymerization). In particular, the resin can be synthesized in the same manner as the resin (C). A specific embodiment of the resin (CP) having at least one of a fluorine atom or a ruthenium atom is proposed below. -146- 201033733

-147- 201033733

-148- 201033733

-149- 201033733

-150- 201033733

0 people. 0 people. Seven O people. c

FaC person CF3 .CFa

.CF3

•^4) -Μ^· O 乂. 0*^0

Jr^i -rfr 〇人. 0^0 F, Λ $4F2 FaC such as F3 F2CyCF:

R4i. people.

R4i

FjC^F, 〇人〇 0 people.

[4] Solvents Examples of a solvent which can be used at the time of preparing the sensitized ray or radiation-sensitive resin composition by dissolving the components described above include an organic solvent such as a carboxylic acid alkylene glycol monoalkyl group. Ether ester, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having a carbon number of 4 to 10), a monoketone compound which may include a ring (having carbon) Preferably, the number is from 4 to 10, the alkylene carbonate, the alkyl alkoxyacetate and the alkyl pyruvate. -151- 201033733 The preferred embodiment of the carboxylic acid alkylene glycol monoalkyl ether ester comprises propylene glycol monomethyl ether ester (PGMEA, also known as 1-methoxy-2-ethylpropane), acetic acid Propylene glycol monoethyl ether ester, propylene glycol monopropyl acetate, propylene glycol monobutyl ether acetate, propionic acid propylene glycol monomethyl ether propylene glycol monoethyl ether ester, ethylene glycol monomethyl ether ester and acetic acid alcohol Ethyl ether ester. Preferred examples of the alkylene glycol monoalkyl ether include propylene glycol ether (PGME, also known as 1-methoxy-2-propanol), propylene glycol monoether, propylene glycol monopropyl ether, propylene glycol single Butyl ether, ethylene glycol monomethyl and ethylene glycol monoethyl ether. Preferred examples of the lactate alkyl ester include methyl lactate, propyl lactate and butyl lactate. Preferred examples of the alkoxypropionic acid alkyl ester include 3-ethoxypropyl ester, methyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-methoxyacetate. Preferred examples of the cyclic lactone include propiolactone, cold-ester, r-butyrolactone, α-methyl-r-butyrolactone, /3-methyl-r-butan 7-pentane Preferred examples of the monoketone compound which may contain a ring include esters, 7-caprolactone, 7-octyl vinegar and 0:_diabase _7-butyl include 2-but-3-methylbutanone, tertiary butyl Ethyl ethyl ketone, 2-pentanone, 3-pentanone, 3-methylpentanone ' 4-methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2- J: 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexyl-1 hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methylheptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, acetic acid Oxyl ether, propylenediethyl monoethyl ether ester, acid ethyl propane 3 ester, decyl ester. Ketone, ketone-2-ketone, ί, 3-yl-3-3-octyl-152-201033733 ketone, 2-nonanone, 3-fluorenone, 5-fluorenone, 2-nonanone, 3-fluorenone , 4-fluorenone, 5-hexen-2-one, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethyl Cyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2- Dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, and 3-methylcycloheptanone . Preferred examples of the alkylene carbonate include propylene carbonate, vinyl carbonate, ethylene carbonate, and butylene carbonate.较佳 Preferred examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-(2-ethoxyethoxy)ethyl acetate, and acetic acid 3 -Methoxy-3-methylbutyl ester and 1-methoxy-2-propyl acetate. Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate and propyl pyruvate. The solvent which can be preferably used is a solvent having a boiling point of 130 ° C or higher at normal temperature and at atmospheric pressure, and specific examples thereof include cyclopentanone, 7 • butyrolactone, cyclohexanone, ethyl lactate, Ethylene glycol monoethyl ether acetate, © propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, ethyl pyruvate, 2-ethoxyethyl acetate, 2-(2-ethyl acetate) Oxyethoxyethyl)ethyl ester and propylene carbonate. In the present invention, one of these solvents may be used alone or two or more kinds thereof may be used in combination. In the present invention, a mixed solvent prepared by mixing a solvent containing a hydroxyl group in the structure and a solvent containing no hydroxyl group can be used as the organic solvent. -153- 201033733 Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethyl lactate . Among these, propylene glycol monomethyl ether and lactic acid ethyl acetate are preferred. Examples of the solvent containing no hydroxyl group include propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, r-butyrolactone, cyclohexanone, butyl acetate, N-methyl Pyrrolidone, N,N-dimethylacetamide and dimethyl submilling. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, 7-butyrolactone, cyclohexanone and butyl acetate are preferred 'and propylene glycol monomethyl ether acetate, Ethyl ethoxypropionate and 2-heptanone are most preferred. The mixing ratio of the solvent containing a hydroxyl group to a solvent containing no hydroxyl group (by mass) is usually from 1/99 to 99/1, preferably from 10/90 to 90/10, and from 20/80 to 60/40. good. In view of uniformity of the coating layer, the ratio of the solvent containing no hydroxyl group contained in the mixed solvent is particularly preferably 50% by mass or more. The solvent is preferably a mixed solvent of two or more solvents comprising propylene glycol monomethyl ether acetate (PGMEA). [5] Basic compound The photosensitive ray or radiation sensitive resin composition of the present invention preferably contains a basic compound for reducing the change in performance with aging from exposure to heating. The basic compound is preferably a compound having a structure represented by the following formulas (A) to (E): -154- 201033733

(A)

=4-n4—i_l_ (C> (〇) (E) In the formulae (A) and (E), each of R2QG, R201 and R2G2 may be the same or different 'it represents a hydrogen atom, an alkyl group (having a carbon number of 1) Preferred to 20), a cycloalkyl group (having preferably a carbon number of 3 to 20) or an aryl group (having a carbon number of 6 to 20); and R2 〇1 and r2<)2 may be bonded together to form a ring" R2〇 3. Each of r2Q4, r2〇5 and r2Q6 may be the same or different and represents an alkyl group having a carbon number of 1 to 20. As the alkyl group, the alkyl group having a substituent is preferably an amine alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms or a cyanoalkyl group having 1 to 20 carbon atoms. The alkyl group in the formulae (A) and (E) is preferably unsubstituted. Preferred examples of the compound include anthracene, aminopyrrolidine, pyrazole, pyrazoline, hydrazine, aminomorphine, aminoalkylmorpholine and piperidine. More preferred embodiments of the compound include compounds having an imidazole structure, a dioxonium bicyclic structure, a hydrazone hydroxide structure, a carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure; having a hydroxyl group and/or an ether bond An alkylamine derivative; and an aniline derivative having a hydroxyl group and/or an ether bond. Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of the compound having a diterpene bicyclic structure include 1,4-dioxabicyclo[2,2,2]octane, 1,5-dioxabicyclo[4,3,0]non-5-ene and 1 , 8-terpene double ring [5,4,0] eleven-7-

Alkene. Examples of the compound having a ruthenium hydroxide structure include H-155-201033733 butylammonium hydroxide, triarylsulfonium hydroxide, benzoquinone hydroxide and cesium hydroxide having a 2-sided oxyalkyl group, particularly , triphenylsulfonium hydroxide, tris(tert-butylphenyl)phosphonium hydroxide, bis(tributylphenyl)iodine hydroxide, benzamidine methylthiophene gun and 2-oxo hydroxide Propylthiophene. Examples of the compound having a carboxylic acid gun structure include a compound in which the anion portion of the compound having a KOH structure becomes a carboxylate such as acetate, adamantane-1 carboxylate, and perfluoroalkyl carboxylate. Examples of the compound having a trialkylamine structure include tri(n-butyl)amine and tris(n-octyl)amine. Examples of the aniline compound include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline and N,N-dihexylaniline. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine. Examples of the aniline derivative having a hydroxyl group and/or an ether bond include ruthenium, osmium-bis(hydroxyethyl)aniline. Other preferred basic compounds include phenoxy-containing amine compounds, phenoxy-containing ammonium salt compounds, sulfonate group-containing amine compounds, and sulfonate group-containing ammonium salt compounds. As the amine compound, a primary, secondary or tertiary amine compound, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom can be preferably used. The amine compound is more preferably a tertiary amine compound. In the amine compound, as long as at least one alkyl group (having preferably 1 to 20 carbon atoms) is bonded to a nitrogen atom, a cycloalkyl group (having preferably a carbon number of 3 to 20 or an aryl group) in addition to an alkyl group (having Preferably, the carbon number of 6 to 12 is bonded to the nitrogen atom. The amine compound preferably has an oxygen atom in the alkyl chain to form an oxygen alkyl group. The number of oxygen alkyl groups in the molecule is 1 or more -156 to 201033733, more preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, an oxygen-extended ethyl group (-CH2CH20-) and an oxygen-extended propyl group (-CH(CH3)CH2〇- or -CH2CH2CH20-) are preferred, and an oxygen-extended ethyl group is more preferred. As the ammonium salt compound, a primary, secondary, tertiary or quaternary ammonium salt compound, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom can be preferably used. In the ammonium salt compound, as long as at least one alkyl group (having preferably 1 to 20 carbon atoms) is bonded to a nitrogen atom, a cycloalkyl group (having preferably 3 to 20 carbon atoms) or an aryl group (except for an alkyl group) It has a carbon number of 6 to 12, preferably bonded to the nitrogen proton. The ammonium salt compound preferably has an oxygen atom in the alkyl chain to form an oxygen alkyl group. The number of oxygen alkyl groups in the molecule is 1 or more, preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, an oxygen-extended ethyl group (_CH2CH20-) and an oxygen-extension propyl group (-CH(CH3)CH20- or -CH2CH2CH20-) are preferred, and an oxygen-extended ethyl group is more preferred. Examples of the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate and a phosphate, and a halogen atom and a sulfonate are preferred. The halogen atom is preferably chlorine, desert or iodine; and the sulfonate is preferably an organic acid salt having a carbon number of 丨 to 2 〇. The organic sulfonate includes an alkylsulfonate having from 1 to 20 carbon atoms and an arylsulfonate. The alkyl group of the alkyl sulfonate may have a substituent ' and examples of the substituent include fluorine, chlorine, bromine, alkoxy, decyl and aryl. Specific examples of the hospital base sulfonate include methanesulfonate, ethanesulfonate, butyrate, hexanoate, octanesulfonate, benzyl sulfonate, tri-methanesulfonate, five Fluoroethanesulfonate and nonafluorobutanesulfonate. The aryl group of the arylsulfonate includes a benzene ring, a naphthalene ring and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent ' and the substituent is a linear or branched -157-201033733 alkyl group having a carbon number of 1 to 6, or a cycloalkyl group having a carbon number of 3 to 6 is preferred. Specific examples of such linear or branched alkyl and cycloalkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl and cyclohexyl. Other examples of the substituent include an alkoxy group having a carbon number of 1 to 6, a halogen atom, a cyano group, a nitro group, a fluorenyl group, and a decyloxy group. The phenoxy group-containing amine compound and the phenoxy group-containing ammonium salt compound are compounds in which the alkyl group of the amine compound or the ammonium salt compound has a phenoxy group at the terminal end opposite to the nitrogen atom. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylate group, a sulfonate group, an aryl group, an aralkyl group, and an anthracene group. And aryloxy. The substitution position of the substituent may be any position from 2 to 6 positions, and the number of the substituents may be any one in the range of from 1 to 5. The compound preferably has at least one oxygen alkyl group between the phenoxy group and the nitrogen atom. The number of oxygen alkyl groups in the molecule is 1 or more, and more preferably from 3 to 9 is more preferably from 4 to 6. Among the oxygen alkyl groups, an oxygen-extended ethyl group (-CH2CH2〇- and an oxygen-extended propyl group (-ch(ch3)ch2o- or -ch2ch2ch2o-) is preferred, and an oxygen-extended ethyl group is more preferred. The sulfonate group in the amine compound of the ester group and the ammonium salt compound containing a sulfonate group may be any one of an alkyl sulfonate, a cycloalkyl sulfonate and an aryl sulfonate. In the example of the sulfonate, the alkyl group has a carbon number of 1 to 20; in the case of the cycloalkyl sulfonate, the cycloalkyl group has a carbon number of 3 to 20; and the aryl sulfonic acid In the example of the ester, the aryl group preferably has a carbon number of 6 to 12. The alkyl sulfonate, cycloalkyl sulfonate and aryl sulfonate may have a substituent, and the substituent is a halogen atom and a cyanogen. Base, -158-201033733 Preferably, a nitro group, a carboxyl group, a carboxylate group or a sulfonate group. The compound preferably has at least one oxygen-extended alkyl group between the sulfonate group and the nitrogen atom. The number of oxygen alkyl groups is 1 or more, and preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, oxygen-extended ethyl (-CH2CH20-) and oxygen-extended propyl (- CH(CH3)CH20- or -CH2CH2CH2〇-) Good, and the oxygen better stretch ethyl. Examples of the basic compound, the following compounds are also preferred.

One of these basic compounds may be used alone or two or more of them may be used in combination. The amount of the basic compound to be used is usually from 0.001 to 10% by mass, preferably from 0.01 to 5% by mass, based on the total solid content of the sensitized ray or the radiation-sensitive resin composition. The ratio of the acid generator to the basic compound blended in the composition is an acid generator/basic compound (in terms of moles) = preferably from 2.5 to 300. That is, in view of sensitivity and resolution, the molar ratio is preferably 2.5 or more; and from the viewpoint of suppressing resolution, since the photoresist pattern is reduced with age thickening after exposure to heat treatment, 300 Or less preferred. The acid generator/basic compound (in terms of moles) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150. It is preferred to use the test compound at a ratio of the low-159-201033733 molecular compound (D) having a group which can be removed by an acid as described below, and a molar ratio of ioo/o to 10/90. a low molecular compound (D)/an inert compound having a group capable of leaving by an acid action, more particularly a molar ratio (a low molecular compound having a group capable of leaving by an acid action (D) /Basic compound) 100/0 to 3 0/70 'Mole ratio (low molecular compound (D) / basic compound having a group which can be removed by acid) ι〇〇 / 〇 to 50/50 Better yet. Incidentally, the basic compound herein does not include the low molecular compound (D) having a group which can be removed by an acid, and when this is also a basic compound. [6] Low Molecular Compound (D) Having a Group Departable by Acid Action The composition of the present invention may include a low molecular compound (D) having a group capable of leaving by an acid action (sometimes referred to as For component (D)). The group which can be removed by acid is not particularly limited, but an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxy group or a hemiamine aldehyde (hemiaminal) The ether group is preferred, and the urethane group or the semi-amine aldehyde ether group is more preferred. The molecular weight of the low molecular compound having a group capable of leaving by acid action is preferably from 1 Torr to 1, preferably from 1 Torr to 700, more preferably from 1 Torr to 500. In the case where the low molecular compound having a group which can be removed by an acid has a tertiary ester structure, the compound is preferably a carboxylate or an unsaturated carboxylate represented by the following formula (la):

201033733 In the formula (1), each R1 independently represents a monoaliphatic cyclic hydrocarbon group (having preferably 4 to 20 carbon atoms) or a derivative thereof or an alkyl group (having preferably 1 to 4 carbon atoms), At least one R1 is an alicyclic hydrocarbon group or a derivative thereof; or at the same time, any two R1 groups are bonded to each other with a carbon atom to which they are bonded to form a divalent alicyclic hydrocarbon group (having preferably a carbon number of 4 to 20) or The derivative, the remaining Ri represents an alkyl group (having preferably a carbon number of 1 to 4) or a monovalent alicyclic hydrocarbon group (having a carbon number of 4 to 20 is preferred) or a derivative thereof. Each X independently represents a hydrogen atom or a hydroxyl group, and at least one X 〇 is a hydroxyl group. A represents a single bond or a divalent linking group, and a single bond or a group represented by -D-COO- (wherein D represents an alkylene group (having preferably a carbon number of 1 to 4) is preferable. In the formula (la), examples of the divalent linking group as A include a methylene group, a methylene carbonyl group, a methylene carbonyloxy group, an ethyl group, an ethyl carbonyl group, and an ethyl carbonyl group. A propyl group, a propyl propyl group, a propyl carbonyl group, and a methylene carbonyl group are preferred. In the formula (la), the R! monovalent alicyclic hydrocarbon group (having a carbon number of 4 to 20 is preferred) and the divalent alicyclic hydrocarbon group (having a carbon number) formed by combining any two Ls with each other Examples of 4 to 20 preferred) include derivatives derived from norvanane, tricyclodecane, tetracyclododecane or cycloalkane (such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane). a group consisting of an alicyclic ring of an alkane; and the group consisting of an alicyclic ring consisting of one or more or one or more groups having a carbon number of 1 to 4 (such as methyl or ethyl) 'N-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl and tert-butyl) and cycloalkyl-substituted groups. Among these alicyclic hydrocarbon groups, a group consisting of an alicyclic ring derived from a dioxin, a tricyclic brothel, -161-201033733 tetracyclododecane, adamantane, cyclopentane or cyclohexane And a group in which the group consisting of the alicyclic ring is substituted by the above alkyl group is preferred. Examples of derivatives of the alicyclic hydrocarbon group include groups having one or more or one or more groups of the following substituents, such as a hydroxyl group; a carboxyl group; a pendant oxygen group (ie, =0); having a carbon number of 1 to 4 Hydroxyalkyl, for example, hydroxymethyl, h hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 2-hydroxylated a 3-hydroxybutyl group and a 4-hydroxybutyl group; an alkoxy group having 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, 2-methylpropoxy, 1-methylpropoxy and tert-butoxy; cyano; and cyanoalkyl having 2 to 5 carbon atoms, for example, cyanomethyl, 2-cyanoethyl, 3 - cyanopropyl and 4-cyanobutyl. Among these substituents, a hydroxyl group, a carboxyl group, a methylol group, a cyano group and a cyanomethyl group are preferred. Examples of the alkyl group of R1 include an alkyl group having a carbon number of 1 to 4, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropane. Base and tertiary butyl. Among these alkyl groups, a methyl group, an ethyl group, a n-propyl group and an isopropyl group are preferred. Specific preferred embodiments include the following compounds. -162- 201033733

In the case where the low molecular compound is an unsaturated carboxylic acid ester, the compound is preferably a (meth) acrylate. A specific embodiment of the (meth)acrylic acid tertiary ester having a tertiary alkyl group as a group which can be removed by an acid is proposed below, but the invention is not limited thereto. (In the equation, Rx represents H, CH3, CF3 or CH2OH, and Rxa and Rxb each represent an alkyl group having a carbon number of 1 to 4.) -163- 201033733

As the low molecular compound (D) having a group which can be removed by an acid, a commercially available product can be used or the compound can be synthesized by a known method. Similarly, it can be borrowed on a nitrogen atom. As the component D, an amine derivative of a group which is removed by an acid action is preferred. This component D may have a protecting group-containing urethane group on the nitrogen atom. The protecting group constituting the urethane group can be represented by the following formula (d-1): -164- 201033733

(d - 1)

In the formula (d-1), each R independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, an arylalkyl group or an alkoxyalkyl group. Each 玟 can be combined with each other R' to form a ring. R' is preferably a linear or branched alkyl group, a cycloalkyl group or an aryl group, more preferably a branched alkyl group or a cycloalkyl group.

The following describes the specific structure of the group represented by the formula (d-Ι) >ΛΧ人>〇^ 人义 Axq 气 Ά ΛΡ vVp from vVP ?人分vV分v^> Ά

Λ— ΛΧ- Λχ^ Kxoi^ \Λ

This component D can also be composed by arbitrarily combining with the structure represented by the formula (d-1).

Eight A'

〇Μ·

The intercalated basic compound -165- 201033733 This component D is more preferably a compound having a structure represented by the following formula (A). Incidentally, the component D may be a compound corresponding to the basic compound described above as long as it has a low molecular compound capable of leaving a group by acid action.

(A) In the formula (A), each Ra each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Similarly, when n = 2, the two Ras may be the same or different, and the two Ras may be bonded to each other to form a heterocyclic hydrocarbon group (having a carbon number of 20 or less) or a derivative thereof. Each Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. At least two Rbs may be combined to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof. η represents an integer of 0 to 2, and m represents an integer of 1 to 3 and n + m = 3. In formula (A), the Ra, Rb, and the aryl group and the aryl group may be replaced by the following functional groups, such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, A morpholinyl group and a pendant oxygen group, an alkoxy group or a halogen atom. The alkyl, cycloalkyl, aryl and aralkyl groups of Ra and Rb (each of which may be substituted by a functional group, an alkoxy group or a halogen atom as described above) Examples include: -166-201033733 Derived from linear or branched alkanes (such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, decane, decane, undecane, and ten a group of a dialkyl); or a group derived from an alkane substituted by one or more or one or more groups of cycloalkyl groups such as cyclobutyl, cyclopentyl and cyclohexyl; derived from a cycloalkane ( a group such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, and adamantane; or the group derived from cycloalkane is composed of one or more or One or more groups of linear or branched alkyl groups (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, decylmethyl, and tert-butyl) substituted groups a group derived from an aromatic compound such as benzene, naphthalene, and anthracene; or a group derived from an aromatic compound consisting of one or more or one Or a plurality of groups of linear or branched alkyl groups (such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl and tert-butyl) substituted groups a group derived from a heterocyclic compound such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, hydrazine, porphyrin, quinoline, perhydroquinoline, oxazole, and benzimidazole. Or a group substituted with a group derived from a heterocyclic compound by a group derived from one or more groups or one or more groups of linear or branched alkyl or aromatic compounds; the group derived from a linear or branched alkane a group or a group derived from a cycloalkane group substituted with one or more groups derived from one or more groups of aromatic compounds, such as a phenyl group, a naphthyl group and an anthracenyl group; and the above substituents are functional groups a group substituted with a group such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, and a pendant oxygen group. Examples of the divalent heterocyclic hydrocarbon group (having preferably having a carbon number of 1 to 20) or a derivative thereof formed by bonding Ra to each other include a group derived from a compound of the following heterocyclic ring-167-201033733, such as pyridine Steep, piperazine, morpholine, indole, 4,5,6-tetrahydropyrimidine, 1,2,3,4-tetrahydropyrazine, 1,2,3,6-tetrahydropyridine, liters, 4-V benzopyrene, benzodiazepine, 5-tTf benzotrimium ih-i, 2,3 - triterpenoid, 1,4,7 - tricyclic ring broth, four 哩, 7 -吖Π, 0 哩, benzopyrene, imipen [1,2-&]pyridine, (18,48)-( + )- 2,5-diguanidine [2.2.1]g Institute, 1,5,7-triazine bicyclo[4.4.0]non-5-ene, anthracene, porphyrin, 12,3,4_tetrahydroquinoxaline, perhydropipeline and hydrazine, 5, 9-三吖环十二院; and the group derived from the heterocyclic compound is substituted by one or more groups or groups of the following groups: linear or branched alkane derived groups, naphthenic derived a group derived from an aromatic compound, a group derived from a heterocyclic compound, and the following functional groups: such as a hydroxyl group, a cyano group, an amino group 'pyrrolidinyl group, a piperidine group , It Fu oxo group and morpholinyl. Particular embodiments which are particularly preferred in the present invention include N-tertiary butoxycarbonyldi-n-octylamine, N-tertiary butoxycarbonyldi-n-decylamine, N-tertiary butoxycarbonyldi-n-decylamine , N-tertiary butoxycarbonyldicyclohexylamine, N-tertiary butoxycarbonyl-1-adamantylamine, N-tertiary butoxycarbonyl-2-adamantylamine, N-third Butoxycarbonyl-N-methyl-1-adamantylamine, (S)-(-)-l-(tertiary butoxycarbonyl)·2·pyrrole methanol, (R)-( + )- L-(tertiary butoxycarbonyl)-2-pyrrolidinemethanol, N-tertiary butoxycarbonyl-4-hydroxypiperidine, N-tertiary butoxycarbonylpyrrolidine, N-tertiary butoxy Carbonylmorpholine, N-tertiary butoxycarbonyl pipe trap, N,N-bis-tertiary butoxycarbonyl-1-adamantylamine, N,N-di-tertiary butoxycarbonyl-N- Base-b-adamantylamine, N-tertiary butoxycarbonyl-4,4'-diaminodiphenylmethane, N,N,-bis-tert-butoxycarbonylhexamethylenediamine, n,n, n,,n'-tetra-tertiary butoxycarbonylhexyl-168 - 201033733 diamine, N,N'-bis-tertiary butoxycarbonyl-1>7-diaminoheptane, n,n'- Double three-stage butoxy -1,8-diaminooctane, n,N'-bis-tertiary butoxycarbonyl-1,9-diamino fluorene, N,N'.di-tertiary butoxycarbonyldiamine hydrazine焼,N,N'-bis-two-butoxycarbonyl, hydrazine, diaminododecane, n,n,_di-tertiary butoxycarbonyl-4,4'-diaminodiphenyl Methane, n-tertiary butoxycarbonylbenzimidazole, N-tertiary butoxycarbonyl-2-methylbenzimidazole and N-tertiarybutoxycarbonyl-2-phenylbenzoquinone.

Specific embodiments of component D which are particularly preferred in the present invention are set forth below, but the invention is not limited thereto.

'169. 201033733

(D-37)

(D-3Q

ο

々N people. Fire ^. Long time (1 > 42) (D-38)

ΗΝ" Ό Ο

ό (045) e

ο ο •Λ Ν people

P-47) Again. Seven (D-46) (D-4B) 0 two w. w》0 again.兮HCTv HO (D-4S) P-50) (D-51) (D-52) The compound represented by the formula (A) can be described by, for example, "Protective Groups in Organic" (Protective Groups in Organic Synthesis) The method in '4th Edition' is readily synthesized from commercially available amines. The most general method is a method for causing a dicarbonate or a haloformate to act on a commercially available amine to obtain the compound. In the equation, X represents a halogen atom, and 1 and Rb have the same meanings as Ra and Rb in the above formula (A). -170- 201033733

Α Α Ά R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R R The low molecular compound (D), or two or more of these compounds may be mixed and used. In the present invention, the amount of the low molecular compound (D) having a group capable of leaving by acid action is usually from o.ooi to 20% by mass, and from 0.001 to 10% by mass, preferably from 0.01 to More preferably, 5 mass%, based on the total solid compound in which the composition is combined with the basic compound mentioned below. When the acid generator is used in the composition and the low molecular compound having a group capable of leaving by acid action, the ratio between the two is an acid-producing agent/[having an acid by acid The low molecular compound (D) which acts on the leaving group + the basic compound described above (in terms of moles) = preferably from 2.5 to 3 Å. That is to say, 'the molar ratio is preferably 2.5 or more in consideration of sensitivity and resolution; and from the viewpoint of suppressing the resolution, since the photoresist pattern is reduced with age thickening after exposure to heat treatment, 3 〇〇 or less preferred. The acid generator / [low molecular compound (D) having a group capable of leaving by acid action + the above-mentioned test compound] (in terms of mole) is more preferably from 5 〇 to 2 , from 7.0 It is better to 150. -171- 201033733 [7] Surfactant The sensitized ray or radiation sensitive resin composition of the present invention may further comprise a surfactant, and in the case of including a surfactant, the composition includes fluorine-containing and/or ruthenium-containing Any one or two or more of a surfactant (a fluorine-containing surfactant, a ruthenium-containing surfactant, and a surfactant containing both a fluorine atom and a ruthenium atom) is preferable. By incorporating the above-described surfactant into the sensitized ray or radiation sensitive resin composition of the present invention, when an exposure light source of 25 nm or shorter (especially 220 nm or shorter) is used, Provides a photoresist pattern with good performance for sensitivity, resolution, and adhesion and less development defects. On the other hand, when the amount of the surfactant added is small (for example, set to 10 ppm or less), the uneven distribution of the surface of the component (C) to the surface is more successfully allowed, so that the surface of the photoresist film can be Made more hydrophobic and can improve water flow during immersion exposure. Examples of the fluorine-containing and/or cerium-containing surfactant include surfactants described in JP-A-62-36663, JP -A-61-226746, JP-A-61-226745, JP-A-62- 1 709 5 0 , JP-A-63 - 3 4 5 40 , JP-A-7-23 0 1 65 , JP- A- 8-628 3 4 , JP-A-9- 5 44 3 2 , JP-A-9-5988, JP-A-2002-277862 and US Patent 5,405,720, 5,360,692 ' 5,529,88 1 ' 5,296,3 3 0 > 5,43 6,09 8 ' 5,5 76,1 43 -5,294,5 1 1 and 5,824,45 1. The following commercially available surfactants can also be used as they are. Examples of commercially available surfactants that may be used include fluorine-172-201033733 surfactants and cerium-containing surfactants, such as EFtop EF301 and EF3 03 (by New Akita Chemicals Co., Ltd.) ) (made by Shin-Akita Kasei K. Κ·); Florad FC430, 431 and 4430 (manufactured by Sumitomo 3 M Inc.); Megaface F171, F173, F176, F189, F113, F110, F177, F120 and R〇8 (manufactured by Dainippon Ink & Chemicals, Inc.); Surflon S-3 82, SC101, 102 , 103, 104, 105 and 106 (manufactured by As ah i Glass 〇 Co., Ltd.); Troysol S-366 (manufactured by Troy Chemical); GF-3 00 and GF-150 (manufactured by Toagosei Chemical Industry Co., Ltd.); Snake Fulong S-393 (Seimi Chemical Co., Ltd.) Manufacturing); EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF35, EP352, E F8 (H, EF802 and EF601 (manufactured by JEMCO Inc.); PF636, PF656, PF6320 and PF6520 (manufactured by OMNOVA); and FTX-204G, © 208G, 2 1 8G 230G, 204D, 208D, 2 1 2D, 2 1 8D and 222D (manufactured by NEOS Co., Ltd.) In addition, polyoxyalkylene polymer KP-341 (by Shin-Etsu Chemical Co., Ltd.) Ltd. (manufactured by Shin-Etsu Chemical Co., Ltd.) as the cerium-containing surfactant. As for the surfactant, in addition to these known surfactants, it may be used to have a derivative derived from a fluorine-aliphatic compound. a surfactant of a polymer of a fluorine-aliphatic group, wherein the fluorine-aliphatic compound is adjusted by a polymerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer-173) - 201033733 Method) Manufactured. The fluoro-aliphatic compound can be synthesized by the method described in JP-A-2002-90991. The fluoro-aliphatic group-containing polymer is a fluorine-containing aliphatic group monomer and (poly(oxyalkylene)) acrylate and/or (poly(oxyalkylene)) methacrylate The copolymer is preferred; and the polymer may have an irregular distribution or may be a block copolymer. Examples of the poly(oxyalkylene) group include poly(oxyethyl), poly(oxypropyl) and poly(oxybutylene). The group may also be an alkylene group having different chain lengths in the same chain, such as block-bonded poly(oxyethyl, ethyloxy, and oxyethyl) and block-linked poly( Oxygen extended ethyl and oxygen extended propyl). Furthermore, the copolymer of the fluorine-containing aliphatic group monomer and (poly(oxyalkylene)) acrylate (or methacrylate) is not limited to the binary copolymer, but may also be synchronized by Copolymerizing two or more different fluorine-fatty group monomers or two or more different (poly(oxyalkylene)) acrylates (or methacrylates) Or more or more copolymers. Examples thereof include the following commercially available surfactants: Mecafes F178 'F-470, F-473, F-475, F-476 and F-472 (manufactured by Otsuka Ink and Chemical Co., Ltd.) And further comprising a copolymer of a C6F13 group-containing acrylate (or methacrylate) and (poly(oxyalkylene)) acrylate (or methacrylate), and an acrylate having a C3F7 group ( Or a copolymer of (methacrylate) and (poly(oxyethylidene)) acrylate (or methacrylate) and (poly(oxypropyl)) acrylate (or methacrylate). In the present invention, a surfactant other than the fluorine-containing and/or barium-containing surfactant may also be used. Specific examples thereof include nonionic surfactants - 174 - 201033733 such as polyoxyethylene ethyl ethers (eg, polyoxyethylidene laurate, polyoxyethylidene ether, polyoxyalkylene) Ethyl cetyl ether, polyoxyethylene ethyl olefin ether), polyoxyethylene ethyl aryl ether (for example, polyoxyethylene ethyl octyl phenol ether, polyoxyethyl decyl phenol) Ether), polyoxyethylene ethyl/polyoxypropyl propyl block copolymer, sorbitan fatty acid esters (for example, sorbitan monolaurate, sorbitan monopalmitate, monostearyl) Acid sorbitan ester, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, and polyoxyethyl sorbitan sorbitol fatty acid ester (For example, polyoxyethylene ethyl laurate sorbitan ester, polyoxyethylene ethyl palmitate sorbitan ester, polyoxyethylene ethyl monostearate sorbitan ester, polyoxyethylene A sorbitan ester of trioleic acid, polysorbate sorbitan ester of ethyl tristearate). One of the surfactants may be used alone or in combination. The surfactant is preferably used in an amount of from 0 to 2% by mass, more preferably from 0.0001 to 2% by mass, even more preferably from 0.0005 to 1% by mass, based on the photosensitive ray-ray or radiation-sensitive resin composition. The total solids content is correct (the total amount excludes the solvent). [8] Carboxylic acid gun The sensitized ray or radiant resin composition of the present invention may comprise a carboxylic acid gun. Examples of the carboxylic acid key include cerium carboxylate, cerium carboxylate, and ammonium carboxylate. In particular, the carboxylate is preferably an iodide salt or a phosphonium salt. Further, the carboxylate residue of the carboxylate used in the present invention does not contain an aromatic group and is preferably free from a carbon-carbon double bond. The anion moiety is preferably an alkylcarboxylate anion having a linear number of carbon atoms of 1 to 30 or a branch of -175 to 201033733, a monocyclic or polycyclic ring, and the alkoxide-containing carboxylate anion partially or completely substituted by fluorine. Better. The alkyl chain can include an oxygen atom. Thanks to this architecture, penetration of 22 nm or less is ensured, sensitivity and resolution are improved, and isolated/dense deviations and exposure edges are improved. Examples of the fluorine-substituted carboxylate anion include fluoroacetate, difluoroacetate, trifluoroacetate, pentafluoropropionate, heptafluorobutyrate, nonafluoropentanoate, perfluorododecane An acid salt, a perfluorotridecanoate, a perfluorocyclohexane carboxylate, and a 2,2-bistrifluoromethylpropionate anion. These carboxylate salts can be synthesized by reacting cesium hydroxide, iodine or ammonium and a carboxylic acid with silver oxide in a suitable solvent. The carboxylate content in the composition is usually from 0.1 to 20% by mass, and preferably from 0.5 to 10% by mass, more preferably from 1 to 7% by mass, based on the total solid content of the composition. . [9] A dissolution inhibiting compound having a molecular weight of 3,000 or less and capable of decomposing by an acid action to increase solubility in an alkali developer. The photosensitive radiation or radiation sensitive resin composition of the present invention may include a molecular weight of 3,000 or less. And a dissolution inhibiting compound which can be decomposed by an acid action to increase the solubility in an alkaline developer (hereinafter, referred to as "a dissolution inhibiting compound"). The dissolution inhibiting compound is preferably an alicyclic or aliphatic compound comprising an acid-decomposable group (such as the acid-decomposable group described in the SPIE meeting record '2724, 3 55 (1 996)). Cholic acid derivatives), so as not to reduce the penetration of light of 220 nm or shorter. Examples of the acid-decomposable group and the alicyclic structure are the same as those described above for the resin of the component -176-201033733 (A). In an example of exposing the sensitized ray or radiation sensitive resin composition of the present invention by KrF excimer laser or by electron beam irradiation, the composition includes a phenolic hydroxyl group of the phenol compound substituted by an acid-decomposable group The structure is preferred. The phenol compound is preferably a compound containing from 1 to 9 phenol skeletons, more preferably from 2 to 6 phenol skeletons. The solubility-inhibiting compound used in the present invention has a molecular weight of 3,000 or less, preferably from 300 to 3,000, more preferably from 500 to 2,500. The amount of the dissolution inhibiting compound to be added is preferably from 2 to 50% by mass, more preferably from 3 to 30% by mass, even more preferably from 5 to 10% by mass, based on the composition of the sensitizing ray or the radiation-sensitive resin. The total solids content is correct. Specific examples of the dissolution inhibiting compound are set forth below, but the present invention is not limited thereto.

[10] Other Additives The sensitized ray or radiation sensitive resin composition of the present invention may further include, for example, a dye, a plasticizer, a photosensitizer, a light absorbing agent, and a compound for accelerating dissolution in a developer, if necessary. , having a phenolic compound having a molecular weight of 1,000 or less, or a carboxy-containing alicyclic or aliphatic compound -177-201033733). The phenolic compound having a molecular weight of 1,000 or less can be described by those skilled in the art, for example, in JP-A-4-122938, JP-A-2-28531, U.S. Patent 4,916,210, and European Patent No. 219,294. The method is readily synthesized. Specific examples of the carboxyl group-containing alicyclic or aliphatic compound include, but are not limited to, carboxylic acid derivatives having a steroid structure (such as cholic acid, deoxycholic acid, and lithocholic acid), Adamantanecarboxylic acid derivative, adamantane dicarboxylic acid, cyclohexanecarboxylic acid, and cyclohexanedicarboxylic acid. @ [1 1 ] Pattern forming method The present invention also relates to a photoresist film formed using the sensitized ray or radiation sensitive resin composition of the present invention. Further, the pattern forming method of the present invention comprises the steps of immersing exposure and developing the photoresist film. The photosensitive ray or radiation absorbing resin composition of the present invention is preferably used in a film thickness of 30 to 250 nm from the viewpoint of improving the resolution, and more preferably from 30 to 200 nm. This film thickness can be obtained by setting the solid content concentration in the sensitized ray or the sensitizing ray ray resin composition to an appropriate range, thereby imparting appropriate viscosity and improving coating ability and film forming property. The total solid content concentration in the photosensitive ray or radiation sensitive resin composition is usually from 1.0 to 10% by mass, preferably from 1.0 to 8.0% by mass, more preferably from 1.0 to 6.0% by mass. The sensitized ray or radiation sensitive resin composition of the present invention is used by dissolving the above components in a predetermined organic solvent (preferably in the mixed solvent described in the above-mentioned -178-337337), and filtering the solution. And coating it on a predetermined carrier as follows. The filter for filtration is preferably made of polytetrafluoroethylene, polyethylene or nylon, preferably having a pore size of 0.1 μm or less, preferably 0.05 μm or less, 0.03 μm or less and more. good. For example, when a precision integrated circuit component is used, the sensitized ray or radiation sensitive resin composition is coated on the substrate by a suitable coating method such as a centrifugal coater or a coater (for example, coating) The ruthenium/ruthenium dioxide substrate is dried and dried to form a photoresist film.照射 The photoresist film is irradiated with actinic radiation or radiation through a predetermined mask, and then preferably baked (heated), subjected to development and rinsing, whereby a good pattern is obtained. Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, and electron beam, but the radiation is preferably a far-ultraviolet light having a wavelength of 250 nm or shorter. 220 nm or shorter is better, from 1 to 200 nm and even better. Specific examples thereof include KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), ©F2 excimer laser light (157 nm), X-ray and electron beam, and ArF excimer thunder. Shooting light,? 2 excimer laser light and EUV (13 nm) are preferred. Incidentally, in the present invention, the radiation includes electromagnetic waves such as ultraviolet light and X-rays. An antireflection film may be provided in advance on the substrate by coating before forming the photoresist film. The antireflection film used may be an inorganic film type such as titanium, titanium oxide, titanium nitride, chromium oxide, carbon and amorphous germanium; or an organic thin film type composed of a light absorber and a polymer material of -179-201033733. As for the organic anti-reflective film, commercially available organic anti-reflective films such as DUV30 series and DUV-40 series manufactured by Brewer Science, Inc., and Lily Co., Ltd. (Shipley Co.,

AR-2, AR-3 and AR-5 manufactured by Ltd.). In the developing step, an alkaline developer is used as follows. The alkaline developer which can be used for the positive photoresist composition is an alkaline aqueous solution of, for example, inorganic hydrazine such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and aqueous ammonia; primary amine , such as ethylamine and n-propylamine; secondary amines, such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alcoholamines such as dimethylethanolamine and Triethanolamine; a quaternary ammonium salt such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; or a cyclic amine such as pyrrole and piperidine. Further, in addition, an alkaline developer may be used after adding an appropriate amount of an alcohol and a surfactant. The alkali concentration of the alkaline developer is usually from 0.1 to 20% by mass. The pH of the alkaline developer is usually from 10.0 to 15.0. Similarly, an aqueous alkaline solution described above may be used after adding an appropriate amount of an alcohol and a surfactant. As the washing liquid, pure water is used, and in addition, an appropriate amount of the surfactant may be added and the pure water may be used. After development or rinsing, the developer or lotion adhered to the pattern can be removed by supercritical fluid treatment. It is also possible to perform exposure (immersion exposure) by mounting a liquid having a higher refractive index than air (immersion medium) between the photoresist film and the lens of -180-201033733 when irradiated with actinic rays or radiation. By this exposure, the resolution can be improved. The immersion medium used may be any liquid as long as it has a refractive index higher than that of air, but pure water is preferred. The following describes the immersion liquid used in immersion exposure. The immersion liquid is preferably a liquid that can penetrate light at an exposure wavelength and a liquid having a refractive index temperature coefficient as small as possible to reduce optical image distortion projected on the photoresist film. In particular, when the exposure light source is an ArF quasi-divided laser (wavelength: 193 nm), 'in addition to the above-described description', it is preferable to use water in consideration of ease of availability and ease of use. Further, from the viewpoint of further increasing the refractive index, a medium having a refractive index of 1.5 or more can also be used. This medium can be an aqueous solution or an organic solvent. In the case of using water as the immersion liquid, a small ratio of the additive (liquid) may be added for the purpose of reducing the surface tension of the water and increasing the surface activity, wherein the additive does not dissolve the photoresist film on the wafer, and only A negligible effect is provided on the optical coating at the bottom surface of the lens element. The hydrazine additive is preferably an aliphatic alcohol having a refractive index almost equal to water' and specific examples thereof include methanol, ethanol and isopropanol. By adding an alcohol having a refractive index almost equal to water, even when the alcohol component in water evaporates and its content concentration changes, it is advantageous to make the refractive index change of the entire liquid very small. On the other hand, if the 193 nm light opaque substance or the impurity having a refractive index greatly different from that of water is alternately mixed, this will cause the optical image projected on the photoresist film to be deformed. Therefore, the water used is preferably distilled water. Pure water obtained by further filtering distilled water through an ion exchange filter or its -181-201033733 analog can also be used. The water resistance is preferably 18.3 MQcm or more, and the TOC (total organic carbon) is 20 ppb or less. Likewise, the water is preferably subjected to a degassing treatment. The lithographic etching performance can be improved by increasing the refractive index of the immersion liquid. From this point of view, an additive for increasing the refractive index may be added to the water, or water may be replaced with hydrophobic water (D20). In order to prevent direct contact between the photoresist film and the immersion liquid, a film slightly soluble in the immersion liquid may be provided between the immersion liquid and the photoresist film formed of the sensitized ray or radiation sensitive resin composition of the present invention (after this) , sometimes referred to as "surface overlay"). The functions required for the surface covering layer are adaptability to the coating as a photoresist coating, penetration to actinic rays or radiation (especially at 193 nm), and lack of solubility in the immersion liquid. The surface covering layer is not compatible with the photoresist and can be uniformly coated as the photoresist coating layer. Considering the penetration of light of 193 nm, the surface covering layer is preferably a polymer which does not contain a large amount of aromatics, and specific examples thereof include a hydrocarbon polymer, an acrylate polymer, a polymethacrylic acid, a poly Acrylic acid, polyvinyl ether, cerium-containing polymer and fluoropolymer. The hydrophobic resin (C) described above is also suitable as the surface covering layer. The optical lens is contaminated if impurities are dissolved from the surface covering layer into the immersion liquid. In this regard, the amount of the residual monomer component of the polymer contained in the surface covering layer is preferably small. When the surface covering layer is peeled off, a developer may be used or a release agent may be used separately. The release agent is preferably a solvent which is less permeable to the photoresist film. From the viewpoint that the peeling step of the -182 to 201033733 can be performed in synchronism with the developing step of the photoresist film, the surface covering layer can be preferably peeled off by an alkali developer, and in order to be peeled off by an alkali developer, the surface The cover layer is preferably acidic, but the surface cover layer may be neutral or basic in view of not intermixing with the photoresist film. As the refractive index between the surface covering layer and the immersion liquid is not different, the resolution is improved. In the case of using water as an immersion liquid upon exposure with an ArF excimer laser (wavelength: 193 nm), the surface covering layer for ArF immersion exposure has a refractive index close to that of an immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, the surface covering layer preferably contains a fluorine atom. Similarly, the surface covering layer is preferably a film in consideration of the transmittance and the refractive index. The surface covering layer may not be mixed with the photoresist film and further preferably not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the surface coating layer solvent is preferably a solvent which is slightly soluble in the positive photoresist composition and a water-insoluble medium. Further, when the immersion liquid is an organic solvent, the surface covering layer is soluble in water or insoluble in water. EXAMPLES The present invention is described in more detail below with reference to examples, but the contents of the present invention should not be construed as being limited thereto. Monomer Synthesis Example 1 (Synthesis of Compound (4)): The following compound (1) was synthesized by the method described in the International Publication No. WO 07/037213, the specification. In 35.00 g of the compound (1), 150.00 g of water was added and 27.93 g of NaOH was added in a step -183-201033733. The obtained mixture was stirred under heating and reflux for 9 hours, made acidic by the addition of hydrochloric acid, and then extracted with ethyl acetate. The organic layer was combined and concentrated to obtain 36.90 g of compound (2) (yield: 93%). 1H-NMR (400 MHz, in (CD3) 2CO): δ (ppm) = l. 5 6- 1.5 9 ( 1 Η) > 1 . 6 8 - 1.7 2 ( 1 Η) > 2 . 1 3 - 2.1 5 (1 Η) > 2.13-2·47(2Η), 3·49-3·51(1Η), 3.68(1Η), 4.45 -4.46( 1 Η). In 20.00 g of the compound (2), 200 ml of CHC13 was added, and further, 5.90 g of 1,1,1,3,3,3-hexafluoroisopropyl alcohol and 30.00 g of 4-dimethylamine were added. Pyridine. The obtained mixture was stirred, and 22.00 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride was added to the resulting solution. After stirring for 3 hours, the reaction solution was added to 500 ml of IN HC1 and the reaction was terminated. The organic layer was further washed with IN HCl, and then washed with water and concentrated to obtain 3 0·0 g of Compound (3) (yield: 85%). 1H-NMR (400 MHz, in (CD3)2CO): 5 (ppm) = 1.62 (1H) 1.91-1, 95 (1Η), 2.21-2.24 (1 Η), 2·45-2.53 (2Η) ), 3·61-3·63 (1Η), 3.76 (1Η), 4.32-4.58 (1Η), 6.46·6.53 (1Η). In 15.00 g of the compound (3), 300.00 g of toluene was added, and 3.70 g of methacrylic acid and 4.2 g of p-toluenesulfonic acid monohydrate were further added. The obtained mixture was refluxed for 15 hours while removing the produced water by azeotropy. The reaction solution was concentrated, and the concentrate was purified by column chromatography to obtain 1 1 · 70 g of Compound (4) (yield: 65 %). -184 - 201033733 iH-NMRWOO MHz, in (CD3)2CO): 5(ppm)=l . 76- 1.79(1 Η) , 1.93(3H) > 2.1 6 - 2.2 2 (2 Η) ' 2.57-2.61(1Η) ♦ 2.7 6-2.8 1 (1 Η) > 3.7 3 - 3.7 4 ( 1 Η) > 4.73(1Η)-4.84-4.86(1Η) * 5.6 9 - 5.7 Ο (1 Η) >6.12(1Η)> 6.5 Ο - 6.5 6 (1 Η) °

Monomer Synthesis Example 2 (Synthesis of Compound (8)): 〇In 17.09 g of methyl glycolate (5) (manufactured by TCI), '30.000 g of THF was added and 21.15 g of triethylamine was further added. . The obtained mixture was cooled to 〇 ° C, and further, 2 0.8 5 g of chlorinated methacrylic acid was added dropwise. The resulting solution was returned to room temperature, stirred for 2 hours, and extracted with ethyl acetate. The organic layer was collected and additionally MgS04 was added. This mixture was filtered and concentrated to give 28.51 g of Compound (6) (yield: 95%). !Η-ΝΜΚ (400 MHz, in (CD3)2CO): 〇6 (ppm) = l .94-2.04(3H) , 3.7 1 - 3.7 2 (3 Η) , 4.73 (2 Η), 5.72 (1 Η) , 6.1 5 (1Η). In 28.5 g of the compound (6), 180 ml of acetone was added. The resulting mixture was cooled to 〇 ° C and added dropwise to a solution of 1 80 mL of IN NaOH. After stirring for 30 minutes, the solution was made acidic by the addition of hydrochloric acid, and then extracted with ethyl acetate. The organic layer was collected and additionally Mg S04 was added. This mixture was concentrated and concentrated to obtain 21.2 g of the compound (7) (yield: 8 2%). -185-201033733 1H-NMR (400 MHz, in (CD3)2CO): 5 (ppm) = l .94- 1.97(3H) » 4.7 1 - 4.7 2 ( 2 H) > 5.7 0 - 5.7 1 (1 H) > 6·15(1 H). In 15.00 g of the compound (7), 300 g of toluene was added, and 7.00 g of the compound (3) and 3.80 g of p-toluenesulfonic acid monohydrate were further added. The obtained mixture was refluxed for 6 hours while removing water produced by azeotropy. The reaction solution was concentrated, and the concentrate was purified by column chromatography to afford 13.52 g of Compound (8) (yield: 71%). 1H-NMR (400 MHz, in (CD3)2CO) ·· 3 (ppm)=l.77- 1.7 8 ( 1 H), 1.9 5 - 1.96 (3Η), 2·11-2·20 (2Η) , 2.56-2.61(1Η) , 2 _ 7 3 - 2.7 4 ( 1 Η) , 3.7 3 - 3.7 5 ( 1 Η), 4·77-4.82 (4 Η), 5·74 (1 Η), 6.16 (1 Η) , 6.52 - 6.5 3 ( 1 Η).

Monomer Synthesis Example 3 (Synthesis of Compound (9)): Compound (9) was synthesized in the same manner as in Monomer Synthesis Example 1, except that 2, 2, 3, 3, 4, 4, 4 were used. - Heptafluoro-1-butanol was substituted for 1,1,1,3,3,3-hexafluoroisopropyl alcohol (yield in three steps: 30%). 1 H-NMR (400 MHz ' in (CD3) 2CO): -186 - 201033733 5 (ppm) = 1.73 - 1.76 (1 H) , 1.93 (3H) > 2.1 3 - 2.1 7 ( 1 H) ' 2.57-2.61(lH) , 2 · 7 1 - 2 · 7 2 (1 H ) , 2.7 7 - 2.8 1 (1 H) ' 3·65-3·67(1Η), 4.69(1H)' 4.79-4·80 (1Η), 4.9 5.00 (2H), 5.68-5.69 (1Η), 6.1 1 - 6 · 1 2 (1 H ).

O Monomer Synthesis Example 4 (Synthesis of Compound (10)): Compound (10) was synthesized in the same manner as in Monomer Synthesis Example 1, except that hydrazine, decyl-trifluoro-p-heptanol was used. ^1,1,3,3,3-hexafluoroisopropyl alcohol (yield in three steps: 42%). 1H-NMR (400 MHz, in (CD3)2C〇) 5 (ppm) = l .73-1 ·88 (1Η) , 1.93 (3Η) , 2 · 〇8 · 2 · 1 7 ( 1 Η) ' 2.56-2.61(1Η) , 2.71 -2.72(1Η) , 2.7 7 - 2.8 1 (1 Η) ' 3·66-3·68(1Η), 4.69(1Η)' 4.79-4.81(1Η),4.93-5.01 (2Η), ❹ 5·68-5·69 (1Η), 6.1 1-6.12 (1Η).

Monomer Synthesis Example 5 (Synthesis of Compound (11)): Compound (11) was synthesized in the same manner as in Monomer Synthesis Example 1, except that 2,3,5,6-tetrafluoro-4- was used. (Trifluoromethyl)phenol substituted -187-201033733 1,1,1,3,3,3-hexafluoroisopropyl alcohol (yield in three steps: 23%). 1 H-NMR (4 〇〇 MHz ' in (CD3) 2CO): 5 (ppm) = 1.88-1.9 l (lH) ' 1.94 (3H) , 2.1 0 - 2.2 8 (2 Η) ' 2.66-2.71 ( 1Η) * 2.80(1Η) > 3.9 2 - 3.9 3 ( 1 Η) - 4.77(1H) > 4.90-4.92(lH), 5.70-5·71(1Η) ' 6.13-6·14(1Η).

Synthesis Example 1: Synthesis of Resin (C-8) Under a nitrogen atmosphere, 6.4 g of propylene glycol monomethyl ether acetate (PGMEA) was charged into a three-necked flask and heated to 80 °C. Here, within 4 hours, a polymerization initiation by adding 17.5 g of the compound (1), 4.0 g of the compound (2), and a ratio of 5.0 mol% (based on the monomer) was added dropwise. Agent V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in a solution prepared in 58.0 g of PGM EA. After completion of the dropwise addition, the reaction was further carried out at 80 ° C for 4 hours. The resulting reaction solution was left to stand until it was cooled, and then added dropwise to a mixed solution of 1,300 g of methanol/150 g of distilled water in 20 minutes, and the precipitated powder was collected by filtration and dried. As a result, 15.2 g of a polymer (C-8) was obtained. The obtained polymer (C-8) had a weight average molecular weight of 8,0 〇 (in terms of standard polystyrene) and a polydispersity (Mw/Mn) of 1.3. -188- 201033733

The other resin (c) shown in the above table was synthesized in the same manner. Synthesis Example 2: Synthesis of Resin (1) Q In a nitrogen atmosphere, 8.6 g of cyclohexanone was charged into a three-necked flask and heated to 80 °C. Here, within 6 hours, 9.8 g of 2-adamantyl-isopropyl methacrylate, 4.4 g of methacrylic acid di-m-cyclohexane, and 8.9 g of norbornane were added dropwise. Ester methacrylate and a ratio of 8 mol % (based on the monomer) of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries Co., Ltd.) dissolved in 79 g of cyclohexanone . After completion of the dropwise addition, the reaction was further carried out at 80 ° C for 2 hours. The resulting reaction solution was left to stand until it was cooled, and then it was dropwise added to 800 ml of a mixed solution of hexane/200 ml of ethyl acetate in 20 minutes Q and the precipitated powder was collected by filtration. And dried, as a result, 19 g of a resin (1) was obtained. The obtained resin had a weight average molecular weight of 8,800 (in terms of standard polystyrene) and a polydispersity (Mwmn) of 1.9. The other resin (A) shown below was synthesized in the same manner. The structure of the acid-decomposable resin (A) used in the examples is shown below. Similarly, the molar ratio, weight average molecular weight (Mw), and polydispersity (Mw/Mn) of the repeating unit (from the left side in the structural formula) in each resin are shown in the following table. -189 - 201033733

-190- (11)201033733

(13)

(14)

-191- 201033733

Table 2 Resin (A) Composition Mw Mw/Mn (1) 50/10/40 8800 1.9 (2) 40/20/40 7000 1.6 (3) 40/10/35/5/10 10000 1.7 (4) 40 /10/40/10 11000 1.8 (5) 40/15/20/25 8500 1.6 (6) 10/40/25/25 12000 1.8 (7) 50/20/30 6500 1.6 (B) 40/10/50 8000 1.7 (9 25/25/50 9000 1.8 (10) 50/10/40 11000 1.8 (Π) 50/10/40 8000 1.7 Resin (A) Composition Mw Mw/Mn (12) 40/10/40/10 7000 1.7 (13) 20/15/35/30 10000 i·7 If (14) 45/10/35/10 8500 1.7 (15) 50/40/10 10000 1.6 (16) 10/40/40/10 9000 1.8 ( 17) 55/10/35 12000 1.8 (18) 40/15/20/25 9000 1.7 (19) 15/30/10/28/17 10000 1.7 (20) 40/10/32.5/17.5 9200 1.8 (21) 40/10/30/20 8500 1.7 -192- 201033733 <Preparation of photoresist> The components shown in the following list are dissolved in a solvent to prepare a solution having a solid content concentration of 5% by mass, and The obtained solution was filtered through a polyethylene filter having a pore size of 0.1 μm to prepare a positive photoresist composition. The prepared positive photoresist composition was evaluated by the following method, and the results are shown in the table. In the table, the resin in "resin (2g)" means resin (A). <Image Performance Test> © [Exposure Condition: ArF Immersion Exposure] An organic anti-reflection film (ARC29A, manufactured by Nissan Chemical Industries, Ltd.) was coated on a 12-inch diameter silicon wafer. And baking at 205 ° C for 60 seconds to form a 98 nm thick anti-reflective film, and coating the positive photoresist composition prepared above and baking at 120 ° C for 60 seconds to form 120 Nai A thick photoresist film. Exposure was performed by using a 6% halftone mask with a line width of 75 nm and a spacing pattern of 5% by using an ArF excimer laser immersion scanner Q (XT1250i, manufactured by ASML, NA: 0.85) Obtained wafers As for the immersion liquid, ultrapure water is used. Thereafter, the wafer was heated at 120 ° C for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (2.38 mass%) for 30 seconds, rinsed with pure water and spin dried to obtain a photoresist pattern. [Line Edge Roughness (LER)] Regarding the 5 μm edge range in the longitudinal direction of the 1:1 line and the spacer pattern having a line width of 75 nm, by a Critical Dimension SEM (S-8840, Hitachi Ltd. (193-201033733) "Measures the distance from the reference line that should appear from the edge at 50 o'clock, and calculates 3 σ after determining the standard deviation. When the 値 (nano) is less than 5.0, the grade A of the sample; when it is at least 7.0 from 5.0, the grade Β; and when it is 7.0 or more, the grade C. A small size indicates a higher performance. [Scum] A scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.) was used to observe development residue (scum) in a resist pattern having a line width of 75 nm, and when no scum was generated at all The grade A of the sample; grade D when the scum is strongly produced; and grade B or C when the scum level is between. [Evaluation of development defect] Using the defect inspection device (KL A 2360 (trade name)' manufactured by KLA Tianke Co., Ltd. (1〇^!^11〇〇1*1^(1.)] The pixel size of the inspection device is set to 0.16 μm and the threshold is set to 20, and the measurement is performed in a random mode to detect development defects extracted from the difference when the superimposed pixel unit and the reference image are generated. (1 square centimeter) of the number of development defects. When the 値 is less than 〇5, 'the grade A of the sample; when it is from 0.5 at least 0.7, grade B; when from 〇7 to at least 1.0, grade C; And when 1 · 〇 or greater, the lower level D ° 指示 indicates higher performance. [Bubble Defect] Coated organic anti-reflective film (ARC29A) on a 12-inch diameter 矽 wafer, by Nissan Chemical Industry Co., Ltd. Manufactured] and baked at 2 〇 5 ° C for 60 seconds to form a 78 nm thick anti-reflective film 'and coated with a positive photoresist composition prepared above - 194-201033733, and on a hot plate Heating and drying at 120 ° C for 60 seconds to form a 100 nm thick photoresist film. Line width 75 nm 1: 6% halftone mask with 1 line and spacer pattern, obtained using an ArF excimer laser immersion scanner (XT 1 2 5 0i, manufactured by ASML, NA: 0.85) For the immersion liquid, ultrapure water is used. Thereafter, the wafer is heated on a hot plate at Π ° C for 60 seconds ' at a step of 2 3 ° C to have a concentration of 2.3 8 mass % The tetramethylammonium hydroxide aqueous solution was developed for 60 seconds, rinsed with pure water for 40 seconds, and then dried to obtain a photoresist pattern. The sample obtained by measuring KLA2 3 60 (manufactured by KLA Sky Co., Ltd.) was used. Number of development defects of the wafer. The critical dimension SEMS9380 manufactured by Hitachi, Ltd. was used to observe the detected defective portion of the defect, and the number of bubble defects was measured. When the number of bubble defects was 〇/cm 2 'the grade A of the sample Level B when more than 〇 to 0.01/cm 2 or less; level C when more than 〇0.01 to 0.1/cm 2 ; and level D when more than 0.1/cm 2 . Shape] Observed use is formed in the same way as in bubble defect assessment a separation pattern of 85 nm, and a grade A of the sample when the shape of the pattern is rectangular; a grade B when almost rectangular; a grade C when slightly tapered; and a grade D when a film is missing <Test of other properties> -195-201033733 [Amount of acid produced by dissolution] The prepared positive photoresist composition was coated on a 8 inch diameter tantalum wafer and baked at 120 °C. 60 seconds to form a 160 nm thick photoresist film. Subsequently, the entire surface of the 8-inch wafer was exposed at 30 mJ/cm 2 using an ArF excimer laser exposure machine (PAS 5500/1 1 〇0, manufactured by ASML). The wafer was immersed in addition to the pure deionization of 100 ml of ultrapure water generating device (Milli-Q, manufactured by Nihon Millipore K.K.). In the quartz container of water, and collecting the substances that have been dissolved into the water. The amount of this acid solution into the aqueous solution was quantitatively measured by LC-MS. LC device: 2695 MS device manufactured by Waters: esquire 3000, manufactured by Brucker Daltonics to measure ionic species with mass 299 by LC-MS device ( The detection intensity corresponding to the nonafluorobutanesulfonate anion), and the amount of segregation of nonafluorobutanesulfonic acid. The same method was also used to calculate the amount of elution of other anions. When the amount of dissolution is 1.0 χιό-1 Q mol/cm 2 /s or more, the grade c of the sample; when from ι·〇χΐ (τ12 mol/cm 2 / sec at least ι.〇χΐο· 1 ϋ mol / cm ^ 2 / sec, grade β; and when less than ι · 〇χ w12 mol / cm ^ 2 / sec, grade Α. [Reverse contact angle] The prepared positive photoresist composition is coated in diameter 8 inches on the chopped wafer and at 1 2 0. (: Bake for 60 seconds to form a 160 mm thick photoresist film. 23 ± 3 X at room temperature: and 45 ± 5 % humidity Next, a dynamic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) was used to measure the receding contact angle of water droplets by an expansion-contraction method at a rate of 6 μm. Liters per second inhalation of droplets having a starting droplet size of 35 microliters for 5 seconds' and using the enthalpy when the dynamic contact angle is stable during inhalation as the receding contact angle. When the number of receding contact angles is large At this time, water can follow the scan at a higher speed. [Particles (Aging Stability)] With respect to the positive photoresist composition prepared above, A particle counter manufactured by RION Co., Ltd. to count the number of particles in the solution immediately after preparation (particle starting enthalpy) and to stand in the solution at 4 ° C The number of particles after 1 week (the number of particles after aging), and the increase in the number of particles calculated by (number of particles after aging) - (particle starting enthalpy) is measured. Here, the count is contained in 1 ml of solution. a particle having a particle diameter of 0.25 μm or more. When the number of particles is increased to 0.2 particles/ml or less, the grade A of the sample; when from more than 0.2 particles/ml to 1/ml, grade B; Grade C when more than 1 granule/ml to 5 granules/ml from 〇; and grade D when more than 5 granules/ml. -197- Evaluation result bubble defect <<<<<<<< c <<<c<<<<<<<<<<<<<<<<<<<<<<<<<<<><<<<<<<<<<<<<<<<<<<<<<<<<<<<> One C0 0Q CQ 0Q PQ 03 CQ 0Q m CQ ca CQ CQ ca m QQ CQ CQ ca QQ CQ 0Q CQ <<<<< Back contact angle (degrees) Ο R vn in 〇vn SS VO R vn vn Ϊ0 o VQ SS VQ 1^1 溶S acid soluble Dong <<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<><<<>><<>< PQ < CO < QQ 0Q CQ <<< scum <<<<<<<<<<<<<<<<<<<<;<<<<<<<<<<<<<<<<<<<<<<<<<<< c <<<<<<<<<<<<<<<<<<<<<<<<<<> -K3) W-K3) W-3(3) W-6(3) W-5(4) Wl(4) W-6(4) i W-3(3)丨W-4(2) W-4(2) W -4(2) W-4(2) 1 W-4 (2) \ W-6(3) W-6(2) W-6(2) W-6(2) W-6(2) W-6(2) W*6(2) W-4 (2) Wl/W-4(l/l) W-4 W-5(2) W-2(3) W-4(2) W-4(2) W-4(2) Resin (〇/(〇>)(mg) C-7(80) C-8(80) C- 72(80) Cl(40) C-6(80) C-9(80) C-50(40) | 0-56(80) CM 2(50) C-14(80) 072(80) C- 7(160) C-7(80) C-7{240) C-19K80) i C-6(80) C-9(80) 0212(80) 1 C-209/CP-75(80/8) C-237(80) C-232(80) C-7/CP-75(75/5) C-8(80) C-7(80) C-2(XX80) Cl 55(80) 0155(80 ) C-172(80) G155/CP-23(40/40) Curved compound flooded) N-5/N-K7/7) Ν-5(7) N-3(6) N-6(10) N' 3(6) N-6(10) Nl(7) ! N-4(I3) | N-2(9) N-5/N-1W) N-5/N-K7/7) N-5/N-K7 /7) N-5/N-ia/7) N-5/N-K7/7) N-7(7) N-3(10) N-3(10) _0) 1 N-3/N-8C7/7 ) 1 N-3/N-8(7/7) N-3/N-8W) N-5/N-K7/7) N-5(7) N-5/N-H7A7) Nl(IO) N-3(6) N-5/N-U7") N-5/N-K7/7) N-5/N-K7/7) Solvent (ratio, by mass) SL-2/SL-4 60/ 40 SL-4/SL-2 40/60 SL-4/SL-2 40/60 SL-^M/SL-G 40/59/1 SL-2/SL-4 70/30 SL-3/SL- 4 30^70 SL-^L^/SL-S 40/58/2 SL-I/SL-2 60/40 SL-2^L-4/SL-6 40/59/1 丨SL-2/SL -4 60/40 丨SL-2/SL-4 60/40 SL-2/SL-4 60/40 SL-2/SL-4 60/40 SL-2/SL-4 60/40 1 SL-4ySL -2 40/60 | SL-2/SL-4 70/30 ! SL-2/SL-4 60 /40 SL-2/SL-4 60/40 SL-2/SL-4 60/40 SL-2/SL-4 60/40 SL-2/SL-4 60/40 SL-2/SL-4 60 /40 SL-4/SL-2 40/60 SL-2/SL-4 60/40 SL-2/SL-4 60/40 SL-l/SL-2 60/40 SL-2/SL-4 60 /40 SL-2/SL-4 60/40 SL-2/SL-4 60/40 Photoacid generator (gram) z38(100) ζ55(90) Y-7(100) z55(100) z2( 100) Y-3(100) 280(100) z66(100) I 767(100) ] Z66/Y-65(60/40) z66(100) z66(100) z66(100) z66(100) z46( 90) Yl(lOO) PAG24(100) z55(100) i- 1 z80/z66(50/50) 1 PAG 丨6(100) z80/266(5Q/50) z38(100) z55(90) Z38( 100) Yl(lOO) zl(lOO) z66(100) z66(100) z66(100) Resin (2g) —1 Buddy 0 2 2 12 QO — \r\ V*» wl OO OO inch 1-1 VI 1/5(1/1) tj- vn vn Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 1 Embodiment 9 i 1 Embodiment 1 Embodiment li Implementation Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 I embodiment 29 1 201033733 -im ° e 瓤璀)m* i 1

QL - 08 - - -

9L s

9L

9L

LL reward malaria i i 倒 rib (梂 iBft ® WKi (wii (4i w*3* # 丑) ift Li

(employment basin I δτΛν

(S-AV

S^M (inch)'"

S'M

(S'M (§6-0 (0S)S0 §S'<D/6I10 is §)3 §)3 S8)3

<s-RL.dolL.U §)8ό (0露ό(08)6_u

(m--N ω'Ν

§'N/S

(Os-N

SI) 9-N

(os_N

(os_N

(C5-N/'N

S'N

(OI)'N (2)6.2 i9 3s/3,ls

Ol'ls/KIS 0i3s/3s 0se3s/2s osm3s/2s 0se3s/2s ie'm-ls oi'm-ls 09/0 inch 3 piano Js i9'ns (001)3⁄4 (06)3⁄4 (813⁄4 (§) 'Λ

(i'A

(i'A (ΟΟΙ)'λ §ι)8Ώ (06ΚΏ (§)Ι.Λ S3§ 61 8 - inch i - i lei -丽*

- capsule K i for -ii 9cfi

s shock K -i 6£i owi *«)£* Evaluation result Bubble defect QQ 〇Q Ο u Q uou Pattern shape QQ 〇QQ u Q uuu Particle QQUQQ u Q oou Back contact angle crossing) S VQ S JO vn vn o Acid elution amount UU CQ U 03 < CQ PQ << development defect 〇UUQU o UU CQ m scum i _I QQQQQ OQ QD QQ m LER 〇03 CJ CJ 〇< U 〇<< Synthetic surfactant (mg) W-4(2) i W-4(2) W-4(2) W-4(2) W-2(3) W-2(3) W-4(3) W-4(3) W- 6(2) W-6(2) Resin (〇/(CP)(mg) * H-K80) Η-2(80) H-3(80) H-2(80) H-4(80) H-5( 80) !Polymer 2 (80) Poly 4 (80) Inert Compound (mg): 1 ________J N-5/N-K7 (7) N-5/N-K7") Ν-5/Ν-Κ7/7 N-5/N-K7") N-3(6) N-3(6) N-5/N-K7/7) N-5/Nl(7") N-8(10) N-3/N-8(7 /7) Solvent (ratio 'by mass) SL-2/SL-4 60/40 SL-2/SL-4 60/40 SL-2/SL-4 60/40 SL-2/SL-4 60/ 40 SL-l/SL-2 60/40 SL-l/SL-2 60/40 SL-2/SL-4 60/40 SL-2/SL-4 60/40 SL-2/SL-4 60/ 40 i- SL-2/SL-4 60/40 Photoacid generator (mg) z66(100) z80(100) ζ66(100) z66(100) Z80(110) z80(110) z66(110) 1 266(110) 1 z55(100) PAG16(100) Resin (2. g) vn w-» S Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparison Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 661 201033733 The meanings in the table are as follows. The acid generator and the resin (C) correspond to those exemplified above as the examples.

39 tt59

61 (Polymer 4) Mw=7600 Mw/Mn^l.e OH C¥tf^C (Polymer 2) MW*7600 MwAiiFl0 0 persons.

OH CCM) Mw«6000 -200- 201033733

[Basic compound] Nl : N,N-dibutylaniline N-2 : N,N-dihexylaniline N-3 : 2,6-diisopropylaniline © N-4 : Tri-n-octylamine N- 5 : N,N-dihydroxyethylaniline N-6 : 2,4,5-triphenylimidazole N-7 : 2-[2-{2-(2,2-dimethoxy-phenoxy) Ethoxy)ethyl}-bis-(2-methoxyethyl)]-amine N-8 : 2,4,6-tris-tert-butylaniline N-9 : N-tertiary pentyloxycarbonyl -4-hydroxypiperidine [surfactant] 〇W-1 : Mecan Fiss F176 (manufactured by Dainippon Ink and Chemical Co., Ltd., Fluoride) W-2: Mecca Fiss R08 (manufactured by Dainippon Ink and Chemical Co., Ltd.) 'Fluorine and lanthanum>> W-3: Polyoxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd., containing yttrium) W-4: Wrong Iso S-366 (manufactured by Misaki Chemical) W-5 : PF65 6 (manufactured by Onova, fluorine) -201 - 201033733 W-6: PF6320 (manufactured by Onova, fluorine) [Solvent] SL-1: cyclohexanone SL-2: propylene glycol monomethyl acetate Ethyl ether ester (PGMEA) SL-3: ethyl lactate SL-4: propylene glycol monomethyl ether (PGME) SL-5 : r • butyrolactone, SL-6: propylene carbonate, as seen in Table 3, Line edge roughness, scum, development lack , Analysis of the amount of acid solution, immersed in the exposure of flowability, particle shape and pattern of the whole liquid immersion bubble defects terms' resist pattern using the positive resist composition of the invention is formed has excellent performance. Industrial Applicability According to the present invention, it is possible to provide a sensitized ray or a radiation-sensitive resin composition capable of forming improved line edge roughness and scum generation, reducing development defects, ensuring that only slightly acid is dissolved into the immersion liquid, and immersing The liquid has good fluidity, and various patterns of properties in terms of particle suppression, pattern shape, and bubble defect prevention; and a pattern forming method using the same. This application is filed on December 12, 2008, filed on December 2, 2008, filed on JP 200 8 -3 1 77 5 4, March 6, 2009, JP 2009-054291, April 3, 2009. JP 2009-091616, JP 2009-131275, filed May 29, 2009, and JP 2009-251478, filed on Jan. 29, 2009, the entire disclosure of which is hereby incorporated by reference in its entirety. -202- 201033733 [Simple description of the diagram] None. [Main component symbol description] None.

-203-

Claims (1)

201033733 VII. Patent application scope: 1 · A photosensitive ray or radiation sensitive resin composition comprising: (A) a resin capable of increasing the solubility of the resin (A) in an alkaline developer by an acid action; and (C) a resin having at least one of a fluorine atom or a ruthenium atom and comprising one having at least two or more represented by -COO- in a structure represented by formula (KA-1) or (KB-1) Repeating unit (C) of polarity converting group: Its ZZ represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, a guanamine group, an aryl group, a lactone ring group or an electron withdrawing group, and when a plurality of Zka are present, the plurality of Zka may The same or different; each Zka may be combined with each other zka to form a ring; nka represents an integer of 0 to 10; each of 〇xkbl and xkb2 independently represents an electron withdrawing group; nkb and nkb' each independently represent 0 or 1; and Rkti to Rkb4 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an electron withdrawing group; and at least two members of Rk»2 and Xkbl may be bonded to each other to form a ring; And at least two members of Rkb3, Rkb4 and Xkb2 may be combined with each other to form a ring. 2. The sensitized ray or radiation sensitive resin composition of claim 1, wherein the repeating unit (C) has at least two or more polar switching groups on one side of the chain and A repeating unit (C') of at least one of a fluorine atom or a helium atom. 3. The photosensitive ray or radiation sensitive resin composition of claim 1, wherein the repeating unit (c) is a weight having at least two or more polar converting groups and having no fluorine atom or germanium atom The covering unit (c*); and the resin (C) further include a repeating unit having at least one of a fluorine atom or a ruthenium atom. 4. The sensitized ray or radiation sensitive resin composition of claim 1, wherein the repeating unit (C" is a repeating unit (C") having at least two or more polarities on one side chain a conversion group having at least one of a fluorine atom or a ruthenium atom in a side chain different from the side chain in the same repeating unit. 5. A sensitizing ray or a radiation sensitive resin as claimed in claim 1 a composition, wherein the repeating unit (c) has a structure represented by the following formula (KY-1): Wherein each of Rkyl and Rky4 independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether-205-201033733 group united to a Rky 1 group; Such as the crusting of the product * primogen monocyclic, hydroxy, cyano, aryl or aryl; Rkyl and Rky4 can be bonded to the same atom to form a double bond; Rky2 and Rky3 each independently represent An electron withdrawing group; or a combination of Rky2 to form a lactone ring, and at least two members of Rky3 being an electron withdrawing group Rkyl, Rky2, and Rky4 may be bonded to each other to form a monocyclic or polycyclic structure; and Rkbi to Rkb4, nkb, and Nkb' has the same meaning as in the formula (KB-1). The photosensitive ray or radiation sensitive resin group of the first aspect of the patent range 9 wherein the repeating unit (C) has a structure represented by the following formula (KY-2). Wherein each of Rky6 to Rky 10 independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, a guanamine group or an aryl group; Two or more members to RkylO may be bonded to each other to form a polycyclic structure; Rky5 represents an electron withdrawing group; and Rkbi, Rkb2 and nkb have the same meanings as in the formula (KB-1). -206-201033733. The photosensitive ray or radiation sensitive resin composition of claim 1, wherein the resin (C) has at least one of the formulae (F2) to (F4) and (CS-1) a group represented by any of (CS-3): Ree (F2) (F3) (F4) - a Κβ7 ～OH ❹ wherein each of R57 to R6 8 independently represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group or an aryl group, and the restriction condition is at least r57 to r61 At least one of R62 to R64 and at least one of R65 to r68 each independently represent a fluorine atom or a hospital group containing at least one hydrogen atom replaced by a fluorine atom, and R.62 and R63 may be bonded to each other to form a ring: O Ls R12—Sl-R14 Rl$ (CS-1) wherein each of Riz to R26 independently represents a linear or branched alkyl or cycloalkyl group; and each of L:} to L5 represents a single bond or a divalent linking group; ; and η represent integers 1 to 5. -207- 201033733 8 - Photosensitive ray or radiation sensitive resin composition as claimed in claim 7 wherein the resin (C) includes at least one of the formulae (F2) to (F4) and (CS-1) An acrylate or methacrylate repeating unit of the group represented by any of (CS-3). 9. The photosensitive ray or radiation sensitive resin composition according to claim 1, wherein the resin (C) is contained in an amount of from 0.1 to 1% by mass in the composition of the sensitized ray or the radiation sensitive resin. The total solids content in the product is correct. 1 . The photosensitive ray or radiation sensitive resin composition of claim 1, further comprising: (B) a compound capable of generating an acid after irradiation with actinic rays or radiation. The photosensitive ray or radiation sensitive resin composition of claim 1, wherein the resin (A) comprises a repeating unit having a lactone structure. 1. The photosensitive ray or radiation sensitive resin composition of claim 1, wherein the resin (A) has a monocyclic or polycyclic acid-decomposable group. A photoresist film formed from a photosensitive ray or a radiation sensitive resin composition as in the first aspect of the patent application. A pattern forming method comprising: immersing exposure and developing a photoresist film as in claim 13 of the patent application. -208- 201033733 IV. Designation of Representative Representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: