TW201033732A - Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the composition - Google Patents

Abstract

Provided is an actinic ray-sensitive or radiation-sensitive resin composition including: (A) a resin capable of increasing the solubility in an alkali developer by the action of an acid, (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation, and (C) a resin which contains (c) a repeating unit having at least one polarity conversion group and has at least either a fluorine atom or a silicon atom.

Description

201033732 VI. Description of the Invention: [Technical Field] The present invention relates to a sensitized ray or radiation sensitive resin composition, that is, a method of use in a semiconductor (such as 1C), or a liquid crystal A photosensitive ray or radiation sensitive resin composition in the manufacture of a circuit board, a thermal sensing head, and the like or other photolithographic etching method; and a pattern forming method using the composition. More specifically, the present invention relates to a 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; a resin in the photoresist composition; and a pattern forming method using the positive photoresist composition used in the synthesis of the resin. [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 so-called immersion method of the refractive index liquid (hereafter Q is referred to as "immersion liquid") in an attempt to improve the resolution by shortening the wavelength. This immersion method is effective for all pattern shapes, and in addition, it can be combined with super-analytical techniques such as phase shifting methods and modified lighting methods under current research. Because of the appearance of photoresist for KrF excimer lasers (24 8 nm), an image forming method called chemical amplification has been used as an image forming method for photoresist to compensate for the decrease in sensitivity due to light absorption. For example, the image forming method by positive chemical amplification is an acid generated by decomposition of an acid generator in an exposed region after exposure, and the resulting acid is used as a 201033732 reaction catalyst for baking after exposure ( In PEB: post-exposure baking, an alkali-insoluble group is converted into an alkali-soluble group, and an image forming method of removing an exposed region by alkaline development is performed. The ArF excimer laser (193 nm) using this chemical amplification mechanism currently has the majority of photoresist, but when the photoresist is exposed by immersion, it involves causing the formed line pattern to collapse while the component is being fabricated. The pattern causing the defect is collapsed, or the performance of the line edge roughness of the roughened pattern sidewall is not satisfied.

Similarly, it has been pointed out that when the chemically amplified photoresist is applied to an immersion exposure, the photoresist layer is exposed to 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 Flowing out of the photoresist layer. In order to solve this problem, in JP-A-2006-309245 (as used herein, the name "JP-A" means "unexamined announcement of Japanese patent application"", JP-A-2007 An example of preventing the outflow by adding a resin containing a halogen atom or a fluorine atom has been described in JP-A-2007 - 1 8248 8 and JP-A-2007-153982.

In addition, as for a photoresist material which has a slight change in shape during dry exposure and immersion exposure and which is excellent in process feasibility, JP-A-2008-111103 discloses a photoresist to which a specific polymer compound has been added, wherein This compound has a fluorine atom and a lactone structure. Further, in the immersion exposure method, when exposure is performed using a scanning type immersion exposure machine 'unless the immersion liquid moves as the lens moves, the exposure speed is lowered and this may affect productivity. In the case where the immersion liquid is water, the photoresist film is preferably hydrophobic because of good water flow. -4- 201033732 Furthermore, even when immersion exposure is performed using the technique described above, it is required to further reduce development defects or scum generation called BLOB defects. 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 acid dissolution, line edge roughness, development defects, and scum generation, and ensuring immersion exposure. A photoresist pattern having a good fluidity of the immersion liquid; and a pattern forming method using the sensitized ray or the radiation-sensitive resin composition. The present inventors have achieved the present invention because of the intensive study of the objectives described above. <1> A photosensitive ray or radiation sensitive resin composition comprising: (A) a resin capable of increasing solubility in an alkali developer by an acid action; (B) capable of actinic ray or radiation a compound which generates an acid upon irradiation; and (C) a resin comprising a repeating unit (c) having at least one polarity converting group and having at least one of a fluorine atom or a germanium atom. Q <2> The sensitized ray or radiation sensitive resin composition as described in the above <1>, wherein the repeating unit (c) has at least one of a fluorine atom or a ruthenium atom. <3> The sensitized ray or radiation sensitive resin composition as described in the above <1> or <2>, wherein the repeating unit (c) has the following formula (KA-1) and (KB) -1) at least one of the partial structures represented, and the polar conversion group is represented by X in a partial structure represented by the formula (KA-1) or (KB-1): 201033732

YVX-Ύ2 (kb-D wherein X represents any one of residual acid vinegar, acid anhydride, quinone imine, carboxylic acid thioester, carbonate, sulfate, and sulfonate; and γ1 and Y2 may be the same or different, It is a photosensitive ray or a radiation-sensitive resin composition as described in any one of the above items <1> to <3>, wherein the repeating unit ( c) includes at least one of the partial structures represented by the following formulas (KAdd) to (KA-1-17): ά ό R aa @ KAr1-1 ICA.1.9 KA-1-3^ KA-1-4^) ΚΑ-Ι-δ^

&lt;5&gt; The sensitized ray or radiation sensitive resin composition as described in any one of the above &lt;1&gt; to &lt;4&gt; wherein the repeating unit (Ο has at least one of the following formulas (F2) ) to (F4) and groups represented by formula (CS-1) to (CS-3): 201033732

among them

Each of R57 to r68 independently represents a hydrogen atom, a fluorine atom or a hospital group, and is limited to at least one of R57 to Rei, at least one of R62 to r64, and at least one of R65 to R68 is a fluorine atom or a fluorine-based group. And R62 and R63 can be combined with each other to form a ring; I Rt2 - Ri$ (CS-1)

Rie-S 〇^®-R« Rit[ Hie (CS-2)

Wherein each of r12 to r26 independently represents an alkyl group or a cycloalkyl group; each of Q 1^3 to 1^5 represents a single bond or a divalent linking group; and η represents an integer of 1 to 5. &lt;6&gt; The sensitized ray or radiation sensitive resin composition as described in any one of the above-mentioned <1> to <5>, wherein the resin (Α) includes one represented by the following formula (3) Repeating unit: Ruler 7

(8)

A

201033732 wherein A represents an ester bond (-COO-) or a guanamine bond (-CONH-); R 〇 represents an alkylene group, a cycloalkyl group or a combination thereof; and when a plurality of R 存在 are present, 'each Rg is Same or different from each other Rg; z represents an ether bond, an ester bond, a carbonyl bond, a guanamine bond, a urethane bond, or a urea bond; and when there are a plurality of 2, each Z may be Other z are the same or different;

Rs represents a monovalent organic group having a lactone structure; n〇 is the number of repeats of the structure represented by -Ro-Z- in the repeating unit represented by the formula (3) and represents an integer of 1 to 5; R7 represents a hydrogen atom, a halogen atom or an alkyl group. &lt;7&gt; The sensitized ray or radiation sensitive resin composition as described in any one of the above-mentioned <1> to <6>, wherein the composition is derived from a compound after irradiation with actinic rays or radiation (B) The acid has a molecular weight of 300 or more, and includes a monocyclic or polycyclic, alicyclic or aromatic ring which may contain a hetero atom. A photosensitive ray or radiation sensitive resin composition as described in any one of the above-mentioned items <1> to <7>, wherein the content of the resin (C) is from 0.1 to 10% by mass based on the sensitized ray Or the total solid content of the radiation sensitive resin composition. &lt;9&gt; The sensitized ray or radiation sensitive resin composition described in any one of the above &lt;1&gt; to &lt;8&gt;, wherein the composition is formed from the sensitized ray or the radiation sensitive resin composition The photosensitive film has a receding contact angle with water of 70 or more. &lt;10&gt; A photoresist film which is formed from the sensitized ray or radiation sensitive resin composition described in any of the above &lt;1&gt; to &lt;9&gt;&lt;11&gt; A pattern forming method comprising the steps of immersing exposure and developing the photoresist film described in the above &lt;10&gt;. [Embodiment] The present invention is described in detail below. Incidentally, in the present invention, when a group (atomic group) is indicated without specifically indicating whether it is substituted or unsubstituted, the group includes a group having no substituent and a group having a substituent. both. For example, &quot;alkyl&quot; 0 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 designation "actinic ray" or "radiation" means, for example, a bright line spectrum of a mercury lamp, a typical far ultraviolet ray, an extreme ultraviolet ray, an X ray or an electron beam which is an excimer laser. In the present invention, &quot;light&quot; means actinic radiation or radiation.

Furthermore, in the present invention, unless otherwise indicated, "exposure" includes not only exposure with a mercury lamp, a typical far ultraviolet ray, an X-ray, an EUV light, or the like, which is a quasi-molecular laser. Moreover, it also includes a resin (A) which can increase the solubility in an alkaline developer by an acid action by a particle beam (such as an electron beam and an ion beam) [1]. The resin (A) can be used by a resin which increases the solubility in an alkaline developer, and which has a property capable of decomposing by an acid to produce an alkali-soluble group in one or both of the main chain and the side chain of the resin. a group (sometimes referred to as an &quot;acid-decomposable group&quot;) resin. The acid-decomposable group has an alkali-soluble group which can be decomposed and decomposed by the action of acid 201033732. The structure of the group protected is preferred. 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, and a ruthenium imine. Group, (alkyl alkyl) (alkylcarbonyl) methylene, (alkyl alkyl) (alkane) a carbonyl) quinone imine group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl) quinone imine group, a bis(alkylfluorenyl)methylene group, a bis(alkyl ruthenium) fluorene group Amine group, tris(alkylcarbonyl)methylene group and tris(alkylindenyl)methylene group. Among these alkali-soluble groups, carboxyl group, fluorinated alcohol group (six

Preferably, fluoroisopropanol and a sulfonic acid group are preferred. The group which is preferably a group which is an acid-decomposable group is a group in which a hydrogen atom of the 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 acid action include -C(R36)(R37)(R3 8) and -C(R0,)(1102)(01139). In the formula, each of R36 to R39 independently represents an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group or an alkenyl group; and R3 6 and R3 7 may be bonded to each other to form a ring. '

Each of Roi and R〇2 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 preferably a mercaptoester group, an enol ester group, an acetal acetate group, a tertiary alkyl ester group or the like, and the tertiary alkyl ester group is more good. The resin (A) preferably comprises a repeating unit having an acid-decomposable group. The repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following formula (AI): -10-201033732]RX1 (punching cr^o--rx2 KX3)

In the formula (AI), Xai 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, and the monovalent organic group includes, for example, an alkyl group having a carbon number of 5 or less and a mercapto group, and an alkyl group having a carbon number of 3 or less is preferable, and a methyl group is more preferable. 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. Each of RU to Rx3 independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). The two members from which they are derived may combine 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 a _〇_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 a carbon number of 1 to 5, and a -CH2- group or a -(CH2)3- group is more preferable. 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 RX1 to Rx3 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 tetracyclic fluorenyl group, or a tetracyclic group Alkyl and adamantyl. The cycloalkyl group 201033732 formed by combining two members derived from the scales \1 to RX3 is preferably as follows: a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; or a polycyclic cycloalkyl group such as a lower Mercapto, tetracyclononyl, tetracyclododecyl and adamantyl; cycloalkyl having a monocyclic ring having 5 to 6 carbon atoms is more preferred.

A specific example in which Rxi is a methyl group or an ethyl group and Rx2 is bonded to Rx3 to form a cycloalkyl group as described above is preferred. The repeating unit having an acid-decomposable group preferably has a monocyclic or polycyclic acid-decomposable group. The monocyclic acid-decomposable group includes the above

Any one of Rx! to Rx3 is an example of a monocyclic cycloalkyl group; and an example in which two members from Han\1 to Rx3 are combined to form a monocyclic cycloalkyl group, and the monocyclic cycloalkyl group It is preferably a cyclopentyl group or a cyclohexyl group. The polycyclic acid-decomposable group includes an example of a cyclopentyl group in which any one of the ruthenium to Rx3 is a polycyclic ring; and an example in which two members from the scales \1 to Rx3 are combined to form a polycyclic cycloalkyl group, Further, the polycyclic cycloalkyl group is a norbornyl group, a tetracyclononyl group, a tetracyclododecyl group or an adamantyl group. Each of these groups may have a substituent, and an embodiment of the substituent

The alkyl group (preferably having a carbon number of 1 to 4), a halogen atom, a hydroxyl group, an alkoxy group (preferably having a carbon number of 1 to 4), a carboxyl group and an alkoxycarbonyl group (having preferably a carbon number of 2 to 6) are preferable. The substituent has a carbon number of 8 or less. The content of the repeating unit having an acid-decomposable group is preferably from 2 to 50 mol%, more preferably from 25 to 45 mol%, and is based on all the repeating units in the resin (A). . A specific preferred embodiment of the repeating unit having the acid-decomposable group is proposed below, but the invention is not limited thereto. (In the formula, Rx represents H, CH3, CF3 or CH2OH, and Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms.) -12- 201033732

π 12 13 14 15

-13- 201033732 In the following formula, 'X' stands for Η, CH3, CF3 or CH2OH.

-14 - 201033732

The resin (A) is a resin having at least one of the repeating unit represented by the formula (i) or the repeating unit represented by the formula (2) as the repeating unit represented by the formula (AI) Better.

In the formulae (1) and (2), each of 'R 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 preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. 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. -15-201033732 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, R5 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, 1^ and R2 have the same meanings as those in the formula (1). R1 ο

(1-1) The repeating unit represented by the formula (2) is preferably a repeating unit represented by the following formula (2-1): -16- 201033732 r3 〇人(2-1) R5--R4 In the formula (2-1), R3 to Rs have the same meanings as those in the formula (2).

Rio represents a substituent containing a polar group. In a 0 instance where there are multiple ri〇, each Rio may be the same or different from every other RlQ. Examples of the polar group-containing substituent include a polar group itself such as a hydroxyl group, a cyano group, an amine group, an alkylguanamine group, and a sulfonamide group; and a linear or branched group having such a polar group Hospital or cycloalkyl. The polar group-containing substituent is preferably an alkyl group having a hydroxyl group, a branched alkyl group having a hydroxyl group is more preferable, and the branched alkyl group is preferably an isopropyl group. P represents an integer of 0 to 15»p is an integer of 0 to 2, preferably 0 or 1. The resin (A) may comprise a plurality of repeating monohydric units containing an acid-decomposable group. As described above, the resin (A) is at least one of a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2) as a repeat represented by the formula (AI). The resin of the unit is preferred. In another specific example, the resin (A) is a repeating unit comprising at least two types represented by the formula (1) or a repeating unit represented by the formula (1) and the formula (2) Both of the indicated repeating units are preferably used as the resin of the repeating unit represented by the formula (AI). Similarly, the photoresist composition of the present invention may comprise a plurality of resins (A), and the repeats 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 (i) and a resin (A) containing a repeating unit represented by the formula (2) may be used in combination. The following is a preferred combination when the resin (A) comprises a plurality of repeating units containing an acid-decomposable group and when a plurality of resins (A) contain different repeating units containing an acid-decomposable group. Example. In the following formula, 'each R' independently represents a hydrogen atom or a methyl group.

-18- 201033732 The resin (A) preferably comprises a 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. The re-unit containing the internal vine group which can be contained in the resin (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 5- to 7-membered ring lactone structure, and the other ring structure is in the form of a bicyclic or spiro structure. The structure thickened to the 5- to 7-membered ring lactone structure is preferred. The resin preferably comprises a repeating unit having an internal vinegar structure represented by any one of the following formulae (LC 1-1) to (LC1-17). 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 (LC 1-17) good. Line edge roughness and development defects are improved by using a specific lactone structure.

(Rbji)n2 (Rb^)n2 (Rb^n2

(Rba)n2 -19- 201033732

The lactone moiety may or may not have a substituent (Rb2). Preferred examples of the substituent (Rb2) 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, an alkyl group having a carbon number of 1 to 4, a cyano group, and an acid-decomposable group are more preferable. N2 represents an integer of 0 to 4. When n2 is an integer of 2 or more, each substituent (Rb2) may be the same as or different from each other substituent (Rb2), and likewise, one substituent (Rb2) may be bonded to another substituent (Rb2). To form a ring. The repeating unit having the lactone structure represented by any one of the formulae (LC1-1) to (LC1-17) includes a repeating unit represented by the following formula (All):

Rb〇

In the formula (All), Rb〇 represents a hydrogen atom, a halogen atom or an alkyl group having a carbon number of 1 to 4 which may have a substituent. Preferred examples of the substituent which the alkyl group of Rbo may have include a hydroxyl group and a halogen atom. The halogen atom of the Rb〇 includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb 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 preferable.

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 group containing a combination thereof, and a single bond or The divalent linking group represented by -Abi-COr is preferred.

Ab! represents a linear or branched alkyl or monocyclic or polycyclic cycloalkane-20-201033732 group, and a methylene group, an ethyl group, a cyclohexylene group, an exo-adamantyl group or a pendant group is preferred. . v represents a group having a lactone structure, and particularly includes 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 one optical isomer, the optical purity (ee) is preferably 90% or more, more preferably 95% 0 or more. 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%, in the resin (A). All repeating units in the standard shall prevail. The unit represented by the free form (All), when Ab is a single bond, the repeating unit having a particularly preferred lactone group includes the repeating unit shown below. The pattern profile and the isolation/separation bias are improved by selecting the most desirable lactone group. Q Rx represents a hydrogen atom, an alkyl group which may have a substituent or a halogen atom, and a hydrogen atom, a methyl group or an alkyl group having a substituent (that is, a 'hydroxymethyl group or an ethyl methoxymethyl group) is preferred. _ 21 - 201033732

In particular, in order to further enhance the effect of the present invention, the resin (A) preferably comprises a repeating unit having a lactone structure represented by the following formula (3):

In the formula (3), A represents an ester bond (-COO-) or a guanamine bond (-CONH-). Representative (when a plurality of R 〇 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 carbonyl bond, a guanamine bond, a urethane bond or a urea bond). Ο R8 represents a monovalent organic group having a lactone structure. No is the number of repetitions of the structure represented by -Ro-Ζ- in the repeating unit represented by 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. The alkylene group and the extended cycloalkyl group each may have a substituent. Z is preferably an ether bond or an ester bond, and the ester bond is more preferred. The alkyl group of b is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or a methyl group of 22 to 201033732, 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; an anthracene group, a hydroxyl group; an alkoxy group such as a methoxy group, an ethoxy group, Isopropoxy, tert-butoxy and benzyloxy; and anthracenyloxy such as ethoxylated and propyloxy. 117 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. The alkylene group in Ro is preferably a chain alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5, and examples thereof include a methylene group, an ethyl group and a propyl group. The cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 20, and 0 examples thereof include a cyclohexylene group, a cyclopentylene group, a fluorenyl group and an adamantane group. In order for the effect of the present invention to occur, the alkyl group is more preferred and the methylene group is particularly preferred. The lactone-containing structural substituent represented by R8 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 preferable. A structure in which n2 is an integer of 2 or less in (LC 1-1) to (LC 1-1 7) is more preferable. 118 is preferably a monovalent organic group having an unsubstituted lactone structure or a monovalent organic group containing a lactone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent, and having a cyano group as a substituent. The monovalent organic group of the lactone structure (cyanolactone) is more preferred. The specific embodiment of the lactone-containing structural repeating unit represented by the following formula (3) is proposed below, but the present invention is not limited thereto. In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent or a halogen atom, and a hydrogen atom, a methyl group or an alkyl group having a substituent (that is, a hydroxymethyl group or an acetoxy group) Methyl) is preferred. -23- 201033732

The repeating unit having a lactone structure is preferably a repeating unit represented by the following formula (1)-::

The same meaning. R9 represents (in the presence of a plurality of r9, each independently represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an 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 a number of substituents and represents an integer of 0 to 5»m is preferably 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. Examples of the cycloalkyl group include 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 oxy group of the present invention include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. These groups may have a substituent, and examples of the substituent include 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 fluorogenic group -24-201033732). R9 is preferably a methyl group, a cyano group or an alkoxycarbonyl 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 β-position of the carbonyl group of the lactone, and more preferably at the α· position. The specific embodiment of the repeating unit having the lactone-containing structural group represented by the formula (3-1) is proposed below, but the invention is not limited thereto. In the formula, 0 R represents a hydrogen atom, an alkyl group which may have a substituent or a halogen atom, and a hydrogen atom, a methyl group or an alkyl group having a substituent (that is, a hydroxymethyl group or an acetoxy group) Base) is preferred.

The repeating unit having a lactone group usually has an optical isomer, but any optical isomer can be used. Nr -厶J · 201033732 The content of the repeating unit having a lactone group is from 15 to 6 mol%, preferably from 20 to 50 mol%, more preferably from 30 to 50 mol%, The total repeating unit in the resin is taken as the standard. It is also possible to use two or more lactone repeating units selected from the formula (AII) in combination to enhance the effects of the present invention. In the case of combining the use of the repeating unit, it is preferable to use two or more kinds of repeating units selected from the lactone repeating unit of the formula (3-i) and nQ of 1. It is also preferred to combine a lactone repeating unit in which Ab in the formula (All) is a single bond with a lactone repeating unit derived from the formula (3-1) and n〇. In addition to the repeating unit represented by the formulas (AI) and (All), the resin (A) preferably comprises a repeating unit having a hydroxyl group or a cyano group. The adhesion of the repeating unit ' 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 which has been substituted with a hydroxyl group or a cyano group, and preferably contains no acid-decomposable group. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure which has been 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 bis-adamantyl 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, dihydroxyadamantyl and cyano substituted萡基. The alicyclic hydrocarbon structure which has been substituted by a hydroxyl group or a cyano group is preferably a partial structure represented by the following formulas (Vila) to (Vnd): 201033732

In the formulae (Vila) to (Vlie), each of R2C to R4C independently represents a hydrogen atom, a hydroxyl 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 in which one or two members from R2c to R4c are a hydroxyl group and the remainder is a hydrogen atom is preferred. In the formula (Vila), two members from R2c Ο to R4c are preferably a hydroxyl group and the remainder being a hydrogen atom. The repetitive unit having a partial structure represented by the formulas (Vila) to (Vlld) includes a repetitive unit represented by the following formulas (All a) to (AI Id), and is repeated by the formula (Alla) The unit is preferred.

❹ In the formulae (Alla) to (Alld), RlC represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R2C to R4c have the same meaning as r2C to r4C in the formulae (VIIa) to (vIIc). The content of the repeating unit having a hydroxyl group or a cyano group is from 5 to 40 mol%, preferably from 5 to 30 mol. The ear percentage is more preferably from 1 〇 to 25 mol%, more preferably, in all the repeating units in the resin (A). The specific implementation of the repeating unit having a hydroxyl group or a cyano group is proposed below.

The resin (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 maple quinone imine group, a bis-indenylene imine group, and an aliphatic alcohol substituted with an electron withdrawing group at the oc-position (such as six Fluoroisopropanol group). The resin preferably comprises a repeating unit having a carboxyl group. By including the repeating unit having an alkali-soluble group, the resolution in the use of forming the contact hole is increased. 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 (for example, by a reciprocating unit of 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 alkali-soluble group is used in the polymerization using a polymerization initiator or a chain transfer agent containing a base which is soluble in a base. It is preferred that the group introduces repeating v 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 0 to 20 mol%, more preferably from 3 to 15 mol%, even more preferably from 5 to 1 mol%. All of the repeating units in the resin (A) are accurate. The specific embodiment of the repeating unit having a group soluble in hydrazine is proposed below, but the invention is not limited thereto. -28- 201033732 (In the formula, Rx is H, CH3, CF3 or CH2OH.)

The repeating unit having at least one 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, and a cyano group. 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 has a cyano group substituted with a lactone structure of (LC 1-4) is preferred. The resin (A) further preferably comprises a repeating unit represented by the formula (1) which does not have a radical or an aromatic group. take

(4)

In the formula (4), r5 represents a hydrocarbon group having at least one cyclic structure and having no hydroxy-29-201033732 group or a cyano group.

Ra represents a hydrogen atom, an alkyl group or a -CH2-0-Ra2 group, wherein 1132 represents an alkyl group or a fluorenyl group. Examples of Ra include a hydrogen atom, a methyl group, and a trifluoromethyl group. 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 Cyclohexenyl. 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 Q group. Examples of hydrocarbon groups which are accumulated in the ring include dicyclohexyl and perhydronaphthyl. 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 homobeledane ring, adamantane ring, tricyclo[5.2.1.02,6]decane ring and tricyclo[4.3.1.12' 5] undecane ring), and a 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, Argon-helium ring, perhydrophenanthrene ring, perhydroethane naphthalene ring, perhydrofluorene ring, perhydroindene ring and perhydroindole ring. Preferred examples of the crosslinked cyclic hydrocarbon ring include a thiol group, an adamantyl group, a bicyclooctyl group, and a tricyclo[5.2.1.0''6]decyl group. Among these crosslinked cyclic hydrocarbon rings, a thiol group and an adamantyl group are more preferable. 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 group protecting from -30 to 201033732. 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 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, anthraceneoxycarbonyl groups, and aralkoxycarbonyl groups. The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms; the substituted methyl group is 0 methoxymethyl, methoxythiomethyl, benzyloxymethyl, tert-butoxymethyl Or 2-methoxyethoxymethyl is preferred; the substituted ethyl group is 1-ethoxyethyl or 1-methyl-1-methoxyethyl; the thiol group has carbon The aliphatic sulfhydryl groups of 1 to 6 are preferably, such as a methyl group, an ethionyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, a pentamidine group, and a pentamidine group; and the alkoxycarbonyl group has a carbon number of 2 The alkoxycarbonyl group to 4 is preferred. The resin (A) may not include a repeating unit represented by the formula (4) and having no repeating unit of a hydroxyl group or a cyano group, but when the resin contains the repeating unit, the one having the formula (4) The content of the repeating unit indicating the repeating unit having no hydroxyl group or cyano group is preferably from 10 to 40 mol%, more preferably from 10 to 20 mol%, and all repeating in the resin (A) The unit shall prevail. The specific embodiment of the repeating unit represented by the formula (4) is proposed below, but the present invention is not limited thereto. In the formula, Ra represents H, CH3 or CF3.

201033732 In addition to the above-described description, in order to control dry etching resistance, adaptability to standard developer, adhesion to a substrate, photoresist shape, and properties usually required for photoresist such as resolution, heat resistance, and sensitivity In addition to the repetitive structural unit, the resin (A) may comprise a plurality of repetitive structural units. Embodiments of the repetitive structural unit include, but are not limited to, repetitive structural units corresponding to the monomers described below. Due to this repetitive structural unit, the properties required for the resin (A) can be skillfully controlled, in particular, (1) solubility in a coating solvent, (2) film forming properties (glass transition point), and (3) alkali development Capacity, (4) film loss (selection of hydrophilic, hydrophobic or alkali-soluble groups), (5) adhesion of unexposed areas to the substrate, (6) dry etching resistance, and the like . 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 repeating structural units described above may be copolymerized. In the resin (A), the molar ratio of the respective repetitive structural units included is appropriately determined to control the dry etching resistance of the photoresist, the suitability to the standard developer, the adhesion to the substrate, The photoresist profile and the properties normally required for 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 (A) does not have an aromatic group in view of the transmittance to ArF light. 201033732 Particularly in the resin, the ratio of the aromatic group-containing repeat is 5 mol% or less preferably '3 mol% or less, and is preferably 〇mol% (that is, It is preferred that the resin (A) has a monocyclic or polycyclic alicyclic hydrocarbon structure. Similarly, in view of compatibility with the resin (C), the resin (A) is preferably not contained in a fluorine atom or a ruthenium atom. The resin (A) is preferably a resin in which all of the repeating units are composed of a repeating unit based on (meth) acrylate. In this example, the repeating unit of all the turns may be a methacrylate-based repeating unit, the entire repeating unit may be an acrylate-based repeating unit, or all of the overlapping units may be a methacrylate-based repeating unit and an acrylate-based repeating unit, but the acrylate-based repeating unit is 50% by mole or less preferably (to all weight) The cover unit shall prevail). Likewise, preferred copolymerized polymers comprise from (2) to 5 mole % of (meth) acrylate based on the acid-decomposable group represented by formula (AI). a unit, from 20 to 50 mol% of a repeating unit based on a (meth) acrylate containing a quinone Q group, from 5 to 30 mol% having an alicyclic hydrocarbon structure which has been substituted by a hydroxy group or a cyano group A (meth) acrylate based resurfacing unit, and from 0 to 20 mol% of other (meth) acrylate based resurfacing units. 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 high energy beam (for example, EUV) having a wavelength of 50 nm or shorter, (A) is represented by a repeating unit represented by (AI). The resin (A) further comprises a hydroxystyrene-based repeating unit, and the hydroxystyrene-based repeating unit is made of a squeegee-knife. 201033732 The acid-decomposing group is preferably 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 comprises a repeating unit consisting of: a tertiary butoxycarbonyloxystyrene, a 1-alkoxyethoxystyrene or (a) Base) Alkyl triacrylate. A repeating unit composed of 2-alkyl-2.adamantyl (meth) acrylate or dialkyl (1-adamantyl)methyl (meth) acrylate is more preferable.

The resin (A) can be synthesized by a usual method (for example, radical polymerization). Examples of the general synthetic method 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 monomeric species and the starter is added dropwise to the hot solvent. The dropping polymerization method is preferred. Examples of the reaction solvent include tetrahydrofuran, 1,4-dioxane, ethers (such as diisopropyl ether), ketones (such as methyl ethyl ketone and methyl isobutyl ketone), and ester solvents ( Such as ethyl acetate), guanamine solvent (such as dimethylformamide and dimethylacetamide), and a solvent which can dissolve the composition of the present invention, such as propylene glycol monomethyl ether acetate (PGMEA) Also known as 1-methoxy-2-ethenyloxypropane, propylene glycol monomethyl ether (PGME, also known as Ο 1-methoxy-2-propanol) and cyclohexanone. It is more preferable to carry out the polymerization using the same solvent as that used in the photosensitive ray or the 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 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 -34-201033732 group 'cyano or 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 completion of the reaction, 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, more preferably from 60 to 10 ° C. . ❹

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 only Extracting ultrafiltration using those having a molecular weight not greater than a specific enthalpy; the resin solution is added dropwise to the poor solvent to cure the resin in a poor solvent, thus removing residual monomers and the like A reprecipitation method; and a purification method in a solid state, such as a method in which a resin slurry which has been separated by filtration is subjected to washing with a poor solvent. For example, the resin is contacted by contacting the reaction solution with a solvent which is slightly soluble or insoluble in the resin (a poor solvent having a volume of 10 times or less, preferably 10 to 5 times the reaction solution). Solid precipitation. The solvent (precipitating or reprecipitating solvent) used in the operation of precipitating or reprecipitating from the polymer solution may be sufficient if it is a poor solvent for the polymer, and the solvent which can be used may be, for example, depending on the kind of the polymer. The following are suitably selected: a hydrocarbon, a halogenated hydrocarbon, a nitro compound, an ether, a ketone, an ester, a carbonate, an alcohol, a citric acid, water, and a mixed solvent containing the solvent. Among these solvents, a solvent containing at least an alcohol (particularly methanol or the like) or water is preferably -35-201033732 as the precipitation or reprecipitation solvent. The content of the precipitation or reprecipitation solvent to be used may be appropriately selected in consideration of efficiency, productivity, and the like, but generally, the content is from 100 to 10 per 100 parts by mass of the polymer solution, 〇〇〇 The parts by mass are 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 can be appropriately selected in consideration of efficiency or operability, but is usually preferably from 0 to 50 t in the vicinity of room temperature (e.g., from about 20 to 35 ° C). The 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 solid-liquid separation (such as filtration and centrifugation) which is generally used, followed by drying and use. Filtration under pressure is preferred using a solvent resistant filter element. 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 at a temperature of from 30 to 5 ° C). Incidentally, once the resin is precipitated and separated, the resin may be dissolved again in a solvent, and then placed in contact with a solvent which is slightly soluble or insoluble in the resin. That is, the following methods can be used, including: after completion of the free radical polymerization, the polymer is brought into contact with a solvent which is slightly soluble or insoluble to the polymer to precipitate a resin (step a); Separating the resin from the solution (step b); dissolving the resin in a solvent again to prepare a resin solution A (step c); bringing the resin solution A to a slightly soluble or a resin Insoluble solvent contact, and the volume of the solvent is less than 10 times (5 times or less) of the resin solution A to precipitate a resin solid (step d); and separating the precipitated resin (step e). 201033732 In terms of polystyrene, the weight average molecular weight of the resin (A) is preferably from 1, 200 to 200,000, more preferably from 2,000 to 20,000, even more preferably from 3,000 to 15,000, and from 5,000 by the GPC method. It is even better to 13,000. By setting the weight average molecular weight to from 1,000 to 200,000, heat resistance, dry etching resistance, and developing ability can be prevented from being lowered; similarly, since the viscosity is improved, the film formation property can be prevented from being lowered. The polydispersity (molecular weight distribution) is usually from 1 to 3, preferably from 1 to 2.6, more preferably from 1 to 2, still more preferably from 1.4 to 2.0. When the polydispersity is small, the resolution of 0 and the shape of the photoresist are better, the sidewalls of the photoresist pattern are smoother, and the properties in terms of roughness are improved. The amount of the resin (A) to be added is usually from 50 to 99% by mass, preferably from 70 to 98% by mass, based on the total solid content of the composition. In the present invention, as for the resin (A), it may be used. A resin or a plurality of resins may be used in combination. [2] Compound (B) capable of generating an acid after irradiation with actinic rays or radiation The composition of the present invention includes a compound capable of producing an acid after irradiation with actinic rays or radiation (hereinafter sometimes referred to as "Acid generator". The acid generator which can be used can be suitably selected from the following: a photoinitiator for cationic photopolymerization, a photoinitiator for radical photopolymerization, and a light for dyes. Decolorizer, photodecolorizer, compound known to produce acid after irradiation with actinic radiation or radiation, and used in micro-resistance or the like, and mixtures thereof. Examples of this compound include diazonium salt, rust Salt, shovel salt, strontium salt, sulfhydrazine sulfonate, sulfonium sulfonate, diazonium dioxime, diterpene and o-nitrobenzyl sulfonate 0 -37- 201033732 from the acid generator, from the following formula The compounds represented by (ZI), (ZII) and (ZIII) are preferred.

R2041~^205

^206一丨 |· 〇

〇II S-R207II ο (ΖΠΙ) In the formula (ZI), each of R2()1, R2Q2 and R2Q3 independently represents an organic group. As for the carbon number of the organic groups of R2G1, R2G2 and R2Q3, which are usually from

1 to 30, and preferably from 1 to 20. Two members from R2 οι to R2 03 may be combined 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 R2 03 include an alkyl group (e.g., butyl group, pentyl group). Z· represents a non-nucleophilic anion. As an example of the non-nucleophilic anion of Z, which includes a sulfonate anion, a carboxylate anion, a ruthenium imine anion, a bis(alkyl fluorenyl) group

An anthracene anion and a tris(alkylindenyl)methyl anion. The non-nucleophilic anion is an anion having a very low ability to cause a nucleophilic reaction, and the nucleophilic reaction in the molecule suppresses decomposition with aging. 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-38-201033732 moiety in the aliphatic sulfonate anion and the aliphatic carboxylate may be an alkyl group or a cycloalkyl group, but has an alkyl group having 1 to 30 carbon atoms or a carbon number of 3 to 30. The cycloalkyl group is preferred, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, secondary butyl, pentyl, neopentyl, hexyl, heptyl, octyl Base, fluorenyl, fluorenyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nineteen Alkyl, decyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl and fluorenyl. The 0 aromatic group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group having 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 至 to 14 are preferred. , alkoxycarbonyl (preferably having 2 to 7 carbon atoms), mercapto (preferably having 2 to 12 carbon atoms), alkoxycarbonyloxy (preferably having 2 to 7 carbon atoms), alkylthio group (having preferably a carbon number of 1 to 15), an alkyl maple group (preferably having a carbon number of 1 to 15), an alkylimine group (having preferably a carbon number of 1 to 15), and an aryloxy maple group. (having preferably 6 to 20 carbon atoms), alkylaryloxy maple (preferably having 7 to 20 carbon atoms), cycloalkylaryloxy maple (having preferably 10 to 20 carbon atoms), The alkyloxyalkyloxy group (having preferably 5 to 20 carbon atoms) and the cycloalkylalkyloxyalkyloxy group (having preferably 8 to 20 carbon atoms) are preferred. As for the aryl group and ring structure in each group, the embodiment of the substituent further includes 2010 alkyl group (having preferably having a carbon number of 1 to 15). The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having a carbon number of 6 to 12, 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 aralkylcarboxylate anion may have a substituent. Examples of the substituent include the same halogen atom, alkyl group, cycloalkyl group, alkoxy group as those in the aromatic sulfonate anion.

Base and alkylthio group. Examples of the maple quinone imine anion include a saccharin anion.

The alkyl group in the bis(alkylindenyl)indolide anion and the tris(alkylindenyl)methyl anion is preferably an alkyl group having 1 to 5 carbon atoms, and examples thereof include methyl group and ethyl group. Base, propyl, isopropyl, n-butyl, isobutyl, secondary butyl, pentyl and neopentyl. Examples of the substituent of the alkyl group include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxy maple group, an aryloxy group, and a cycloalkylaryloxy group. The alkyl group which is ground and substituted with a fluorine atom is preferred. Incidentally, the two alkyl groups in the bis(alkyl Maple) quinone imine anion may be the same or different. Similarly, the plurality of alkyl groups in the tris(alkylbehenyl)methyl anion may be the same or different. In particular, the bis(alkyl Maple) quinone imine anion and the tris(alkylindenyl)methyl anion are anions represented by the following formula (A3) or (A4):

-40-

In the formulae (A3) and (A4), γ is preferably an alkyl group having at least one fluorine atom and an alkylene group having 2 to 4 carbon atoms. The alkyl group contains an oxygen atom. Υ is preferably a perfluoroalkyl group having a carbon number of 2 to 4, preferably tetrafluoroethyl, hexafluoropropyl or octafluorobutyl. In the formula (Α4), 'R represents an alkyl group or a cycloalkyl group. The alkylene chain in the alkyl group may contain an oxygen atom. The compounding examples having an anion represented by the formula (A3) or (?4) include those as in the specific examples of JP-A-2005-221721. Other examples of such non-nucleophilic anions include boron of fluorinated phosphorus and fluorinated ruthenium. The non-nucleophilic anion of the oxime is preferably the following: an aliphatic sulfonate anion substituted with a fluorine atom at the position of the sulfonic acid, an aromatic sulfonate anion substituted with a fluorine atom atom group, the alkyl group A substituted tris(alkylmercapto)anthracene anion, or a fluorinated tris(alkylfranky)methyl anion of the alkyl group. The non-nucleophilic anion having a carbon number of 4 to 8 perfluoroaliphatic sulfonate anion or having a fluoroortane sulfonate anion, a nonafluorobutane sulfonate anion, a perfluoroacid anion, pentafluorobenzenesulfonic acid The salt anion or the 3,5-bis(trifluorosulfonate anion is more preferably. As for the organic group of the Rm, Κ2〇2 and R2〇3, the compound (ZI-1) described later is included. a group of (ZI-2) and (ZI-3). The compound may be a compound having a plurality of compounds represented by the formula (ZI), for example, one having a compound represented by the formula (ZI) The extension chain may be packaged, and the fluorinated at least α- or fluorine-containing atom atom is taken as a phenyloctane sulfomethyl)benzoquinone having a corresponding structure. At least one of R 2 0 1 -41 to 201033732 to R 2 〇 3 is bonded via a single bond or a linking group to at least one of R 2 () 1 to R 2 〇 3 in another compound represented by the formula (ZI) Structure of the compound. This component (ZI) is more preferably a compound (ZI-1), (ZI-2) or (ZI-3) described below. The compound (ZI-1) is an arylsulfonium compound in which at least one of 112()1 to R2G3 in the formula (ZI) is an aryl group, that is, a compound having an aryl group as a cation. In the arylsulfonium compound, R2()1 to R2〇3 may all be an aryl group, or a part of R2&lt;n to R2C3 may be an aryl group and the remainder is an alkyl group or a cycloalkyl group. Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an arylbicycloalkylsulfonium compound. The aryl group in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and the phenyl group is more preferred. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an anthracene residue, a benzofuran residue, and a benzothiophene residue. In the example where the aryl hydrazine compound has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl or cycloalkyl group (if desired) present 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 include methyl, ethyl, propyl, n-butyl, secondary butyl, tert-butyl, cyclopropyl, cyclobutyl and cyclohexyl. The aryl group, the alkyl group and the cycloalkyl group of the ruthenium 2 () 1 to R 2 Q 3 may have an alkyl group (for example, having a carbon number of 1 to 15), a cycloalkyl group (for example, having a carbon number of 3 to 15), - 42-201033732 An aryl group (for example, having a carbon number of 6 to 14), an alkoxy group (for example, having a carbon number of 1 to 15), a halogen atom, a hydroxyl group or a phenylthio group as a substituent. The substituent is a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms, preferably having carbon The alkyl group having 1 to 4 or the alkoxy group having 1 to 4 carbon atoms is more preferable. The substituent may be substituted on either of the three members to R2G3 or may be substituted on all of the three members. In the case where R2Q1 to R2G3 are aryl groups, the substituent substitution is preferably at the position of the aryl group. This compound (ΖΙ-2) is described below. This compound (ΖΙ-2) is a compound in which each of R2()1 to R2Q3 in the formula (ΖΙ) independently represents an organic group having no aromatic ring. As used herein, the aromatic ring includes an aromatic ring containing a hetero atom. The aromatic-free organic group as R2Q1 to R2Q3 has a carbon number of usually from 1 to 30, and preferably from 1 to 20. R2 01 to R2 03 each independently represent an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, a linear or branched 2-sided oxyalkyl group, a 2-sided oxocycloalkyl group or an alkoxycarbonyl group. The methyl group is more preferred, and the linear or branched 2-sided oxyalkyl group is more preferably. The alkyl group and the cycloalkyl group of R2 &lt;h to R2〇3 are linear or branched alkyl groups having a carbon number of 1 to 10 (e.g., methyl, ethyl, propyl, butyl, pentyl) and having a carbon number A cycloalkyl group of 3 to 10 (for example, a cyclopentyl group, a cyclohexyl group, a norbornyl group) is preferred. The alkyl group is more preferably a 2-sided oxyalkyl group or an alkoxycarbonylmethyl group. The cycloalkyl group is more preferably a 2-sided oxocycloalkyl group. The 2-sided oxyalkyl group may be linear or branched, and a group having &gt; C = 0 at the 2-position of the alkyl group described above is preferred. The 2-sided oxocycloalkyl group is preferably a group having a 201033732 &gt; € = 0 at the 2-position of the cycloalkyl group described above. The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (e.g., methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group). Each of R2〇i to R2〇3 may be further substituted by a halogen atom, an alkoxy group (for example, having a carbon number of 1 to 5), a hydroxyl group, a cyano group or a nitro group. This compound (ΖΙ·3) is a compound represented by the following formula (ZI-3), and is a compound having a benzoguanidine salt structure.

In the formula (ΖΙ-3), R!. Each of R5e independently represents the hydrogen source

a linear, branched or branched alkyl group (having preferably a carbon number of 1 to 12), a cycloalkyl group (having preferably a carbon number of 3 to 8), a linear or branched alkoxy group (in the case of a linear alkoxy group, having a carbon The number is from 1 to 12; and in the case of a branched alkoxy group, preferably from 3 to 8, or a halogen atom. Ruler 6. And R7e each independently represent a hydrogen atom, a linear or branched alkyl group (having preferably a carbon number of 1 to 12) or a cycloalkyl group (having preferably a carbon number of 3 to 8). Each of RX and Ry independently represents a linear or branched alkyl group (having preferably a carbon number of 1 to 12), a cycloalkyl group (having preferably a carbon number of 3 to 8), an allyl group or a vinyl group. From Rlc to R5e, Re. With κ~7. Any two or more members of the pair or with the Ry pair may be joined together to form a ring structure. This ring structure may contain an oxygen atom, a sulfur atom, an ester bond or a brewing amine bond.

ZcT represents a non-nucleophilic anion, and the examples thereof are the same as those of the non-nucleophilic anion of -44-201033732 in the formula (ZI). 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. Specific preferred embodiments of the compound (ZI-3) are disclosed in paragraphs 0046 and 0047 of JP-A-2004-233661 and paragraphs 0040 to 0 04 6 of JP-A-2003-35948 as examples. Compound. In the formulae (ZII) and (ZIII), each of r2〇4 to r2〇7 independently represents an aryl group, an alkyl group or a cycloalkyl group. The aryl group, the alkyl group and the cycloalkyl group of R2〇4 to R2Q7 are the same as the aryl group, the alkyl group and the cycloalkyl group of the rule 2()1 to R2G3 in the compound (ZI-1). Each of the aryl group, the alkyl group and the cycloalkyl group of R2〇4 to R2〇7 may have a substituent. Examples of the substituent include those which the aryl group, the alkyl group and the cycloalkyl group of R2G1 to R2Q3 in the compound (ZI-1) may have. Represents a non-nucleophilic anion, and the examples thereof are the same as those of the non-nucleophilic anion of the formula (ZI). Other examples of the acid generator include compounds represented by the following formulas (ZIV), (ZV) Λ and (ZVI):

ΑΓ3~S〇2&lt;S〇2—Af4 (ZIV) R208*S〇2〇_N (ZV) In the formulae (ZIV) to (ZVI), each of Ar3 and Ar4 independently represents an aryl group. Each of R2〇8, R2G9 and RnG independently represents an alkyl group, a cycloalkyl group or an aryl group. A represents an alkyl group, an alkenyl group or an aryl group. -45- 201033732 Among the acid generators, the compounds represented by the formulae (ZI) to (ZIII) are more preferable.

The acid generator is preferably a compound which produces an acid having a sulfonic acid group or a quinone imine group, a compound which produces a monovalent perfluoroalkanesulfonic acid, and a monovalent aromatic which is substituted by a fluorine atom or a fluorine atom group. a compound of a sulfonic acid, or a monovalent imidic acid compound which is substituted by a fluorine atom or a fluorine atom-containing group, preferably a fluorine-substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid, or a fluorine-substituted sulfonium. Amine acids or fluorinated methic acid sulfonium salts are more preferred. In particular, the acid generator which can be used is preferably a compound which produces a fluorine-substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid or a fluorine-substituted sulfimine, wherein the pKa of the acid produced is - 1 or less, and in this example, the sensitivity can be increased. From the acid generator, the following particularly preferred embodiments are presented.

-46- 201033732 (α S, CF3SO3·(η) (α: C4F9S03-

CeFt7S〇3- (z3) (Φ+ (:[Φ

C^F^COO· pFs ^ P -O3S ^1753⁄4-

(z5) cf9 (z7) {0i + C2F5OC2F4SO3* (4) (4)

Ch3coo- (z9)

^s-^-F 〇-s-〇-sft3s-^-F (z1〇) (z11)

C^FqSOj* o (z13)

(Z12)

Bu〇~^3~ s+c4ft&gt;

FeSOr O^O- &lt;z14)

(z16) (~f~〇^+ c*f*s〇3· (ΗΌ)·;+ ·°33_^&quot;ρ (*18) (z19) (z17)

201033732 CJF^O^· (*22) c^Or * (Z25) 1 〇 Γ N-O-S-CFj O (z28) /—v ? y* 9 O-s^s λ^f o o (z31)

CFsSQr (Z21) CP3SOr ' (z24) dx^. -卜 (z27) O Hz 〇 ii ·* a s-c-s o i (230) C«FirS〇3r (Z23) aj^

C^fSOT (z26) (Bc^N-〇fCFi °(«29) .s^c-s-h- O 0 1 (z32)

Me〇-

CN

-rcp3

HsCH2CH2C-S-〇, CFS CFj ^ one. JO^. o -S-CH2CHiiCH3 b (z33) (234) \s/&gt; CFsSOr C4FeS〇r (*35) (Z36)

MeO • Or c^Fgsor (238)

CeF-|7S〇3- (z37) OBu 〇φ CASOr (z41) (239)

(z40) 〇4FgS〇3- o

(z43) -48- 201033732

(ζ47) ο

(245) ο

C4FsS〇r

〇 严 〇 ιβΗη C4F9SO3- C4FeSQ C4F»S〇a- (246)

(252) (Ζ50) (ζ51)

(〇)*s+ ^»8^°+|··Λ&lt;ϊ,5Ηϊ, (0}3^ •°»s-f+〇++csHe_〇~/^

(ζ59) ο (ζ58) Ο F Ο

ο (Ζ60) (Or Ο

C2F5 〇=S-. 2 yield 5 Ο (α 3—c4f. S* (ζ61) 〇=S—〇4Fg Ο (ζ62) -- 201033732

C*FjS〇3· (ζ64) Η

C4F9S03- (ζβ5&gt; (Ζ63) (〇)τ ο -C%S-CF2CFa〇F2-S-Nv Ο

+ -OsS-CF2CFiCF2-SN Ο \t (ζββ) (ζ67&gt;9 9 -OaS-CFiCFiCFa-SO-^^—(^3)&quot;S+ ^°&quot;|-^~|'0,:2〇 ^0,=2&quot;|

Ο Μ S-F (*6β) (ζ69) (^^~s+ F3C4'N_i-cFiCFiCiv 曼.〇~0~0 Ο · ο (ζ70&gt;

-〇3s (Ο): ο II o=s-c3f7 汧 *Ν, 0==S—C3F7 II (z71) 〇9 S+ O^S-CFaCW§-N ) (273) (α (Or

F F (274) Yue (oh·{Bu f)3 (〇ϋ一奶休休77)

(Q^S+CiF5S〇3- (^S+ C3F7SO3- (z79) (z80) (^S+ CeF«S〇3-(z81) -50- 201033732

(z90) (291)

-51- 201033732

Also, a preferred acid generator includes a compound represented by the following formula (I) and a compound capable of producing an acid represented by the following formula (P1).

In view of obtaining the effect of the present invention, the acid generator is such that the acid (produced acid) produced after irradiation with actinic rays or radiation has a molecular weight of 300 or more, and the acid has a monocyclic or polycyclic ring, A compound of an alicyclic or aromatic ring which may contain a hetero atom is preferred. For example, a compound capable of producing the acid can be selected from the above-described acid generator, and a compound represented by the following formula (I) and a compound capable of producing an acid represented by the following formula (P1) are preferably selected. .

The molecular weight of the acid produced is preferably 320 or more, more preferably 340 or more and most preferably 350 or more. The upper limit of the molecular weight is preferably 600 or less, more preferably 500 or less.

© Θ X

(I) (wherein X + represents an organic counterion and R represents a hydrogen atom or an organic group). In the formula (I), 'R represents a hydrogen atom or an organic group, and an organic group having a carbon number of 1 to 40 is preferred, an organic group having a carbon number of 3 to 20 is more preferable, and the following formula (II) The organic group represented is the best. -52- 201033732 The organic group of R is sufficient if it has one or more carbon atoms, and the organic group bonded to the oxygen atom in the ester bond shown in formula (I) is a carbon atom. Preferably, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and a 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, one of these groups may have another substituent, or the organic group may have a substituent such as a hydroxyl group, a decyl group, a decyloxy group, an oxy group (= 0) or a halogen atom. As for the structure of the R, the structure represented by the following formula (II) is preferable. ❹

-(CH2)n-Rc-(Y)ffl (II) In the formula (II), Rc represents a monocyclic or polycyclic carbon group having a carbon number of 3 to 30, which may include a cyclic ether or a ring. a thioether, a cyclic hydrazine, a cyclic carbonate, a lactone or an indoleamine structure; γ represents a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a hydrocarbon group having 1 to 10 carbon atoms, and a hydroxyl group having 1 to 10 carbon atoms. An alkyl group, an alkoxy group having 1 to 10 carbon atoms, a fluorenyl group having 1 to 1 carbon number, an alkoxycarbonyl group having 2 to 10 carbon atoms, a decyloxy group having 2 to 10 carbon atoms, having carbon a number of 2 to 10 alkoxyalkyl groups or a haloalkyl group having a carbon number of 1 to 8; m = from 0 to 6; when there are a plurality of Y's, each Y may be the same as or different from each other Y ; and n = from 0 to 10. The total number of carbon atoms constituting the R group represented by the formula (?1) is 4 Å or less. Preferably, n = from 〇 to 3 and Rc is a monocyclic or polycyclic cyclic organic group having 7 to 16 carbon atoms. The molecular weight of the compound represented by the formula (I) is usually from 300 to 1,000, and preferably from 400 to 800, more preferably from 500 to 700. Examples of the X+ organic counterion include phosphonium cations and iodine-53-201033732 ions. Preferable specific examples of the compound represented by the formula (I) include compounds represented by the formulas (ZSCi) and (ZIC1):

R201 FF R202^S^R203Q^|&quot;fY〇'R ^2〇4-%2〇50〇-|^〇'« ^C1 Z|C1 In the formula (zsc ,, the definition of R and better The range is the same as those defined in the formula (I).

The definitions, specific examples, preferred examples and the like of the R2 0 1 , R2Q2 and R2Q3 are the same as those of R20!, R2Q2 and R203 in the formula (ZI). In the formula (ZIC1), the definition and preferred range of the R are the same as those defined in the formula (I). The definitions, specific examples, preferred examples and analogs thereof of R2Q4 and R2〇5 are the same as those of R2〇4 and R2〇5 in the formula (ZII). Specific examples of the compound represented by the formula (I) are proposed below, but the invention is not limited to these compounds. In this equation, the molecular weight of the anion in each compound is shown. -54- 201033732 ptj :323.29 ^ &amp;«:311.24 ^ ^1:32333

Qf-7&gt; 〇 〇rV. * Cold aV. -^9 〇r-i) : 353.38 wide 308.31 Q wide ·1 . Well known ^ q^Iq HV® 〇r. You 兮 0^-4) 〇r-5) ¢/-6) j^V :325.31 Q F **: 341.31 p. ^:339.33 03⁄4 mV· 03⁄4e.仇梦 h cXd hw®- σ·0) &lt;v-r&gt; ^Vj :33Τ.3β ^*: 351.34 pS trait: 389.27 ❹ CM〇&gt;CM1&gt;〇M2&gt;

CM 4) CMS) ^Λ: 375.41 0^-13⁄4

MHI: 385.41 ^ rape ": SISI.39 Q F each. * Participation. Gap cr-ιβ) CM 7) CM 8) 〇 (y^〇ih°^cy (f^4r^〇- (fxS^ih0^^ CM® (Y-20) (V-21) Molecular enthalpy: 3B7. 34 Molecular weight: 351.30 0^-23⁄4 0^-23) -55- 201033732 A The amount of rape: 257^23cfe.^〇

® . θ, Good quantity: 24321 ) lV5x> CY-25) Molecule*: 231*20

(★29) (Y-24) Q, foot Q punishment a^s^· (Y-27) ^*:189.12 广| Good amount: still (ΤΌ0^ crbe〇^ 17&amp;09 cm (Υ·31) ^ f*:253^5 |p»K Liver Molecular Weight: 343&lt;41 'ΌιιΗυ (Y-33) (Y-34)

aV‘ molecular weight mo Q| crbe〇^

9 9 Molecular weight: 32333 °^°te (Y-3B) (Y-37) 0T-3B)

(^33⁄4 Molecular Weight: 203.23 0 a^b00^ crd0^' (4) _ ^4:25321 Ό-°η ^ »*:251.1β

ΗΗ*2Βδ·21

Molecular weight: 32 WO 77 丁慕· (^Q9〇^f'^9 〇M2) (Υ·44)

ρ. ^*:275Λ Q f Q ρ Liver (Y-4S) ΓΜ6) (V-47) Rape 1::32333

CM8) ^«V ^Λ:2Β327 ^ ^ 13⁄40°^^ crbe〇^' (Υ-49) (Y-60) -56- 201033732 Molecular weight: 275.16 e〇lV^ Molecular weight: 259.16 , 0ΐήΓ〇Τ?ρ &lt;ν·5ί】

Caterpillar: 273.23 0&lt;-52) (V-53) Molecular halo: 249.17 (Υ-54)

Molecular weight: 261,18 molecular smoke: 275.20

The most profit: 255.17 (V-S5) θο-| cr-m (10)) Molecular weight: 39153

(TO Molecular Most: M1.32 ^^: 339.29 |^v ^*: 35t59CfsX) (XX)e〇·^^ (Y-99) (Υ-60) (Υ·61&gt;

Cn _ J/ _ 201033732

aae〇-lV^ °^e〇lV^&gt; 〇eJ^°W^y (pour) (Y-S9) 0 (heart 70)

The root compound represented by the formula (I) can be synthesized by a known method (for example, the method described in JP-A-2007-161707).

: Configurable As for the compound represented by the formula (I), two or more kinds can be used in combination with one type #. &lt;Acidity As for the acid generator, it is also preferred to produce a compound of the formula (4) which is represented by the following formula (Ρ 1). Ho3s

(Pi) -58- 201033732 In the formula (P1), each of 1 to Rs independently represents a hydrogen atom, a fluorenyl group, a cycloalkyl group, a halogen atom or a hydroxyl group; and R9 represents a hydrogen atom, an alkyl group, a cycloalkyl group, Alkenyl, indenyl or -SOaRs; A represents a divalent linking group or a single bond containing a hetero atom; Rs represents an alkyl group, a cycloalkyl group or an aryl group; and each of ml to m4 independently represents an integer from 0 to 12, The constraint is m3+m4g 1, m5 represents an integer of 1 to 3, and when any one of ml to m5 is an integer of 2 or more, the plurality of members 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 substituted fluorenyl group. Examples of the hetero atom-containing divalent linking group of the A include an oxygen atom, -CO-, -CONR-, -S02NR-, -CONRCO-, -S02NRC0-, -S02NRS02-, and -OCONR-, wherein R represents A hydrogen atom, an alkyl group or a cycloalkyl group. Each of 1 to R8 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, wherein Rx represents an alkyl group, a cycloalkyl Q group, an aryl group or a heteroaryl group, and a cycloalkyl group or an aryl group is preferred. In the formula (P1), the 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 (P1) is preferably a structure represented by the following formula (1-A):

(1-A) -jy - 201033732 In the formula (1A), 1^ to r9, a and ml to m5 each have the same meaning as 1 to R9, A and mi to m5 in the formula (P1); And M + represents an organic counter cation. The organic counterion represented by M + is preferably iodine or ruthenium ion, and the ruthenium ion is better. The acid represented by the formula (P1) is preferably a structure represented by the following formulas (1_B) to (1_D): ?F3 if1?1? FF / FF\ f H〇3S-ff-〇Re H〇3S -|- | I j-OR, 1--1) 〇-&gt;=CF2 ,,J&quot; FFHHF FV CFsF/me (1~®) OC) (1-D) In Equations (lB) to (lD) Wherein r9 has the same meaning as R9 in the formula (P1); and m6 represents an integer 〇 to 2. In particular, a compound capable of producing an acid represented by the formula (P1) is preferably represented by the following formulas (1-E) to (1-G): ©Θ f ?Fa MO3S-I~(-013⁄4 F Η (1^) M^S- (1-F) ®Θ ^ U 〇r9 mo3s—|—[4o—|—m-ο—1=cf2 F p\ cf3 (1-G) In -E) to (1-G), r9 and M + have the same meaning as M in the formula (1_A), and m6 has the same meaning as m6 in the formula (i_D). A specific embodiment of the compound of the acid represented by the formula (P1) 'but the invention is not limited thereto" 201033732

(Χ2) (Χ4)

(Χ8) (Χ8)

(Χ10) (Χ12)

°4-h3 a 八廿 0ιγΛ=7~Γγ γ^] 0 F Η ° :383.27

(Κ13) (Κ15)

(Χ14) (Χ16) -61 - 201033732 (X18)

11 (X25)

Molecular weight: 229.1Q

Molecular weight: 161,11 (X26) OFF 〇 〇

Molecular setting: 267.18 (X27)

Cut Ti | I°^ΗΗ- O F F -) (X28) t: 329 25 asb〇1 OFF 0 F F Molecular weight: 309 26

(X31) (X29)

(X3G) (X32) -62- 201033732

(X33)

(X37) (X39) (X35)

(X34) (X36) (Χ3Θ)

Λ O F F F F F Fέ8&gt; ^+f〇-h+〇+M-〇^ off cf3 f cf3 f

(X40) (X42) (X43) Molecular Weight: 609.14

Λ O F F F F F 0-S-(-0-|——1-0 (X44) CF3 F CF3 F Most: 559.13 -- 201033732

j r» &gt; *

HOOC T o Molecular maximum: 315, 27 (X47)

o (X48) Molecular setting: 333.21

-64- 201033732 Ο

Ο Tao

(Χ58) (Χ60)

t u r" CF3 F

OFF

Me〇-CH=N-〇^-H-〇+~h〇 F CN OFF F F (X85) 0 F CF3 =N-o-s—|—|—a cf3 off (X6B)

-65 - 201033732 The compound capable of generating an acid (such as a compound represented by formula (I) or (1-A)) in the composition of the photosensitive ray or radiation sensitive resin after irradiation with actinic rays or radiation The content is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 10% by mass, still more preferably from 1 to 7% by mass, based on the total solid content of the sensitized ray or the radiation-sensitive resin composition. [3] Resin (C) having a repeating unit containing at least one polarity converting group and having at least one of fluorine atoms or germanium atoms (C) The photosensitive ray or radiation sensitive resin composition of the present invention comprises (C) one having at least a repeating unit of a polar converting group (〇, a resin having at least one of a fluorine atom or a germanium atom. The resin (C) has hydrophobicity, and in particular, to reduce development defects, the addition of the resin (C) is more Preferably, the polar conversion group is a group which can be decomposed by the action of an alkaline developer to increase the solubility in the inert developer. Examples thereof include a lactone group and a carboxylate group. (-COO-), an acid anhydride group (-C(Q)OC(O)-), a quinone imine group (-NHCONH-), a carboxylic acid thioester group (-C0S-), a carbonate group ( -OC(O)O-), a sulfate group (-0S020-) and a sulfonate group (-so2o-). Attached directly to the backbone in the repeating unit (such as acrylate) An ester group which is poor in function to increase solubility in an alkaline developer by decomposition by an alkaline developer' and does not include In the polar conversion group of the present invention, the embodiment of the repeating unit (c) includes the structure represented by the formula (K0): 201033732 (Κ〇)

In the formula, Rk1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group or a group having a polar conversion group;

Ru represents an alkyl group, a cycloalkyl group, an aryl group or a group having a polar conversion group, which is restricted to have a polarity-switching group of at least one of Rm2 and Rk2. Incidentally, as described above, the ester group directly bonded to the main chain of the repeating unit represented by the formula (K0) is not contained in the polar conversion group of the present invention. The polar conversion group is preferably a group represented by X in a partial structure represented by the formula (KA-1) or (KB-1):

In the formulae (KA-1) and (KB-1), X represents a carboxylate group··-COO-, an acid anhydride group: -C(0)0C(0)-, a quinone imine group:- NHCONH-, a carboxylic acid thioester group: -COS-, a carbonate group: -0C(0)0-, a sulfate group: -OS020-, or a sulfonate group: -S020-. Each of Y1 and Y2 may be the same or different and represents an electron withdrawing group. Incidentally, the repeating unit (C) has a preferred polarity-switching group by including a group having a partial structure represented by the formula (KA_1) or (KB-1), but as in Y1 and Y2 In the example of the structure represented by the formula (KA-1) or the structure represented by the formula (KB-1), when the partial structure does not have a bond, the group having the partial structure is one. A group having a monovalent or larger valence group derived from the removal of at least one arbitrary hydrogen atom in the 201033732 partial structure. The partial structure represented by the formula (KA-1) or (KB-1) is bonded to the main chain of the resin (C) via a substituent at an arbitrary position. The partial structure represented by the formula (KA-1) is a structure in which a ring structure is formed together with a group such as X. In the formula (KA-1), X is a carboxylate group (that is, an example of forming a lactone ring structure such as KA-1), an acid anhydride group or a carbonate group.

Preferably, the carboxylate group is more preferred. The ring structure represented by the formula (KA-1) may have a substituent, and may have, for example, nka substituents Zkal.

Zkal represents (each of which is independently represented when a plurality of Zkal are present) 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.

Zkal can be combined with each other to form a ring. Examples of the ring formed by bonding Zkal to each other include a cycloalkyl ring and a heterocyclic ring (e.g., a cyclic ether ring, a lactone ring). Nka represents an integer 〇 to 1〇, and an integer 〇 to 8 is preferred, and the integer 0 is

5 is better, integers 1 to 4 are better and integers 1 to 3 are optimal. As for the electron withdrawing group Zkal, it has the same meaning as the Y1 and Y2 electron withdrawing groups (typically halogen atoms) described later. The above electron withdrawing group may be substituted by another electron withdrawing group.

Zkal is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group or an electron withdrawing group and is preferably an alkyl group, a cycloalkyl group or an electron withdrawing group. 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 -68 to 201033732 group or the like is preferred. The preferred embodiment of the electron withdrawing group is the same as those of the Y1 and Y2 described later. As the embodiment of the halogen atom zkal, it includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred. As the alkylzkal, it 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, butyl, and tertiary. Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 0-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, tert-butyl, isopentyl, and tertiary pentyl groups. , 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. As the cycloalkyl group Zkal, it may have a substituent, may be monocyclic or polycyclic, and may be crosslinked. For example, the cycloalkyl group can have a bridged structure. The cycloalkyl group of the mono q ring is preferably a cycloalkyl group having a carbon number of 3 to 8, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group and a cyclooctyl group. Examples of the 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 6 to 20 carbon atoms is preferred, and examples thereof include adamantyl, norbornyl, isodecyl, fluorenyl, dicyclopentyl, (X-pixel) groups. , tricyclodecyl, tetracyclododecyl and androstanyl. As for the cycloalkyl, the following structure is also preferred. Incidentally, one of the carbon atoms in the cycloalkyl group may be a hetero atom such as oxygen. Atomic) replacement -69- 201033732 (13) oa«) (25) (2«) □&gt; O Q&gt; WW (3)

O〇 . CO CO

&lt;4) (S) W 1 CO 〇〇〇 ^ /fi\ /Λ o? (ie&gt; (Π) (U) 〇 5°

(IS) &gt;A (W) ^ 〇4 Jb (20) (21) (both (») A ob \ ,,c\ i^c\ nm (24) ^ &lt;d^\ (M) WW 01 ) ^ (4) 04) Example knows ^bb. .

W ¢57) (4) W ω ^ ^? £&gt; («) («&gt; («) {43) 〇5) ® (4)(45) (46} 〇〇Ο 〇(47) (48) (49 (50) The preferred alicyclic moiety comprises adamantyl, norantantyl, naphthyl, tricyclodecyl, tetracyclododecyl, norbornyl, cedarol, cyclohexyl , cycloheptyl, cyclooctyl, cyclodecyl and cyclododecyl. adamantyl, naphthyl group, thiol group, cedar group, cyclohexyl, cycloheptyl, cyclooctyl, ring More preferably, the alkyl group, the cyclododecyl group and the tricyclodecyl group. 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. Alkyl groups are preferred, 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 to 4. The alkoxy group is preferably more than -70 to 201033732, such as methoxy, ethoxy, propoxy and butoxy. Examples of the substituent which the alkyl group and the alkoxy group may have include a hydroxyl group, a halogen atom and an alkane. An oxy group (having preferably a carbon number of 1 to 4). The lactone ring of the Zkal Examples of the group include a group derived from a hydrogen atom removed in a structure represented by any one of the formulae (KA-1-1) to (KA-1-17) described later. Examples of the base include phenyl and naphthyl.

Examples of the substituent which the alkyl group, the cycloalkyl group and the aryl group of zkal may further have include a hydroxyl group, a halogen atom (for example, fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an alkyl group described above, Alkoxy (such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, n-butoxy, isobutoxy, bis-butoxy and tert-butoxy) , alkoxycarbonyl (such as methoxycarbonyl and ethoxycarbonyl), aralkyl (such as benzyl, phenethyl and decyl), aralkyloxy, fluorenyl (such as formazan, B) Anthracenyl, butyl fluorenyl, benzamidine, cinnamyl and pentamidine), anthraceneoxy (such as butanoxy), alkenyl, alkenyloxy (such as vinyloxy, propenyloxy, alkene) as described above Propyloxy and butenyloxy), an aryl group as described above, an aryloxy group (such as a phenoxy group), and an aryloxycarbonyl group (such as a benzhydryloxy group). In a preferred embodiment, X in the formula (KA-1) is a carboxylate group ' and a partial structure represented by the formula (KA-1) is a lactone ring, 5 to 7 lactone The ring is preferred. Incidentally, it is preferable to condense to another 5 to 7-membered lactone in the form of a bicyclic or spiro structure as shown in (KA-1-1) to (KA-1-1 7) below. The ring 'is a partial structure represented by the formula (KA-1). The actual 201033732 embodiment of the ring structure to which the ring structure represented by the formula (KA-1) can be combined includes those shown in the following (KA-ll) to (KA-1-17) and according to the subsequent structure. . The structure including the lactone ring structure represented by the formula (KA-1) is preferably a structure represented by any one of the following (KA-1-1) to (KA-1-17). The lactone structure can be bonded directly to the backbone. Preferred structures are (KA-1 -1), (KA-1 -4) ' (KA-1-5), (KA-1.6), (KA-1-13), (KA-1-14) And (KA-1-17) 〇

The structure comprising the lactone ring structure described above may or may not have a substituent. The preferred embodiment of the substituent is the same as those which may be possessed by the ring structure represented by the formula (KA-1). Some lactone structures have optical isomers, but any optical I# isomer can be used. The 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. In the formula (KB·1), X is preferably a carboxylate group (-COO-). In the formula (KB-1), each of γι and γ2 independently represents an electron withdrawing group. -72 - 201033732 The electron withdrawing group is preferably a partial structure represented by the following formula (EW). In the formula (EW), * means a bond directly bonded to (KA-1) or directly bonded to a bond of X in (KB-1).

Kwl *· R©w2 (EW)

In the formula (EW), new is the number of overlaps of the linking group represented by -C(Rewl)(Rew2)- and represents an integer of 0 or 1. In the case where new is 0, this indicates that the bond is formed by a single bond and Yewl is directly bonded.

Yewi is a halogen atom, a cyano group, a nitrile group, a nitro group, a halogen (cyclo)alkyl group or a halogeno group represented by -C(Rfl)(Rf2)-Rf3 described later, an oxy group, a carbonyl group, a fluorenyl group. , Ya Fengji or a combination thereof. The electron withdrawing group can be, for example, a structure shown below. The designation &quot;halo(cyclo)alkyl&quot; refers to an alkyl or cycloalkyl group that is at least partially halogenated. Each of Re W3 and Rew4 independently represents an arbitrary structure. The partial structure represented by the formula (EW) may have an electron withdrawing group and a bonding such as a resin main chain (regardless of the structure of Rew3 and Rew4), but an alkyl group, a ring-based group or a fluorinated group is preferred.

*C—N— t

•S—N—R· II I 1^0 Rew3

In the case where Yewl is a divalent or larger valence group, the remaining bond forms a bond with any atom or substituent. At least any one of the groups of Yewl, Rewl and Rew2 may be bonded to the main chain of the resin (C) via a further substituent. R-try -/J - 201033732

Yewl is preferably a halogen atom or a halogen (cyclo)alkyl group or a halogen aryl group represented by -C(Rfl)(Rf2)-Rf3.

Each of Rewl and Rew2 independently represents an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. At least two members from Rewl, Rew2, and Yewl may be combined with each other to form a ring.

Rn represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group or a perhaloaryl group, and a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group is preferred, a fluorine atom or three

More fluoromethyl groups.

Each of Rf2 and Rf3 independently represents a hydrogen atom, a halogen atom or an organic group, and 1^2 is bonded to Rf3 to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group and an alkoxy group, and these groups may be substituted by a halogen atom (preferably a fluorine atom). It is preferred that each of Rf2 and Rn is a (halo)alkyl group. Rf2 is preferably the same group as Rn or is bonded to Rf3 to form a ring.

Rf2 and Rf3 may be combined to form a ring, and examples of the ring formed include a (halo)cycloalkyl ring and a (halo)aryl ring.

Examples of the (halo)alkyl group in Rn to Rn include an alkyl group in Zkal and a halogenated structure thereof. Examples of (per)halocycloalkyl and (per)haloaryl groups in the Rn to Rn or in the ring formed by the combination of Rf2 and Rn include a halogenation reaction derived from a cycloalkyl group in Zkal The structure is preferably a fluorocycloalkyl group represented by -C(4)F(2n_2&gt;H and a perfluoroaryl group represented by -(:(a) 彳(1)(1), wherein the carbon number η is not particularly limited, but from 5 to 1 3 Preferably, 6 is more preferably. The ring formed by bonding at least two members of Rewl, Rew2 and Yewl to each other is preferably a cycloalkyl or heterocyclic group, and the heterocyclic group is internally-74- 201033732 Preferably, the ester ring group. Examples of the lactone ring include structures represented by the formulae (KA-ll) to (KA-1-17). Incidentally, the repeating unit (c) may have a plurality of a partial structure represented by the formula (KAH), a plurality of partial structures represented by the formula (KB-1), or a partial structure of the formula (KA-1) and a partial structure of the formula (KB-1). This partial structure of the formula (KA-1) may also be partially or completely provided as an electron withdrawing group of Y1 or Y2 in the formula (KB-1). For example, X in the formula (KA-1) a carboxylate group Wherein, the carboxylate group can be used as an electron withdrawing group of Y1 or Y2 in the formula (KB-1). The repeating unit (c) can be a repeating unit (c'), which is One side of the chain having at least one of a fluorine atom or a ruthenium atom and a polar conversion group; a repeating unit (C*) having a polar conversion group and having no fluorine atom or ruthenium atom: or a repetitive unit (C&quot; ) having a polarity-switching group on one side chain while having at least one of fluorine atoms or germanium atoms in the side chain of the different side chain in the same repeating unit, but the resin (C) includes heavy The covering unit (c') is preferable as the repeating unit (c). That is, it is preferable that the repeating unit having at least Q-polarity-switching groups (the fluorene has at least one of a fluorine atom or a germanium atom). In the example where the resin (C) includes the repeating unit (c*), the resin is a repeating unit (repeating unit (cl) described later) containing any one having at least a fluorine atom or a ruthenium atom. The copolymer is preferred. Similarly, in the repeating unit (c&quot;, the polarity conversion The side chain of the group and the side chain having at least one of fluorine atoms or germanium atoms are bonded to the same carbon atom in the main chain, that is, have a positional relationship of the following formula (K1). Wherein Β1 represents a partial structure having a polar converting group and 201033732 B2 represents a partial structure having at least one of a fluorine atom or a ruthenium atom. B1 才,七(K1) B2 Similarly, in the repeating unit (C In the *) and repeating unit (C&quot;), the polarity converting group is preferably a partial structure represented by -COO- in the structure of the formula (KA-I). The polar conversion group is decomposed by the action of an alkali developer to achieve a polar conversion, whereby the receding contact angle of the resin composition film with water after alkali development can be reduced. The resin composition film has a receding contact angle with water of 50° or less after alkali development, at a temperature during exposure (usually at room temperature of 23±3° C.) and a humidity of 45±5%. , 4 (Τ or smaller is better, 35° or smaller and better and 30° or smaller is the best. The receding contact angle is the contact measured when the contact line on the droplet-substrate interface is retracted. Angle, and it is known that this is generally useful in simulating the mobility of droplets in a dynamic state. In a simple manner, the receding contact angle can be defined as when the droplets ejected from the tip of the needle land on the substrate, then When the droplet is drawn into the needle again, the contact angle at the time of the droplet interface is retracted. Generally, the receding contact angle can be measured by a contact angle measuring method called an expansion/contraction method. (C) The hydrolysis rate to the alkaline developer is 〇〇〇1 nm/sec or more, preferably 0.01 nm/sec or more, 01 nm/sec or more and more preferably 1 Best for nano/second or larger. The hydrolysis rate of the resin (C) to the alkaline developer is a resin formed by the resin 201033732 (C) alone. Film thickness, which is a rate of reduction when treated with tmah (aqueous solution of tetramethylammonium hydroxide) (2.38 mass%) at 23t: The resin (C) of the present invention contains one having at least two or more polarity transitions The repeating unit (c) of the group, preferably a resin (C1) having at least one of a fluorine atom or a ruthenium atom, is preferred in the case where the repeating unit (c) has at least two polarity-switching groups. The repeating unit (c) preferably has a partial structure having two polarity converting groups represented by the following formula (KY-1). Incidentally, when the structure represented by the formula (KY-1) does not have one In the case of a bond, this is a monovalent or larger valence group resulting from the removal of at least one arbitrary hydrogen atom in the structure.

In the formula (KY-1), 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 group, a hydroxyl group, a cyano group, Amidoxime group or 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 part of the carbonyl group (= 0) »

Each of Rky2 and Rky3 independently represents an electron withdrawing group, or when Rkyl is combined with Rky2 to form a lactone ring, Rky3 is an electron withdrawing group. The lactone ring formed is preferably a structure of (KA-1-1) to (KA-1-17). Examples of the electron withdrawing group are the same as those of Y1 and Y2 in the formula (KB-1), and a halogen atom and a halogen (cyclo)alkyl group or a halogen represented by -C(Rfl)(Rf2)-Rf3 The aryl group is preferred. In a preferred embodiment, Rky3 is a halogen atom or a halo(cyclo)alkyl or haloaryl group represented by -C(Rfl)(Rf2)-Rf3, and Rky2 and f-tm-II-201033732

Rkyl combines to form a lactone ring or an electron withdrawing group which does not contain a halogen atom.

Rkyl, Rky2 and 1^^ may be bonded to each other to form a monocyclic or polycyclic structure.

Specific examples of Rkyl and Rky4 include the same groups as those of Zkal in formula (KA-1). The structure in which the lactone ring formed by combining the ruthenium and Rky2 is (KA-1-1) to (KA-1-17) is preferable. The examples of the electron withdrawing group are the same as those of Y1 and Y2 in the formula (KB-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 monovalent or larger valence group which generates at least one arbitrary hydrogen atom removed from the structure.

In the formula (KY-2), each of Rky6 to Rkyio independently represents a hydrogen atom, a _ atom, a group, a ring group, a aryl group, a decyloxy group, an oxy group, an ether group, a hydroxyl group, A cyano group, a guanamine group or an aryl group.

Two or more members of Rky 6 to Rkyl 0 may be bonded to each other to form a monocyclic or polycyclic structure.

Rky5 represents an electron withdrawing group. The examples of the electron withdrawing group are the same as those of Y1 and Y2, and a halogen atom and a halogen (cyclo)alkyl group or a halogen aryl group represented by -C(Rn)(Rn)-Rf3 are preferred.

Specific examples of Rky5 to RkylO include the same groups as those of 201033732 zkal in 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), 'Zkal and nka have the same meanings as in the formula (ΚΑ-1). Rky5 has the same meaning as in the formula (KY-2).

Lky stands for a base, an oxygen atom or a sulfur atom. Examples of the Lky's extended base include methylene and ethyl. Lky is preferably an oxygen atom or a methylene group, and a methylene group is more preferred. The repeating unit (C) is not limited as long as it is a rectifying unit obtained by polymerization (such as addition polymerization, condensation polymerization, and addition condensation), but is 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 an α- or β-position), a styrene-based repeating unit (including at (X- or β-0 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, Malayanya) An amine) repeating unit, an acrylate-based repeating unit, a styrene-based repeating unit, a vinyl ether-based repeating unit, and a decene-based repeating unit are preferred, and An acrylate-based repeating unit, a vinyl ether-based repeating unit, and a decene-based repeating unit are preferred, and an acrylate-based repeating unit is preferred. The more specific structure of the unit (C) is preferably a repeating unit having a partial structure shown in the following -79 - 201033732. The repeating unit (C) may be a repeating unit having a partial structure shown below.

In the formula (CC), Z! represents (when there are a plurality of 21, each of which is independently represented by a single bond, an ether bond, an ester bond, a guanamine bond, a urethane bond or a urea bond), and The ester bond is preferred. Z2 represents (when a plurality of Z2 are present, each independently represents a chain or a cyclic alkyl group, and has an alkylene group having 1 or 2 carbon atoms or a cycloalkyl group having a carbon number of 5 to 10) good. Each Ta independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, a guanamine group, an aryl group or an electron withdrawing group (having a Y1 in the formula (KB-1) and The Y2 electron withdrawing group has the same meaning), and an alkyl group, a cycloalkyl group or an electron withdrawing group is preferred, and an electron withdrawing group is more preferable. When there are a plurality of Tas, the Tas may be combined with each other to form a ring. L〇 represents a single bond or a (m+1)-valent hydrocarbon group (having a carbon number of 20 or less) and a single bond is preferred. When m is 1, a single bond is formed as L〇. The (m+1) valent hydrocarbon group as L 代表 represents (m+i) valence formed by removing m-Ι arbitrary hydrogen atoms from, for example, an alkyl group, a cycloalkyl group, a phenyl group, or a combination thereof. Hydrocarbon group. Each L independently represents a carbonyl, carbonyloxy or ether group.

Tc represents a hydrogen atom, an alkyl group, a cycloalkyl group, a nitrile group, a hydroxyl group, a guanamine group, an aryl group or an electron withdrawing group (having the same γ ΐ and γ 2 electron withdrawing groups in the formula (KB-1) Meaning). -80- 201033732 * represents the bond to the main or side chain of the resin. That is, a partial structure represented by the formula (cc) may be directly bonded to the main chain, or a partial structure represented by the formula (CC) may be bonded to the resin side chain. Incidentally, the bond to the main chain is a bond to an atom existing in a bond forming the main chain, and the bond of the opposite side chain exists in a portion other than the main structure for the bond structure. The bond of the atom. m represents an integer of 1 to 28 and is preferably an integer of 1 to 3, more preferably 1. k represents an integer of 0 to 2, and 1 is preferred. 〇

q is a group (the number of repetitions of Z2-Z〇 and represents an integer of 0 to 5, and preferably from 0 to 2. r represents an integer 〇 to 5. instead of -(L)r-Tc, -L described above 〇-(Ta)m may be substituted. There is a fluorine atom at the terminal of the lactone or a side chain different from the side chain on the sugar lactone side in the same repeating unit (c&quot;) It is also preferred to have a fluorine atom. The carbon number of the alkyl group as Z2 is preferably from 1 to 30, more preferably from 1 to 20, in the case of a linear alkyl group; and in the case of a branched alkyl group, More preferably from 3 to 30, more preferably from 3 to 20. A specific embodiment of the alkylene group as R2 comprises a group derived from the removal of an arbitrary hydrogen atom in a particular embodiment of an alkyl group such as Zkal described above. The cyclic alkyl group as Z2 is preferably a cyclic alkyl group having 3 to 8, and specific examples thereof include a group derived from the removal of an arbitrary hydrogen atom from a cycloalkyl group such as Zkal described above. The preferred carbon number of the alkyl group and the cycloalkyl group as Ta and Tc and the specific examples are the same as those described above for the alkyl group and the cycloalkyl group as Zkal. η 1 • 01 - 201033732 The alkoxy group as Ta is preferably an alkoxy group having 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group and a butoxy group. The aryl group as Ta and Tc is The aryl group having 6 to 12 carbon atoms is preferred, and examples thereof include a phenyl group and a naphthyl group. The preferred carbon number of the alkylene group and the extended cycloalkyl group as LQ and the specific examples and the above pair are used as redundant 2 The descriptions of the alkyl and cyclic alkyl groups are the same.

As for the repetitive unit (the more specific structure of the crucible, the repetitive unit having the partial structure shown below is preferable.

(ca-2) (Ta)m

In the formulae (ca-2) and (cb-2), η represents an integer of 0 to 11 and an integer of 0 to 5 is preferable, and 1 or 2 is more preferable. Ρ represents an integer 〇 to 5 and an integer of 0 to 3 is preferred, and 1 or 2 is more preferred.

Each Tb independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, a guanamine group, an aryl group or an electron withdrawing group (having a Y1 in the formula (KB-1) and The Y2 electron withdrawing group has the same meaning), and an alkyl group, a cycloalkyl group or an electron withdrawing group is preferred. When there are a plurality of Tbs, Tb can be combined with each other to form a ring. * represents a pair of primary or side chain bonds of the resin. That is, a partial structure represented by the formula (ca-2) or (cb-2) may be directly bonded to the main chain, or a partial structure represented by the formula (ca-2) or (cb-2) may be Bonded to the side chain of the resin.

Zi, Z2, Ta, Tc, L, *, m, q and r have the same meanings as those in the formula (cc), and the preferred specific examples are also the same. -82- 201033732

In the formula (KY-4), R2 represents a chain or a cyclic alkyl group, and when a plurality of R2 are present, each R2 may be the same as or different from each other R2. R·3 represents a linear, branched or cyclic hydrocarbon group in which part or all of hydrogen atoms constituting the carbon are replaced by fluorine atoms. 0 R4 represents a halogen atom, a cyano group, a hydroxyl group, a guanamine group, a hospital group, a ring-based group, an alkoxy group, a phenyl group, a fluorenyl group, an alkoxy group or a R_C(=(:)) or RC ( = 0) a group represented by 0- (wherein R represents an alkyl group or a cycloalkyl group). When there are a plurality of R·4, each R4 may be the same as or different from each other R4, and two or more r4 may be combined to form a ring. X represents an alkyl group, an oxygen atom or a sulfur atom. Representative of Z and Za (when there are a plurality of Z or Za, each of z or Za is independently represented by a single bond, an ether bond, an ester bond, a guanamine bond, an amine formmate bond or a urea bond) And when there are a plurality of Z or Za, each of Z or Za may be the same or different from each other Z or Za. * represents a pair of primary or side chain bonds of the resin. 〇 is the number of substituents and represents the integer 1 to 7. m is the number of substituents and represents an integer 〇 to 7. η is the number of repetitions and represents an integer 〇 to 5. The structure of -R^Z- is preferably a structure represented by -(CH^-COO- (wherein 1 represents an integer of 1 to 5). The preferred carbon number range of the chain or cyclic alkyl group as R2 and Specific -83-201033732 The examples are the same as those described for the alkyl and cyclic alkyl groups in Z2 of formula (cc). The carbon number of the linear, branched or cyclic hydrocarbon group as R3 is linear. In the examples of the hydrocarbon group, it is preferably from 1 to 30, more preferably from 1 to 20, more preferably from 3 to 30, more preferably from 3 to 20 in the case of branched hydrocarbon groups; and an example of a cyclic hydrocarbon group. In particular, from 6 to 20. Specific examples of R3 include specific embodiments of alkyl and cycloalkyl groups as described above for Zkal.

The preferred carbon number and specific examples of the alkyl group and the cycloalkyl group as R4 and R are the same as those described above for the alkyl group and the cycloalkyl group as Zkal. The fluorenyl group as R4 is preferably a fluorenyl group having 1 to 6 carbon atoms, and examples thereof include a fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl group, an isobutyl group, a amyl group and a pentamidine group. Examples of the alkyl moiety in the alkoxy and alkoxycarbonyl groups as R4 include linear, branched or cyclic alkyl moieties, and the preferred carbon number of the alkyl moiety and the specific examples and pairs described above as Zkal Those descriptions of alkyl and cycloalkyl are the same.

Examples of the alkylene group as X include a chain or a cyclic alkyl group, and preferred carbon numbers thereof and specific examples are the same as those described for the chain alkyl group and the cyclic alkyl group as R2. The repeating unit of the partial structure represented by the formula (KY-5) is more preferable.

(KY-5) In the formula (KY-5), R2 represents a chain or a cyclic alkyl group and when a complex is present - 84-

201033732 For several R2, each Rz may be the same as each other r2 or does not represent a linear, branched or cyclic hydrocarbon group from some or all of the hydrogen atoms constituting the carbon. a group represented by a halogen atom, a cyano group, a hydroxyl group, a decyl group alkyl group, an alkoxy group, a phenyl group, a fluorenyl group, an alkoxycarbonyl group or a group represented by RC(=0)0- (wherein R represents an alkane When the ring or ring has a plurality of R4, each R4 may be combined with each other 1^4 phase and two or more R4 to form a ring. X represents an alkylene group, an oxygen atom or a sulfur atom. A bond, an ether bond, an ester bond, a guanamine bond, an amine urea bond, and when a plurality of Z are present, each Z may be the same or different. * represents a bond to the main or side chain of the resin. The number of repeats and the integer 〇 to 5. m is the number of substituents and represents an integer 〇 to 7. The preferred range of carbon numbers in the heart to FU and X and those described in the specific formula (KY-4) The structure of -R2-Z- is preferably represented by -(CHzh-COO-; representing integers 1 to 5).

*—X'-A-O-C-X * -X'-A-C-O-X

II II 〇(rf-1) 〇(rf-2) In the formulae (rf-1) and (rf-2), X represents an electron withdrawing substituent, an oxycarbonyl group, an alkyl group substituted by a fluorine atom or It is preferred to extend the cycloalkyl group through fluorine. A represents a single bond or a divalent same as represented by -C(RX)(Ry)-. Fluorine atom substitution, alkyl group, ring R-C (= 0)- or hospital base). When they are different or different,

a formate bond or each of the other Z examples and a linking group in which a carbonyl group is substituted with a carbonyloxy atom, -85-201033732 wherein Rx and Ry each independently represent a hydrogen atom, a fluorine atom, An alkyl group (which preferably has 1 to 6 carbon atoms, and which may be substituted by a fluorine atom or the like) or a cycloalkyl group (having preferably 5 to 12 carbon atoms, and which may be substituted by a fluorine atom or the like) Rx and Ry are each preferably a hydrogen atom, an alkyl group or an alkyl group substituted by a fluorine atom. X represents an electron withdrawing group, and a fluorinated alkyl group, a fluorinated cycloalkyl group, or a fluorine or a fluorinated alkyl group is substituted. The aryl group or the aralkyl group substituted by fluorine or a fluorinated alkyl group is preferred. * represents a bond to the main or side chain of the resin, that is, bonded to the resin via a single bond or a linking group. The bond of the main chain. When X' is a carbonyloxy group or an oxycarbonyl group, A is not a single bond. The carbon number of the alkyl group in the alkylene group substituted with a fluorine atom as X' is linearly stretched. In the case of the alkyl group, it is preferably from 1 to 30, more preferably from 1 to 20; and in the case of the branched alkyl group, it is preferably from 3 to 30, more preferably from 3 to 20. Particular examples of the alkyl group include a group which is formed by removing an arbitrary hydrogen atom from a specific embodiment of the alkyl group such as Zkal described above. The fluorine-substituted alkylene group is preferably a perfluoroalkyl group. The cycloalkylene group in the cycloalkylene group substituted with a fluorine atom of X' is preferably a cycloalkyl group having a carbon number of 3 to 8, and specific examples thereof include a cycloalkane which is produced from Zkal as described above. In the particular embodiment, a group of an arbitrary hydrogen atom is removed. Preferably, the fluorine-substituted cycloalkyl group is a perfluorocyclic ring group. The alkyl group in the fluorinated alkyl group as X The carbon number is preferably from 1 to 30 in the example of the linear alkyl group from '1 to more; and in the case of the branched base group, preferably from 3 to 30, more preferably from 3 to 20. The specificity of the alkyl group. -86-201033732 The examples include specific examples of the alkyl group of zkal as described above. The fluorinated alkyl group is preferably a perfluoroalkyl group. The cycloalkyl group in the fluorinated cycloalkyl group as X has a carbon number. A cycloalkyl group of 3 to 8 is preferred, and specific examples thereof include a specific example of a cycloalkyl group such as the above Zkal. The perfluorocycloalkyl group is preferred. The aryl group in the aryl group in which X is substituted by fluorine or a fluorinated alkyl group is preferably an aryl group having a carbon number of 6 to 12, and examples thereof include a phenyl group and a naphthyl group. Specific examples of the fluorinated alkyl group in the aryl group substituted by a fluorinated alkyl group are the same as those described above for Q as a fluorinated alkyl group of X. The X is substituted by fluorine or a fluorinated alkyl group. The alkyl group in the aralkyl group is preferably an aralkyl group having a carbon number of 6 to 12, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group. Specific examples of the fluorinated alkyl group in the aralkyl group substituted by the fluorinated alkyl group are the same as those described for the fluorinated alkyl group as X. The following repetitive unit having a polar conversion group is proposed (c a specific embodiment, but the invention is not limited thereto. 〇

Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. 201033732

-88- 201033732

-89 - 201033732

201033732

r\ 1 • yi - 201033732

^2?· Jr^

〇丄〇 o person ο 〇, 0sfeOMe ο ΟγΟ 〇γ° 0F3 C3F7 &lt;=3ρ7

-92- 201033732

201033732

-94- 201033732 The resin (C) 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 film formed from the sensitized ray or the radiation-sensitive resin composition, and when the immersion medium is water, the surface of the film can be improved The receding contact angle of the water and the fluidity of the immersion liquid. The film has a receding contact angle of preferably from 60 to 90° at a temperature during exposure (usually at room temperature of 23 ± 3 ° C) and a humidity of 45 ± 5 %, more preferably 65° or more, 70° or Bigger and better, and 75° or larger is better. As described above, the resin (C) is unevenly distributed to the interface, but unlike the surfactant, it does not necessarily have to have a hydrophilic group in the molecule and may not contribute to the uniform mixing of the polar/nonpolar substance. In the immersion exposure step, the immersion liquid needs to move on the wafer along with the movement of the exposure head that scans the wafer at high speed and forms an exposure pattern. Therefore, the contact angle of the immersion liquid with the photoresist film in a dynamic state is important, and the photoresist needs to have an exposure head which allows the droplet to follow the high-speed scanning without Q. The resin (C) has at least one of a fluorine atom or a ruthenium atom, thereby improving the hydrophobicity (water flowability) on the surface of the photoresist and reducing the development residue (scum). The aryl group having a fluorine atom-containing alkyl group, a fluorine atom-containing cycloalkyl group or a fluorine atom-containing aryl group is preferable as a repeating unit of a partial structure of the fluorine atom-containing repeating unit. The fluorine atom-containing alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 1 to 4, and at least one hydrogen atom is replaced by a fluorine atom 95-201033732 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 substituted by a fluorine atom and further having another substituent. The aryl group of the fluorine atom is an aryl group (e.g., phenyl group, naphthyl group) having at least one hydrogen atom which is substituted by a fluorine atom and which may further have other substituents. The fluorine atom-containing alkyl group, the fluorine atom-containing cycloalkyl group, and the fluorine atom-containing aryl group are preferably a group represented by any one of the following formulas (F2) to (F4), but the invention is not limited thereto. .

Ree

ReiPeo 764 R57 Ru Rea

Rez -OH Rot 〇 (4) (4) CF4) In the formulae (F2) to (F4), each of R57 to R68 independently represents a hydrogen atom 'fluorine atom or an alkyl group (linear or branched), and the restrictions are R57 to Rei At least one of R62 to R64 and at least one of R65 to R68 are 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 R61 and R65 to R67 are fluorine atoms. Each of R62, r63 and R68 is preferably a fluoroalkyl group (preferably having a carbon number of 1 to 4), and a perfluoroalkyl group having a carbon number of 1 to 4 is more preferable. R62 and r63 may be bonded to each other to form a ring. R64 is preferably a hydrogen atom. 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-96-201033732 , hexafluoro(2-methyl)isopropyl, nonafluorobutyl, octafluoroisobutyl, nonafluorohexyl, nonafluorotributyl, perfluoroisopentyl, perfluorooctyl, perfluoro(three Methyl) hexyl, 2,2,3,3-tetrafluorocyclobutyl and perfluorocyclohexyl. Among these, hexafluoroisopropyl, heptafluoroisopropyl, hexafluoro(2-methyl)isopropyl, octafluoroisobutyl, nonafluorotributyl and perfluoroisopentyl are preferred, and Hexafluoroisopropyl and heptafluoroisopropyl are preferred. Specific examples of the group represented by the formula (F4) include -C(CF3)2OH, -C(C2F5)2OH, _C(CF3)(CH3)OH, and 0-CH(CF3)〇H, and -C (CF3) 2OH is preferred. The fluorine-containing partial structure may be directly bonded to the main chain, or may be bonded to the main chain via a single group selected from the group consisting of: a combination of two or more groups: an alkyl group, A phenyl group, an ether group, a thioether group, a carbonyl group, an ester group, a guanamine group, a urethane group, and a ureido group. As for the repeating unit having a fluorine atom, those shown below are preferable. W3 (C I I a)

-^CH2-Ch) - -(·ΟΗ2-Οη)- 〇^ ? W5 We (c- I c) (σ- I d) In the formula, each of Rio and Rii independently represents a hydrogen atom, fluorine Atom or alkyl. The alkyl group is preferably a linear or branched group having a carbon number of 1 to 4 and may have a substituent, and the embodiment thereof particularly includes a fluorinated hospital base. Each of w3 to w6 independently represents an organic group having at least one or more fluorine atoms. Specific examples thereof include atomic groups of (F2) to (F4). In addition to these repetitive units, the resin (c) may include the following unit as r\n -yt- 201033732, a repeating unit having a fluorine atom. Q·..^ * R5 R7 l!2 f w2 (c-ii) (c-m)

In the formula, each of R4 to r7 independently represents a hydrogen atom, a fluorine atom or an alkyl group, and a linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and the alkyl group may have a substituent. Embodiments thereof specifically include a fluorinated alkyl group. However, at least one of R4 to R7 represents a fluorine atom. R4 and R5 or R6 and Κ·7 form a ring. 2 represents an organic group containing at least one fluorine atom. Specific examples thereof include 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.

Q represents an alicyclic structure. The alicyclic structure may have a substituent, may be monocyclic or polycyclic, and may be crosslinked. The monocyclic alicyclic structure is preferably a cycloalkyl group having 3 to 8 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 a carbon atom in the cycloalkyl group may be placed by a hetero atom such as an oxygen atom - 98 - 201033732 The repetitive unit containing a ruthenium atom is described below. The repeating unit containing a ruthenium atom preferably has an alkyl fluorenyl structure (trialkyl decyl group) or a cyclic siloxane structure as a partial structure of the ruthenium containing atom. Specific examples of the alkyl fluorenyl structure and the cyclic oxirane structure include groups represented by the following formulae (CS-1) to (CS-3):

(CS-l) (CS-2) (CS-3)

I

%» In the formulae (CS-1) to (CS-3), each of Rlz to rZ6 independently represents a linear or branched alkyl group (having preferably a carbon number of 1 to 20) or a cycloalkyl group (having a carbon number of 3) Up to 20 is preferred). Each of L3 to Ls represents a single bond or a divalent linking group. The divalent linking group is a single group selected from the group consisting of a combination of two or more groups: an alkyl group, a phenyl group, an ether group, a thioether group, a carbonyl group. , an ester group, a guanamine group, a urethane group, and a urea group. π represents an integer of 1 to 5. It is preferable that n is an integer of 2 to 4. In the resin (C), the content of the repeating unit (c) is preferably from 1 〇 to 100 mol%, more preferably from 20 to 100 mol%, and from 3 〇 to 1 〇〇 mol% and more. The best and the best from 40 to 1 mole are based on all the repeating units in the resin (c). The content of the ix repeating unit (c) is preferably from 1 〇 to 1 〇〇 mol%, preferably from 100 摩尔%, and more preferably from 3 〇 to 100 摩尔%, and from 4 〇. To -99-201033732 100% Mox is the best, taking all the repeating units in the resin (c) as the standard. The content of the repeating unit (C*) is preferably from 5 to 70 mol%, more preferably from 5 to mol%, from 1 to 50 mol%, and more preferably from 1 to 4 mol. /. Most preferably, all of the repeating units in the resin (C) are taken as the standard. The content of the reciprocating unit having at least one of fluorine atoms or deuterium atoms (which is used together with the reciprocating unit (c*)) is preferably from 1 95 to 95 mol%, preferably from 丨5 to 85 mol. Preferably, °/〇 is from 20 to 80 mol% and more preferably from 25 to 75 mol%, which is based on all the repeating units in the resin (C). The content of the repeating unit (c") is preferably from 1 〇 to 1 〇〇 mol%, more preferably from 2 〇 to 100 摩尔%, even more preferably from 30 to 1 〇〇 mol% and from 4 〇. To 100 〇% by weight, based on all the repeating units in the resin (C). The fluorine atom or the ruthenium atom in the resin (C) may be present in the resin main chain or may be substituted on the side. The resin (C) may further comprise a repeating unit (cl) having at least one of fluorine atoms or germanium atoms, which is different from the repeating units (c,) and (c"). The examples of the fluorine atom-containing partial structure in the repeating unit (cl) are the same as those described above, and the groups represented by the formulae (F2) to (F4) are preferred. The embodiment of the structure containing the ruthenium atom in the repeating unit (cl) is the same as those described above, and the groups represented by the formulae (CS-1) to (CS-3) are preferred. It is preferred that the repeating unit (cl) having at least a fluorine atom or a ruthenium atom is 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, Xl represents a hydrogen atom, _CH3, _F-100-201033732

» rv -I ιυ 丄- 201033732

F3c -102 201033732

The resin (C) may further comprise at least one selected from the group consisting of the following groups (χ)

And (Ζ) groups: (X) a group soluble in the test; and (Ζ) a group which can be decomposed by an acid action. Examples of the alkali-soluble group (X) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a ruthenium imine group, Alkyl-based (alkylcarbonyl)methylene, (alkylalkyl)(alkylcarbonyl)indenylene group, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide a group, a bis(alkylindenyl)methylene group, a bis(alkyl ruthenium) fluorenylene group, a tri(alkylcarbonyl)methylene group, and a tris(alkyl ruthenium)methylene group. 1 ΑΟ -丄 * 201033732 Preferred base-soluble groups are fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups and bis(carbonyl)methylene groups. The repeating unit having a base-soluble group (x) includes a repeating unit in which an alkali-soluble group is directly bonded to the resin main chain (such as by weight of acrylic acid or methyl bisenoic acid) a unit that is soluble in a base, bonded to a repeating unit of the resin backbone via a linking group; and by using a polymerization initiator or chain transfer containing a soluble group during polymerization The agent, the alkali-soluble group is introduced into the repeating unit of the polymer chain terminal; and these repeating units are all preferably. The content of the repeating unit having the alkali-soluble group (x) is preferably from 丨 to 50 mol%, more preferably from 3 to 35 mol%, even more preferably from 5 to 30 mol%. All of the repeating units in the resin (C) are accurate. The specific embodiment of the repeating unit having the alkali-soluble group (x) is proposed below, but the invention is not limited thereto. In a particular embodiment, Rx represents Η, CH3, CH2OH or CF3. 201033732

-105- 201033732 The embodiment having a group (z) which can be decomposed by an acid action, a recoating unit contained in the resin (c), and an acid-decomposable group having a description of the resin (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):

Rx1 (CAI) - Rx2 In the formula (CAI), Xai 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 monovalent organic group is preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group.乂&amp;1 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. Each of the sizes 1 to Rx3 independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). Two members from Rxi 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 an -O-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 a carbon number of 1 to 5 - 106 to 201033732, and a -ch2- group or a -(ch2)3- group is more preferable. The alkyl group of Rx1 to Rx3 is preferably an alkyl group having a carbon number of 1 to 4, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. The cycloalkyl group of RX1 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 tetracyclodecyl group, or a tetracyclic ten group. Dialkyl and adamantyl. The cycloalkyl group Q formed by combining two members derived from 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 lower A cycloalkyl group having a mercapto group, a tetracyclodecylalkyl group, a tetracyclododecyl group, and an adamantyl group, and having a monocyclic ring having 5 to 6 carbon atoms is more preferable.

A specific example in which Rxi is a methyl group or an ethyl group and Rx2 is bonded to Rx3 to form a cycloalkyl group as described above is 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 alkoxy group. A carbonyl group (having a carbon number of 2 to 6). The substituted Q group has a carbon number of 8 or less. In the resin (C), the content of the repeating unit having a group (z) which can be decomposed by an acid action is preferably from 1 to 80 mol%, and is from 1 Torr to 80 mol%. More preferably, it is more preferably from 20 to 60 mol%, which is based on all the repeating units in the resin (c). The LWR can be improved by having a group (2) which can be decomposed by an acid action. The resin (C) may further comprise other resurfacing units. Preferred specific examples of other repeating units include the following: (cyl) a repeating unit having a fluorine atom and/or a ruthenium atom and which is stable to the acid and slightly soluble - 107 - 201033732 or insoluble in an inert developer; a repeating unit which does not have a fluorine atom and a halogen 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 (χ) 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 (3〇 and (2). In (cyl) and (cy2) The term "slightly soluble or insoluble in the test developer" in the repeating unit means that (cyl) and (Cy2) do not contain a group soluble in hydrazine or can be acted upon by an acid or a base. The developer produces a group of a base-soluble group (for example, an acid-decomposable group or a polar group). The repeating units (cyl) and (cy2) have an alicyclic ring containing no polar group. The hydrocarbon structure is preferred. Preferred examples of the repeating units (cyl) to (cy4) are described below. The repeating unit (cyl) (Cy2) by weight coating unit represented by the following formula (CIII) preferred:

Rc31

Lea (απ)

I RC32 In the formula (CIII), Re3i 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. Rc31 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 preferable.

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, for example, by a group containing a halogen atom or a fluorine atom. -108- 201033732

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. 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, such as a phenyl group or a naphthyl group; and these groups may have a substituent.

Rc32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom. The L·. The divalent linking group of 3 is preferably an alkylene group (having preferably a carbon number of 1 to 5), an oxygen group, a phenyl group or an ester bond (a group represented by -COO-). Preferably, the repeating units (cyl) and (cy2) are repeating units represented by the following formula (C4) or (C5):

❹ In the formulae (C4) and (C5), 'Re5 represents a hydrocarbon group having 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 -CHs-O-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 preferable. The cyclic structure possessed by Res includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkane-109-201033732 group having a carbon number of 3 to 12 and a cycloalkenyl group having a carbon number of 3 to 12. 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. 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 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 preferably 1-ethoxyethyl or 1-methyl-1-methoxyethyl; the fluorenyl group has a carbon number 1 to 6 are preferably an aliphatic fluorenyl group such as a fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, a amyl fluorenyl group and a pentenyl group; and the alkoxycarbonyl group has a carbon number of 2 to The alkoxycarbonyl group of 4 is preferred. The alkyl group of Rd is a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxycarbonyl group or an alkylcarbonyloxy group. These groups may be substituted by a fluorine atom or a halogen atom. -110- 201033732 The R. The alkyl group of 6 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, 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 n is an integer of 2 or more, each Rc6 0 may be the same as or different from each other Re6. RC6 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 preferred. The repeating units (cyl) and (cy2) are also preferably the repeating unit represented by the following formula (CII-AB):

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): Λ Λ Λ -11 丄- 201033732

In the formulae (CII-AB1) and (CII-AB2), 'Rcl3, to rc16 each independently represent a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group. At least two members from Re13' 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 stands for H, CH3, CH2OH, CF3 or CN.

-112- 201033732 The repeating units (cy 3) and (cy 4) are preferably 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, dihydroxyadamantyl and substituted by cyano group. The repeating unit having this atomic group includes a repeating unit represented by the following formulas (CAIIa) to (CAIId):

(CAIIa)

In the formulae (CAIIa) to (CAIId), R1C 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. The structure from which one or two members of R2c to R4c are a hydroxyl group and the remainder is a 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. Specific embodiments of the repeating units (cy3) and (cy4) are proposed below, but the invention is not limited thereto. • 113 - 201033732 〇\ 〇\ 〇人免八—φ«Λι Λ The content of the repeated single 兀(cyl) to (cy4) is preferably from 5 to 40 mol%, from 5 to 3 〇mol% Preferably, it is more preferably from 1 to 25 mol%, and all of the repeating units in the resin (C) are taken as the standard. The resin (C) may have a plurality of repeating units (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 / β. More preferably, it is 8% by mass, based on the molecular weight of the resin (C). Similarly, the fluorine atom-containing repeating unit is preferably from 1 Torr to 100% by mass, more preferably from 30 to 1% by mass, based on all 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 (C). Similarly, the halogen 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 resin (C) 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. The resin (C) in the sensitized ray or radiation sensitive resin composition can be used by appropriately adjusting the content thereof to provide a sensitized ray or radiation sensitive resin film having a receding contact angle within the above range, but The content of -114-201033732 is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 10% by mass, more preferably from 1 to 9% by mass, and even more preferably from 0.5 to 8% by mass. The total solid content of the ray or radiation sensitive resin composition is correct. Similar to the resin as the resin, it is of course preferable that the amount of impurities (such as metal) is small in the resin (C), and likewise, the content of the residual monomer or oligomer component is from 〇 to 10 by mass. % is more preferable, preferably from 〇 to 5% by mass, and more preferably from 〇 to 1% by mass. When these conditions are satisfied, a photoresist having no foreign matter in the liquid or having a sensitivity that does not change with aging or the like is obtained. Similarly, considering the resolution, the photoresist profile, the sidewalls of the photoresist pattern, the roughness, and the like, the molecular weight distribution (Mw/Mn, sometimes referred to as &quot;polydispersity&quot;) is from 1 to 3 Good, better from 1 to 2, better from 1 to 1.8 and best from 1 to 1.5. As the resin (C)', a variety of commercially available products can be used or the resin can be synthesized similarly to the resin (A) by a usual method (e.g., 'radical polymerization). Specific examples of the resin (C) are set forth below. Similarly, the molar ratio, weight average molecular weight (Mw), and polydispersity (Mw/Mn) of the repeating unit of each resin Q (corresponding to the repeating unit from the left) are shown in Table 1 below. 1 1 r -11J - 201033732

O~ f3c^cf3

R4r o person.

ο.

-116 201033732

(C-26) 201033732

-118- 201033732

-119 - 201033732

(C-65)

-120- 201033732

(C-69)

-121 - 201033732

(C-M

(C Na 0^0

-122- 201033732

201033732

124- 201033732

-125 - 201033732

Ο (C-130)

201033732

-127 - 201033732

-128- 201033732

-129- 201033732

-130- 201033732

-131 - 201033732

〇

132 201033732

(C-197)

(C-198)

-133- 201033732

-134- 201033732

-135- 201033732

-136- 201033732

(0258)

1 (C-267) {C-268)

137- 201033732

(C-273)

(C-275) -138- 201033732

201033732

-140- 201033732

(C-290)

(C-303)

141 201033732

(C-308) CF3

Cf3 (C-313)

-142- 201033732 Table 1

Resin composition Mw Mw/Mn Cl 100 6000 1.5 C-2 100 7500 1.4 C-3 100 6000 1.4 04 100 9000 1.5 C-5 100 6000 1.4 C-6 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-IO 70/30 7000 1.4 C-ll 50/10/40 9000 1.6 C-12 80/20 6000 1,4 CM3 40/ 30/30 9500 1.4 C-14 50/50 8000 1.4 C-15 70/30 7000 1.4 C-16 100 6000 1.4 C-17 100 8000 1.4 C-18 40/20/40 6000 1.4 C-19 40/60 5000 1.5 C-20 30/40/30 7000 1.4 C-2l 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-29 60/20/20 6500 1.4 C-30 70/30 6500 1.4 C -31 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 Resin composition Mw Mw /Mn C-36 50/50 5000 1.5 C-37 30/30/30/5/5 6000 1.5 C-38 50/50 4500 1.4 C-39 80/20 5000 1.4 C-40 100 5000 1.4 C-41 100 9000 1.5 C-42 100 10000 1.5 C-43 90/10 8500 1.4 C-44 30/30/30/10 5500 1.4 C-45 60/30/10 6500 1.4 C-46 70/30 6500 1.4 C-47 30/20/50 7000 1.4 C-48 80/20 8000 1.5 C-49 60/30/10 6000 1.4 C-50 60 /40 8000 1.5 051 50/50 9500 1.4 C-52 90/10 8000 1.5 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-57 100 6000 1.4 C-58 90/10 8000 1,4 C-59 80/20 7000 1.5 C-60 50/20/30 6000 1.4 C-61 60/40 4500 1.5 C- 62 100 6500 1.4 C-63 80/10/10 7000 1.5 C-64 90/10 9000 1.5 C-65 70/30 8000 1.4 C-66 35/30/10/5/20 7000 1.4 C-67 100 6500 1.4 C-68 80/20 6500 1.4 C-69 70/20/10 7000 1.4 C-70 60/30/10 9000 1,5 1 i ο -- 201033732 Table ι (continued) Resin composition Mw Mw/Mn 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 L5 C-75 100 5500 1.5 C-76 90/10 6500 1.4 077 90/10 7500 1.3 C-78 50/10/20/20 6000 1.5 C-79 70/30 5000 1.3 C-80 70/10/20 8500 1,5 C-81 80/20 5500 1,3 C-82 100 8000 1.3 C-83 85/5/10 6500 1.4 C-84 80/20 8000 1.5 C-85 60/30/10 10000 1.5 C-86 100 8000 1.5 C-87 55/30/5/10 8000 1.3 C-88 40/30/30 6000 1.3 C-89 70/30 6500 1.3 C-90 90/10 8000 1.5 C-91 70/20/10 6500 1.5 C-92 100 7000 1.4 C-93 100 6000 1.5 C-94 100 13000 1.4 C-95 100 4000 1.4 096 100 6000 1.5 C-97 100 10000 1.4 C-98 100 7500 1.5 C-99 50/50 6500 1.4 C-100 50/50 8500 1.4 C-101 80/20 7000 1.3 C-102 50/20/30 4500 1.3 C-103 90/10 5500 1.3 C-104 60/30/10 6000 1.5 C-105 80/20 8000 1.3 Resin composition Mw Mw/Mn C-106 50/ 45/5 7500 1.4 C-107 80/20 7000 1.5 C-108 30/30/30/10 9000 1.6 C-109 70/30 8000 1.3 C-110 50/30/20 9000 1.4 C-I11 60/10/ 30 6000 1.5 C-112 60/5/35 8000 1.5 C-113 50/40/10 9500 1.5 C-114 80/20 7000 1.5 C-115 90/10 6000 1.2 C-116 40/20/30/10 8000 1,3 C-117 50/50 6000 1.5 C-118 100 9500 1.4 C-119 50/20/20/10 8000 1.5 C-120 75/10/10/5 7000 1.3 C-121 30/30/10/ 30 5500 1.3 C-122 100 8000 1.3 C-123 100 9500 1.5 C-124 100 9000 1.6 C-125 90/10 9500 1.3 C-126 70/30 7500 1.5 C-127 70/30 8000 1.3 0128 85/15 6000 1.5 0129 90/10 7000 1,6 C-130 50/20/30 5000 1.3 0131 60/20/20 4000 1.4 0132 50/30/20 6500 1.4 CM33 70/10/20 7000 1.4 C-134 80/10/10 9000 1.4 C-135 60/40 8000 1.5 CM 36 30/70 9000 1.4 C-137 70/15/15 7500 1.5 C-138 70/30 8000 1.4 C-139 75/5/10/10 6000 1.5 C-140 70/30 5500 1.5 144- 201033732 Table ι (continued)

Resin composition Mw Mw/Mn C-141 50/25/25 6500 1.4 C-142 100 9000 1.6 C-143 50/40/10 7000 1.4 C-144 50/50 9000 1.4 0145 50/30/20 8000 1.4 0146 50/50 9000 1.5 C-147 48/50/2 6000 1.4 C-148 50/50 9000 1.5 C-149 50/25/25 6000 1.4 C-150 50/50 9500 1.5 C-151 50/50 8000 1.5 C -152 50/50 7000 1.4 C-153 95/5 3000 1.4 C-154 100 5000 1.4 C-155 50/50 6000 1.5 0156 50/50 4000 1.5 C-157 100 8000 1.4 C-158 80/20 4500 1.4 C -159 80/20 3500 1.4 C-160 70/30 7000 1.4 C-161 50/50 10000 1.3 C-162 95/5 4500 1.4 C-163 90/10 8500 1.4 C-164 25/50/25 6000 1.5 C -165 40/40/10/10 6500 1.4 C-166 100 8000 1.4 C-167 100 6500 1.4 C-168 80/20 5000 1.3 C-169 40/30/30 4500 1,5 C-170 90/10 3000 1.4 C-171 100 4500 1.4 C-172 100 3500 1.4 C-173 60/40 5000 1.4 C-174 90/10 6000 1,4 C-175 100 4000 1.5 Resin composition Mw Mw/Mn C-176 100 8000 1.4 C-177 100 5000 1.4 C-178 100 10000 1.5 C-179 100 6000 1.4 C-180 100 7000 1.3 C-181 100 5500 1.4 C-182 100 8000 1.3 C-183 90/10 4500 1.4 C-184 80 /20 6000 1.4 C-185 70/30 5500 1.6 C-186 85/15 8500 1.4 C-187 90/10 3000 1.3 C-188 70/30 4500 1.4 C-189 75/25 6500 1.4 C-190 55/45 8500 1.3 C-191 90/10 5500 1.4 C-192 75/25 9000 1.4 C-193 70/30 10000 1.5 C-194 70/30 5000 1.4 C-195 80/20 7000 1.4 C-196 85/15 4500 1.4 C-197 80/20 3500 1.5 C-198 75/25 6000 1.4 C-199 100 5000 1.4 C-200 80/20 6000 1.4 C-201 80/20 8000 1.5 C-202 100 4500 1.5 C-203 70/30 3500 1.4 C-204 80/20 10000 1.4 C-205 80/20 7000 1.4 C-206 90/10 4000 1.4 C-207 80/15/5 10000 1.4 C-208 85/10/5 5000 1.5 C-209 90 /8/2 13000 1.5 C-210 85/10/5 6000 1.5 201033732 Table 1 (continued) Resin composition Mw Mw/Mn C-211 90/8/2 8000 1.4 C-212 50/50 12000 1.5 0213 50/ 50 8000 1.3 C-214 85/15 6500 1.5 C-215 85/15 4000 1.5 C-216 90/10 7500 1.6 C-217 90/10 3500 1.5 C-218 95/5 5500 1.4 C-219 85/10/ 5 5000 1.5 C-220 88/10/2 13000 1.4 C-221 90/8/2 12000 1.5 C-222 90/8/2 11000 1.4 C-223 90/8/2 9000 1.5 C-224 50/50 6000 1.5 C-225 50/50 8000 1.5 C-226 80/20 450 0 1.3 0227 85/15 8500 1.6 C-228 90/10 10000 1.4 C-229 90/10 3500 1.5 C-230 95/5 4500 1.5 C-231 50/50 4000 1.5 C-232 80/18/2 6000 1.5 C-233 90/8/2 9500 1.5 C-234 80/20 6500 1,4 C-235 90/10 8000 1.5 C-236 100 8000 1.5 C-237 95/5 4500 1.5 C-238 90/10 10000 1.5 0239 100 6500 1.4 C-240 80/20 6500 1.4 C-241 70/20/10 7000 L4 C-242 90/10 7000 1.6 C-243 50/20/30 5000 1.3 Ct244 40/30/30 5000 1.4 C- 245 60/40 6000 1.4 Resin composition Mav Mw/Mn C-246 40/20/40 7000 1.4 C-247 40/30/30 8000 1.5 C-248 40/30/30 9500 1.5 C-249 60/40 9500 1.5 C-250 40/40/20 &quot; 7500 1.4 C-251 80/20 9000 1.5 C-252 80/20 9000 1.5 C-253 40/30/15/15 7000 1.4 C-254 60/40 8500 L4 C -255 50/30/20 8000 1.4 C-256 30/30/40 9500 1.5 C-257 30/50/20 8000 1.3 C-258 30/50/20 8000 1.3 C-259 40/40/20 6500 1.4 C -260 50/30/20 6000 1.4 C-261 80/20 8500 1.5 C-262 20/80 10000 1.5 C-263 100 8500 1.5 C-264 100 6000 1.4 C-265 90/10 8000 1,4 C-266 30/70 9000 1.6 C-267 50/50 4000 1.3 C-268 100 6500 1.4 C-269 80/20 6500 1.4 146- 201033732 Table ι (continued)

Resin composition Mw Mw/Mn C-270 30/70 6500 1.4 C-271 80/10/10 7000 1.4 C-272 30/70 9000 1.4 C-273 60/30/10 8000 1.4 C-274 80/20 9000 1.5 C-275 60/35/5 6000 1.4 0276 40/60 9000 1.5 C-277 60/30/10 8000 1.4 C-278 65/20/15 9500 1.5 C-279 85/15 8000 1.5 C-280 90/ 10 7000 1.4 C-281 100 8000 1.3 0282 100 9500 1.5 C-283 100 9000 1.6 C-284 90/10 9500 1.3 C-285 70/30 7500 1.5 C-286 90/10 8000 1.3 C-287 80/20 6000 1.5 C-288 90/10 7000 1.6 C-289 50/20/30 6500 1.3 C-290 80/20 12000 1.6 C-291 70/30 8500 1.5 C-292 80/20 15000 1.6 C-293 60/40 6000 1.4 C-294 40/60 8000 1.5 0295 50/50 8000 1.5 C-296 80/20 6000 1.4 C-297 50/50 4000 1.5 C-298 50/50 8000 1.6 C-299 50/50 4000 1.5 C-300 50/50 8000 1.6 C-301 100 8000 1.5 C-302 100 7000 1.4 C-303 60/40 7000 1.5 C-304 50/30/20 8000 1.5 Resin composition Mw Mw/Mn C-305 100 5000 1.6 C- 306 60/40 5500 1.5 C-307 60/40 6000 1.5 C-308 100 4500 1.5 0309 70/30 5000 1.5 C-310 50/50 6000 1.5 C-311 70/30 6500 1.6 C-312 50/50 5000 1 . 5 C-313 70/30 6000 1.5 C-314 100 7500 1.6 As for the resin (c), one type may be used alone or in combination.

Similarly, it is preferred to use a resin (CP) having at least one of fluorine atoms or germanium atoms in combination with 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 (CP) having at least one of fluorine atoms or ruthenium atoms (with the resin) (C) There are differences). By including the resin (C) and the resin (CP), -147-201033732, 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 film enhances the receding contact angle of water on the surface of the photoresist film and the fluidity of the immersion liquid. 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, but the content is preferably from 10,000 to 5% by mass, more preferably from 0.01 to 5% by mass, from 0.01. It is more preferably 4% by mass, and more preferably 〇1 to 3% by mass, based on the total solid content of the sensitized ray or the radiation-sensitive resin composition. As described above, the resin (CP) is unevenly distributed to the interface, but unlike the surfactant, it does not necessarily have to have a hydrophilic group in the molecule and may not contribute to uniform mixing of the polar/nonpolar substance. A fluorine atom or a ruthenium atom in the resin (CP) having at least a fluorine atom or a ruthenium atom may be present in the main chain of the resin 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 substituted by a fluorine atom and further having another substituent. The fluorine atom-containing cycloalkyl group is a monocyclic or polycyclic cycloalkyl group having at least one hydrogen atom substituted by a fluorine atom and further having another substituent. The aryl group of the fluorine atom is an aryl group (e.g., phenyl group, naphthyl group) having at least one hydrogen atom which is substituted by a fluorine atom and which may further have other substituents. -148 - 201033732 Preferred examples of the fluorine atom-containing alkyl group, the fluorine atom-containing cycloalkyl group, and the fluorine atom-containing aryl group include the formulas (F2) to (F4) described above for the resin (C). The group indicated, but the invention is not limited thereto. In the present invention, it is preferred to include a group represented by the formulae (F2) to (F 4) in the (meth) acrylate-based repeating unit. A specific embodiment of the repeating unit having a fluorine atom is proposed below, but the invention is not limited thereto.

In a particular embodiment, ' represents a hydrogen atom, _CH3, -F or -CF3. X2 represents -F or -CF3.

-149 - 201033732

-150- 201033732

The resin (CP) is preferably a tree having a courtyard-based sand-based structure (preferably a three-base sand-based base) or a cyclic siloxane structure as a partial structure of the ruthenium-containing atom. Specific examples of the alkyl fluorenyl structure and the cyclic oxirane 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 alkali; and (z) capable of being acid-based A group that decomposes. Specific examples of these groups are the same as those described above for the resin (c). The embodiment of the repeating unit comprising the group 201033732 group (Z) capable of decomposing by acid action in the resin (CP) and those having the acid-decomposable group described for the resin (A) The cover unit is the same. In the resin (cp), the content of the repeating unit having a group (Z) which can be decomposed by an acid action is preferably from 1 to 8 mol%, more preferably from 10 to 80 mol%, from 20 to 60 mol% and more preferably 'takes all the repeating units in the resin (CP). The resin (CP) may further have a repeating unit represented by the above formula (cm) relating to the resin. In the example in which the resin (cp) contains a fluorine atom, the fluorine atom content is preferably from 5 to 80% by mass, more preferably from 10 to 80% by mass, based on the molecular weight of the resin (CP). The fluorine atom-containing repeating unit is preferably from 10 to 100% by mass, more preferably from 30 to 100% by mass, based on all of the repeating units in the resin (CP). The resin (CP) contains a halogen atom. In the example, 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 atom-containing repeating unit is preferably from 1 至 to 100% by mass, more preferably from 20 to 100% by mass, based on all the repeating units in the resin (CP). The resin (CP) has a standard polystyrene equivalent average molecular weight of from 1, 〇〇〇 to 100,000, more preferably from 1,000 to 50,000, and even more preferably from 2,000 to 15,000. The resin (CP) can be synthesized and purified in the same manner as the resin (A), and the amount of impurities such as metal is of course preferably 'and the same, the content of the residual monomer or oligomer component From 〇 to 1% by mass, preferably 'from 〇 to 5% by mass, more preferably from 0 to 1% by mass. By satisfying these conditions, it is possible to obtain a sensitized ray or a radiation-sensitive resin composition which does not have a foreign substance in the liquid or which has a sensitivity which does not change with the aging effect. Furthermore, considering the resolution, the photoresist profile, the sidewall of the photoresist pattern, the roughness, and the like, the molecular weight distribution (Mw/Mn, sometimes referred to as &quot;polydispersity&quot;) is preferably from 1 to 3. It is better from 1 to 2, better from 1 to 1.8 and best from 1 to 1.5. As the resin (CP), a variety of commercially available products can be used, or the resin can be purified in the same manner as the resin (A) or 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. Similarly, the molar ratio, weight average molecular weight (Mw), and polydispersity (Mw/Mn) of the repeating unit of each resin (corresponding to the repeating unit from the left side) are shown in Table 2 below. 〇 -153 - 201033732 •r4r 040 〇人? , milk thistle ή -(cf2cf2^ f3c ten Cl^ OH (CP-2)

OH (CP-3) ^4-°13⁄4 ~s\~ OH (CP-Λ) iCP^&gt;

Ccp-1)

(CP-23) (CP-24)

-154- 201033732

·τγ 0^0 Ο^ΟΗ f3c eight cf3

(CR>2Q 0^0 V,

0^0

H° C^FaC7 〇H (CP-33) 0&gt;^WV&lt;0 (CP-29)

6C eight cf3

o^o o^o 0^*01F eight is L (cp-as)

-155 - 201033732

&lt;CP-51) (CP-32) (CP-53) ^^4)

-156- 201033732

(CFS5)

(CP-57)

-157- 201033732

(CP41) (CP-8G) 0-^0 0人Ο 0?0 0^0 0^0 0^0 V \ V V- One (CP-82) (CP-83) r4r Wr Hr -r&gt; r r-ψ 0^0 0*^0 0^0 ?h2 o^o C^g (CP44)

Ryry 〇\'YV

(CP-85) (CP-86) (CP-87)

(CP-88) (CF^89) (QP*30&gt; (CP-91) -158- 201033732

(CR^Q (CP&lt;9?) ^CFa Cf^

W+ 4^4+. people. O丄. 〇5Of3c^CX&lt;c^ ^ mH ^3〇 hocf3 (CP-99) ❹ 0^0 . Hey. . Hey? 〇Λ〇 〇^〇kφ φ Α φ cold η ηρβ Τ ml CFa 〇 CF3 VJ w* Fgc (CP&gt;KX) (CP-1Q1)

FaC ΌΗ (CM02)

H^· ^ 0 people. 0^0 F2 0^0fiVcFa F2a ^ ^ic^HCfS

(CP-1D6) (CP-107)

F3C Ten Milk OH (GP-1D9) ❹ -159 - 201033732 Table 2 Resin Composition Mw Mw/Mn CP-1 50/50 6000 L5 CP-2 50/50 7500 1.4 CP-3 50/50 6000 1.4 CP-4 100 9000 1.5 CP-5 50/50 6000 1.4 CP-6 40/60 8000 1.4 CP-7 60/40 6000 1.4 CP-8 50/50 6500 1.4 CP-9 50/50 8000 1.4 CP-10 50/50 6500 1.4 CP-11 50/50 10000 1.6 CP-12 40/60 7500 1.4 CP-13 40/60 6500 1.4 CP-14 100 8500 1.4 CP-15 40/60 7000 1.4 CP-16 60/40 7500 1.4 CP-17 40/60 6000 1.4 CP-18 50/30/20 5000 1.4 CP-19 40/60 8500 1.5 CP-20 40/60 5500 1.4 CP-21 50/50 6000 1.4 CP-22 40/20/40 5500 1.4 CP -23 100 9500 1.5 CP-24 40/60 8500 1.4 CP-25 50/10/40 8000 1.5 CP-26 50/50 6000 1.4 CP-27 50/50 5000 1.4 CP-28 70/30 9000 1.4 CP-29 50/50 7500 1.4 CP-30 60/40 9000 1.5 Resin composition Mw Mw/Mn CP-31 80/20 10000 1.5 CP-32 40/60 8500 1.4 CP-33 30/70 5500 1.4 CP-34 20/40 /40 6500 1.4 CP-35 20/50/30 7000 1.4 CP-36 35/35/30 9000 1.5 CP-37 25/45/30 9000 1.5 CP-38 30/50/20 6000 1,4 CP-39 40 /40/20 8000 1.5 CP-40 10/50/40 7000 1.4 C P-41 30/30/40 6500 1.3 CP-42 40/30/30 8000 1.5 CP-43 40/40/20 6000 1.3 CP-44 50/20/30 9500 1.5 CP-45 45/40/15 7000 1.3 OM6 50/30/20 8000 1.5 CP-47 35/25/40 10000 1.5 CP-48 50/50 8000 1.5 CP»49 100 5000 1.3 CP-50 100 6000 1.3 CP-51 100 4500 1.3 CP-52 100 5000 1.5 CP-53 100 5000 1.5 CP-54 100 5500 1.4 CP-55 50/50 9000 1.5 CP-56 80/20 9000 1.5 CP-57 50/50 6500 1.4 CP-58 50/25/25 6500 1.5 CP-59 58 /38/2/2 4500 1.4 CP-60 40/40/20 5500 1.5 -160- 201033732 Table 2 (continued)

Resin composition Mw Mw/Mn CP-61 60/40 8000 1.4 CP-62 50/50 7500 1.3 CP-63 50/50 8000 1.3 CP-64 50/50 7000 1.3 CP-65 50/50 8000 1.5 CP-66 60/40 6000 1.3 CP-67 70/30 8000 1.4 CP-68 100 8000 1.5 CP-69 50/50 9500 1.6 CP-70 50/50 7000 1.3 CP-71 100 6000 1.4 CP-72 100 8000 1.5 CP-73 100 7000 1.5 CP-74 50/50 6000 1.5 CP-75 70/30 6000 1.5 CP-76 50/50 4000 1.2 CP-77 60/40 6000 1.3 CP-78 80/20 8000 1.5 CP-79 50/50 6000 1.4 CP-80 80/20 7000 1.5 CP-81 100 5000 1.3 CP-82 50/50 4000 1.3 CP-83 50/50 6000 1.3 CP-84 30/30/40 6000 1.5 CP-85 50/50 8000 1.6 CP -86 50/50 7000 1.3 CP-87 50/50 6000 1.5 CP-88 60/40 4500 1.3 CP-89 50/50 7500 1.5 CP-90 60/40 8000 1.6 Resin composition Mw Mw/Mn CP-91 60 /40 6000 1.3 CP-92 50/50 4500 1.3 CP-93 50/50 5000 1,4 CP-94 50/50 3500 1.3 CP-95 40/30/30 4500 1.4 CP-96 50/45/5 5000 1.5 CP-97 20/80 10000 1.5 CP-98 30/70 9500 1.4 CP-99 20/80 7500 1.3 CP-100 100 5500 1.5 CP-101 80/20 5000 1.3 CP-102 70/30 8000 1.4 CP-103 80 /20 9500 1.4 CP-104 80/20 7000 1.4 CP-105 80/20 5000 1.5 CP-106 100 10500 1.4 CP-107 100 8000 1.5 CP-108 90/10 9500 1.5 CP-109 40/40/20 5000 1.4

The film formed from the sensitized ray or the radiation-sensitive resin composition of the present invention may have a high refractive index by mounting between the photoresist film and the lens when irradiated with actinic rays or radiation (immersion exposure). The exposure is carried out in a liquid of air (immersion medium). 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 temperature coefficient of refraction that is as small as possible in order to reduce optical image distortion projected on the photoresist film. In particular, when the exposure light source is an ArF quasi-201033732 molecular laser (wavelength: 193 nm), in addition to the above-described viewpoints, it is preferable to use water in consideration of ease of availability and ease of use. Further, a medium having a refractive index of 1.5 or higher can also be used from the viewpoint of further increasing the refractive index. 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 while The optical coating at the bottom of the lens element provides only a negligible effect. The 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 is evaporated and its content concentration is changed, 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 an impurity having a refractive index greatly different from that of water is alternately mixed, this causes deformation of the optical image projected on the photoresist film. Therefore, the water used is preferably distilled water. It is also possible to use pure water obtained by further filtering distilled water through an ion exchange filter or the like. The electric resistance of water as the immersion liquid is preferably 18.3 MQcm or more, and the TOC (total organic carbon) is 20 Ppb or less is better. Similarly, 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 water, or water may be replaced with hydrophobic water (D 2 0). In order to prevent direct contact of the film with the immersion liquid, a film slightly soluble in the immersion liquid of the sinking-162-201033732 may be provided between the film formed by the composition of the present invention and the immersion liquid (hereinafter, sometimes referred to as &quot;surface coverage,,). The function required for the surface covering layer is to be suitable for the coating layer of the coating as a photoresist, to be transparent to radiation particularly at 193 nm, and to have limited solubility in immersion liquid. The surface covering layer is not compatible with the photoresist and can be uniformly coated as a coating layer of the photoresist. In view of transparency to 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, polymethacrylic acid, polyacrylic acid, Polyethyl hydrazine) Ether, hydrazine-containing polymer and fluoropolymer. The hydrophobic resins (C) and (CP) described above are also suitable as the surface covering layer. The optical lens is contaminated if impurities are dissolved from the surface covering into the immersion liquid. In this view, the amount of the residual monomer component of the polymer contained in the surface covering layer is preferably small. On the peeling of the surface covering layer, 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 film. From the viewpoint that the stripping step can be carried out in synchronism with the development step of the film, the surface Q cover layer can be preferably peeled off by an alkali developer, and the surface coat layer is acidic in order to be peeled off by an alkali developer. Preferably, the surface covering layer may be neutral or alkaline in view of the non-interactive mixing with the film. As the refractive index between the surface covering layer and the immersion liquid does not differ, the degree of resolution increases. In the case where water is used as the immersion liquid by 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 the 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, in view of transparency and refractive index, the surface covering is preferably a film of -163 - 201033732. The surface covering layer may not be mixed with the film and further preferably not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the surface coating layer is preferably a solvent which is slightly soluble in the composition used in the present invention and a water-insoluble medium. In the example where the immersion liquid is an organic solvent, the surface covering layer is soluble in water or insoluble in water. [4] Solvents Examples of a solvent which can be used at the time of preparing the photosensitive 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 contain a ring (having carbon) Preferably, the number is from 4 to 10, the alkylene carbonate, the alkyl alkoxyacetate and the alkyl pyruvate. Preferred examples of the carboxylic acid alkylene glycol monoalkyl ether ester include propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-ethoxypropane), propylene glycol acetate Monoethyl ether ester, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether ester, propionic acid propylene glycol monoethyl ether ester, ethylene glycol monomethyl ether ester and Ethylene glycol ethylene glycol monoethyl ether ester. Preferred examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl group. Ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Preferred examples of the lactate alkyl ester include methyl lactate, ethyl lactate, propyl lactate and butyl lactate. -164-201033732 Preferred examples of the alkoxypropionic acid alkyl ester include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate and 3- Ethyl methoxypropionate. Preferred examples of the cyclic lactone include (3-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butene Esters, γ-valerolactone, γ-caprolactone, γ-octanolactone and α-hydroxy-γ-butyrolactone. Preferred examples of the ring-containing monoketone compound include 2-butanone,

3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-methyl-3 -pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2-hexyl Ketone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-glycol Ketone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-indanone, 3-indanone, 5-anthone, 2-indanone, 3-indanone, 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-di Methylcyclohexanone, 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. Preferred examples of the alkoxyacetic acid alkyl ester 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. - 丄OJ - 201033732 The solvent which can be preferably used is a solvent having a boiling point of 130 ° C or higher at ordinary temperature and atmospheric pressure, and specific examples thereof include cyclopentanone, γ-butyrolactone, cyclohexanone Ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, 2-(2-acetic acid) 2-ethoxyethoxy)ethyl ester and propylene carbonate. In the present invention, one of these solvents may be used alone or two or more 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. As the solvent containing a hydroxyl group and a solvent not containing a hydroxyl group, the compounds exemplified above as the examples can be appropriately selected, but preferred examples of the solvent containing a hydroxyl group include an alkylene glycol monoalkyl ether and an alkyl lactate. , and propylene glycol monomethyl ether and ethyl lactate are more preferred. Preferred examples of the solvent containing no hydroxyl group include an alkylene glycol monoalkyl ether acetate, an alkoxypropionic acid alkyl ester, a monoketone compound which may contain a ring, a cyclic lactone, and an alkyl acetate. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, γ-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 the solvent containing no hydroxyl group (by mass) is preferably from 1/99 to 99/1 ' and preferably from 10/90 to 90/10, and from 20/80 to 60/40. Better. In view of uniformity of the coating layer, a mixed solvent containing the solvent containing no hydroxyl group in a ratio of 50% by mass or more is preferred. The solvent comprises propylene glycol monomethyl ether acetate preferably, and a mixed solvent of a single solvent of propylene di-166-201033732 alcohol monomethyl ether ester or two or more solvents containing propylene glycol monomethyl ether acetate. good. [5] Basic compound The sensitized ray or radiation sensitive resin composition of the present invention preferably comprises a basic compound to reduce the performance as a function of aging from exposure to heating. The basic compound is preferably a compound having a structure represented by the following formulas (A) to (E).

4-i (B)

In the formulae (A) and (E), R2()&lt;), R2G1 and R2e2 may be the same or different and represent a hydrogen atom, an alkyl group (having preferably a carbon number of 1 to 20), a cycloalkyl group ( It has preferably a carbon number of 3 to 20 or an aryl group (having a carbon number of 6 to 20); and R2C)1 and r2G2 may be bonded together to form a ring. Each of r2°3, r2()4, r2G5 and r2Q6 may be the same or different and represents an alkyl group having 1 to 20 carbon atoms. As the alkyl group, the alkyl group having a substituent is preferably an amino group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms or a cyano 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, pyridinium, pyrazoline, piperazine, aminofenorphline, aminoalkylmorpholine and piperidine. More preferred embodiments of the compound include compounds having an imidazole structure, a dioxindole structure, a oxidizer gun structure, a carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure; an alkane having a hydroxyl group and/or an ether bond; Amine derivatives: and aniline derivatives having a hydroxyl group and/or an ether bond. -167 - 201033732 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-biindole bicyclo[5,4,0]undec-7-ene. Examples of the compound having a hydrazone structure include tetrabutylammonium hydroxide, triarylphosphonium hydroxide, benzoguanidine hydrazide, and cesium hydroxide having a 2-sided oxyalkyl group, particularly, hydrazine hydroxide Phenylhydrazine, tris(tert-butylphenyl)phosphonium hydroxide, bis(tri-butylphenyl) hydroxide, benzylhydrazine methylthiophene gun and 2-oxopropylthiophene hydroxide . Examples of the compound having a carboxylate 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 carboxylic acid ester. 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, anthracene, fluorene-dibutylaniline and anthracene, fluorene-dihexylaniline. Examples of the alkylamine derivative having a hydroxyl group and/or an ether bond include ethanolamine, diethanolamine, triethanolamine, hydrazine-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 a phenoxy-containing amine compound, a phenoxy-containing ammonium salt compound, a sulfonate group-containing amine compound, and a sulfonate group-containing ammonium salt compound. In the phenoxy-containing amine compound, the phenoxy-containing ammonium salt compound, the sulfonate group-containing amine compound, and the sulfonate group-containing ammonium salt compound, at least one alkyl group is bonded to the nitrogen atom Preferably. Similarly, it is preferred to include an oxygen atom in the alkyl chain -168 to 201033732 to form an oxygen alkyl group. The number of alkylene groups in the molecule is 1 or more, and preferably from 3 to 9, more preferably from 4 to 6. Among the oxygen alkyl groups, the structures of -CH2CH20-, -CH(CH3)CH20- and -CH2CH2CH20- are preferred. Specific examples of the phenoxy-containing amine compound, the phenoxy-containing ammonium salt compound, the sulfonate group-containing amine compound, and the sulfonate group-containing ammonium salt compound include, but are not limited to, Compounds (C 1-1) to (C3-3) in [0066] of U.S. Patent Application Publication No. 200 7/0 224,539. 0 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 solid content of the sensitized ray or the radiation-sensitive resin composition. [6] Low molecular compound (D) having a group capable of leaving by acid action The composition of the present invention may comprise a low molecular compound (D) having a group capable of leaving by an acid action (sometimes Refers to &quot;component(D)&quot;). The group which can be removed by the acid for Q is not particularly limited, but an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxy group or a semi-amino aldehyde. The (hemiaminal) 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 which can be removed by an acid is preferably from 100 to 1,000, more preferably from 100 to 700, still more preferably from 100 to 50,000. In the example in which the low molecular compound having a group capable of leaving by acid action has a tertiary ester structure, the compound is a carboxylic acid ester or an unsaturated carboxylic acid represented by the following formula (la) -169 - 201033732 Ester is preferred:

In the formula (1a), each R1 each independently represents a monovalent alicyclic hydrocarbon group (having preferably 4 to 20 carbon atoms) or a derivative thereof or an alkyl group (having preferably 1 to 4 carbon atoms) while 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 to form a divalent alicyclic hydrocarbon group (having preferably having a carbon number of 4 to 20) or a derivative thereof, together with the carbon atom to which they are bonded. The remaining Ri represents an alkyl group (preferably having 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 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- is preferred (wherein D represents an alkylene group (having preferably a carbon number of 1 to 4)). 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. The group is a propyl group, a propyl carbonyl group and a propyl carbonyloxy group, and a methylene carbonyl group is preferred. In the formula (la), the monovalent alicyclic hydrocarbon group of R1 (preferably having a carbon number of 4 to 20) and a divalent alicyclic hydrocarbon group formed by bonding any two R1 to each other (having a carbon number of 4 to 20) Preferred embodiments include those derived from norbornane, tricyclodecane, tetracyclododecane, adamantane or cycloalkane (such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane). a group consisting of an alicyclic ring of an alkane; and the above-described group consisting of an alicyclic ring consisting of one or more or -170-201033732 one or more groups of alkyl groups having a carbon number of 1 to 4 ( For example, methyl, 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 norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclopentane or cyclohexane, and the lipid The group consisting of a cyclocyclic ring is preferably a group substituted with the above alkyl group. Examples of the derivative of the alicyclic hydrocarbon group include a group having one or more or one or more groups of substituents, wherein the substituent has a hydroxyl group such as a hydroxyl group; a carboxyl group; a 0 side oxygen group (i.e., =0); A hydroxyalkyl group having 1 to 4 carbon atoms, for example, hydroxymethyl, hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl Base, 2-hydroxybutyl, 3-hydroxybutyl and 4-hydroxybutyl; alkoxy having 1 to 4 carbon atoms, for example, methoxy, ethoxy, n-propoxy, isopropoxy , n-butoxy, 2-methylpropoxy, 1-methylpropoxy and tert-butoxy; and cyanoalkyl having 2 to 5 carbon atoms, for example, cyanomethyl, 2-cyano Ethyl, 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 this 1 include a hospital 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. -171- 201033732

-172- 201033732 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 1 to 4 carbon atoms.)

-173 - 201033732 As for the low molecular compound (D) having a group capable of leaving by acid action, a commercially available product can be used or the compound can be synthesized by a known method. Similarly, an amine derivative having a group capable of leaving by an acid action on a nitrogen atom is preferable as the component D. This component D may have a protecting group-containing urethane group on a nitrogen atom. The protecting group constituting the urethane group can be represented by the following formula (d-l): Ο R,

(d-1) In the formula (d-Ι), each R' each independently represents a hydrogen atom, a linear, branched or cycloalkyl group, an aryl group, an arylalkyl group or an alkoxyalkyl group. Each R' 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, and a linear or branched alkyl group or a cycloalkyl group is more preferred. The specific structure of the group represented by the formula (d-1) is proposed below. 201033732 'Λχ人&gt;〇 Λ&gt;ο vVc-υΛό&gt;^ \Λ〇^0 vV(0 yl〇jP vVP vV^ /.;£^ Λ^Ρ Λ^κ&gt; Λ^φ

Righteousness

ν^Χφ yV^J) \乂. ^^ νΛ). nA〇Mvq,Λ^0| ^°^〇), person

201033732 This component D can also be composed by any combination of the basic compound described above and the structure represented by the formula (d-Ι). 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 is a low molecular compound having a group which can be removed by an acid action.

In the formula (A), each Ra independently represents a hydrogen atom, a hospital group, a ring-based group, an aryl group or an aromatic 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 heterocycloalkyl 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 aromatic 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 〇 to 2, and m represents an integer of 1 to 3 and n + m = 3. In the formula (A), the alkyl, cycloalkyl, aryl and aralkyl groups of Ra and Rb 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, or the like. A porphyrin group and a pendant oxygen group, an alkoxy group or a halogen atom. The alkyl, cycloalkyl, aryl and aralkyl groups of R (these alkyl, cycloalkyl, aryl and aralkyl groups may be substituted by a functional group, alkoxy or halogen-176-201033732 atom as described above) Examples include: groups derived from linear or branched alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, decane, decane, undecane and twelve And 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 such as cyclobutane, a group of cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, and adamantane; and the group derived from cycloalkane is one or more or one or more sets of linear Or a group substituted with a branched alkyl group such as 0 methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl and tert-butyl; derived from a group of an aromatic compound such as benzene, naphthalene and anthracene; and the group derived from the aromatic compound is one or more or one or more sets of linear or a group substituted with a branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl and tert-butyl; a group of a ring compound such as pyrrolidine, piperidine, morphine, tetrahydrofuran, tetrahydropyran, hydrazine, porphyrin, quinoline, perhydroquinoline, carbazole 0 and benzimidazole; a group derived from a group derived from one or more or one or more groups of linear or branched alkyl or aromatic compounds; the group derived from a linear or branched alkane or derived from a group in which a cycloalkane group is substituted with a group derived from one or more or one or more groups of aromatic compounds, such as a phenyl group, a naphthyl group, and an anthracenyl group; and the above substituent is a monofunctional group such as a hydroxyl group. a group substituted with a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, and a pendant oxy 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 compound 177 ^ 201033732, such as pyrrole , piperazine, morpholine, 1,4,5,6-tetrazine, 1,2,3,4-tetrahydroquinoline, ruthenium 2,3,6-tetrahydropyridine, homopiperazine , 4-indolobenzimidazole, benzotriazole, 5-nonylbenzotriazole, 1H-1,2,3-triazole, 1,4,7-trioxancyclodecane, tetrazole, 7- Anthracene, carbazole, benzimidazole, imidazo[l,2-a]pyridine, (lS,4S)-( + )-2,5-dioxabicyclo[2.2.1]heptane, 1,5 , 7-triterpenic ring [4.4.0] 癸-5-ene, anthracene, porphyrin, 1,2,3,4·tetrahydroquinoxaline, perhydroquinoline and 1,5,9-three Anthracene-dodecane; and a group derived from a heterocyclic compound substituted by one or more or one or more groups of the following groups: a group derived from a linear or branched alkane, a group derived from a cycloalkane a group derived from an aromatic compound, a group derived from a heterocyclic compound, and a functional group. (such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group) , morpholinyl and pendant oxygen groups). Particular embodiments which are particularly preferred in the present invention include fluorene-tertiary butoxycarbonyldi-n-octylamine, fluorene-tertiary butoxycarbonyldi-n-decylamine, fluorene-tertiary butoxycarbonyldi-n-decylamine, Ν· Tert-butyloxycarbonyldicyclohexylamine, Ν_tertiary butoxycarbonyl-1-adamantylamine, fluorene-tertiary butoxycarbonyl_2-adamantylamine, Ν-tertiary Oxycarbonyl-indole-methyl-1-adamantylamine, (s)-(-)-l-(tertiary butoxycarbonyl)-2-pyrrolidinemethanol, + tert-butoxycarbonyl)- 2-pyrrolidinemethanol, N-tertiary butoxycarbonyl-4-hydroxypiperidine, N-tertiary butoxycarbonylpyrrolidine, N-tertiary butoxycarbonylmorphine, N-tertiary butoxide Base forging ruthenium, N,N-bis-tertiary butoxycarbonyl-fluorene-adamantylamine, N,N-bis-di-butoxycarbonyl-N-methyl-adamantylamine, N_three Butoxycarbonyl-4,4'-diaminodiphenylmethane, ν,ν'-bis-tertiary butoxycarbonylhexamethylenediamine N,N,N',N'-tetra-tertiary butoxy Hexyl hexamethylenediamine, n,N,_di-di-butoxybutyryl-1,7-diaminoheptane, n,N,_dual tertiary tert-butoxycarbonyl-178- 201033732 _1,8 -diaminooctane,; ^,; ^, _ di-tertiary butoxycarbonyl-1,9-diamino fluorene, N,N'-bis-di-butoxycarbonyl-no•diamine癸, n, n, bis-tertiary butoxycarbonyl-1,12-diaminododecane, n,N,-di-tertiary butoxycarbonyl- 4,4'-diaminodiphenyl Methane, N_tertiary butoxycarbonylbenzimidazole, N-tertiary butoxycarbonyl-2-methylbenzimidazole, and ruthenium tert-butoxycarbonyl-2-phenylbenzimidazole. Specific embodiments of component D which are particularly preferred in the present invention are set forth below, but the invention is not limited thereto. 〇

179 - 201033732

(0-21) (0-23⁄4 (D-23)

•180- 201033732

(D-38)

(D-39)

O O O V/ j people 〇 O people. (D^4) ό人N人HN人ό ό χ

ο ο 乂 ό ο 人. (D-45) (D-46) Ο Ο ¢)-47) Ο

ΗΟ

(Ρ-4Β) Deaf.丄〉r^N (D-4S) Ο Λ (D-50) (D-61) Ο

, CN ο ο (D-52) (D-53) (D-54) (D*5£) 201033732 The compound represented by the formula (A) can be described by, for example, "protecting groups in organic synthesis" The method of Protective Groups in Organic Synthesis, 4th Edition, is readily synthesized from commercially available amines. The most general method is a method of 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 Ra and Rb have the same meanings as Ra and Rb in the formula (A).

In the present invention, a low molecular compound (D) having a group capable of leaving by an acid action may be used alone, or two or more kinds of the compounds may be mixed and used. In the present invention, the low molecular compound (D) having a group capable of leaving by acid action is usually used in an amount of from 0.001 to 20% by mass, preferably from 0.001 to 10% by mass, from 0 to 〇1. More preferably, it is 5% by mass, based on the total solid compound in which the composition is combined with the basic compound described above. The ratio between the acid generator and the low molecular compound (D) having a group capable of leaving by acid action is an acid generator / [having the ability to leave by acid action) Low molecular compound (1)) + basic compound (in terms of moles) = preferably from 2.5 to 300. That is to say, considering -182-201033732 to sensitivity and resolution 'the molar ratio is preferably 2.5 or more; and from the viewpoint of suppressing the resolution due to the reduction of the photoresist pattern with the aging thickening after exposure to heat treatment Look, 300 or less is better. The acid generator / [low molecular compound (D) + basic compound having a group capable of leaving by acid action (in terms of moles) is more preferably from 5.0 to 2 Torr, and from 7.0 to 150. good. [7] Surfactant The sensitized ray or radiation sensitive resin composition of the present invention may or may not further comprise a surfactant, and in the case of including a surfactant, 0 the surfactant is 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 22 nm or shorter) is used, This provides a photoresist pattern with good performance in terms of sensitivity, resolution and adhesion and less development defects.

On the other hand, when the amount of the surfactant added is reduced (for example, to 10 ppm or less), the uneven distribution of the component (C) to the surface is more successfully achieved so that the surface of the photoresist film can be It becomes more hydrophobic and improves the fluidity of water during immersion exposure. Examples of the fluorine-containing and/or rhodium-containing surfactant include surfactants described in JP-A-62-36663, JP-A-61-226746, JP-A-6 1 -226745, JP -A-62 - 1 70950 , JP-A-63 - 34540 , JP-A-7-23 0 1 65 , JP-A-8-62834 , JP-A-9-54432 , JP-A-9-5988 JP-A-2002-277862 and U.S. Patents 5,405,720, -183 - 201033732 5,360,692' 5,529,881' 5,296,330' 5,436,098' 5,576,143' 5,294,511 and 5,824,451. The following commercially available surfactants can also be used as they are. Examples of commercially available surfactants that can be used include fluorosurfactants and cerium-containing surfactants such as EFtop EF301 and EF3 03 (by Shin-Akita Chemicals Co., Ltd.) AkiTa Kasei K. K.)); Florad FC430, 431 and 4430 (manufactured by Sumitomo 3M I n c.); Megaface F171, F173, F176, F189 , F113, F110, F177, F120 and R08 (manufactured by Dainippon Ink &amp; Chemicals, Inc.); Surflon S- 3 82, SC101, 102, 103, 104, 105 and 106 (manufactured by Asahi Glass Co., Ltd.); Tr〇ysol S-3 66 (manufactured by Troy Chemical); GF-300 and GF -150 (manufactured by Toagosei Chemical Industry Co., Ltd.); Serpentoon S-393 (manufactured by Seimi Chemical Co., Ltd.); Love EF121, EF122A' EF122B &gt; RF122C &gt; EF125M, EF135M, EF35 EF352, EF8 (H, EF802 and E F601 (manufactured by JEMCO Inc.); PF6 3 6, PF6 5 6, PF63 2 0 and PF6520 (manufactured by OMNOVA); and FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, and 222D (manufactured by NEOS Co., Ltd.) In addition, polyoxyalkylene polymer KP-341 (by Shin-Etsu Chemical Co., Ltd. (Shin- Etsu Chemical Co., Ltd.) is used as the cerium-containing surfactant. As for the surfactant, in addition to these known surfactants, -184-201033732 can be used with 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 telomerization method) or an oligomerization method (also referred to as an oligomer method) The fluorine-aliphatic compound can be synthesized by the method described in [0241] and [0242] of JP-A-2002-90991. The copolymer having a fluorine-aliphatic group may also be fluorine-containing. Monomer of aliphatic groups with (poly(oxyalkylene)) acrylate and/or (poly(oxyalkylene) )) Of a copolymer of methyl acrylate.

As for the commercially available surfactants, examples thereof include Mecca 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 a (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 such as polyoxyethylene ethyl ethers (e.g., 'polyoxyethylene ethyl lauryl ether, polyoxyethyl stearyl ether), polyoxyethyl ether Alkyl aryl ethers (for example, polyoxyethylene ethyl octyl phenol ether, polyoxyethyl decyl phenol ether), polyoxyethylene ethyl polyoxyalkylene block copolymer, sorbitan Fatty acid esters (for example, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate), and polyoxygen Dehydrated sorbitan fatty acid esters (eg 'polyoxy-extended ethyl laurate sorbitan ester, polyoxy-extended ethyl monopalmitate de-185 - 201033732 sorbitan ester, polyoxy-extension ethyl single Sorbitan stearate, polysorbate sorbitan monoethyl trioleate, polysorbate ethyl sorbitan sorbitan ester). The amount of the surfactant which can be used alone or in combination with some of the surfactants is preferably from 0.000 1 to 2% by mass, more preferably from 0.01 to 1% by mass, based on the sensitized ray. Or the total amount of the radiation sensitive resin composition shall prevail (excluding the solvent). [8] Carboxylic acid gun The sensitized ray or radiation sensitive resin composition of the present invention may contain iron carboxylic acid. The carboxylate is preferably a phosphonium salt or a phosphonium salt. The anion moiety is preferably a linear, branched, monocyclic or polycyclic alkyl ester anion having a carbon number of 1 to 30, and the above carboxylate anion has a part or all of an alkyl group which is more preferably substituted by fluorine. The alkyl chain can comprise an oxygen atom. Thanks to this architecture, transparency to 220 nm or shorter light, improved sensitivity and resolution, and improved solitary/dense deviation and exposure edges are guaranteed. 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. The content of the carboxylate in the composition is usually from 0.1 to 20% of stomach, 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 alkaline developer -186-201033732 which has a molecular weight of 3,000 or less and can be decomposed by an acid action to increase The solubility-inhibiting compound in the solubility of an alkaline developer (hereinafter, sometimes referred to as &quot;dissolution inhibiting compound&quot;) is a group containing an acid-decomposable group (such as described in the SPIE meeting record, 2724, 3 5 5 The alicyclic or aliphatic compound of the cholic acid derivative containing an acid-decomposable group in (1 996) is preferred so as not to reduce the transmittance to 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 (A). In the 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 solvo-inhibiting compound has a phenolic hydroxyl group of a phenol compound substituted by an acid-decomposable group. The structure is better. The phenol compound is preferably a compound containing from 1 to 9 phenol skeletons, more preferably from 2 to 6 phenol skeletons. The amount of the dissolution inhibiting compound to be added is preferably from 3 to 50% by mass, more preferably from 5 to 40% by mass, based on the solid content of the sensitized ray or the radiation sensitive resin composition. Specific examples of the dissolution inhibiting compound are set forth below, but the present invention is not limited thereto.

[1〇] Other Additives-187 - 201033732 If necessary, the photosensitive 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 an accelerated dissolution agent in the developer. a compound (for example, an acid compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound having a carboxyl group). The phenolic compound having a molecular weight of 1, hydrazine or less can be used by those skilled in the art, and by way of example, for example, in JP-A-4-122938, JP-A-2-28531, U.S. Patent 4,916,210, and European Patent 219,294. The method of the present invention 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 cyclohexane dicarboxylic acid. [11] Pattern forming method From the viewpoint of improving the resolution, it is preferred to use the sensitized ray or radiation sensitive resin composition of the present invention at a film thickness of 30 to 250 nm (more preferably from 30 to 200 nm). The film thickness can be obtained by setting the solid content concentration in the sensitized ray or the radiation sensitive 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 sensitized ray or radiation sensitive resin composition is usually from 1 to 10% by mass, and preferably from 1 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 above-described mixed solvent) 'filtering solution and coating it as follows Scheduled -188- 201033732 on the carrier. The filter used for filtration is a filter made of polytetrafluoroethylene or polyethylene, having a pore size of 0.1 μm or less, 〇 5 μm or less, preferably 0.0 3 μm or smaller. Better. For example, when used in the manufacture of precision integrated circuit components, a suitable coating method such as a centrifugal coater or a coater is applied to the substrate or the radiation sensitive resin composition (for example, On the substrate of bismuth/cerium oxide), and dried to form a photosensitive film (light film). The sensitization is irradiated with actinic radiation or radiation via a predetermined mask and then preferably baked (heated), subjected to development and rinsing, whereby a pattern is obtained. Examples of the actinic ray or radiation include infrared light, visible light, far ultraviolet light, extreme ultraviolet light, X-ray, and electron beam, but the far ultraviolet light having a wavelength of 250 nm or shorter is preferably 220 nm. The rice is shorter and better, from 1 to 200 nm. Specific examples thereof include excimer lasers (2 48 nm), ArF excimer lasers (193 nm), molecular lasers (157 nm), and X-rays, and ArF excimer lasers, molecular lasers, and EUV (13 nm) is preferred. The provided film may be preliminarily coated on the substrate before the formation of the photosensitive film. The antireflection film used may be an inorganic film type such as titanium, titanium, titanium nitride, chromium oxide, carbon, and amorphous germanium; or an organic film type composed of a light absorbing agent material. As the organic anti-reflective film, a commercially available organic anti-reflective film such as DUV30-based olefin manufactured by Brewer Science, Inc., or a light-resistant resist film can be used. , purple or spokes or KrF F2 quasi-F2 quasi-anti-diox and poly, in Ruhrer and -189-201033732 DUV-40 series, and AR manufactured by ShiPley Co., Ltd. -2, AR-3 and AR-5. As for the test developer used in the development step, a quaternary ammonium salt (typically tetramethylammonium hydroxide) is usually used 'but other than this, an inorganic base, a primary amine, a secondary amine, and the like may be used. An aqueous alkaline solution of a primary amine, an alcoholamine, a cyclic amine or the like. 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 1 Torr to 15.0. Similarly, an aqueous alkaline solution as described above may be used after each of an appropriate amount of an alcohol and a surfactant may be added. As the washing liquid, pure water is used, and further, an appropriate amount of the surfactant may be added to use the pure water. After development or rinsing, the developer or lotion adhered to the pattern can be removed by supercritical fluid treatment. EXAMPLES The invention is described in more detail below with reference to examples, but the invention should not be construed as being limited thereto. &lt;Synthesis Example 1: Synthesis of Resin (C-8)&gt; The following compound (1) was synthesized by the method described in the International Patent Publication No. WO 07/037213, the specification. In 35.00 g of the compound (1), 150.00 g of water was added and 27.30 g of NaOH was further added. The mixture was stirred under heating and reflux for 9 hours. It was made acidic by the addition of hydrochloric acid, and then extracted with ethyl acetate - 190 - 201033732. The organic layer was combined and concentrated to obtain 36.90 g of compound (2) (yield: 9 3%). 1H-NMR (400 MHz, in (CD3)2CO): δ(ρριη)= 1.5 6- 1.5 9( 1 H), 1.68-1.72 ( 1 H), 2.13-2.15(1H), 2·13-2.47 (2Η), 3.49-3.51 (1Η), 3.68 (1Η)' 4.45-4.46 (1Η). In 20.00 g of the compound (2), 200 ml of CHC13 was added, and further 50.90 g of 1,1,1,3,3,3-hexafluoroisopropyl alcohol and 30.00 g of 4-dimethylamino group were added. Pyridine. The obtained mixture was stirred, and 22.00 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide was added to the solution resulting from the 0. After stirring for 3 hours, the reaction solution was added to 500 ml of 1NHC1 and the reaction was terminated. The organic layer was further washed with 1NHC1, then washed with water and concentrated to obtain 30.00 g of Compound (3) (yield: 85%). 1H-NMR (400 MHz in (CD3)2CO): 6 (ppm) = 1.62 (1 Η) &gt; 1.9 1 -1.9 5 (1 Η ) , 2.2 1 - 2.2 4 ( 1 Η), 2.45 -2.5 3 (2Η) &gt; 3.6 1 - 3.6 3 (1 Η ) . 3.76(1Η)- 4.3 2 - 4.5 8 ( 1 Η) &gt; Ο 6·46-6.53 ( 1 Η). In 15.00 g of the compound (3), 300. g of toluene was added, and 3.70 g of methacrylic acid and 4.20 g of p-toluenesulfonic acid monohydrate were further added. The obtained mixture was refluxed for 15 hours while removing the produced water by azeotropy. Concentration of the reaction solution 'and purification of the concentrate by column chromatography' to obtain 11.70 g of the compound (4) (yield: 65% b 1 H-NMR (4 〇〇 MHz ' in (CD3) 2CO) : 5(ppm)= 1 . 76- 1 . 79( 1 Η) , 1 . 9 3 (3 Η) ' 2.1 6 - 2.2 2 (2 Η), 2.57-2.61 (1Η)&gt; 2.76-2.81 (2Η )&gt;3.73-3.74(1Η)&gt;4.73(1Η)&gt; -191 - 201033732 4·84-4·86(1Η), 5.69- 5,70( 1 Η),6·12(1Η), 6.50 -6.56 (1 H).

In 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 of 17.5 g of the compound (4), 4.0 g of the butyl methacrylate, and a ratio of 5.0 mol% (based on the monomer) was added dropwise. The initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 58.0 g of a solution prepared by PGMEA. 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 1,3 g of methanol/150 g of distilled water in 20 minutes, and the precipitated powder was collected by filtration. And drying, as a result, 15.2 g of a resin (C-8) was obtained. The resin (C_8) had a weight average molecular weight of 8,000 and a polydispersity (Mw/Mn) of 1.3 in terms of standard polystyrene. &lt;Synthesis Example 2: Synthesis of Resin (C-94)&gt;

192-201033732 300.0 g of methanol was added to 150·0 g of ethyl 4-cyclohexanonecarboxylate (d), followed by stirring, and an aqueous solution of sodium hydroxide (containing 35.3 g of hydrogen) was added dropwise at 25 °C. a mixed solution of sodium oxide and 300.0 g of distilled water). After 3 hours, it was confirmed that (d) disappeared and the reaction solution was added dropwise to 45.7 g of concentrated hydrochloric acid. Subsequently, 2,400 g of ethyl acetate was added, the resulting mixture was washed 5 times with distilled water and the organic layer was concentrated to obtain 63 g of compound (e). Further, 43.7 g of the above obtained (e), 394.0 g of chloroform, 0 77.6 g of 1,1,1,3,3,3-hexafluoro-2-propanol and 3.8 g of dimethylamino group were added. Pyridine, followed by stirring, and 64.9 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride were added. After stirring at 25 ° C for 3 hours, it was confirmed that (e) disappeared, and the reaction solution was added dropwise to IN hydrochloric acid. The resulting solution was stirred, and the organic layer was collected, washed twice with 1N hydrochloric acid and then distilled water 5 times, and then concentrated to obtain 70.0 g of compound (f). Using 32.1 g of the compound (f) and 26.0 g of the compound (B), the reaction was carried out under acidic conditions to obtain 10.0 g of the objective compound (g). 1 In a nitrogen atmosphere, 10.1 g of PGME A was charged into a three-necked flask and heated to 80 °C. Here, within 4 hours, a polymerization initiator V-601 was obtained by dropwise addition of 36.3 g of the compound (g) and a ratio of 2.5 mol% (according to the monomer) (from the light purification industry) Co., Ltd. manufactured) a solution prepared by dissolving in 96.8 grams of PGMEA. 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 drying, as a result, 25.1 g of a resin (C-94) was obtained. 201033732 In terms of standard polystyrene, the resin (C-94) has a weight average molecular weight of 13,0 Å and a polydispersity (Mw/Mn) of 1.4. The other resins (C) shown in Tables 4 and 5 later were synthesized in the same manner. &lt;Synthesis Example 3: Synthesis of Resin (1)&gt; 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 dihydroxyadamantyl methacrylate, and 8.9 g of norbornane lactone were added dropwise. A solution prepared by dissolving a methacrylate and a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries Co., Ltd.) in a ratio of 8 mol% (based on the monomer) in 79 g of cyclohexanone. After completion of the dropwise addition, the reaction was further carried out at 8 (TC for 2 hours. The resulting reaction solution was left to stand until it was cooled, and then it was added dropwise to 800 ml of hexane/200 in 2 minutes. A mixed solution of ethyl acetate in ml, and the precipitated powder were collected by filtration and dried to obtain 19 g of a resin (1). The weight average molecular weight of the obtained resin was 8,8 in terms of standard polystyrene. The enthalpy and polydispersity (Mw/Mn) was 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 in each resin (from the left side in the structural formula) are shown in Table 3 below. 194- 201033732

-195 - 201033732

-196- 201033732 Table 3

Resin (A) Composition (molar ratio) M w M w/Mn 1 50/10/40 8 8 00 1.9 2 40/20/40 7000 1.6 3 40/10/35/5/10 1 0000 1.7 4 40 /10/40/10 11000 1.8 5 40/15/20/25 8 5 00 1.6 6 10/40/25/25 1 2000 1.8 7 50/20/30 65 00 1.6 8 40/10/50 8 000 1.7 9 25/25/50 9000 1.8 10 50/10/40 11000 1 .8 11 50/10/40 8000 1.7 12 40/ 1 0/40/1 0 7000 1 .7 13 20/15/35/30 1 0000 1.7 14 45/10/35/10 8 5 00 1 .7 15 50/40/1 0 1 0000 1.6 16 10/40/40/10 9000 1.8 17 55/10/35 1 2000 1.8 18 40/15/20/ 25 9000 1.7 19 40/15/30/15 7 5 00 1.6 20 40/15/45 8 000 1 .6 2 1 40/40/10/10 9 5 00 1.8 22 35/15/25/25 1 0000 1.7 23 20/15/45/20 800 0 1 .6 24 25/35/15/25 9000 1.8 25 15/30/10/33/22 1 0000 1 .7 26 20/10/40/30 1 0500 1.6 - 197 - 201033732 &lt;Preparation of sensitized ray or radiation sensitive resin composition&gt; The components shown in the following Tables 4 and 5 are dissolved in a solvent to prepare a solution having a solid content concentration of 5% by mass, and obtained The solution was filtered through a polyethylene sterilizer having a pore size of 1.1 μm. Sense actinic rays or radiation-sensitive resin composition (positive-type photosensitive resin composition). The positive photosensitive resin composition prepared was evaluated by the following method, and the results are shown in Tables 4 and 5. In the table, the resin in &quot;resin (2g)&quot; means resin (A).

&lt;Image Performance Test&gt; [Exposure Condition: ArF Immersion Exposure]

An organic anti-reflective film (ARC29 A, manufactured by Nissan Chemical Industries, Ltd.) was coated on a 12-inch diameter tantalum wafer and baked at 205 ° C for 60 seconds to form A 98 nm thick antireflection film was coated with the positive photosensitive resin composition prepared above and baked at 120 ° C for 60 seconds to form a 120 nm thick photosensitive film. Using an ArF excimer laser immersion scanner (XT 1 2 5 0i, manufactured by AS ML, ΝΑ: 0.85) via a 6% halftone mask with a line width of 75 nm and a spacing pattern of 1:1 Expose the obtained wafer. 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 % by 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 line pattern, by Critical Dimension SEM (S-8840, manufactured by Hitachi Ltd.) At 50 o'clock, the measured distance from the edge should be -198- 201033732, and after calculating the standard deviation, 'calculate 3σ. When the enthalpy is less than 5.0 nm, the sample is grade A; when it is from 5 · 〇 nanometer to less than 7.0 nm, grade B; and when it is 7.0 nm or more, grade C. A small size indicates a higher performance. [Scum] The development residue (scum) in a resist pattern having a line width of 75 nm was observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.); and when scum was not generated at all , the sample is grade A; grade D when scum is strongly produced 0; and grade B or C when scum level is between. [Evaluation of development defect] Using a defect inspection device (KLA2360 (trade name), manufactured by KLA Tencor Ltd.), the pixel size of the defect inspection device was set to 0.16 μm and the threshold was set to 20, measuring the pattern formed on the poly-xylene wafer (12-inch diameter) as described above in a random mode to detect development from the difference Q generated when the pixel unit is superimposed on the reference image defect. Calculate the number of development defects per unit area (pieces per square centimeter). When the enthalpy is less than 0.5, the sample is grade A; when it is from 0.5 at least 0.7, grade B; when from 0.7 at least 1.0, grade C; and when 1.0 or greater, grade D. A small size indicates a higher performance. [Amount of Separation of Acid Produced] The prepared positive photosensitive resin composition was applied onto a tantalum wafer having a diameter of 8 inches and at 120. (: Bake for 60 seconds to form a 120 nm thick photosensitive film. Subsequently, an ArF excimer laser exposure machine (PAS5500/1100, manufactured by ASML) was used to expose the 8 at 30 mJ/cm 2 201033732. The entire surface of the enamel wafer. Immerse the wafer in a 100 ml-supplied ultrapure water generator (Milli-Q, by hon本米里坡(股) (Nihon Millipore Κ· K.) Manufactured in a deionized pure water quartz container, and collects the material that has been eluted into the water. The amount of this acid eluted into the aqueous solution is quantitatively measured by LC-MS. LC device: 2695 by watt Waters manufactures MS device: eSquire 3000, manufactured by Brucker D a 11 ο nics, measuring the detected mass with mass 299 by LC-MS device The strength of the species (corresponding to the anion of nonafluorobutanesulfonate) and the amount of segregation of nonafluorobutanesulfonic acid. The amount of dissolution is also calculated for the other anions in the same manner. When the amount of dissolution is 1.0x1 〇 _1 () mole / square centimeter / second or more, the sample Level C; when from 1.0xl0_12mol/cm2/s at least 1·0χ10_1()m/cm2/s, level B; and when less than 1.0xl (T12 mol/cm2/s, Grade Α [Retraction contact angle] The prepared positive photosensitive resin composition was coated on a 8 inch diameter wafer and baked at 120 ° C for 60 seconds to form a 120 nm thick photosensitive film. The receding contact angle of the water drop was measured by a expansion-contraction method using a dynamic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). The suction was carried out at a rate of 6 μl/sec. The initial droplet size is 35 microliters of droplets for 5 seconds, and when the dynamic contact angle is set during the inhalation, the enthalpy is used as the receding contact angle. The environment is carried out at room temperature of 23 ± 3 t and humidity of 45 ± 4%. Measure. When the number of back contact angles is large, the water can follow the scan at a higher speed. -200- 201033732 〇ο 寸 1 1 Back contact angle (degrees) oo ο JO ο ο Ο oo JQ o JO Jn ο o JO v〇o The amount of acid dissolved in &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&gt;&lt;&lt;&lt;&gt;&lt;&lt;&lt;&gt;&gt;&lt;&lt;&lt;&gt; CQ &lt; ffl scum &lt; ca &lt;&lt;&lt; PQ &lt; 〇Q &lt; CQ &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&gt;&lt;&lt;&gt;&lt;&gt; ^S rn, δ δ »&quot;Η 5 cn rn δ cn δ ss »n *«H /^Js δ ri s rn /—N w- r? Resin (CX mg) § ύ | rp 0 rH ό I νο &lt;Ν ΰ I ΰ S g (S ό »η &lt;Λ V—Η ΰ /-s Ο o' &lt;N CJ ό gN to oo ό S' 00 fn ό /—V § ύ § ϋ gs 00 00 Cfs ό 1 ό S' rp ύ § cn^ S ό /--V g OO 3 V〇^ •«HU | 00 ό § ώ Basic compound (mg) 1 5 έ /·-s 卜 i 00 &lt; 00 »&quot;Μ »〇2 /—&gt; cn Ζ S' έ zs cn έ sm έ z έ ΡΓ τ*Η S cn s Z 1 vp 1 5 Solvent (ratio, by mass) 1 S hJ CO II CO 1 § 1 S'1 1 w* i 3 t/3 gs § two SG tN ri % ο ri 二ζ Π 1 /—s ON ( o ϊ〇CN OS o /—s OS JQ s VO 3 C/DS' § o CN o J ?5 gs s 1 3 (7) gs Guide CO oo ic o -j T nJ w ?4 hJ sj /--s 1 O cs hJ CO /—»N ON !Q ov〇J3 2 C/D GO 1 § II CO $ /^N s CO Photoacid generator (mg) S' ο in •Q ' SN—✓ /^S Ο of § •μ ri gv ι«Η ί S'&quot; ***H r·^ cn gv cn^ inch〇'S gs i OS $ oo Ώ gs S'* QS' ri Ϊ gv o oo 'S % S—✓ Ό VO N in' CJ og J2 Ό 'SS' Resin (2g) (N m ★ »Τϊ ν〇ΐ&gt; 00 OS 〇(S ” 4 〇v〇卜 oo inch w- &gt;»&quot;H Example 1 (N m 揖 κ κ tt tt κ κ 实施 实施 实施 实施 实施 m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m m闺弑 闺弑 w-&gt; 揖m 握 grip surface embodiment 17 oo ί m K embodiment 19 series ii embodiment 21 201033732 (hall) inch 嗽眯 11 11 «§ $ Vi jn JQ jn JQ og in oo ο ο The amount of JQ o acid dissolved &lt; CQ &lt;&lt;&lt; PQ &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;;&lt;&lt;&lt;&lt; m &lt;&lt;&lt; m P0 CQ m CQ &lt;&lt; CQ paper down &lt; PQ &lt;&lt;&lt;&lt; PQ &lt; CQ &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; ntj Surfactant (mg) S Ϊ δ l δ tj- ss cs 8 δ δ ls /—N Ϊ δ rn /·—Ν ν〇s δ ri δ Ϊ Resin (CX mg) _1 § ό S' o cn 0 I rn ό | 00 ΰ I cn ύ § ^w· ϋ I m ύ S' 〇〇ά S' 00 oo ϋ S'* 00 cs On tN ό 00 ss i! cL u 1&gt;M ό v〇| vi 卜 (L cn ό § o ϋ g ό τ-* »—Η ό § »*Η Ο 0 s 穸ό /—sg 〇\ 6 £ 碱性 Basic compound “g) 丫1 5 00 % wz 1-^ ^H z ί^1 ό /^s »?rz /gs WV» ά Ri »n Θ O cn Q i 1 fi; wi op z /—V i op % 1 5 00 z ν«-^ »—Η ζ § rn w Z fO z 1 芩OO Solvent (ratio, by mass): 1 ______ ! w gs 苳§ is Λ ζΠ S' , i cs § CN 1 1 ΰ ΧΑ 1 S' 1 s fN II CO 1 s So rs hJ C/D s I Λ C/2 S' , CS II C/ 3 /~v 1 ci έ 53⁄4 S' Guide 2 52 S' sw* C/3 ΪΝ f /--Ν ^Η Ss »η ο rs S' 1 S Rf { i cs ύ S' t § r? Λ ΧΛ gs ts 厶 (N photoacid generator (mg) _ _1_ — 1— | 〇X 1 XNS' Ο \〇戈 f gs 〇/--V 〇vi s 〇〇X /^V gv o T—&gt;v〇戈〇vo&quot; 'S 1·^ V—✓ •s ο CO 乂1 ο 00 Ν O »~HN gs *—&lt; TH W* 1 S' 〇fi resin (2g) O «Ν π rn vr&gt; VI CN CN ΟΝ rj m 卜1—^ ΓΛ grip K ?5 m rl grip IX 闺m m series m b cs grip κ mm IK OS &lt;s Μ 荽mwmmmm &lt;S mmg K m cn m Grip K Example 34 to 闺κ ν〇ΓΛ Series 1« Series m 00 OS ΓΛ Bracelet 〇 i Series m 201033732 Ο ο (鲣鹚) inch credit m 1 face contact Angle ") 〇Ο JO JQ oo Ο jn JO jn jn pj JO g Acid dissolution amount &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; c development defect 0Q &lt; m OQ CQ OQ &lt;&lt; PQ CQ CQ ω &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; CQ &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; LER &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; Lt &lt;&lt; 丨 photoresist composition surfactant "克) δ δ op δ NO δ 1 - H / &lt; -sais / * - s Ci i / &lt; - &gt;&lt; N Ϊ 3 l ^ —se /—s /—s VO W-4(2) ! W-4(2) W-4(2) Resin (C) (mg) _i S cs ό /—so •n ϋ | *n ό § Cn ό 1 •n 3 5S ό § ύ /—sg 豸ό S ϋ gs 00 5〇ό 00 co&quot; ΰ /•&quot;S t ό § X 00 ό ss 'O ό C-303/C-6 (80 /40) C-308(80) Cl/CP-64 (80/7) Basic compound (mg) js cn 2 G&quot; cn % 'Ό w- z gs rM ϊ〇έ 5 vp z 'w* Ϊ in Z w »-H 1 »n Z m 5 QS' gs w Q /—so cn z N-4(7) Nl(10) N-3(10) Solvent 仳 rate 'by mass) S' 1 t Os § t 二ΧΛ O , w , CN f ? 5 5s 00 o to j lJ CS Guided by two gs s I ? 5 S' § Ji CO cs Two-conductor two KA § ¥ CN § cs . CO cs j CO gs sw· CO ?5 II C/5 /-so § II CN SL-2/SL-4(60/40) SL-2/SL-4(60/40) SL-2/SL-4(60/40) Light Acid generator (mg) o 1—^ oo 〇o' 00^ S—✓ Ώ S' o o&quot; 戈o SN 1 «o' CJ o OO 'S o 'S gs o 'S 1-H ri ; 〇 F—M o X38(100) z66(100) z66(100) Resin (2g 1 1 〇 〇 m m ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Bracelet i 闺w Bracelet Example 51 1 Example 52 I Example 53 m Yellow IK Example 55 Example 56 Example 57 ·§- 201033732 (Millennium) inch evaluation results face contact angle crossing) JQ § gi vn The amount of acid eluted &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt; LER ! 1 _1 &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;&gt; S /—S Ci cn w* 1 Resin (C) (mg) § ¥ ΰ S' ss sg 3 CN 6 g ό § CN ό § /—S gg &lt;N ΰ g ri ό Basic compound (3⁄43⁄4) g η δ CO s oo ri 1 δ i: δ vp έ s 1 wz Solvent (ratio 'by mass) Ο ri S'&quot; o aJ 1 CS S' O (N Ji (Λ /*-&gt; 1 F» H ri S'* f&quot; H Ij w Ji r5 Two C/3 S' O KA Photoacid generator (mg) fS Ώ gs 1 *—4 i S'* *B&gt;4 1 Gs o free gs 〇s N resin (2g) rH inch (S rs 00 in m series i series S series s s 滔In; 3 series « 闺 闺 闺 2010 201033732 οο Ιο揪 evaluation result receding contact angle (degree «The amount of η S acid dissolved U PQ u PQ PQ 11 UUQ u Q Scum QQ 〇Q 〇UU o U 〇Photoresist composition surfactant ^mm W y—V /«—s Ci cn&quot; ri δ shed (c) (mg) 1 S' E § § / -N g CS^ Basic compound __mm^ Color 1 »Γ) c »〇1 cn S cn Solvent (ratio, by mass) /—s Ο δ ¥ CM § W1 i ?5 2 C/3 S' sw* i ?5 S' 1 s 00 s Jl (7) Photoacid generator (mg) o »Λϊ N o V&quot;) «〇NU^i Q « «Η Ϊ Resin (2 g) 卜rH Comparative Example 1 Comparative Example 2 1 Comparative Example 3 1 丨 Comparative Example 4 1 Comparative Example 5 201033732 The meanings in Tables 4 and 5 and the resin (C') are as follows. The acid generator, the resin (C) and the component (D) correspond to those exemplified above as examples. [Basic compound] N-1 : 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: tris(methoxyethoxyethyl)amine N-8: 2-[2 -{2-(2,2-dimethoxy-phenoxyethoxy)ethyl}_bis-(2-methoxyethyl)l-amine [surfactant] W-1: Mecafes F176 (manufactured by Dainippon Ink and Chemical Co., Ltd., containing gas) W-2: Mecca Fiss R〇8 (manufactured by Dainippon Ink and Chemical Co., Ltd., containing gas and helium) W-3: Polyoxane polymer KP -341 (manufactured by Shin-Etsu Chemical Co., Ltd., containing yttrium) W-4: Wrong Iso S-3 66 (manufactured by Suga Chemicals) W-5: PF6 5 6 (manufactured by Onova, fluorine) W- 6: PF6320 (manufactured by Onova, fluorine) [Solvent] SL-1: cyclohexanone SL-2: propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetone 201033732 oxy Propane) SL-3: ethyl lactate SL-4: propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol) SL-5: γ-butyrolactone SL-6: propylene carbonate [ Resin (C')] Table 6 Resin Composition M w Μ w/Mn C,-l 40/40/20 7 5 00 1.4 c,-2 100 6000 1 .3

It can be seen from Tables 4 and 5 that the photoresist pattern formed by using the sensitized ray or the radiation-sensitive resin composition of the present invention has line edge roughness, scum, development defects, and fluidity to the immersion liquid during immersion exposure. All in all, they all have excellent performance. Industrial Feasibility According to the present invention, it is possible to provide a photoresist pattern which is improved in acid elution, line edge roughness, development defects, and scum generation, and which ensures good fluidity to an immersion liquid upon immersion exposure. The sensitized ray or radiation absorbing resin composition of the present invention is suitably used as a positive photosensitive resin composition, particularly as a positive photoresist composition. The complete disclosure of Japanese Patent Application No. 2008-317752 filed on December 12, 2008, 2008-317754 filed on December 12, 2008, and 2009-122470 filed on May 20, 2009, if complete This is incorporated herein by reference in its entirety, and in its application, PCT//201033732. [Simple description of the diagram] Μ [Description of main component symbols]

Claims (1)

201033732 VII. Patent application scope: 1. A photosensitive ray or radiation sensitive resin composition comprising: (A) a resin capable of increasing solubility in an alkaline developer by an acid action; (B) capable of a compound which generates an acid after irradiation with an actinic ray or radiation; and (C) a resin comprising a repeating unit (c) having at least one polar group and at least one of a fluorine atom or a ruthenium atom. The photosensitive ray or radiation sensitive resin composition of claim 1, wherein the repeating unit (c) has at least one of a fluorine atom or a ruthenium atom. 3. The sensitized ray or radiation sensitive resin composition of claim 1, wherein the repeating unit (c) has at least a partial structure represented by the following formulas (KA-1) and (KB-1) One, and the polarity converting group is represented by X in a partial structure represented by the formula (KA-1) or (KB-1): Wherein X represents any one of a carboxylic acid ester, an acid anhydride, a quinone imine, a carboxylic acid thioester, a carbonate, a sulfate, and a sulfonate; and each of Y1 and Y2 may be the same or different and represents an electron withdrawing group. 4. The sensitized ray or radiation sensitive resin composition of claim 1, wherein -209-201033732 the repeating unit (C) comprises the following formula (KA-ll) to (KA-1-17) At least one of the partial structures indicated: ^ 6 Raaa KA-1-1 ka-1-2 KArl-3^5 1^1-43⁄4 KA^sb ΚΛτ1-6^ 5. The sensitized ray or radiation sensitive resin composition of claim 1, wherein the repeating unit (c) has at least one of any of the following formulae (F2) to (F4) and (CS-1) Group represented by (CS-3): R Ming^64 Res ^67 Rea--OH Re2 Rea (F3) (F4) Each of R57 to Re8 independently represents a hydrogen atom, a fluorine atom or an alkyl group, and is limited to at least one of R57 to r61, at least one of R62 to r64, and at least one of R65 to R68 is a fluorine atom or a fluoroalkyl group; And R·62 and Rh may be combined with each other to form a ring; -210- 201033732 (CS-1) (CS-2) &lt;CS-3) wherein each of R12 to R26 independently represents an alkyl group or a cycloalkyl group; . Each of L5 represents a single bond or a divalent linking group; and η represents an integer of 1 to 5. 6 _ The photosensitive ray or radiation sensitive resin composition of claim 1, wherein the resin (Α) comprises a repeating unit represented by the following formula (3): (3) Q wherein Α represents a vinegar bond (-COO-) or a guanamine bond (_c〇NH_); represents an alkylene group, a cycloalkyl group or a combination thereof; and when there are a plurality of R〇, each rd Available with every other R. Same or different; Z represents an ether bond, an ester bond, a carbonyl bond, a guanamine bond, a urethane bond or a urea bond; and when there are a plurality of 2, each z may be the same or different from each other z : Rs represents a monovalent organic group having a lactone structure; n〇 is the number of repeats of the structure of 201033732 represented by _R〇_z_ in the repeating unit represented by the formula (3) and represents an integer 1 to 5; and R7 represents a hydrogen atom, a halogen atom or an alkyl group. 7. The sensitized ray or radiation sensitive resin composition of claim 1, wherein the acid derived from the compound (B) after irradiation with actinic rays or radiation has a molecular weight of 300 or more, and includes a single Ring or polycyclic, alicyclic or aromatic ring, and may include heteroatoms. 8. The photosensitive ray or radiation sensitive resin composition of claim 1, wherein the resin (C) is contained in an amount of from 0.1 to 1% by mass based on the total solids of the sensitized ray or radiation sensitive resin composition The content is subject to standard. 9. The photosensitive ray or radiation sensitive resin composition according to claim 1, wherein the photosensitive film formed from the sensitized ray or the radiation sensitive resin composition has a back contact angle of 7 〇 with water. Or bigger. A photoresist film which is formed from a sensitized ray or a radiation-sensitive resin composition as disclosed in any one of claims 1 to 9. A pattern forming method which comprises the steps of immersion exposure and development of a photoresist film as in the application of claim 10th. -212- 201033732 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: 201033732 Manual (Do not change the format and order of this manual, please do not fill in the ※ part) ※Application number: ※Application曰: Article 1卩(:Classification: I. Invention name: (Chinese/English) Photosensitive ray or Radiation-sensitive resin composition and pattern forming method using the same. ACTINIC RAY-SENSITIVE OR RADIATION-SENSITIVE RESIN COMPOSITION AND PATTERN FORMING METHOD USING THE COMPOSITION 2. Abstract: The present invention provides a sensitized ray or a radiation-sensitive resin composition And comprising: (A) a resin capable of increasing solubility in an alkaline developer by an acid action, (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (C) a resin comprising a repeating monoterpene (c) having at least one polar converting group and having at least one of a fluorine atom or a sand atom. III. Abstract: Provided is an actinic ray-sensitive or radiation-sensitive resin composition including: A) a resin capable of increasing the solubility in an alkali developer by the action of An acid, (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation, and (C) a resin which contains (c) a repeating unit having at least one polarity conversion group and has at least either a fluorine Atom or a silicon atom. 201033732 Manual (Do not change the format and order of this manual, please do not fill in the ※ part) ※Application number: ※Application曰: Article 1卩(:Classification: I. Invention name: (Chinese/English) Photosensitive ray or Radiation-sensitive resin composition and pattern forming method using the same. ACTINIC RAY-SENSITIVE OR RADIATION-SENSITIVE RESIN COMPOSITION AND PATTERN FORMING METHOD USING THE COMPOSITION 2. Abstract: The present invention provides a sensitized ray or a radiation-sensitive resin composition And comprising: (A) a resin capable of increasing solubility in an alkaline developer by an acid action, (B) a compound capable of generating an acid upon irradiation with actinic rays or radiation, and (C) a resin comprising a repeating monoterpene (c) having at least one polar converting group and having at least one of a fluorine atom or a sand atom. III. Abstract: Provided is an actinic ray-sensitive or radiation-sensitive resin composition including: A) a resin capable of increasing the solubility in an alkali developer by the action of An acid, (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation, and (C) a resin which contains (c) a repeating unit having at least one polarity conversion group and has at least either a fluorine 201033732 IV. Designated representative map: (1) The representative representative of the case is: No. (2) The symbolic symbol of the representative figure is simple: Sister. 5. If there is a chemical formula in this case, please reveal the best Chemical formula showing the characteristics of the invention: