TW201202272A - Radiation-sensitive resin composition - Google Patents

Abstract

Disclosed is a radiation-sensitive resin composition that can be formed into a resist pattern with low LWR and an excellent pattern shape. The radiation-sensitive resin composition includes [A] an acid-dissociable group containing polymer that has structural units (I) represented by formula (1), and [B] a compound represented by formula (2). In formula (1), M+ is preferably at least one onium cation selected from a group comprising onium cations respectively represented by formula (3) and formula (4).

Description

201202272 VI. Description of the Invention: [Technical Field] The present invention relates to a linear resin composition which is used in the manufacture of a circuit substrate such as a semiconductor such as 1C, a thermal sensing head, and the like, and other photo-etching steps. [Prior Art] The chemically amplified type sensitive radiation linear resin composition generates an acid by a radiation portion such as a far-ultraviolet light representing a molecular laser or an ArF excimer laser, reacts the acid as a catalyst, and changes the exposure. The exposure portion forms a composition of light on the substrate with respect to the dissolution rate of the developing solution. For more precise line width control, for example, when the design of the device is less than half a micron, the chemical amplification type impedance is not only good, but the LWR (Line Roughness) of the line deviation index of the photoresist pattern is also small, and the pattern is small. The shape of the rectangle becomes important. Such a fine shape, controlling the diffusion rate of the generated acid is an important method to achieve this, and it is known that a technique for forming a neutral compound in a sensitive linear resin is being reviewed, particularly in the exposure portion due to dissociation and loss of acid diffusion. Controllability, when the acid diffusion control agent is added, the high-exposure portion and the unexposed portion are compared (refer to Japanese Patent Publication No. Hei 2-27660, JP-A-2009-5 3 68 8). However, even if the LWR or the shape of the pattern is used, performance is not sufficient. Liquid, sensitive radiation

KrF is projected on the exposed part and the resistive type. The size is excellent. Width is to be controlled. In the case of the addition of a base acid, the technique of the invention is disclosed in Japanese Patent Application No. 2009-53688 [Patent Document 1] JP-A-2009-53688. OBJECTS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above matters, and an object thereof is to provide a radiation-sensitive linear resin composition capable of forming a photoresist pattern having a small LWR and excellent pattern shape. Means for Solving the Problem The invention of the above-mentioned problem is a sensitive radiation linear resin composition containing an acid dissociable group-containing polymer having the structural unit (I) represented by the following formula (I). Hereinafter, it is also referred to as "[A] polymer"), and [B] a compound represented by the following formula (2) (hereinafter also referred to as "[β] compound")" [Chemical Formula 1] / R1.

M+b I ONSHO η \ 1/ FI0 — F (In the formula (1), R1 is a hydrogen atom, a fluorine atom, a trifluoromethyl group or an alkyl group having a carbon number of i to 3. E is a single bond or -COO-. R2 is a divalent 201202272 hydrocarbon group having a carbon number of 1 to 2 Å. A part or all of the hydrogen atom of the hydrocarbon group may be a fluorine atom; η is an integer of 0 to 5; M + is a gun cation) [Chemical 2] Υ-R3 —X— Q+ (2) (In the formula (2), hydrazine is a hydrogen atom, a hydroxyl group, an acryl fluorenyl group or a fluorenyl group; R 3 is a divalent hydrocarbon group having a carbon number of 1 to 20 or -RZR,-; independently is a carbon number of 1 a divalent hydrocarbon group of -20; Ζ is -Ο-, -CO, -OCO-, -ΝΗ-, -NHCO- or -CONH-; X is --SO / or -N_-S02-R"; R" is One or all of the hydrogen atoms of the monovalent hydrocarbon group having 1 to 20 carbon atoms may be substituted by a fluorine atom; and combined with each other to form a ring; Q + is a key cation) The radiation sensitive linear resin composition of the present invention contains a structure The unit (I) and the acid-dissociable group [A] polymer and the compound of the specific structure [B]. [A] The structure of the polymer | is a unit which generates an acid by exposure, and therefore the polymer exhibits a homogeneous acid diffusion and is expanded by the acid from the exposed portion to the unexposed portion. Further, the acid diffusion of the acid-diffused light portion in the exposed portion is controlled by the compound [B]. The linear radiation resin composition of the sensitized radiation can be formed by the combination of the compound and the compound of [B], and the acid diffusion is highly controlled to form a photoresist pattern having a small LWR and an excellent shape of the pattern (1). M + is substituted with at least one type of key cation selected from the group consisting of the key cations shown in the following formulas (3) and (4), and the methacrylic acid R and R' each -, -C Ο 〇- C00·, , the hydrocarbon group, R and R, the above specific has the above-mentioned, in the position (1), so it can be controlled by dispersion, and is not exposed to A] polymerization, and the junction j 〇 and the following formula are good 201202272 [Chemical 3] Ο)

Fp R4b-S+~R4c (In the formula (3), R4a, R4b and .R4e are each independently an i-valent hydrocarbon group having a carbon number of 30 or a monovalent heterocyclic group having a nuclear number of 4 to 30. However, the above hydrocarbon group and hetero One or all of the hydrogen atoms of the ring group may be substituted. Further, any two of R4a, R4b and R4<: are bonded to each other to form a cyclic structure together with the sulfur atom to which they are bonded.) R5a-丨+-R5b (4) (In the formula (4), 115:1 and R5b are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms or a monovalent heterocyclic group having 4 to 30 carbon atoms; One or all of the gas atoms of the above hydrocarbon group and the heterocyclic group may be substituted. Further, R5a and R5b are bonded to each other, and may form a cyclic structure together with the iodine atom to which they are bonded) in the above [A] polymer Since the key cation of M + has the specific structure described above, the sensitivity of the linear radiation resin composition can be improved, and as a result, the LWR of the obtained photoresist pattern is more suppressed, and the pattern shape is more excellent. The compound [B] is preferably at least one compound selected from the group consisting of the compounds represented by the following formulas (2-1) to (2-6). -8 - 201202272 【化5】

.OH

Oc〇〇-Q+ (2-1) (2-2) 〇人0 〇人. | Deaf. I 1 R7 R7 | Ν' Q+ | S03_ Q+ R6 Ν' Q+

I o=s=o

I cf3 (2-3) o=s=o I cf3 (2-4) , COO· Q+ (2-5) (2-6) (in equations (2-1) to (2-6), R6 is a monovalent chain hydrocarbon group having 1 to 6 carbon atoms. Each of R7 is independently a divalent chain hydrocarbon group having 1 to 6 carbon atoms. The definition of Q + is the same as the above formula (2).) The compound [B] has the above specific structure. It can improve acid diffusion control. As a result, the LWR of the resist pattern formed by the sensitive radiation linear resin composition is further suppressed, and the pattern shape is more excellent. The polymer [A] is preferably a structure having a structural unit represented by the following formula (5). -9 - (5) (5)201202272 [Chem. 6]

(In the formula (5), the definition of 'R1 is the same as the above formula (1). R8, r9 and R1Q are each independently an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms. However, 'R9 and R1' () in order to combine with each other, together with the carbon atoms to which they are combined, form a cycloalkanediyl group having a carbon number of 4 to 20.) [A] The polymer further has a structural unit (Π) as an acid dissociable group. It can improve the ease of acid dissociation. As a result, the LWR of the photoresist pattern obtained from the radiation-sensitive linear resin composition can be further suppressed, and the pattern shape is more excellent. [Effects of the Invention] The radiation sensitive linear resin composition of the present invention has a resist pattern which is small in LWR and excellent in shape. [Form of the Invention] <The radiation sensitive linear resin composition> The radiation sensitive linear resin composition of the present invention contains the [A] polymer and the compound [B]. Further, any component may be contained in a range that does not impair the effects of the present invention. The respective constituents will be described below. 201202272 &lt;[A] Polymer&gt; The polymer [A] is a polymer having an acid dissociable group having a structural unit (I). The structural unit (I) is a unit which decomposes by exposure and generates an acid, but by being present in the polymer [A], homogeneous acid diffusion can be exhibited, and the diffusion of acid from the exposed portion to the unexposed portion is affected. control. Further, the polymer [A] is a polymer which exhibits an alkali-insoluble or alkali-insoluble property, and has a protective group (acid-dissociable group) which can be detached by the action of an acid, and exhibits alkali solubility by removing the protecting group by the action of an acid. . [A] The polymer may have one or more acid dissociable groups. The structural unit having an acid-dissociable group is not particularly limited, and a preferred example of the structural unit (II) described later can be mentioned. [Structural unit (I)] The structural unit (I) is a structural unit represented by the above formula (1). In the above formula (1), R1 is a hydrogen atom, a fluorine atom, a trifluoromethyl group or an alkyl group having 1 to 3 carbon atoms is a single bond or -(:00-.112 is a divalent hydrocarbon group having 1 to 20 carbon atoms; A part or all of the hydrogen atom of the hydrocarbon group may be substituted by a fluorine atom. N is an integer of 0 to 5. M + is a key cation. The alkyl group having 1 to 3 carbon atoms represented by the above R 1 may, for example, be a A hydrogen atom or a methyl group is preferable. The divalent hydrocarbon group having 1 to 20 carbon atoms represented by the above R 2 may, for example, be a methyl group, an ethyl group or a methyl group. - a chain hydrocarbon group such as a propyl group, a η-butylene group, or a η-amyl pentyl group; a fat such as a cyclopentane, a cyclohexane, a dicyclopentane, a tricyclodecane, a tetracyclododecane or an adamantane; a cyclic hydrocarbon to remove two hydrogen atoms of a divalent alicyclic -11 - 201202272 hydrocarbon group; a part of a divalent hydrocarbon group having the alicyclic hydrocarbon group; an aromatic hydrocarbon group such as a phenyl group, a naphthyl group or a phenylene group a part of a divalent hydrocarbon group having an aromatic ring, etc. The above-mentioned divalent hydrocarbon group may be partially or wholly substituted by fluorine, and as η, preferably 1 to 4. As a formula (1), -R2- Preferred among the structures shown by (CF2)n- tB-cf2-cf2-' -chf-cf2-' -cf2-cf2-cf2-' -CF2-CF2-CF2-CF2- ' -CH2-CH2-CF2-CF2- ' -CH2*CH2'CH2~ CF2_CF2· ' -CH2-CH2'CH2_CH2_CF2'CF2_ ' -CH2_CH2~CH2_CH2_CH2_CF2-CF2-, -CH2-CH2-CHF-CF2- '-CH2-CH2-CH2-CHF-CF2- '-CH2-CH2-CH2-CH2 -CHF-CF2- '-CH2-CH2-CH2-CH2-CH2-CHF-CF2-, -CH2-CF2-, -CH2-CH2-CF2- '-CH2-CH2-CH2-CF2- '-CH2-CH2 -CH2-CH2-CF2-» is preferably a phosphonium cation or an iron iodide cation, and is selected from the group consisting of an iron cation (anthracene cation) represented by the above formula (3) and the above formula (4). Preferably, at least one type of key cation of the group of key cations (iodine cations) is preferred. In the above formula (3), R4a, 1141) and R4e are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms or a number of nuclear atoms. a monovalent heterocyclic group of 4 to 30. However, some or all of the hydrogen atoms of the above hydrocarbon group and heterocyclic group may be substituted. Further, any two of R4a, R4b and R4e are bonded to each other, and together with the sulfur atom to which they are bonded, form a cyclic structure. In the above formula (4), each of the ruler 53 and the group R5b is independently a 1-12-201202272 valent hydrocarbon group having a carbon number of 1 to 3 Å or a monovalent heterocyclic group having a nuclear number of 4 to 30. However, part or all of the hydrogen atom of the heterocyclic group may be substituted. R5b is bonded to each other and may be co-structured with the iodine atom to which they are bonded. a hydrocarbon group having 1 to 30 carbon atoms represented by R5a and R5b in the above formula (3), and an ethyl group, an ethyl group, an η-propyl group, an n-butylene group, and a core extension. a monovalent alicyclic hydrocarbon group such as a cyclopentyl group; a cyclopentyl group, a cyclopentyl group, a cyclohexyl group, a dicyclopentanyl group, a tricyclododecyl group, an adamantyl group; a monovalent hydrocarbon group of an alicyclic hydrocarbon group; ; phenyl, naphthyl, anthracenyl-tolyl, m-tolyl, ρ-tolyl, ρ-hydroxyphenylphenyl, mesitylene, decanoyl, 2,3-xylyl, Base, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethyltolyl, ρ-fluorophenyl, p-difluoromethylphenyl, p-chlorophenyl, hydrazine- A monovalent aromatic hydrocarbon group which may be substituted with an iodophenyl group or the like; a monovalent hydrocarbon group of the above aromatic hydrocarbon group. The R1a, R4b, and R4e in the above formula (3) are preferably a furan group, a thiol group, a pyranyl group, a pyrrolyl group, and a monovalent group having 4 to 30 atomic numbers of R5a and R5b. Azyl, isothiazolyl, isoxazolyl, pyrazinyl, pyrimidinyltetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, tetra-, 3-tetrahydrothiophene-1,1-dioxide Wait. As the substituent having the above hydrocarbon group and heterocyclic group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, a halogenated hydrocarbon group, an alkoxy group, a hydrocarbon group, and R5a and a ring form k are the above formulas (4) a valence chain hydrocarbyl ring fluorenyl group having four parts of an upper, a biphenyl group, a P-methoxy 2,4-dimethylphenyl group, a 3,5-diyl group, and a P-bromobenzene group having the above formula (4 heterocyclic group, such as a thioxyl group, a pyridyl group, a pyridazinyl group, a hydrogenthiofuranyl halogen atom, a group, an amine group, a -13-201202272 thiol group is preferable. As the phosphonium cation represented by the above formula (3), For example, a cation represented by the following formula (i-Ι) to (i-27), etc., and the iodonium cation represented by the above formula (4), for example, may be exemplified by the following formula (ii-Ι)~ (ii-25) The cations shown, etc. [Chem. 7]

-14- 201202272 【化8】

(H3C) 3C

(ί-14)

〇C2H5

(i-22) (Μ5)

15- 201202272 【化9】

Ο I o=s=o I ch3

(i-24)

(i-25)

(i-27) 0 1o=s=o

Ch3 -16- 201202272 [化1 0]QrOΗ3α^〇^,+&quot;0~ (ii-1)

Or order CH3 (ii-2) CH,

CH3 (ii-4)

H3C

H3c &quot;CH, ch3 (ii-5) C2H5 (ii-7 ) CH(CH3)2 (ii-9) C(CH3)3 02N—^r^—1+~N〇2 (ii-14 ) N02ΟγΆ N〇2 o2n (ii-13) -17- 201202272 【化1 1】~~^~&quot;〇CH3 (ii_16)

H3CO OCH3 (ii-17) (iM8)

(H-21) (ii-23) (ii-24) (ii-25) where (i-1), (i-23), (ii-1), (ii-21) and (ii-2) 2) is better. Further, the monovalent cation represented by the above M + can be synthesized, for example, according to the general method described in Advances in Polymer Science, Vol. 62, p. l_48 (1984). The polymer [A] may contain one or more kinds of the above-mentioned monovalent cations represented by M + . The structural unit (I) is, for example, a structural unit represented by the following formula (1 -1 ) to (1 -1 0 ). -18- 201202272 【化1 2】

In the above formulae (1-1) to (1-10), the definitions of R1 and M + are the same as those in the above formula (1). Among them, the structural unit shown by each of the above formulae (1-1), (1-2), (1-4), (1-5), and (1-6) is preferable. The monomer to which the structural unit (I) is added is, for example, a polymerizable compound represented by the following formula (m -1 -1 ) to (m -1 - 2 3 ). -19· 201202272 【化1 3】

CF,

[化1 4]

-20- 201202272

Among them, 'polymerized compounds represented by the above formulas (mll), (m-1-14), (m-1-15), (m -1 -1 6 ), and (m -1 -1 7 ) are preferred. . [Structural unit (II)] [A] The polymer is preferably a structural unit (II) having the structural unit (I) and having the structural unit (II) represented by the above formula (5). The structural unit (II) is a protecting group (acid dissociable group) which is detachable by the action of an acid, and has a function of desorbing the protecting group by an action of an acid and exhibiting alkali solubility in the [A] polymer. -21 - 201202272 In the above formula (5), the definition of R1 is the same as that of the above formula (i), and each of R9 and R is a group having a carbon number of 1 to 4 or a carbon number of 4 to 20 alkyl groups. However, 'R9 and Rie are combined with each other to form a cycloalkanediyl group having 4 to 20 carbon atoms together with the group to which they are combined. The alkyl group having 1 to 4 carbon atoms represented by the above R8, R9 and RIG. Examples thereof include a methyl group, an ethyl group, an η-propyl group, an i-propyl group, an n-butyl group, a 2-methyl group, a 1-methylpropyl group, and a t-butyl group. Among them, a methyl group and an ethyl group are preferred. Examples of the cyclohexane having 4 to 20 carbon atoms represented by R8, R9 and RIG include a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cycloheptyl 'cyclooctyl group; A group having a bridged alicyclic skeleton or the like, such as a cyclopentyl group, a dicyclopentenyl group, a triyl group, a tetracyclododecyl group or an adamantyl group. Examples of the cyclic chain dibasic group having 4 to 20 carbon atoms which are formed by combining R9 and RIQ with each other and carbon to be bonded thereto include, for example, a group in which a cycloalkyl group is removed by one hydrogen atom. Among them, cyclopentene diyl, alkanediyl, cyclooctanediyl, norbornanediyl, adamantanediyl and tetradioxane are preferred, cyclopentanediyl, adamantane diyl and tetra The ring twelve base is better. The structural unit (II) is preferably a structural unit represented by the following formula (5-1) to formula (5-17). The ring carbon of R8 is, for example, a propyl group, a monocyclic cyclononanal atom from the upper cyclohexane cyclododecane. -22- 201202272 【化1 6 R1 -CH2 — C — c=o R1 —|~CH2-C' ~~CH2 — cc=oI o ο (5-2)

R1 R1 ~~CH2 — C ~CH2 - C - c=o I o

(5-4) (5-5) R1 (5-3)

C2H5 (5-8) R1 c=oI 01 ό (5-9) -CH2 — C —J— c=o I o

R1 I (5-6) (5-7)

I r1 —ch2—c ch2—c (5-11) (5-12) c=oI o ~~CH2 - c -J—II 1 c=oc=o H3C — C—CH3 H3C — C — CH3 H3C — C — CH3 R1 —CH2 — c * R1 —CH2 - c - (5-13) 0 1

(5-14)

0 I

(5-15)

I

C = 0 I

c=o c2h5

In the above formula, the definition of R1 is the same as the above formula (1). Among them, the above formulas (5-2), (5-3), (5-4), (5-10), (5-11), (5-12), (5-16), and (5-17) ) Each of the illustrated structures -23- 201202272 is better, with the structural units shown by the above formulas (5-2), (5-3), (5-10), (5-11), and (5-17) It is better. [Structural unit (III)] [A] The polymer is preferably one having at least one structural unit (III) having a structural unit selected from the group consisting of a lactone structure and a structural unit having a cyclic carbonate structure. (ίϋ-28 As a structural unit having a lactone structure, for example, 5-(oxy)-4-oxo-tricyclo[5.2.1.〇3'8]indol-2-yl from (meth)acrylic acid is exemplified. Ester, (meth)acrylic acid-]〇-methoxycarbonyl-5-sideoxy-4-oxo-tricyclo[5.2.1.03'8]non-2-yl ester, (meth)acrylic acid-4-methyl Oxycarbonyl-6-oxo-7-oxo-bicyclo[3.2.1]oct-2-yl ester, (meth)acrylic acid side oxo-8-oxa-bicyclo[3.3.1]non-2-yl ester , (meth)acrylic acid _4·methoxycarbonyl-7-sideoxy-8-oxa-bicyclo[3.3.1]non-2-yl ester, (meth)acrylic acid-2-oxotetrahydropyran -4-yl ester, ethyl-2-oxo-oxytetrahydroindole-pyran-4-yl vinegar, (meth)acrylic acid-4-propyl-2-oxo-oxo-argon _4-based vinegar, (meth)acrylic acid-2,2·dimethyl-oxo-oxytetrahydrofuran_3·yl vinegar, (methyl)propionic acid _4,4-dimethyl-5-side Oxytetrahydrofuran-3-yl ester, (meth)acrylic acid 4,4-dimethyl-2-oxo-tetrahydrofuran-3-yl ester, (meth)acrylic acid _5,5-dimethyl-2 - side Oxytetrazolidine-3-yl ester, (meth)acrylic acid-5-side oxytetrahydrofuran _2_methyl vinegar, (meth)acrylic acid-3,3-dimethyl-5-oxo-tetrahydrofuran-2-yl methyl vinegar, dimethyl oxytetrahydrofuran (meth) acrylate The structural unit of a compound such as a base ester and a structural unit represented by the following formula () -24-201202272). [化1 7]

(»1-1) (iii-2) (iii-3) (iii-4) (iii-5) (iii-6) (iij-7)

(»i-8) (»i-9) (iii-1〇) (iii-11) (iii-12) (iii-13) (iii-14) [Chem. 1 8]

0 0 Ο O 〇 (iii-15) (iii-16) (iii-17) (iii-18) (iiM9&gt;

(i»-20) (iii-21) (iii-22) (iii-23)

(in-24) (ii'-25) (iii-26) (iii-27) (iii-28) In the above formula, the definition of R1 is the same as the above formula (1). -25- 201202272 Among them, the structural unit represented by (iii-6) is preferred. The structural unit having a cyclic carbonate structure may, for example, be a structural unit represented by the following formulas (iv-Ι) to (iv-21). 【化1 91

(iv-17) (ίν-18) (ίν-19) (iv-20) (ίν-21) -26- 201202272 In the above formula, the definition of R1 is the same as the above formula (1). The structural unit represented by the above formula (iv-22) is preferred. &lt;Other structural units&gt; [A] The polymer has structural units (I) to (111), and may be, for example, other structural units. A hydroxyalkyl (meth) acrylate, a hydroxycycloalkyl (meth) acrylate, a hydroxyaryl (meth) acrylate, a structural unit in which a carboxyl group contains a (meth) acrylate, or the like. Wherein, each of the structural units derived from the hydroxycycloalkyl (meth) acrylate and the (meth) propyl succinic acid via the aryl vinegar are each derived from (meth) propyl hydroxyadamantyl amide, (A) The structural unit of hydroxyphenyl acrylate and hydroxy naphthyl (meth) acrylate is preferred. Further, the radiation sensitive linear resin composition may contain two or more kinds of [A] polymers having a copolymerization ratio or a molecular weight, and may contain the polymer of [A] and other polymers. The structural unit constituting the above other polymer may be the above-mentioned structural unit (Π) or the other structural unit mentioned above. The content ratio of the above structural unit (I) is preferably 〇. i 〜 2 〇 mol % 'more preferably 0.1 to 15 mol % for the polymer total structural unit contained in the sensitized linear resin composition. . When used at this content ratio, effects such as an increase in pattern shape or a decrease in LWR can be further sufficiently exhibited. The content ratio of the above structural unit (11) is preferably 2 〇 to 8 〇 -27 - 201202272 摩尔 % 'more preferably 25 to 75 for the polymer total structural unit contained in the sensitive radiation linear resin composition. Moer%. When the film is used at the content ratio, it is excellent in resolution, and a photoresist pattern excellent in adhesion to the substrate can be obtained. The content ratio of the above structural unit (III) is preferably from 1 〇 to 80 mol%, more preferably from 2 〇 to 70 mol%, based on the total structural unit of the polymer contained in the radiation sensitive linear resin composition. When it is used in the content ratio, it is possible to obtain a composition excellent in pattern formability while obtaining excellent adhesion between the resist film and the substrate. The content ratio of the other structural unit is preferably 40 mol% or less, more preferably 30 mol% or less, based on the total polymer unit of the linear composition of the radiation sensitive resin. When it is used at this content ratio, a composition excellent in pattern formability can be obtained. &lt;Method for synthesizing [A] polymer&gt; [A] The method for synthesizing the polymer is not particularly limited, and for example, a polymerizable unsaturated monomer having a composition corresponding to a desired structural unit can be used as a radical polymerization initiator or It is necessary to carry out polymerization in a suitable solvent in the presence of a chain shifting agent or the like to synthesize. Since the radical polymerization initiator can achieve a sufficient polymerization rate, it is preferably added to a sufficiently high concentration. The radical polymerization initiator is not particularly limited, and examples thereof include a thermal polymerization initiator, a redox polymerization initiator, and a photopolymerization initiator. Specifically, a polymerization initiator such as a peroxide or an azo compound can be mentioned. As a more specific radical polymerization initiator, t-butyl hydroperoxide, t-butyl peroxybenzoate, benzamidine peroxide, 2,2'-azobis- 28- 201202272 (2,4-Dimethylvaleronitrile), 2,2,-azobisisobutyronitrile (AIBN), 1,1'-azobis(cyclohexanecarbonitrile), dimethyl- 2,2'-azobisisobutyrate (MAIB) and the like. Examples of the above-mentioned chain shifting agent include a pyrazole derivative 'alkanolthiol' and the like. For the above polymerization operation, a general batch polymerization, a dropping polymerization or the like can be used. For example, the monomer forming each of the structural units (I), ((), and other structural units is dissolved in an organic solvent in a necessary type and amount, in the presence of a radical polymerization initiator, and, if necessary, a chain shifting agent. The polymerization is carried out to obtain [A] a polymer. The polymerization solvent is an organic solvent using a generally soluble monomer, a radical polymerization initiator, and a chain transfer agent. Examples of the organic solvent include a ketone solvent, an ether solvent, an aprotic polar solvent, an ester solvent, an aromatic solvent, a chain or a cyclic aliphatic solvent. Examples of the ketone solvent include methyl ethyl ketone and acetone. Examples of the ether solvent include dialkyl ethers such as methoxydimethyl ether (methylal) and diethyl ether; and cyclic ethers such as tetrahydrofuran and 1,4-dioxane. Examples of the aprotic polar solvent include dimethylformamide and dimethylhydrazine. The ester solvent may, for example, be an alkyl acetate such as ethyl acetate or methyl acetate. Examples of the aromatic solvent include an alkyl group-containing aromatic hydrocarbon solvent such as toluene or xylene; and a halogenated aromatic hydrocarbon solvent such as chlorobenzene. Examples of the aliphatic solvent include a chain aliphatic solvent such as hexane: a cyclic aliphatic solvent such as cyclohexane. The polymerization temperature is usually from 20 ° C to 120 ° C, preferably from 50 ° C to 1 l ° ° C, more preferably from 60 ° C to 100 ° C. Generally, it can be polymerized in the atmosphere, but it is preferably polymerized under an inert gas atmosphere such as -29-201202272 nitrogen or argon. The molecular weight of the resulting [A] polymer can be adjusted by controlling the ratio of the monomer amount to the linkage shift amount. The polymerization time is usually from 0.5 hours to M4 hours, preferably from 1 hour to 7 hours, more preferably from 2 hours to 2 hours. [A] The polymer may have residues from the chain-shifting agent at the end of the molecular chain, may also have no residues from the chain-shifting agent at the end of the molecular chain, or may remain at the end of the molecular chain from the chain. The state of the residue of the mobile agent. The polymer [A] used in the linear radiation-sensitive resin composition and other polymers, although of course less impurities such as halogen and metal, but the residual monomer or oligomer component is below the predetermined enthalpy, for example, by HP LC. The analysis is preferably 0.1% by mass or less, whereby the sensitivity, the resolution, the process stability, and the shape of the pattern can be further improved, and the change in the foreign matter or the sensitivity of the liquid is less, and can be used as an impedance. Sensitive radiation linear resin composition. As a method of purifying the above polymer, for example, the following method can be mentioned. As a method of removing impurities such as a metal, a method of adsorbing a metal in a polymer solution by using an boundary potential filter, or washing a polymer solution with an acidic aqueous solution such as oxalic acid or sulfonic acid, and then removing the metal into a chelate state can be mentioned. Method and so on. Further, as a method for removing the residual monomer or oligomer component to a predetermined enthalpy or less, a liquid extraction method in which residual monomer or oligomer component is removed by combining water washing or a suitable solvent, and only a specific molecular weight or less is extracted and removed. Refining method such as limiting filtration or the like in a solution state, or by dropping a polymer solution into a poor solvent, and then removing the residual -30-201202272 residual monomer after solidification of the polymer in a poor solvent or The polymer sludge separated by filtration is subjected to a purification method in a solid state such as lean. In addition, it is also possible to combine the poor solvents used in the above-mentioned reprecipitation method, and it is not possible to exemplify the properties due to the purification of the polymer, etc., but it is suitable for the physical properties of the ligands, etc. . The weight average molecular weight (hereinafter also referred to as "Mw") of the [A] polymer by gel permeation chromatography (GPC) is 1,000 to 300,000', preferably 2,000 to 300,000, 2,000 to 20,000. [A] The Mw of the polymer is less than 1, and the heat resistance of the impedance tends to decrease. On the other hand, when the temperature is 3 0 0, 0 0 0, the development of the impedance tends to decrease. . Further, the ratio (Mw/Mn) of the polystyrene-converted number average molecular weight (hereinafter referred to as Mw) of the polymer of [A] to the gel permeation layer GPC) is preferably from 1 to 5, more preferably 1~3, 1~1 · 6. &lt;[B] Compound&gt; The radiation sensitive linear resin composition contains the [B] represented by the above formula (2) for controlling the diffusion of the acid, in addition to the polymerization of [A]. The compound [B] acts on the acid produced in the exposure step, and on the other hand, is alkaline by irradiation with active rays or radiation. Therefore, in the case of the sensitized radiation grease composition containing the compound [B], acid is diffused in the exposed portion and controlled in the unexposed portion, so that a good contrast can be obtained. Solvent wash. The polyphenylene of the polymer of the composition is generally good, and is used as a specific excess method ("Μη" is particularly good) to combine into a base to solve the problem and lose linear alkalic acid diffusion -31 - 201202272 The above formula (2) In the above, Y is a hydrogen atom, a hydroxyl group, an acryloyl group or a methacryloyl group. R3 is a divalent hydrocarbon group having 1 to 20 carbon atoms or _r_Z-R, -. R and R' are each independently a carbon number of 1 to 20 A divalent hydrocarbon group: Ζ is -〇-, -CO-, -COO-, -OCO-, -ΝΗ-, -NHCO· or -CONH-. X· is -〇·, -COO·, -S〇r Or -N, S02-R". R" is a monovalent hydrocarbon group having 1 to 20 carbon atoms. A part or all of the hydrogen atom of the hydrocarbon group may be substituted by a fluorine atom. Further, R and R' are bonded to each other to form a ring. Q + is a key cation. Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R 3 , R and R′ include a methyl group, an ethyl group, an η-propyl group, and an η-butyl group. a chain hydrocarbon group such as η-amyl pentyl; removing 2 hydrogens from an alicyclic hydrocarbon such as cyclopentane, cyclohexane, dicyclopentane, tricyclodecane, tetracyclododecane, norbornane or adamantane An alicyclic hydrocarbon group of an atom; a part of a divalent hydrocarbon group having the above alicyclic hydrocarbon group An aromatic hydrocarbon group such as a phenyl group, a naphthyl group or a biphenyl group; a part of a divalent hydrocarbon group having the above aromatic hydrocarbon group; etc. These hydrocarbon groups are partially or wholly hydrogen atoms which may be substituted by a fluorine atom" · When it is -S03_, the compound in which the S03 group and the carbon atom to be bonded are substituted by a fluorine atom or a perfluoroalkyl group is not preferable. As the above-mentioned key cation of Q + , and M in the [A] polymer In the same manner, the key cation is preferably at least one type of key cation selected from the group consisting of a key cation (anthracene cation) represented by the above formula (3) and a key cation (iodine cation) represented by the above formula (4). Preferably, the key cation (germanium cation) represented by the above formula (3) is preferred, and the triphenylphosphonium cation is more preferred. The compound [B] is selected from the above formula (2-1) to (2-6). At least one of the groups of the above-mentioned compounds is preferred. -32-201202272 In the above formulae (2-1) to (2-6), R6 is a monovalent chain hydrocarbon group having 1 to 6 carbon atoms. The divalent chain hydrocarbon group having 1 to 6 carbon atoms. The definition of Q + is the same as the above formula (2). As the monovalent chain hydrocarbon group represented by the above R6, for example, Methyl, ethyl, η-propyl, i.propyl, η-butyl, i-butyl, sec-butyl, t-butyl, η-pentyl, n-hexyl, etc. Preferably, n-butyl group, n-pentyl group and n-hexyl group are preferably n-butyl group. Examples of the divalent chain hydrocarbon group represented by the above R7 include methyl group, ethyl group and η. - propyl, i - propyl, η - butyl, η - pentyl, etc. Among them, ethyl, η-propyl and i-propyl are preferred, and ethyl is extended. Better. Among the compounds represented by the above formulas (2-1) to (2-6), the compounds represented by the formulae (2-1)' (2-2), (2-3) and (2-4) are also preferred. A compound represented by the formula (2-1) is preferred. The content of the compound (B) is preferably from 0.1 to 20 parts by mass, more preferably from 0.5 to 20 parts by mass, based on the viewpoint of the sensitivity and the development property of the impedance. ~10 parts by mass. When the content is less than 0.1 part by mass, the effect of improving the LWR may be insufficient. On the other hand, when it exceeds 20 parts by mass, the sensitivity as an impedance may be remarkably lowered. &lt;arbitrary component&gt; The sensitive radiation linear resin composition may contain, as necessary, a [C] sensitive radiation linear acid generator, [D] acid diffusion control agent, -33-201202272 [E] solvent, F] Additives, etc. &lt;[C]sensitive radiation linear acid generator&gt; The radiation sensitive linear resin composition is a unit having the structural unit (I) of [A] polymer which is produced by exposure, so that it is not necessary to contain other An acid compound, but may also contain other [C] sensitive radiation linear acid generator (hereinafter also referred to as "[C] acid generator"). The above-mentioned [C] acid generator may, for example, be a sulfonium salt such as a phosphonium salt or an iodine salt, an organic halogen compound, a biguanide or a bisazomethane oxime. Preferable specific examples of the above [C] acid generator include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-η-butanesulfonate, and triphenylsulfonium perfluoro- Η-octane sulfonate, triphenylsulfonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate, triphenylsulfonium rod mineral acid Triphenylphosphonium chloride compound such as ester; 4-cyclohexylphenyldiphenylphosphonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylphosphonium hexafluoro-η-butane sulfonate, 4-ring Hexyl phenyl diphenyl honey perfluoro-η - octyl sulphate, 4 · cyclohexyl phenyl diphenyl fluorene 2 - bicyclo [ 2.2.1 ] hept-2-yl-1, 1, 2, 2- 4_cyclohexylphenyl diphenyl g chloro compound such as tetrafluoroethylene vinegar, 4-cyclohexyl phenyl diphenyl camphole sulfonate; 4 · methanesulfonyl phenyl diphenyl fluorene Methanesulfonate, 4 _ _ _ sulfonyl phenyl diphenyl sulfonium hexafluoro-η - butane sulfonate, 4 _ _ _ 醯 醯 phenyl phenyl diphenyl fluorene perfluoro- η octane sulfonate Acid ester, 4-methanesulfonylphenyldiphenylfluorene 2-bicyclo[2.2.1]heptan-2-yl-indole, hydrazine, 2,2-tetrafluoroethane vinegar • 34 - 201202272, 4 -A hospital醯Basic base-based base 樟 扩 扩 扩 等 4 4 4 4 4 4 4 4 4 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; - Butane sulfonate, monophenyl iodide perfluoro-η-octane sulfonate, diphenyl iodonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2- Diphenyl iodide chloride compound such as tetrafluoroethane sulfonate diphenyl iodide camphorsulfonate; bis(4-t-butylphenyl) iodine trifluoromethanesulfonate, bis(4_t_丁Base phenyl) Yao Key Nine-n-Dingyuan vinegar, bis(4_t_butylphenyl) iodine perfluoro- η-octane sulfonate, bis(4-t-butylphenyl) iodine Iron 2 -bicyclo[2.2.1]heptan-2-yl-1,1,2,2-tetrafluorobenzine acid ester, bis(4_t_butylphenyl) iodine camphorsulfonate, etc. T-butylphenyl) iodine chloride compound; (4-n-butoxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-(4-n-butoxynaphthalene- 1-yl)tetrahydrothiophene hexafluoro-n-T alkane sulfonate, 1-(4-η-butoxynaphthalen-1-yl)tetrahydrothiophene-perfluoro-n-octane sulfonate, 1-( 4-n-butoxynaphthalen-1-yl)tetrahydrogen Key 2-bicyclo[2_2.1]hept-2-yl-1,1,2,2-tetra-ruthenium extended ester, 1_(4-11-butoxynaphthalen-1-yl)tetrahydrothiophene 1-(4-η-butoxynaphthalen-1-yl)tetrahydrothiophene key chlorine compound such as molybdenum sulfonate; 1-(6-η-butoxynaphthalen-2-yl)tetrahydrothiophene key three Fluoromethanesulfonate, 1-(6-η-butoxynaphthalen-2-yl)tetrahydrothiophene nonafluoro-η-butanesulfonate, 1-(6-η-butoxynaphthalene-2 -yl)tetrahydrothiophene iron perfluoro-η·octane sulfonate, 1-(6-η-butoxynaphthalen-2-yl)tetrahydrothiophene gun 2-bicyclo[2.2.1]heptan-2- Base-1,1,2,2-tetrafluoroethanesulfonate, 1-(6-η-butoxy-35- 201202272 naphthalen-2-yl)tetrahydrothiophene camphosulfonate, etc. 1-( 4-n-butoxynaphthalene-h group) tetrahydrothiophene key chlorine compound; 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene trifluoromethanesulfonate, 1-( 3,5-Dimethyl-4-hydroxyphenyl)tetrahydrothiophene gun nonafluoro-n-butanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene Fluorine-n-octane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene key 2-bicyclo[2.2.1]hept-2-yl-1,1,2 2-tetrafluoroethane Sulfonic acid ester, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene such as 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene camphorsulfonate Chloride compound; Ν-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3·dicarboxyimine, fluorene-(nonafluoro-η-butanesulfonyl) Oxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimine, fluorene-(perfluoro·η-octanesulfonyloxy)bicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxyimine, fluorene-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy)bicyclo[2.2. 1]hept-5-ene-2,3-dicarboxyimine, Ν-(2-(3-tetracyclo[ 4.4.0.12'5.17'1()]dodecyl)-1,1-difluoro Ethylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimine, anthracene-(camphorsulfonyloxy)bicyclo[2.2.1]hept-5-ene a bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimine compound such as 2,3-dicarboxyimine. The [C] acid generator may be used singly or in combination of two or more. [C] The content of the acid generator is preferably 30 parts by mass or less, and 0.1 to 20 masses per 100 parts by mass of the [A] polymer, from the viewpoint of ensuring sensitivity and development as an impedance. The serving is preferred. When the content of the [C] acid generator exceeds 30 parts by mass, the transparency to radiation is lowered -36 to 201202272, and it is difficult to obtain a rectangular resist pattern. &lt;Dic acid diffusion controlling agent&gt; The radiation sensitive linear resin composition may contain a [D] acid diffusion controlling agent (but 'removing the compound [B]). The compound [B] containing the linear radiation-sensitive resin composition has good acid diffusion controllability, and good resolution, pattern shape, and LWR characteristics can be obtained even if it is not used together with other acid diffusion control agents, but other [D] can be used. Acid diffusion control agent. It is preferred to use a nitrogen-containing compound as the [D] acid diffusion controlling agent. Examples of the nitrogen-containing compound include a compound represented by the following formula (6) (hereinafter also referred to as "nitrogen-containing compound ("), and a compound having two nitrogen atoms in the same molecule (hereinafter also referred to as " a nitrogen-containing compound (Π)", a polyamine-based compound having three or more nitrogen atoms in the same molecule, and a polymer containing a polymerizable compound of a nitrogen atom (hereinafter collectively referred to as "nitrogen-containing compound (III)")) a compound of a guanamine group, a urea compound, a nitrogen-containing heterocyclic compound, etc. [Chem. 2 0] R15a p15b - _ p15c (6) In the above formula (6), 'R15a, R15b and Rl5e are each independently a hydrogen atom and can be substituted. a linear or branched alkyl group, a cycloalkyl group, an aryl group or an aromatic group. Examples of the nitrogen-containing compound (I) include η-hexylamine, η-heptylamine, and η-octylamine. , η-mercaptoamine, η_mercaptoamine, cyclohexylamine, etc. mono(cyclo)alkylamines; di-n-butylamine, di-n-pentylamine, di-n-hexylamine' -37- 201202272 a di(cyclo)alkyl group such as a base amine, a di-n-octylamine, a di-n-decylamine, a hexylmethylamine or a dicyclohexylamine Tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, hexyldimethylamine, methyldicyclohexylamine, tricyclic Hexylamines; 2,2',2"·nitrotriethanol and other substituted alkylanilines, N,N-dimethylaniline, 2-methylaniline 4-methylaniline, 4-nitroaniline An aromatic amine such as diphenylamine, tris, 2,4,6·trit-butyl-N-methylaniline or N-benzodiisopropylaniline. As a nitrogen-containing compound (II), for example N,N,N',N'-tetramethylethylenediamine, tetramethylammoniumdiamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiaminediyl Benzophenone, 4,4'-diaminodiphenylamine phenyl)propane, 2-(3-aminophenyl)-2-(4-amine2-(4-aminophenyl)- 2-(3-hydroxyphenyl)propanyl)-2-(4-hydroxyphenyl)propane, 1,4-bis[1-1-methylethyl]benzene, 1,3-bis[1- (4-Aminophenyl)benzene, bis(2-dimethylaminoethyl)ether, bis(2. ether, 丨-(2-hydroxyethyl)-2-imidazolidinone, N,N,N' , N'-肆(2-hydroxypropyl)ethylenediamine, N, group Ethyltriamine, etc. As the nitrogen-containing compound (III), for example, polyallylamine, 2-dimethylaminoethylpropenylamine di-n-decylamine, cyclic amines; triethylamine: , tri-(cyclo)amines such as tri-n-hexylamine, tri-n-decylamine, and cyclic amine; aniline, N-:, 3-methylaniline, phenylamine, naphthylamine I diethanolamine, 2,6- "Ethylenediamine, hexamethylenediamine diphenyl ether, 4,4'-' 2,2-bis(4-aminophenyl)propane, ί, 2-(4-amino group) Benzene (4-aminophenyl)-yl)-1-methylethyl-diethylaminoethyl) 2-quinoxalinol, hydrazine, Ν', Ν'', Ν''-五甲出Polyethyleneimine, polymer, and the like. -38-201202272 Examples of the compound containing a guanamine group include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-decylamine, and Nt-butoxycarbonyldi-n-decyl group. Amine, Nt-butoxycarbonyldicyclohexylamine, Nt. Butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N- Methyl-1-adamantylamine, (S)-(-)-1-(t-butoxycarbonyl)-2-pyrrolidinemethanol, (R)-(+)butoxycarbonyl)-2- Pyrrolidine methanol, Nt-butoxycarbonyl-4-hydroxypiperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonylpiperazine, N,N-di-t-butoxycarbonyl-1- Adamantylamine, N,N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4'-diaminodiphenylmethane, Ν,Ν'-di-t-butoxycarbonylhexamethyldiamine, N,N,N'N'-tetra-t-butoxycarbonylhexamethyldiamine, N,N'-di -t-butoxycarbonyl-1,7-diaminoheptane, anthracene, Ν'-di-t-butoxycarbonyl-1,8-diaminooctane, N,N'-di-t -butoxycarbonyl-1,9-diaminodecane, N, N '-Di-t-butoxycarbonyl-l,l-diaminodecane, N,N'-di-t-butoxycarbonyl-1,12-diaminododecane, anthracene, fluorene '-Di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole,: Nt-butoxycarbonyl groups such as Nt-butoxycarbonyl-2-phenylbenzimidazole and Nt-butoxycarbonylpyrrolidine contain an amine group compound, and may also be exemplified by formamide or N-methylformamidine. Amine, N,N-dimethylformamide, acetamide 'N-methylacetamide, N,N-dimethylacetamide, acetamide, benzamide, pyrrolidone, N- Methyl pyrrolidone, N-ethinyl-1-adamantylamine, isocyanuric acid ginseng (2-hydroxyethyl), and the like. -39- 201202272 Examples of the urea compound include urea, methyl urea, 1,1-diurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3. - Diphenylurea n-butylthiourea and the like. Examples of the nitrogen-containing heterocyclic compound include imidazole, 4-methyl, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, and methyl-2-methylimidazole. Imidazopyridine such as 1-benzyl-2-(methyl-1H-imidazole), 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine '4-benzene Pyridine, 2-methyl-4-phenylpyridine, nicotinic acid, guanidinium nicotinate, quinoline '4-hydroxyquinoline, 8-oxysporinidine, 2,2': 6', 2" Pyridines such as bipyridyl; piperazines such as piperazine and 1-(2-hydroxy)piperazine; pyrazine, pyrazole, pyridazine, pyrene, pyrrolidine, piperidine, and piperazine Pyridineethanol, 3-piperidine-1,2-diol, morpholine, 4-methylmorpholine, 1·(4-morpholine)ethanol, 4-ethylmorpholine, 3-(N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazin-1-diazabicyclo[2.2.2]octane, etc. As the content of the [D] acid diffusion controlling agent, for [A] The amount of the 10,000 parts by mass is preferably 15 parts by mass or less, more preferably 1 〇 by mass, and particularly preferably 5 parts by mass or less. When the content is 15 parts by mass or less, The sensitivity of the impedance and the development of the exposed area may be lowered. [D] If the content of the acid diffusion controlling agent is 0.001 part by mass, the loyalty of the pattern shape as the impedance may be lowered under the process conditions. &lt;[E] Solvent&gt; Methylimidazolium 1-Benzene; Kispixine, Mercaptoethyl, Quinolpropionylazine, Polymeric Fraction Over Do Not Fear or Ruler -40 - 201202272 The Sensitive Radiation The linear resin composition generally contains a solvent of [E]. As a solvent used for the preparation of the above-mentioned radiation sensitive linear resin composition, if the above [A] polymer, the compound [B] and any component are dissolved or dispersed, However, it is not particularly limited, and examples thereof include linear or branched ketones such as 2-pentanone '2-hexanone and 2-heptanone' 2-octanone; and cyclic rings such as cyclopentanone and cyclohexanone. Ketones; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc.; propylene glycol monoalkyl ether acetate; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate Ethylene glycol monoalkyl ether acetate such as ester; propylene glycol monomethyl ether, Propylene glycol monoalkyl ether such as propylene glycol monoethyl ether; ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; diethylene glycol dimethyl ether, diethylene glycol Diethylene glycol dialkyl ethers such as alcohol diethyl ether; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; methyl 3-methoxypropionate , 3-methoxypropionic acid alkyl esters such as ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate; η-butyl acetate, pyruvic acid An ester such as methyl ester or ethyl pyruvate; an internal guanamine such as Ν-methylpyrrolidone: a lactone such as r-butyrolactone. The solvent (E) may be used alone or in combination of two or more. Among them, the use of -41 - 201202272 from propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ethers, linear, branched or cyclic ketones, 2-hydroxypropionic acid alkyls, 3- At least one of the alkoxypropionic acid alkyl groups and the lactones is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 2-heptanone, cyclohexanone, 2 At least one selected from the group consisting of ethyl hydroxypropionate, ethyl 3-ethoxypropionic acid and r-butyrolactone is more preferably selected from the group consisting of propylene glycol monomethyl ether acetate, cyclohexanone and r At least one of the groups of -butyrolactone is particularly preferred. &lt;[F] Additive&gt; The sensitive radiation linear resin composition may contain, as an additive of [F], for example, an alicyclic additive, a surfactant, a sensitizer, or the like. [Cycloaliphatic Additive] The alicyclic additive is a component which exhibits an effect of further improving the dry etching resistance, the pattern shape, and the adhesion to the substrate. The alicyclic additive may have an acid dissociable group. Examples of the alicyclic additive include t-butyl adamantanecarboxylate, t-butoxycarbonylmethyl ester of 1-adamantanecarboxylate, and α-butanolactone of 1-adamantanecarboxylic acid, and 1, 3-adamantyl dicarboxylic acid di-t-butyl ester, 1-adamantanic acid t-butyl ester, 〗-adamantanic acid t-butoxycarbonyl methyl ester, hydrazine, 3-adamantane diacetic acid di-t- Adamantane derivatives such as butyl ester and 2,5-dimethyl-2,5-di(adamantylcarbonyloxy)hexane; t-butyl deoxycholate t-butoxycarbonyl deoxycholate Methyl ester, 2-ethoxyethyl deoxycholate, 2-cyclohexyloxyethyl deoxycholate, deoxy-42-201202272 3-oxocyclohexyl cholate, tetrahydropyran deoxycholate deoxygenation Deoxycholate such as mevalonate of cholic acid; t-butyl cholate, t-butoxycarbonyl methyl cholate, 2-ethoxyethyl cholate, cholinate 2 - cholesteryl esters such as cyclohexyloxyethyl ester, 3-oxocyclohexyl cholate, tetrahydropyranyl cholinate, and mevalonate of gallstone; dimethyl adipate , alkyl adipate, diethyl adipate, di-n-butyl adipate, di-t-butyl adipate, etc. Acid esters, etc. Further, one type or two or more types of the above alicyclic group additives may be used. [Interfacial Agent] The surfactant is a component which exhibits an effect of improving coatability, streaking, and developing properties. Examples of the above surfactant include polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether, and polyethylene oxide η-octylphenyl group. Other non-ionic surfactants such as ether, polyethylene oxide n-nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate may be mentioned below. ΚΡ 3 4 1 (manufactured by Shin-Etsu Chemical Co., Ltd.), Poly-FlowN〇.75, Νο·95 (manufactured by Kyoei Chemical Co., Ltd.), EftopEF301, EF3 03, EF3 52 (manufactured by TOHKEM PRODUCTS), MEGAFACF171 , with F173 (made by Dainippon Ink Chemical Industry Co., Ltd.), FLUOR ARD FC4 3 0, with FC431 (manufactured by Sumitomo 3M), AashiGuard AG710, SURFLON S-3 8 2, same as SC-101, same as SC-102, with SC- 103, the SC-104, the same SC-105, and the SC-106 (made by Asahi Glass Co., Ltd.), etc. "The above surfactants may be used alone or in combination of two or more. The blending amount of -43 to 201202272 as the surfactant is preferably 100 parts by mass of the [A] polymer. [Sensitizer] The sensitizer is an effect of the sensitivity of the radiation-sensitive linear resin composition, which is an energy source that absorbs radiation and uses this acid generator to increase the amount of acid generated. Examples thereof include carbazoles, benzophenones, and Bengal rose. One type or two or more types of the above sensitizers can be used. The amount of ft blended is preferably 50 for 100 parts by mass of the polymer. &lt;Preparation method of sensitive radiation linear resin composition&gt; The sensitive radiation linear resin composition is generally dissolved in the total solid content concentration (ratio of component composition other than [E] solvent) of 1 to 50% by mass. Preferably, the linear resin composition solution of the radiation sensitive radiation can be carried out by a filter having a pore size of about 0.2 vm. [Embodiment] [Embodiment] Hereinafter, an embodiment will be described, and the embodiment of the present invention will be formed! Body description. However, the invention is not limited to the embodiments. The physical properties of each of the samples were measured by the following methods. 2 parts by mass of the source is transmitted to the light, and the sensitizer is only increased, and the mass of the sensitizer is hereinafter, the mass of the sensitizer is less than or equal to 25% by mass based on the total mass of the solvent in the solvent (E). Each of the following synthesis-44-201202272 [weight average molecular weight (Mw) and number average molecular weight (?n)] For Synthesis Examples 1 to 7, 12 and 13, a GPC column (G2000HXL2, G3 000HXL1, G4000HXL1 manufactured by TOSOH Co., Ltd.) was used. This was carried out by using monodisperse polystyrene as a standard gel permeation chromatography (GPC) under the conditions of a flow rate of 1.0 mL/min under the conditions of a tetrahydrofuran column temperature of 40 ° C as a solvent of dissolution. Determination. For Synthesis Examples 8 to 1, a GPC column (TSKgel a -2500 'TSKgel a -Μ) manufactured by TOSOH Co., Ltd. was used as a GPC column, and a flow rate of 1.0 mL/min was used as a dissolution solvent, and 30 mmol/L of LiBr was dissolved. With 10 mmol/L of dimethylformamide of H3P04, MALLS (DAWN DSP, Celltype K5, laser wavelength 632.8 nm, manufactured by Wyatt Co., Ltd.) was used as a detector under the condition of a column temperature of 40 ° C. Determined by gel permeation chromatography (GPC). [13C-NMR analysis] The measurement was carried out using "JNM-EX2 70" manufactured by JEOL Ltd. &lt;Synthesis of [A] Polymer&gt; Each monomer used in the synthesis of the [A] polymer is shown below. -45- 201202272 【化2 1】 0^0 ΟΤΌ

Cr ο ί

(M-2)

IQ (M-1)

o八o°A o (M-6) 0^0

OH (M-3) (M-4) CF, cf2 o=s=o I 〇- (M-9)

OH (M-13) (M-14)

QfO ό

0^0

OH (M-15) (M-12) [Synthesis Example 1], monomer preparation 19.30 g (46 mol%) of the above monomer (Ml) -46-201202272 (M-7) 5.12 g (4 mol) %) and monomer (m-5) 25.58g (50 mol%) dissolved in 2-butanone l〇〇g' further dissolved 2,2'-azobis(isobutyronitrile) (AIBN) 1.89g ( A monomer solution of 5 mol% for the total number of monomers in the monomer. On the other hand, a 300-mL three-necked flask containing 50 g of 2-butanone was substituted with nitrogen for 30 minutes, and then the mixture was heated to 80 ° C while stirring the reaction vessel, and the monomer solution prepared beforehand was used for 3 hours using a titration funnel. Drop in. The polymerization start reaction time was carried out as the polymerization initiation time, and the polymerization reaction was carried out for 6 hours. After the completion of the polymerization, the precipitated white powder was separated by filtration by cooling the polymerization solution to below 30 ° C under water cooling and then into methanol of 10,000 g. The white powder which was separated by filtration was washed twice with 200 g of methanol in a slurry form, and then separated by filtration and dried at 50 ° C for 17 hours to obtain a white powder polymer (A-1 ) (36.3 g, Yield 72.5%). The polymer (A-1) had Mw of 6,800 and Mw/Mn (molecular weight dispersion) of 1.35, and the result of C-NMR analysis, the structural unit derived from the monomer (M-7): from the single The structural unit of the body (M-1): a copolymer having a content ratio (molar ratio) of 4.0: 45.8: 50.2 from the structural unit of the monomer (M-5). Further, the content ratio of the low molecular weight component having a molecular weight of less than 1,000 of the obtained polymer (A-1) was less than 0.1 mol% as measured by GPC. [Synthesis Examples 2, 4, 5, 6, 8, 9, 10, 11 and 12] In the same manner as in Synthesis Example 1, except that the types and amounts of the monomers shown in the following Table 1 were used, Polymer (A-2), (A-4) ' (A-5), (A-6), (A-8), (A-9), (A-1 0 ), ( -47 - 201202272 A-ll) and (al). Yield (%), Mw, of the obtained polymer

The measurement results of the content ratio (mol%) of Mw/Mn and each structural unit in each polymer are shown in Table 2. [Synthesis Examples 3, 7 and 13] In Synthesis Example 1, the monomer (M-3) was put into a three-necked flask before polymerization, using the type and amount of the monomer shown in the following Table 1, and the synthesis example. In the same manner, polymers (A-3), (A-7) and (A-9) were obtained. The results of the yield (%), Mw, Mw/Mn of the obtained polymer and the content ratio (mol%) of each structural unit in each polymer are shown in Table 2 -48-201202272 [1® Polymerization Starter Moer % νη ίο υ-&gt; to n υη VO Type CP &lt; 2 PQ ♦-H &lt; | AI bn| z ω &lt; | AI bn| Z CQ Η-ί &lt; AI BN 2 CQ H _ _ _ _ _ _ _ _ _ _ 1 00 Γ—i 1 ID τ-Η 1 1 1 Structural unit (III ) Moer % 沄民单单 LO 1 to 1 sm 1 S LO 1 LO 1 CD 1 S LO 1 in 1 S in 1 S Ln 1 LD 1 LO 1 LO 1 structural unit (II) Moer % 妄oo cn monomer_1 τ-Η 1 οα 1 S 00 1 1 I—i 1 ι—Η 1 T-1 1 CO 1 i—i 1 iH 1 Art inch r-H 1 inch rH 1 rH 1 00 1 Structure unit (I) Moer % 寸 inch inch to VO Bu Bu 1 1 Monomer Ο S Bu 1 S Bu 1 Ο Ι S 00 1 Bu 1 Ο Ι Oi 1 s O i—H 1 S i—H ι—Ί 1 s τ-Η r—1 1 s 1 1 Γ &lt; 1 1~1 1 &lt; CM 1 &lt; 00 1 &lt; inch 1 &lt; LO 1 &lt; CD 1 &lt;t&gt; 1 c 00 1 &lt; 1 &lt; o iH 1 &lt; ?-1 iH 1 &lt; τ-Η 1 CO CXI 1 cn 1 Synthesis Example i 1 1 Synthesis Example 2 1 1 Synthesis Example 3 1 丨 Synthesis Example 4 | 1 Synthesis Example 5 1 1 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 1 Synthesis Example 9 1 丨 Synthesis Example i ol 1 Synthesis Example i il 1 Synthesis Example 1 2| Synthesis Example 1 3 -49- 201202272 [CNfi Mw /Μη yr\ CO OO cn as cn ov〇cn 严— 5 1 1 1H ro r-^ 1—H CN r·^ CN Vi 1.46 Mw Ο g ν〇o § v〇O s \D 〇〇VO oooo CO VO o CO v〇oo r- o OO oo 〇 OO r- 〇v〇ov〇 Other Structural unit Mohr% 1 1 1 1 1 1 1 or 4 cs CN 1 1 Monomer 1 1 1 1 1 1 1 OO iH 1 s CO t—( 1 LO rH 1 1 1 Structural unit (III ) Molar % C3 51.0 1 &lt;&lt; wo v〇泛CN ON 1' &lt; l〇CS) »〇V〇cn OJ cn cn cn 佘 monomer LO 1 s ld 1 S LD 1 LD 1 LO 1 S CO 1 % LO 1 LO 1 Ln 1 LO 1 LO 1 LO 1 Ln 1 啩 结构 structural unit (II ) 1 莫 % oo 〇 JO OO inch ON 40.0 OO ON oo inch o 49.9 49.7 monomer ϊ — i 1 s (M 1 CO 1 s 1 r—( 1 r—( 1 Ti 1 CO 1 1—( 1 r—( 1 inch tH 1 inch r—H 1 rH 1 S 00 1 S structural unit (I) Mo % % o inch o Inch t 1 pair 〇 〇 inch o inch v〇oo r- 1 1 monomer 卜 1 % 卜 1 S ο- Ι s Ο Ι S 00 1 Arti 1 I&gt; 1 CT) 1 so iH 1 »—H r -1 1 艺i-H iH 1 Art 1 1 Yield (%) CN CN ON VO V〇VO 03 Oi inch 8 VO m vo jn CN [A] component τ-Η 1 &lt; OO 1 &lt; CO 1 &lt ; inch 1 &lt; uo 1 &lt; CD 1 &lt; 卜 1 &lt; 00 1 &lt; 03 1 &lt; o rH 1 &lt; iH rH 1 &lt; iH 1 CQ oo 1 CQ b Example 1 I b Example 2 II Synthesis Example 3 I | Synthesis Example 4 1 I Synthesis Example 5 II Synthesis Example 6 I Synthesis Example 7 I Synthesis Example 8 I 1 Synthesis Example 9 I 〇Ϊ Chain &lt;Q 1 Synthesis Example 11 | I Synthesis Example 1 2 | Synthesis Example 1 3 - 50 - 201202272 &lt;Preparation of Sensitive Radiation Linear Resin Composition&gt; ΒChemical Inhibitor For the modulation of the linear radiation resin composition for sensitive radiation, [c] sensitive radiation linear acid generator, [D] Acid diffusion and [E] solvent are as follows. [[B] compound] Each compound represented by the following formula (B-1) to (B-5) [Chemical 2 2]

(Β-2)

(Β-4) [[C]sensitive radiation linear acid generator] C-1: triphenylsulfonium nonafluoro-η-butanesulfonate-51 - 201202272 [[D] acid diffusion control agent] Dl : Nt -butoxycarbonyl-4-hydroxypiperidine D-2: tri-n-octylamine [[E] solvent] E-1: propylene glycol monomethyl ether acetate E-2: cyclohexanone E-3 : r - Butyrolactone [Example 1] 100 parts by mass of the mixed polymer (A-1), 7 parts by mass of the compound (B-1), and the solvent (E-1) 1,700 parts by mass, (E-2) 700 The mass fraction and (E-3) 30 mass S parts were filtered, and the obtained mixed liquid was filtered with a membrane filter having a pore size of 200 nm to prepare the radiation sensitive linear resin composition of Example 1. [Examples 2 to 16 and Comparative Examples 1 to 4] In the same manner as in Example 1, except that the types and amounts of the respective components were as follows: in the same manner as in the first embodiment, the examples 2 to 16 were compared and compared. The sensitive radiation linear resin composition of Examples 1 to 4. Further, "- j indicates that the component is not used. -52- 201202272 [cns 丨 Solvent mass fraction 1700/700/30 1700/700/30 1700/700/30 1700/700/30 1700/700/30 1700/700/ 30 1700/700/30 1700/700/30 1700/700/30 1700/700/30 1700/700/30 1400/3300 1400/3300 1400/3300 1400/3300 1400/3300 1700/700/30 1700/700/ 30 1700/700/30 1400/3300 ω Category E-1/E-2/E-3 E-1/E-2/E-3 E-1/E-2/E-3 E-1/E- 2/E-3 E-1/E-2/E-3 E-1/E-2/E-3 E-1/E-2/E-3 Ε-1/Ε-2/Ε-3 Ε -1/Ε-2/Ε-3 E-1/E-2/E-3 E-1/E-2/E-3 El/E-2 El/E-2 El/E-2 El/E -2 El/E-2 E-1/E-2/E-3 E-1/E-2/E-3 E-1/E-2/E-3 Ε-1/Έ-2 Μ 19 藏m 1 parts by mass 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 CN 1 1 (N Μ Q type I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 CM 1 Q r-1 1 Q 1 1 CM 1 Q [C] acid generator mass parts 1 1 1 1 1 1 1 1 1 1 CN 1 1 1 1 1 1 Bub 1 Type 1 1 1 1 1 1 1 1 1 1 i-t 1 o 1 1 1 1 1 1 ι-Η 1 CJ tH 1 U 1 &lt;SQ masses of indus, insignias, insults, instincts, ins and outs PQ T—H 1 CQ τ-Η 1 CQ r—1 1 CQ T—i 1 τ- 1 0Q (Μ 1 CQ CO 1 PQ inch 1 DQ τ-Η 1 CQ CO 1 CQ LO 1 PQ CO 1 CQ LO 1 DQ LO 1 CQ 1 τ—i 1 PQ i—1 1 CQ 1 [A] Component parts by mass 〇〇〇〇〇ο 〇Ο 1—^ o ο o 〇1—H o 〇oo 1—^ 0 1 « oho 〇Type τ-Η 1 &lt; (M 1 &lt; CO 1 &lt; 1 &lt; LO 1 &lt; CD 1 &lt;ϊ&gt; 1 &lt; τ - Η 1 &lt; 〇〇 1 &lt; CO 1 &lt; 1 1 &lt; 00 1 &lt; 1 1 &lt; o τ - Η 1 &lt; rH r - 1 1 &lt; i-1 1 C iH 1 &lt; rH 1 co CM 1 CO CO 1 &lt; r 1 1 embodiment 2 2 Example 3 Example 4 丨 Example 5 I Example 6 1 Example 7 I 丨Example 8 1 Example 9 Example 1 0 Example 1 1 1 Example 1 2| Example 1 3 Example 1 4 1 Example 1 5| Example 1 6 Comparative Example 1 | Comparative Example 2 I Comparative Example 3 Comparison Example 4 -53 - 201202272 &lt;Evaluation of Sensitive Radiation Linear Resin Composition (1) &gt; For each of the radiation sensitive linear resin compositions of Examples 1 to Π and Comparative Examples 1 to 3, the sensitivity was performed by the following method , pattern shape and evaluation of LWR. The results of these assessments are shown in Table 4. [Sensitivity] A laminate of ARC66 (manufactured by Nissan Chemical Industries, Ltd.), which has a thickness of 1 and a thickness of 5%, was used on the surface of the wafer, and each composition solution was applied to a substrate using Clean Truck ACT12 (manufactured by Tokyo Electron). The coating was applied by spin coating, and pre-baked (PB) was performed on a hot plate at a temperature shown in Table 4 for 60 seconds to form an impedance film having a film thickness of 0.09. Then, Lithius Pro-i (manufactured by Tokyo Electron Co., Ltd.) was used on the resist film, and TCX041 (manufactured by JSR) was applied by spin coating, and PB was applied to the hot plate at 90 ° C to form a film thickness of 0.09 / zm. The upper cover film. On the film formed as described above, an ArF excimer laser exposure apparatus "S610C" (number of openings: 1.30) made of Nikon was used for exposure through a mask pattern. After performing PEB for 60 seconds at the temperature shown in Table 4, the image was developed by a 2.38 mass% aqueous solution of tetramethyl hydroxyhydroxide at 23 ° C for 60 seconds, washed with water and dried to form a positive photoresist pattern. type. At this time, the pattern obtained by obtaining the mask of the line and pitch pattern (1L1S) having a diameter of 0.044 m can be an exposure amount of a diameter of 0.044 /zm as the optimum exposure amount, and the optimum exposure amount (unit: mJ) /cm2) as the sensitivity. [Shape shape (section shape of the pattern)] -54- 201202272

The cross-sectional shape of the 〇·〇44 μm line and the pitch obtained at the time of measurement of the above sensitivity was observed by Hitachi High-Technologies Co., Ltd. 4800 00' to evaluate the pattern shape. When the rectangular shape is displayed, "A" (good) is evaluated, and when the shape other than the rectangle is displayed, it is evaluated as "B bad". [LWR (line width roughness)] For the above optimum exposure amount, the impedance film on the substrate will be formed. The 0.044em (lLlS) pattern of the upper layer is measured by the length measurement SEM (model "CG4〇00" made by Hitachi, Ltd.), and the measurement is performed at any point of the pattern.値 Find the LWR (unit: nm) as the number. The LWR is as small as possible. When it is less than 3, it is evaluated as "A" (good), and when it is more than 3. Onm is evaluated as "poor". Figure "S- Estimated as

Shaped production inspection, 3 news. Onm; Γ B 201202272

[Table 4] PB Brewing (°C) PEB (°C) Sensitivity (mJ / cm2) Pattern Shape LWR Number 値 (nm) Evaluation Example 1 110 140 40 A 2.3 A Example 2 110 140 42 A 2.4 A Implementation Example 3 110 140 38 A 2.4 A Example 4 110 140 44 A 2.5 A Example 5 110 140 42 A 2.4 A Example 6 110 140 37 A 2.2 A Example 7 110 140 42 A 2.4 A Example 8 110 140 40 A 2.3 A Example 9 110 140 40 A 2.4 A fl Example 1 0 110 140 40 A 2.4 A Case 1 1 110 140 40 A 2.6 A Comparative Example 1 110 140 38 B 3.8 B Comparative Example 2 110 140 40 B 3.3 B Comparative Example 3 110 140 33 B 3.4 B From the results of Table 4, the radiation sensitive linear resin compositions of Examples 1 to 1 were compared with the radiation sensitive linear resin compositions of Comparative Examples 1 to 3, and exposed to ArF. Among them, a photoresist pattern having a small LWR and having an excellent pattern shape having a rectangular cross section is formed. &lt;Evaluation of Sensitive Radiation Linear Resin Composition (2) &gt; For each of the radiation sensitive linear resin compositions of Examples 1 2 to 16 and Comparative Example 4, the edge roughness and the resolution were quasi-aligned by the following method Evaluation. Their evaluation results are shown in Table 5. [Sensitivity] -56- 201202272 In the "Clean truck ACT-8" manufactured by Tokyo Electron, the radiation-sensitive linear resin composition was spin-coated on a sand wafer, and then subjected to a temperature of 90 seconds as shown in Table 5. PB 'forms an impedance film having a film thickness of 60 nm. Then, a simple electron beam drawing device (type "HL800D" output manufactured by Hitachi, Ltd.; 5 〇 KeV, current density; 5.0 amp / cm 2 ) was used to irradiate the resist film formed as described above with electron beams. After the irradiation of the electron beam, P E B was performed for 90 seconds at the temperature shown in Table 5. Thereafter, a 2.38% tetramethylammonium hydroxide aqueous solution was used, and after 1 minute of stirring at 23 t and developed, it was washed with pure water and dried to form a photoresist pattern. At this time, a line and a pitch pattern (1 L 1 S )' formed by the line portion of the line width of 15 Onm and the interval formed by the adjacent line portion being 1 50 nm (that is, the groove) form a pair. The exposure amount of the line width of 1 is taken as the optimum exposure amount, and the optimum exposure amount is taken as the sensitivity (unit: μ C/cm 2 ). [Edge Roughness] The line pattern of the line and the pitch pattern (1L1S) of the design line width of 150 nm is a scanning electron microscope for semiconductors (trade name "S-9220" of the high-decomposition energy FEB length measuring device, manufactured by Hitachi, Ltd.) Observe. As shown in FIG. 1 and FIG. 2, the shape of the observed shape is the width of the most prominent portion of the unevenness generated along the lateral side 2a of the line portion 2 of the resist film formed on the erbium wafer 1, and The edge roughness (unit: nm) was calculated by designing the difference "ACD" of the line width of 15 〇 nm. [Resolution] -57- 201202272 For the line and pitch pattern (1L ] S ), the minimum line width of the line pattern solved by the optimum exposure amount is taken as the resolution (unit: nm). Fig. 5 PB temperature (°C) PEB temperature (°C) sensitivity/cm2) Nano edge roughness (nm) Resolution (nm) Example 1 2 130 150 50 14 60 Example 1 3 130 140 49 13 60 Example 14 130 140 50 13 60 Example 1 5 130 140 49 12 60 Example 1 6 130 140 48 14 70 Comparative Example i 130 140 50 17 80 From the results of Table 5, Example 1 2~1 The sensitive radiation grease composition of 6 is compared with the radiation sensitive linear resin composition of Comparative Example 1 to form a photoresist pattern which is effective for the electron beam, has a small nanoedge roughness, and is excellent in degree. As shown in the results of Tables 4 and 5, the radiation-sensitive resin composition of the present invention has a LWR or edge roughness suppressed in the case of charged particles such as ultraviolet rays and electron beams such as ArF, and can be formed into a good shape. Pattern shape, excellent resolution of the resist pattern. Sex tree, solvable linearity, moment, industrial availability, the sensitive radiation linear resin composition of the present invention is a photoresist pattern which can be formed into a small size and has a good shape. Therefore, the ray-based resin composition of the present invention is useful as a chemically amplified type of resistance for forming a semiconductor device which is expected to be able to be made into a finer LWR sensitization step in the future. [Simple description of the drawing] [Fig. 1] A plan view of the line pattern when viewed from above. [Fig. 2] A schematic sectional view of a line pattern shape. [Description of main component symbols] 1 : Substrate 2 : Photoresist pattern 2a _· Horizontal side of photoresist pattern -59-

Claims (1)

201202272 VII. Patent application scope: 1. A sensitive radiation linear resin composition characterized by containing [A] a polymer having an acid dissociable group having a structural unit (I) represented by the following formula (1), and [ B] a compound represented by the following formula (2); E—R 2 —f 宁 M+ (1) F Ο (In the formula (1), R 1 is a hydrogen atom, a fluorine atom, a trifluoromethyl group or an alkyl group having 1 to 3 carbon atoms; and E is a single bond or —COO—; R2 is a divalent hydrocarbon group having 1 to 20 carbon atoms, and a part or all of the hydrogen atom of the hydrocarbon group may be substituted by a fluorine atom; η is an integer of 0 to 5; M + is a phosphonium cation) [Chemical 2] Y-R3 -X&quot; Q+ (2) (In the formula (2), Y is a hydrogen atom, a hydroxyl group, an acryloyl group or a methacryloyl group; R3 is a divalent hydrocarbon group having a carbon number of 1 to 20 or -RZ-R'-; R and R' are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms; Ζ is -0-, -(: 0-, -&lt;: 00-, -OCO-, -ΝΗ-, -NHCO- or -CONH - X - is 〇-, -COO., -S03_ or -&gt;r-S02-R"; R" is a monovalent hydrocarbon group having 1 to 20 carbon atoms, a part or all of a hydrogen atom of the hydrocarbon group It can be replaced by a fluorine atom: in addition, R and R' are bonded to each other to form a ring; Q + is a key cation). 2. The radiation sensitive linear resin composition of claim 1, wherein the above formula (1) M + is at least one key cation selected from the group consisting of the key cations represented by the following formula (3) and the following formula (4); -60- 201202272 [ 3] R4a R4b—S+—R4c ( 3 ) (In the formula (3), d and Rh are each independently a carbon number! A valence hydrocarbon group or a nucleus group having a nuclear atom number of 4 to 30; but the above hydrocarbon group and hetero One or all of the hydrogen atoms of the ring group may be substituted; in addition, R4a, R4b and any two of them may be bonded to each other to form a cyclic structure together with the sulfur atom to which they are bonded.) [Chemical 4] R5a_| _R5b (4) (In the formula (4), R5a and R5b are each independently an indolo hydrocarbon group having a carbon number of i to 3 Å or a monovalent heterocyclic group having a nuclear atom number of 4 to 30; however, the above hydrocarbon group and heterocyclic group are One or all of the hydrogen atoms may be substituted: in addition, R5a and R5b are bonded to each other to form a cyclic structure together with the iodine atoms to which they are bonded. 3. The radiation of the sensitive radiation as in claim 1 a resin composition, wherein the compound [B] is at least one compound selected from the group consisting of compounds represented by the following formulas (2-1) to (2-6); -61 - 201202272 [Chemical 5] R6 Ν' Q+ I o=s=o I cf3 (2-3) Q+ G°H ^^coo· (2-1) Deaf. | Deaf. 〇人0 I 1 R7 R7 | | Ν' Q+ =S=0 1 cf3 S03. Q+ 0 丫0 Λ (2-4) (2-5) (2-6) (Formula (2-1)~( In 2-6), R6 is a monovalent chain hydrocarbon group having 1 to 6 carbon atoms; R7 is independently a divalent chain hydrocarbon group having 1 to 6 carbon atoms; and Q + is the same as the above formula (2)) - 4 The sensitive radiation linear resin composition of claim 1, wherein the [A] polymer is a structural unit (Π) further having the following formula (5); R9 -62- (5) 201202272 (In the formula (5), the definition of R1 is the same as the above formula (1); R8, R9 and R1Q are each independently an alkyl group having 1 to 4 carbon atoms or a ring having 4 to 20 carbon atoms. An alkyl group; however, R9 and R1() are bonded to each other to form a cycloalkanediyl group having 4 to 20 carbon atoms together with the carbon atom to which they are bonded. -63-