TWI304153B - Positive resist composition and manufacturing method of resist pattern - Google Patents

Description

1304153 (1) EMBODIMENT OF THE INVENTION [Technical Field of the Invention] The present invention relates to a method for forming a positive-type photoresist composition and a photoresist pattern. The present invention is a Japanese invention applied to the Japanese Patent Office on December 17, 2004. Patent Application No. 2004_3 665 84 is a priority basis, and the content of the present invention is based on the foregoing invention. [Prior Art] In recent years, in the manufacture of semiconductor elements or liquid crystal display elements, with the advancement of the lithography etching technology, the gradual progress has been made toward miniaturization. The method of miniaturization is generally carried out in such a manner that the exposure light source is short-wavelength. Specifically, ultraviolet rays represented by g-line and i-line have been used in the past, but currently, mass-produced KrF excimer lasers (248 nm) are used as the center, and even ArF excimer lasers (193 nm) are introduced again. Mass production.

The aforementioned short-wavelength light source resist has been sought to reproduce the high resolution of the fine-sized pattern and the sensitivity with respect to the short-wavelength light source. In order to satisfy one of the above-mentioned conditions, for example, an enhanced chemical type resist containing a base resin, an acid generator (PAG) which generates an acid by exposure, and a chemical type resist are known to have a base which can increase the exposure portion. The positive form of solubility, and the negative type of alkali solubility of the exposed portion. There are many proposals for enhancing the key salt of PAG used in chemically positive photoresist compositions. For example, the PAG obtained from the triphenylphosphine-based key salt described in the following patent documents, further contains fluorine such as triphenylphosphine nonafluorobutanesulfonate-6-(2) 1304153 ester (TPS-PFBS). Alkylsulfonic acid ions are commonly used as an anion-separating salt acid generator. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A-2003-67347A SUMMARY OF THE INVENTION In the case of realizing a fine-sized photoresist pattern, the pattern size variation (EL offset 0 margin) generated when the amount is changed can be changed. When it is small, and when the size of the photoresist changes, the lineage that is faithful to the dimensionality of the photoresist pattern is extremely important, but it is still extremely difficult to achieve at the same time. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is directed to a method of forming a positive resist composition and a method for forming an EL offset and dimensional fidelity. In order to achieve the above object, the positive resist composition (A) of the present invention increases the alkali-soluble resin component by the action of an acid, and forms a positive photoresist composition (B) of an acid generator component by exposure. It is characterized by containing a cationic acid generator (B1) represented by the following formula (b-Ι) and a structural acid generator (B2) having a structure represented by the following formula (b-2). Sub (acid)

Suppressing the exposure shift, EL- makes the mask ruler (Mask- the above purpose is a photo-resistance pattern to contain the (B) substance, the above-mentioned key salt system of sulfonic acid (3) 1304153 [1]

(b-2) [wherein R1" is an alkyl group, an alkoxy group, a halogen atom or a hydroxyl group; and R2", R3" are each independently an aryl group or an alkyl group which may have a substituent, and η is 0 or an integer from 1 to 3] -C=rN-Ο-S〇2—R21 [wherein R21' is an organic group; R22' is a monovalent organic group or a cyano group]. Further, the present invention Provided is a step of forming a photoresist film on a substrate using the positive photoresist composition of the present invention, and a step of exposing the photoresist film to a step of developing the photoresist film to form a photoresist pattern. Forming method of the type. According to the method of the present invention, it is possible to provide a method for forming a positive resist composition and a resist pattern which can improve EL offset and dimensional fidelity of a resist pattern. <Resin component>;

-8- (4) 1304153 (A) component, which is an alkali-insoluble resin having an acid dissociation dissolution inhibiting group, which can inhibit acid dissociation dissolution by the action of an acid generated by the above component (B) upon exposure. The base dissociates and the (A) component becomes alkali soluble. Therefore, in the formation of the photoresist pattern, when the photoresist composition coated on the substrate is selectively exposed, the alkali solubility of the exposed portion is increased, and alkali development can be performed.

(A) The composition is not specified in any way, and it is possible to use the resin which has been proposed as a base resin for enhancing the chemical resist composition. • The structural unit (al ) (A ) is preferably a structural unit (al ) derived from an acrylate having an acid-dissociable dissolution inhibiting group. Further, in the following description of the positive resist composition, the meaning of the terms is as follows. "Structural unit" means the unit of the monomer constituting the polymer (resin) φ. "Structural unit derived from acrylic acid" means the structural unit formed by the cracking of the ethylenic double bond of acrylic acid. The "structural unit derived from acrylate" means the structural unit composed of the cleavage of the vinyl double bond of the acrylate. In the "structural unit derived from acrylic acid" and "structural unit derived from acrylate", "the alpha position (carbon atom in the alpha position)" is a carbon atom bonded to a carboxyl group unless otherwise specified. Also, "structural units derived from acrylic acid" also contain bonds to ^ -9- 1304153.

A hydrogen atom of a carbon atom may be a structural unit derived from a structural unit of a halogen atom, an alkyl group, a halogenated alkyl group or the like, or a structural unit derived from a propylene ester of a hydrogen atom bonded to a hydrogen atom. Read. Further, the "alkyl group" is a linear, cyclic or branched alkyl group which is not particularly limited. The acid dissociable dissolution inhibiting group in the structural unit (a 1 ) has the resin component (A), and the resin component (A) before dissociation is dissolved in the alkali-insoluble base to suppress the φ property, and the resin component is obtained after dissociation (A). When the whole is changed to alkali solubility, the material which has been proposed to be used as an acid dissociable dissolution inhibiting group for reinforcing a base resin for chemical resist can be used. In general, for example, a carboxyl group of (meth)acrylic acid, a group forming a cyclic or chain-like tertiary alkyl ester, or a group forming a chain or cyclic alkoxyalkyl ester is known. More preferably, it is a carboxyl group of (meth)acrylic acid, and forms a cyclic or chain-like tertiary alkane vinegar. Further, "(meth) acrylate" means any one or both of an acrylate and a methyl propyl acrylate. Wherein the tertiary alkyl ester, for example, a hydrogen atom of a carboxyl group is substituted with an alkyl group or a cycloalkyl group to form an ester, and the oxygen atom at the terminal of the carbonyloxy group (-C(0)-0-) is bonded to the aforementioned A structure obtained by a tertiary carbon atom of an alkyl group or a cycloalkyl group. In the above tertiary alkyl ester, the bond between the oxygen atom and the tertiary carbon atom can be interrupted by the action of an acid. Further, the aforementioned alkyl group or cycloalkyl group may have a substituent. Hereinafter, the acid dissociable group is formed via the constitution of a carboxyl group and a tertiary alkyl ester. The acid dissociation property is simply referred to as "triester alkyl-10-(6) 1304153 ester type acid dissociation. Dissolution inhibition group". Further, a cyclic or chain alkoxyalkyl ester is a result of forming an ester of a carbonyloxy group (-C ( Ο )-\ 〇-) based on a hydrogen atom of a carboxyl group substituted with an alkoxyalkyl group to form an ester. The oxygen atom is bonded to the structure of the alkoxyalkyl group described above, and the alkoxyalkyl ester is cleaved by the action of an acid to bond the oxygen atom to the alkoxyalkyl group. In the structural unit (a 1 ), more specifically, for example, a structural unit represented by the following formula φ (al-0-l) and a structural unit represented by the following formula (al-0-2) are used. One or more selected in the group are preferred. [化3]

(wherein R is a hydrogen atom, a fluorine atom, a lower alkyl group, or a fluorinated lower alkyl group; and X 1 is an acid dissociable dissolution inhibiting group)

-11 (7) 1304153 (wherein R has the same content as described above; X2 is an acid dissociable dissolution inhibiting group; Y2 is an aliphatic cyclic group) • Formula (al-0-l) is a lower class of R The fluorenyl group is a hospital group having 1 to 5 carbon atoms, specifically, 'for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, A lower linear or branched alkyl group such as isopentyl or neopentyl. The fluorinated lower-grade courtyard of R is a hospital base with 1 to 5 carbon atoms, and some or all of the hydrogen atoms of the hospital base can be replaced by fluorine atoms, and all of them are preferably fluorided. . A fluorinated lower alkyl group having 1 to 5 carbon atoms, such as a trifluoromethyl group, a hexafluoroethyl group, a heptafluoropropyl group or a nonafluorobutyl group, is preferred, and a trifluoromethyl group is more preferred. X1 is not particularly limited as long as it is an acid dissociable dissolution inhibiting group, and may be, for example, an alkoxyalkyl group or a tertiary alkyl ester type acid dissociable dissolution inhibiting group, and a tertiary alkyl ester type acid dissociation property. The dissolution inhibiting group is preferred. The tertiary alkyl φ ester type acid dissociable dissolution inhibiting group is, for example, an aliphatic branched acid dissociable dissolution inhibiting group, an acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, and the like. In the above, the scope of the patent application and the term "aliphatic" as used in the specification mean the relative complication with respect to aromatics, that is, the meaning of a group or a compound having no aromaticity. The "aliphatic cyclic group" means a monocyclic or polycyclic group which does not have an aromatic character. The "aliphatic cyclic group" in the structural unit (al) may have a substituent or may not have a substituent. a substituent such as a lower alkyl group having 1 to 5 carbon atoms, a fluorine atom, a fluorinated lower alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom,

-12- (8) (8)

1304153 Oxygen atom (dioxin) and the like. The "aliphatic cyclic group" removes the basic ring structure of the substituent, and does not limit the group (hydrocarbon group) composed of carbon and hydrogen, but a hydrocarbon group is preferred. Further, the "hydrocarbon group" may be either saturated or unsaturated, and generally it is preferably saturated. Preferred is a polycyclic group. Specific examples of the above aliphatic cyclic group may be, for example, a lower alkyl group, a fluorine atom or a fluorinated alkyl group, or a monocyclic alkane, a bicycloalkane or a tricycloalkane which may be unsubstituted. A group obtained by removing one or more hydrogen atoms from a polycyclic alkane such as a tetracycloalkane. Specifically, it is, for example, a monocyclic alkane such as cyclopentane or cyclohexane or a polycyclic alkane such as adamantane, raw spinel, raw spinel, isopentane, tricyclodecane or tetracyclododecane. A group obtained by removing one or more hydrogen atoms or the like. Further, the aliphatic branched acid dissociable dissolution inhibiting group is specifically, for example, tert-butyl or tert-pentyl. An acid dissociable dissolution inhibiting group containing an aliphatic cyclic group, for example, a group having a tertiary carbon atom on a ring skeleton of a cycloalkyl group, etc., specifically, for example, 2-methyl-2-adamantyl group, or 2 - Ethyl-2-adamantyl and the like. Or, as the structural unit shown below, an alkaryl group-like aliphatic cyclic group, and a group of a branched alkyl group having a tertiary carbon atom bonded thereto, and the like. -13- (9) 1304153 【化5】

Wherein R has the same meaning as described above, and R15 and R16 are alkyl groups (may be linear or branched, preferably having a carbon number of 1 to 5). Further, in the alkoxy group, It is preferred to use a base represented by the following formula. 【化6】 C—Ο—R 23 R22

[wherein, R21 and R22 are each independently an alkyl group or a hydrogen atom, and R23 is an alkyl group or a cycloalkyl group. Further, R21 and R23 may form a ring via a terminal bond thereof. In R21 and R22, the carbon number of the base group is preferably from 1 to 15, which may be linear or branched, and may be ethyl, Methyl is preferred and methyl is preferred. Further, in particular, any of R21 and R22 is a hydrogen atom, and the other is preferably a methyl group. R23 is an alkyl group or a cycloalkyl group, and its carbon number is preferably from 1 to 15, which may be linear or branched or cyclic. When R23 is linear or branched, a 14-(10) 1304153 preferably has a carbon number of 1 to 5, preferably an ethyl group or a methyl group, and an ethyl group is most preferred. • When R2 3 is a ring, the carbon number is preferably 4 to 15, and the carbon number is 4 to '12, and the carbon number is 5 to 10. R23, specifically, for example, may be removed by a fluorine atom or a fluorinated alkyl group, or an unsubstituted polycyclic alkane such as a monocyclic chain, a bicycloalkane, a tricycloalkane or a tetracycloalkane. More than one hydrogen atom or the like. Specifically, for example, a monocyclic alkane such as cyclopentane or cyclohexane, or one or more polycyclic chain oximes such as adamantane, borax, isopentane, tricyclodecane or tetracycline are removed. The base of a hydrogen atom, etc. Among them, a group obtained by removing one or more hydrogen atoms from adamantane is preferred. Further, in the above formula, R21 and R23 are each independently an alkyl group having 1 to 5 carbon atoms, and the terminal of R23 may be bonded to the terminal of R21. At this time, R21 and R23 are bonded to the oxygen atom bonded to R23, and the oxygen atom forms a cyclic group with the carbon atom bonded to R21. The ring base is preferably a 4 to 7 member ring, and a 4 to 6 member ring is preferred. Specific examples of the ring group are φ such as tetrahydropyranyl group or tetrahydrofuranyl group. In the formula (al-0-2), R has the same content as described above. X2 is the same as X1 in the formula (al-0-l). Y2 is a divalent aliphatic cyclic group. Since Y2 is a divalent aliphatic cyclic group, the same content as described in the description of the "aliphatic cyclic group" in the above structural unit (al) can be used, in addition to the group in which two or more hydrogen atoms are removed. In the structural unit (a 1 ), more specifically, for example, the structural unit represented by the following formulas (a 1 - 1 ) to (al-4). Isi) -15- 1304153 (11) 【化7】

[In the above formula, X' is a tertiary alkyl ester type acid dissociable dissolution inhibiting group; γ is a lower alkyl group having 1 to 5 carbon atoms or an aliphatic cyclic group; and η is an integer of 0 or 1 to 3; (5) is 〇 or 1; R has the same content as described above; R1' and R2 are each independently a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms; and at least 1 of the above R1, R2 is preferably The hydrogen atom 'is more preferably a hydrogen atom at the same time. η is preferably 0 or i. The content of X is the same as that of the tertiary alkyl ester type acid dissociable dissolution inhibiting group exemplified in the above X 1 . The aliphatic cyclic group of Y is, for example, the same as those exemplified in the description of the "aliphatic cyclic group" in the above structural unit (a 1 ). The following formula (al-Ι) to (al-) 4) A specific example of the structural unit shown, -16- (12) 1304153 [Chemical 8]

—|〇Η2~〇Η^- CH3 —f*CH2—cA~* (CH2)3CH3 (a1 -1 -7) 0=1^ 9Ha ο— CHg (a1-1~10) tX) 100 °t〇 〇十二一# (a1+13) (a1+m (4) publication) CH2—c leaf? H3 〇4 ch3 Ten H2—?10 0, claw eight 0===^ c2h5 0, m) (a1-1 -14)

(a1-1_15) c2h5 -17- (13)1304153 [Chemical 9]

(at-1-19) (a1-1-20) (a1-1-17) (a1-1 -18) ςΗ3 °V) (a1-1-21)

CH3 -CH2 -c~V 0==\ 〒2H5〇, L^

(a1 十 23) t \ :CH2 a ft Ten H "f o==\ ^Hs 〇4 (3) One called tD - (ch2_ch) - 0=A ?H3/CH3 (al-1-24)

O CHJ

CHal ch3 ch3 (a1+25) Reference H2—CH: 〇=v O, CH3

(a1 -1-27) -ch2—chV 0=(^ ～·

(a1-1-28) (a1-1-26) 〇H3 CH2 JC^ 〇H 〇=\ ch3/ch3 0

(a1-1-29) ch3 PH3 -^ch2—c 〇=A ?h3 b (a1-1~30) ,? 2H56 (a1-1-32) -18- (14)1304153 【化1 0】

(al-1-37) (al-1-38)

(a1-1-39) (a1-1-40) (a1-1 - 41)

-19- (15)1304153 【化1 1】

-20- ^8) (16)1304153 【化1 2】

(a Bu 2-7) (a1-2 - 8)

CH3 -ch2—c4-oJ n

-CH2—CHj 4 ,〇

(a1 - 2-12)

-21 - 1304153 (17)[化1 3 ο o

O P ch3 -ch2-〒+

o h3c CH3 , CH2—C-

o

o

C2h5 o o

(al -3-1) ch3 c2h5

H3cr (a1-3~3)

0 O

(a1-3-4)

#

(a1 -3-9)

C2H5 ‘ (al - 3-10) H3C^\ I C2*V (al-3-11) (a Bu 3-12) -22- 1304153 (18) [Chem. 1 4]

〇n CH3 -CH2-〒十 〇==l o

-ch2~ch- -ch2^ch-

(a1-3~21) (a1-3-22) (a1-3-23) (a1~3~24) 23- (19) 1304153 [Chemical 1 5] Ten, jH4 ten mouths 4 0=\ ?

〇 〇 ten CH2J4 ten Ί 0=\) ?i ^ i 〇 〇 〇

Q (al -4 -1) (a1-4- 2) CH3 (a 1-4-3) (a Bu 4·4)

I 4. 4. O 04 Ten H2—CH孓

o o o °ϊθ. name. (a1_4-5) (a1 *~4~6) (a 1-4-8) (a1-4-7) ch3 ten h2-〒+ 0

o O (a1-4-9) fcH2-CH 〇= CHg --f*CH2—CH_

(20) 1304153 [Chem. 1 6]

(a^4H7) (al-H8)

Is (al-4-15) (a1 - 4-16)

(a Bu 4-J9) (a 1-4-20) 25- (21) 1304153

[化1 7]

(a1_4_22> (al-4-23)

(a 1 - 4 to 24)

The structural unit (a 1 ) may be used singly or in combination of two or more. Among them, the structural unit represented by the formulas (al-1) and (al-3) is preferred, and the structural unit represented by the formula (al-1) is more preferable. Specifically, the use of at least one structural unit selected from the group consisting of the formulae (al-1-l) to (al-1-6) or the formula (al-1-35) to (al-1-41) is the most good. -26- (22) 1304153 Further, the structural unit (al) is specifically represented by the following formula (al-1-01) containing the structural unit of the formula (al-1-1) to (abu 4) The unit or the following formula of the structural unit of formula (al-1-36), formula (al-1-38), formula (al-1-39), (al-1·41) (al-1- 02) is better. [化1 8]

(where R is a hydrogen atom or a lower-grade courtyard, and R11 is a lower-grade courtyard) [Chem. 19]

(wherein R is a hydrogen atom or a lower alkyl group, R12 is a lower alkyl group, and h is an integer of 1 to 3). In the formula (al-1-Ol), R has the same content as described above. The lower alkyl group of R11 is the same as the lower alkyl group represented by R, and a methyl group or an ethyl group is preferred. -27- (23) 1304153 In the formula (al-1-02), R has the same content as described above. The lower alkyl group of R12 is the same as the lower alkyl group represented by R, and is preferably methyl or ethyl, and ethyl is preferred. h is preferably 1 or 2, and 2 is the best. In the resin component (A), the ratio of the structural unit (a 1 ) is preferably from 10 to 80 mol %, and from 20 to 70 mol, for the entire structural unit constituting the resin component (A ). The ear % is more preferably, and the optimum of 30 to 50% of the mole is φ. When it is more than the lower limit 値, it can form a pattern when it is a photoresist composition, and it can balance with other structural units when it is below the upper limit 値. • Structural unit (a2) The resin component (A), in addition to the above structural unit (al), may further comprise a structural unit (a2) derived from an acrylate having a monocyclic or polycyclic group containing a lactone. The monocyclic or polycyclic group containing a lactone of the structural unit (a2) can effectively improve the adhesion of the photoresist film to the substrate in the case where the resin φ component (A) component is used to form the photoresist film. Hydrophilicity with the developer, and the like. Further, the monocyclic or polycyclic group containing a lactone at this time is intended to contain a ring group of a ring of the -o-c ( 〇 )- structure. The lactone ring is counted as a ring unit, and in the case of a lactone ring, a monocyclic group is used. When it has other ring structures, it is called a polycyclic group regardless of its structure. The structural unit (a2) may be any one as long as it has the structure (-0-C ( 〇 )-) of the above lactone and a ring group. -28- (24) 1304153 Specifically, a monocyclic group containing a lactone, for example, a radical of which one hydrogen atom is removed by r-butyrolactone, and a polycyclic group containing a lactone, for example, A group obtained by removing one hydrogen atom from a bicycloalkane, a tricycloalkane or a tetracycloalkane of an ester ring. In particular, a group obtained by removing one hydrogen atom from a lactone-containing tricyclic alkane having the following structural formula is preferred from the viewpoint of industrial availability. [化2 0]

The structural unit (a2) is more specifically, for example, a structural unit represented by the following formulas (2a-1) to (2a-5). s)

•29- (25) 1304153

Wherein R has the same content as described above, and R' is a hydrogen atom, a lower alkyl group, or an alkoxy group having 1 to 5 carbon atoms, and m is 0 or 1]. In the formulae (2a-1) to (2a-5), the lower alkyl group content of R' is, for example, the same as the lower alkyl group of R' in the above structural unit (al). Among the formulae (2a-1) to (2a-5), R' is preferably a hydrogen atom from the viewpoint of easy industrial availability. The specific structural units of the above formulae (2a-1) to (2a-5) are as follows: -30-(26) 1304153 [Chem. 2 2] -f〇H-ChV. 4

CH3M γπ3 CH step J)

-CH—CH^-H (32-1-2) ch3 ΪΗ—cV〇4 ,° ch3 ch3 (a2-1-3) CH3 −^CH—cV〇4 , Q’ 〇

O ffH3 〇^> (a2-1-4) (a2-1-5) (a2-1^6) [Chemical 2 3] CH3 0= #

(a2-2-3) (a2-2-1) ° <a2-2-2> 〒H3 CH3 -(CH-C)- -{CH-C)- °=\ o=4 9h3

(a2-2-5)

Sj -31 - 1304153 · (27) [Chem. 2 4]

0= ο γπ3

Ch3

(a2-3*5) -CH — CH_

Ch3 as H

(a2-3-9) - 32- (28)1304153 [Chem. 2 5]

-33- (29) 1304153 [Chem. 2 6]

In the formulae (2a-1) to (2a-5), R' is preferably a hydrogen atom from the viewpoint of industrial impregnation. Among them, it is preferred to use at least one of the formulae (a2-l) to (a2-5). It is more preferable to use at least one of the formulae (a2-l) to (a2-3). Specifically, at least one of the formulas (1), (a2-l-2), (a2-2-l), (a2-2-2), (a2-, (a2-3-2)) is used. , (a2-3-9) and (a2-3-10) selected; i resin component (A), structural unit (a2) can be used alone to obtain the selected d 2 -1 - 3-1丨The best one is -34- (30) 1304153, or two or more types can be used in combination. The ratio of the structural unit (a2) in the resin component (A) is preferably from 5 to 60 mol%, and from 15 to 50 mol%, based on the total of the total structural units constituting the resin component (A). Preferably, it is preferably from 25 to 50% by mole. When it is above the lower limit ,, the structural unit (a2) is more effective, and when it is below the upper limit, it can be balanced with other structural units.

In the present invention, it is more preferable that the resin component (A) is a copolymer obtained by having both the above structural unit (a 1 ) and the structural unit (a2) to enhance the effects of the present invention. • Structural unit (a3) In the resin component (A), in addition to the above structural unit (a), or in addition to the structural units (al) and (a2), an aliphatic hydrocarbon group having a polar group may be further contained (α - The structure φ position (a3) derived from the lower alkyl) acrylate is preferred. When the structural unit (a3) is contained, the hydrophilicity of the polymer compound (A) can be improved, and the affinity with the developer can be improved, and the alkali solubility of the exposed portion can be improved to improve the resolution. The polar group is, for example, a hydroxyalkyl group in which a part of a chlorine atom of a group, an amino group, a benzyl group or a fluorenyl group is substituted with a fluorine atom, and a hydroxyl group is preferred. The aliphatic hydrocarbon group 'e.e., a linear or branched hydrocarbon group having 1 to 1 carbon atoms (preferably an alkylene group), or a polycyclic aliphatic hydrocarbon group (polycyclic group) or the like. The polycyclic group is, for example, a resin which can be used for a composition for a photoresist for an ArF excimer laser, and is appropriately selected from the contents of most proposals. Further, a structural unit derived from an aliphatic enoic acid ester having a hydroxyl group, a cyano group, a carboxyl group and a hydroxyalkyl group substituted with a fluorine atom is more preferable. Removal of the poly-cycloalkane, tricycloalkane, tetracycloalkane

Get the base and so on. Specifically, for example, a group obtained by a polycyclic alkane such as adamantane, tricyclodecane or tetracyclododecane is used. The polycyclic group may be appropriately selected from the group consisting of a polymer (resin component) for the ArF φ composition. In the polycyclic group, the base of the above hydrogen atom, the base of the raw spinel which removes two or more nuttes, and the base of which two or more hydrogen atoms are removed are more suitable for the structural unit (a3), and the hydrocarbon group having a polar group is carbon. When the structural unit derived from the linear or branched hydroxyethyl ester of 1 to 10 is a good group, for example, the structural unit φ structural unit represented by the following formula (a3 -1), (a3-3) Show structural units, etc. Or a polycyclic group of a hydrogen atom of a hospital base, and a propylene ring group, for example, a spine of two or more hydrogen atoms, a pyrene, an isopentane, and a laser having one or more hydrogen atoms excimer laser In the content of the proposal, two of the King Kong Institutes were removed, and the atomic base and the fourth ring were used in the industry. In the case of a halogenated hydrocarbon group in the aliphatic hydrocarbon group, it is represented by a polycyclic ring, and the hydrocarbon group is represented by (a3-2) -36- (32) 1304153.

OH (a3-3) (wherein the content of R is the same as the above, j is an integer from 1 to 3, k is an integer from 1 to 3, t' is an integer from 1 to 3, and 1 is an integer from 1 to 5. , s is an integer from 1 to 3.)

In the formula (a3-l), it is preferable that j is 1 or 2, and 1 is more preferable. In the case where j is 2, it is more preferable that the hydroxyl group is bonded to the 3 and 5 positions of the adamantyl group. In the case where j is 1, the hydroxy group is bonded to the 3 position of the adamantyl group. In the formula (a3-2), it is preferred that k is one. Further, it is preferred that the cyano group is bonded to the 5- or 6-position of the original spinnyl group. In the formula (a3-3), it is preferable that t' is one, and one is preferably one, and s is one. It is preferably a compound in which a terminal of a carboxyl group of acrylic acid is bonded to a 2-pyrrolidyl group or a 3-n-spinylalkyl group. The fluorinated alkyl alcohol is preferably bonded to the 5 or 6 position of the original spinnyl group. The structural unit (a3) may be used singly or in combination of two or more types -37- 8 (33) 1304153. When the resin component (A) has a structural unit (a3), the ratio of the structural unit (a3) in the resin component (A) is 5 to 50 mol% with respect to the entire structural unit constituting the resin component (A). Preferably, it is preferably 15 to 4 5 旲 ear %, and preferably 15 to 35 旲 ear %. • Structural unit (a4)

The resin component (A) may further contain other structural units (a4) other than the above structural units (a1) to (a3) insofar as the effects of the present invention are not impaired. The structural unit (a4) is not particularly limited as long as it is a structural unit that is not classified into the structural units (a1) to (a3). It is possible to use a conventionally known structural unit used for a photoresist composition such as ArF excimer laser or KrF excimer laser (preferably for ArF quasi-mineral laser). The structural unit (a4), for example, contains an aliphatic polycyclic group which is not acid-dissociable, and a structural unit derived from an acrylate or the like is preferred. The polycyclic group is, for example, the same as exemplified in the above structural unit (al), and can be used for ArF excimer laser or KrF excimer laser (preferably for ArF excimer laser). Most of the structural units previously known for use in the resin composition of the photoresist composition. In particular, when at least one selected from the group consisting of a tricyclodecylalkyl group, an adamantyl group, a tetracyclododecyl group, an iso-spinyl group, and a raw spine group is industrially preferable, it is preferable. The polycyclic group may be substituted by a linear -38-(34) 1304153- or branched alkyl group having 1 to 5 carbon atoms. Specifically, the structural unit (a4) is, for example, a structural unit represented by the following formulas (a4-1) to (a4-5). [化2 8]

(wherein R has the same content as described above). The structural unit (a4) is not an essential component of the resin component (A >, which is contained in the resin component (A), and constitutes the present invention. The total structural unit of the resin component (A), the structural unit (a4) is preferably from 1 to 30 mol%, more preferably from 1 to 20 mol%. Resin component (A), for example The monomer (35) 1304153 derived from each structural unit is obtained, for example, by a polymerization reaction using a radical polymerization initiator such as azobisisobutyronitrile (AIBN) by a known radical polymerization or the like. Structural unit (Μ 1 ) Further, the resin component (Α) is a terminal structure having a hydroxyl group bonded to a carbon atom at the terminal of the polymer, and a carbon atom having at least one electron attracting group at the α position of the hydroxyl group is good.

The aforementioned electron attracting group is, for example, a halogen atom or a halogenated alkyl group. A halogen atom such as a fluorine atom, a chlorine atom or the like is preferably a fluorine atom. In the halogenated alkyl group, the halogen is, for example, the same as the aforementioned halogen atom. The number of carbon atoms of the alkyl group is preferably, for example, a lower alkyl group of about 1 to 3, more preferably a methyl group or an ethyl group, and most preferably a methyl group. Specifically, for example, a trifluoromethyl group, a difluoromethyl group, a monofluoromethyl group, a perfluoroethyl group or the like is preferable, and a trifluoromethyl group is particularly preferable. The number of electron attracting groups is 1 or 2, and 2 is preferred. a carbon atom having a bond to a carbon atom, and having a carbon atom at the alpha position of the hydroxyl group, having at least one electron attracting group, more specifically and suitable, for example, having a -CRiR^H group, and R1 and R2 are each independently an alkane a group, a halogen atom, or a halogenated alkyl group, and at least one of which is an electron attracting group selected from a halogen atom or a halogenated alkyl group. The aforementioned halogen atom, or halogenated alkyl group, for example, is the same as described above. The alkyl group is a lower alkyl group such as a methyl group, an ethyl group or a propyl group. Among them, the electron attracting group is preferably a fluorine atom or a fluorinated alkyl group as described above, and in particular, those in which R1 and R2 are each a fluorinated alkyl group are more preferable, and a trifluoromethyl group is preferred. Its -40-(36) 1304153 is better in synthesis or has the effect of reducing LER (Line Edge Roughness).

In the resin component (A), the proportion of the structural unit (Μ 1 ) having a polymer terminal bond-CWVOH group (hereinafter referred to as the "end structure") is used to constitute the resin component (A). In the entire structural unit, it is preferable that the total number of structural units other than the structural unit (Μ 1 ) is 1 mol% or more (preferably 2 mol% or more). Further, the total of the structural units other than the structural unit (Μ 1 ) includes, for example, a structural unit derived from a known polymerization initiator such as azobisisobutyronitrile (ΑΙΒΝ) used in radical polymerization or a main component of a resin. The unit derived from the monomer. The upper limit is not particularly meaningful, and the practical degree due to the production method or the like is, for example, 5 mol% or less. Further, when it is 1 mol% or more, the end effect is introduced, so that development defects can be reduced or the effect of improving LER can be improved. When it is below the lower limit 値, the effect will be degraded. Further, of course, the number of moles of the structural unit (Μ 1 ) is equal to the number of moles of the terminal structure and the number of moles of the hydroxyl group. This terminal structure can be introduced into the polymer terminal by adding a chain transfer agent having a -CRifOH group, for example, by radical polymerization of a monomer and a polymerization initiator to form a polymer. At this time, the structural unit (Μ 1 ) having the terminal structure is a structural unit (Μ 1 ) derived from the chain transfer agent. The chain transfer agent is represented, for example, by the formula "X-R'-CVWOH". In the formula, X is a hydroxyl group or a thiol group. The chain transfer agent is bonded to a polymer terminal by dissociating a hydrogen atom of a hydroxyl group or a thiol group. Therefore, at this time, -41 - (37) 1304153, the structural unit (Ml) is a unit of "X-R'-CWl^OH" in which a hydrogen atom is removed from a hydroxyl group or a thiol group of X. Further, from the viewpoint of reactivity and the like, * 'X is preferably a thiol group. Further, R' in "X-R'-CWi^OH" is a divalent aliphatic hydrocarbon group (which may be linear, branched, or cyclic) or a divalent aromatic hydrocarbon group, wherein A linear or branched aliphatic hydrocarbon group is preferred. The alicyclic group is, for example, a cyclohexylene group, and the aromatic hydrocarbon group is, for example, P-phenylene φ or the like. A linear or branched aliphatic hydrocarbon group, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, etc., and an ethyl group and a propyl group are preferred. Preferred chain shifting agents are, for example, SH-(CH2)m-C(CF3)2-OH (m is an integer from 2 to 4). Among them, a preferred structural unit (Μ1) is, for example, -S-(CH2) m-C(CF3)2-ΟΗ. The ratio of the end structure (the ratio of the structural unit (Μ 1 )), for example, the monomer amount of the feed or the amount of the chain transfer agent described above can be adjusted or the addition time of the chain φ transfer agent can be adjusted to adjust the photoresist composition. It is changed in such a manner that the mass average molecular weight of the resin. Further, in the resin for the photoresist composition after the synthesis, the number of moles of the terminal structure (the number of moles of the structural unit (Ml)) can be determined, for example, by NMR (nuclear magnetic resonance spectroscopy) such as proton-NMR or carbon NMR. . The mass average molecular weight (Mw) of the resin component (A) (the polystyrene conversion standard of the gel permeation chromatography method) is not particularly limited, and is generally preferably from 2,000 to 50,000, more preferably from 3,000 to 30,000. 5,000 to 2,000 is the best. Below the upper limit of the range, when used as a photoresist, -42-(38) 1304153 can exhibit sufficient solubility to a photoresist solvent, and when it is greater than the lower limit of the range, excellent dry etching resistance or excellent light can be obtained. Obstructed cross-sectional shape. Further, the degree of dispersion (Mw/Mn) is preferably from 1.0 to 5.0, more preferably from 1. to 3.0, most preferably from 1.2 to 2.5. <Acid generator component (B) > In the present invention, the φ key salt acid generator (B 1 ) having the cation portion represented by the above formula (b-Ι) is used, and the above formula (b-2) is used. The sulfonate-based acid generator (B2) of the structure shown is an essential component. • (B 1 ) Component In the above formula (b-Ι), R1" is an alkyl group, an alkoxy group, a halogen atom, or a hydroxyl group, and η is an integer of 0 or 1 to 3. When n is 2 or 3, the plural R1" may be the same or different from each other.

The alkyl group of the above R1" is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, a η-butyl group or a tert-butyl group. The alkoxy group of the above R1". Preferably, the alkoxy group having 1 to 5 carbon atoms is preferred, and the methoxy group and the ethoxy group are more preferred. The halogen atom of R1" is preferably a fluorine atom. The η is preferably 0 or 1, and more preferably 〇. In the above formula (b-Ι), R2" and R3" may each independently have The aryl group or the alkyl group of the substituent. The aryl group of R2,,, R3, is not limited, and may be, for example, an aryl group having 6 to 2 carbon atoms, or a part of a hydrogen atom thereof in the aryl group or All may be alkyl, -43-(39) 1304153 decyloxy, halogen atom, substituted by kesi, or 'unsubstituted. aryl, from the viewpoint of inexpensive synthesis, to use carbon number 6 In particular, a phenyl group, a naphthyl group, etc., in the case where the hydrogen atom of the above aryl group is substituted, the content of the alkyl group as the substituent, for example, the alkyl group of the above R1" For the same. In the case where the hydrogen atom of the above aryl group is substituted, the content of the alkoxy group as the substituent is, for example, the same as the alkoxy group of the above R1".

In the case where the hydrogen atom of the above aryl group is substituted, the content of the halogen atom as the substituent is, for example, the same as the halogen atom of the above R1". The above-mentioned R2", R3" is not limited, for example, It is a linear, branched or cyclic alkyl group having a carbon number of 1 to 1 Torr. From the viewpoint of having excellent resolution, it is preferably 1 to 5 carbon atoms, specifically, for example, methyl group and ethyl group. Base, η-propyl, isopropyl, η-butyl, isobutyl, n-pentyl, cyclopentyl, hexyl, cyclohexyl, decyl, decyl, etc., have excellent resolution, or can be inexpensive From the viewpoint of synthesis and the like, for example, a methyl group or the like can be used. The above R2" and R3" are preferably both phenyl groups. (Β 1) The anion portion of the component is not particularly limited, and generally it can be used. A compound which is an anion moiety of a key salt acid generator can be used, for example, a formula of "R4" S〇T (R4" is a linear, branched or cyclic alkyl group or a fluorinated alkyl group). The anion moiety is an anion moiety represented by the following formula (b-3), an anion moiety represented by the following formula (b-4), and the like. 44- (40) 1304153

...(b-3)

...(b-4)

[wherein, X" is a C 2 to 6 alkyl group in which at least one hydrogen atom is replaced by a fluorine atom; Y", Z" are each independently a carbon number of at least one hydrogen atom substituted by a fluorine atom. In the above formula "R4" S03_", R4" is a linear, branched or cyclic or a fluorinated base. The alkyl group in the above R4" is a carbon number of 1. It is preferably 10, and the carbon number is preferably 1 to 8, and the carbon number is preferably 1 to 4. The cyclic alkyl group in the above R4" is a cyclic group represented by the above R2", R3", preferably having a carbon number of 4 to 15, a carbon number of 4 to 10, more preferably a carbon number of 6 to 10; Preferably, the fluorinated alkyl group in the above R4" is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 4. Further, the fluorination ratio of the fluorinated alkyl group (the ratio of fluorine atoms in the alkyl group) is preferably from 10 to 100%, more preferably from 50 to 100%. In particular, a substance obtained by substituting all of a hydrogen atom by a fluorine atom is preferably a linear or cyclic alkyl group or a fluorinated alkyl group which is more preferably R4" to enhance the strength of the acid. In 3), X" is a linear or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and the alkyl group has a carbon number of 2 to 6, preferably 3 to 5 carbon atoms. The best is carbon number 3. -45- (41) 1304153 In the above formula (b-4), Y" and Z" are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and the carbon of the alkyl group The number is from 1 to 1 Torr, preferably from 1 to 7 carbon atoms, and most preferably from 1 to 3 carbon atoms. The carbon number of the alkyl group of the X X group or the carbon number of the alkyl group of the Y" or Z" is preferably in the range of the above carbon number, and is preferably as small as possible because of good solubility to the resist solvent. Further, in the alkyl group of X" or the alkyl group of Y" or Z", the more the number of hydrogen atoms substituted by fluorine atoms is, the stronger the strength of the acid is. The ratio of the fluorine atom in the alkyl group or the alkyl group, that is, the fluorination rate is preferably from 70 to 100%, more preferably from 90 to 100%, most preferably the perfluoroalkylene group in which all the hydrogen atoms are replaced by fluorine atoms. Base or perfluoroalkyl. The anion portion of the component (B1) is preferably an anion moiety represented by the formula "R4" S03_", and R4" is preferably a fluorinated alkyl group. Preferred examples of the component (B1) are, for example, Shown below.

-46-

D (42) 1304153

Among them, at least one selected from the above chemical formulas (bl-oi) to (b1-06) is preferably used. (B2) component In the above formula (b-2), R21 is an organic group, and R22' is a monovalent organic group or a cyano group. In the present invention, the organic group is a group containing a carbon atom, and may contain an atom other than a carbon atom (e.g., a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.)). The organic group of R21' is preferably a linear, branched or cyclic alkyl or aryl alkane. The aforementioned alkyl group or aryl group may have a substituent. The substituent is not limited to -47-(43) 1304153, and may be, for example, a fluorine atom, a linear or cyclic alkyl group having 1 to 6 carbon atoms, or the like. Here, "having a substituent" means that a part or all of an alkane hydrogen atom is replaced by a substituent. The ‘· alkyl group preferably has a carbon number of 1 to 20, preferably 1 to 1 carbon atoms, 1 to 8 carbon atoms, and most preferably 1 to 6 carbon atoms. Alkyl groups, especially those which are partially or fully halogenated, are also referred to as halogenated alkyl groups. Further, the meaning of an alkyl group in which a partially halogenated alkyl φ moiety is substituted by a halogen atom means completely an alkyl group in which a hydrogen atom is entirely substituted by a halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, An atom such as an iodine atom is preferred. That is, the halogenated alkyl group is preferably a fluorinated alkyl group. The aryl group is preferably a carbon number of 4 to 20, more preferably a carbon number of 4 to: and a carbon number of 6 to 10. The aryl group is particularly preferably a partially aryl group. Further, the partially halogenated aryl group means the meaning of the aryl group substituted by the halogen atom of the hydrogen, and the aryl group obtained by completely replacing the halogenated atom of the aromatic φ atom with a halogen atom. R21' is particularly preferably a fluorinated alkyl group having 1 to 4 carbon atoms and 1 to 4 carbon atoms which have no substituent. The organic group of R22' is preferably a linear, branched or cyclic or hydrocarbon group. The alkyl group or the aryl group of R22' is, for example, the same as the above-mentioned alkyl group or aryl group. R22' is particularly preferably a cyano group, a carbon number group having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms. (B2) component, more preferably, for example, the following formula (B-2) is preferably a carty, branched or aryl group, and has a carbon number of 1 to 4 alkyl groups (hereinafter, referred to as a hydrogen halide halogenated hospital) The halogen atom is particularly preferably a fluorine atom or a part of a complete halogen atom, and refers to an alkyl group of hydrogen, or an alkyl group of 1 to 8 exemplified by a fluorenyl group and an aryl group R21'. 3)

-48- (44) 1304153 shows compounds and the like. (B-2) R32—Q=N—OS〇2- R33 R31 [In the formula (B-2), R31 is a cyano group, an unsubstituted alkyl group or a halogenated alkyl group; R32 is an aryl group; R33 is an alkyl group having no substituent or a halogenated alkyl group]

[Chemical 3 2] R35· -C=N—Ο—S02 - R36 R34 [In the formula (B-3), R34 is a cyano group, an unsubstituted alkyl group or a halogenated alkyl group; and R35 is a 2 or 3 valence. An aromatic hydrocarbon group; R36 is an alkyl group or a halogenated alkyl group having no substituent, and P is 2 or 3].

In the above formula (B-2), the unsubstituted alkyl group or the halogenated alkyl group of R31 is preferably a carbon number of 1 to 1 Torr, and a carbon number of 1 to 8 is more preferably 'carbon number 1 to 6 optimal. R31 is preferably a halogenated alkyl group, and more preferably a fluorinated alkyl group. The fluorinated alkyl group in R31 is preferably one in which the hydrogen atom in the alkyl group is fluorinated by 50% or more, more preferably 70% or more, and more preferably 90% or more of the fluorinated one. An aromatic group of R32, such as phenyl or biphenylyl, fluorenyl, naphthyl, anthracyl, phenanthroline, etc. -49-(45) 1304153 A group in which one hydrogen atom is removed, and a heteroaryl group in which a part of a carbon atom constituting the ring of the above-mentioned group is substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. Among them, the base is better. The aryl group of R32 may have a substituent such as an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group or an alkoxy group. The alkyl group or the halogenated alkyl group in the substituent is preferably a carbon number of 1 to 8, more preferably a carbon number of 1 to 4. Further, the halogenated alkyl group is more preferably a chlorinated base.

The alkyl group or the halogenated alkyl group having no substituent of R33 is preferably a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, and most preferably a carbon number of 1 to 6. R33 is preferably a halogenated alkyl group, more preferably a fluorinated alkyl group. The fluorinated alkyl group in R33 preferably has a hydrogen atom in the alkyl group of 50% or more, more preferably 70% or more, and when it is fluorinated by 90% or more, the acid produced can be improved. Better. The most preferred is a perfluorinated alkyl group in which the hydrogen atom is 100% replaced by fluorine. In the above formula (B-3), the unsubstituted alkyl group or the halogenated φ alkyl group of R34 is, for example, the same as the unsubstituted alkyl group or the halogenated alkyl group represented by the above R31. The aromatic hydrocarbon group of 2 or 3 of R35, for example, a group in which one or two hydrogen atoms are further removed from the aryl group of the above R32. The unsubstituted alkyl group or the halogenated alkyl group of R36 is, for example, the same as the unsubstituted alkyl group or the halogenated alkyl group represented by the above R33, and p is preferably 2. (B) Specific examples of the composition, such as α-(ρ-toluenesulfonyloxyimido)--50-(46) 1304153 cyanide, α-(ρ-chlorophenylsulfonate) Amine 3 benzyl cyanide, α - (4-nitrophenylsulfonyloxyimido)-benzyl cyanide, α-(4-nitro-2-trifluoromethylbenzenesulfonyloxyimido) -benzyl cyanide', α-(phenylsulfonyloxyimido)-4-chlorobenzyl cyanide, α-(nonoxyimino)-2,4-dichlorobenzyl cyanide, α -(phenylsulfonylamino)-2,6-dichlorobenzyl cyanide, α-(phenylsulfonyloxyimide 3 ' 4-methoxybenzyl cyanide, α - (2-chlorophenyl) Sulfomethoxyimine, methoxybenzyl cyanide, α-(phenylsulfonyloxyimido)-thien-2-carbonitrile, α-(4-dodecylbenzenesulfonyloxyimido) )-Benzyl cyanide [(ρ-toluenesulfonyloxyimido)-4-methoxyphenyl]acetonitrile, α·[dialkylbenzenesulfonyloxyimino)-4-methoxybenzene Acetonitrile, α-(phenylsulfonyloxyimido)-4-thyl cyanide, α-(methylsulfonylamino)-1-cyclopentenylacetonitrile, α-(methylsulfonate Oxyimido)·hexenylacetonitrile, α-(methylsulfonyloxyimido 1-cycloheptenyl, α-(methylsulfonyloxyimido)-1-cyclooctenylacetonitrile, α-( φ methylsulfonyloxyimino)-1-cyclopentenylacetonitrile , α-(trifluoromethane oxyimino)-cyclohexylacetonitrile, α-(ethylsulfonyloxyimido: . acetonitrile, α-(propylsulfonyloxyimino)-propyl acetonitrile , sulfoximine oxyimino)-cyclopentylacetonitrile, ^-(cyclohexylsulfonyloxy)-cyclohexylacetonitrile, α-(cyclohexylsulfonyloxyimino)-1-cycloacetonitrile, α -(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile (isopropylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(η-sulfonyloxyimino) )-1-cyclopentenylacetonitrile, ethylsulfonyloxy)-1-cyclohexenylacetonitrile, α-(isopropylsulfonyloxyimino) i)-formate benzenesulfonate £ ) )_4_ base B, a - (deca-methoxy- 1-cycloacetonitrile trifluorosulfonate)-ethylcycloheximide pentene, a-butylimine-1 -cyclo-51 - (47) 1304153 hexene Acetonitrile, α-(η-butylsulfonyloxyimido)-1-cyclohexenylacetonitrile, α-(methylsulfonyloxyimino)-phenylacetonitrile, α-(methylsulfonate Oxyimine )-Ρ-methoxyphenylacetonitrile, α-(trifluoromethylsulfonyloxyimido)-phenylacetonitrile, α-(trifluoromethylsulfonyloxyimino)-fluorene-methoxy Phenylacetonitrile, α-(ethylsulfonyloxyimido)-fluorene-methoxyphenylacetonitrile, α-(propylsulfonyloxyimido)-indole-methylphenylacetonitrile, α -( Methylsulfonyloxyimido)-indole-bromophenylacetonitrile and the like.

Further, for example, the following compounds and the like.

-52- (48) 1304153 [Chemical 3 3] CH3—02s—ο- C=N—O—S〇2—CH3

NC

CN

C=N—O—S〇2 C4H9

CF3—O2S—〇-N= , .<y C=N—0—S〇2—CF3

NC

CN t

CF3〇2S—〇—N=C CN

CH30 0&quot;—C=N-0~S〇2—< OCH3

NC CN3-CN-〇S〇2-(CH2)3CH3 CH3-C=N-OS〇2-(CH2)3CH3 •53- (49) 1304153 Further, the above formula (B-2) or (B-3 Among the compounds shown, preferred compounds are shown below. 【化34】

^ ^~s~^ Ο—S02—CF3

C3F7 C —N_0~S〇2—CF3 C3F7 C=N—O—SO2—CF3 C3F7 Ο

C3F7 C-^N—O—S〇2—CF3

(CH2)3 o

0—S〇2—CF3 C3F7 CF3-C—N—O—S〇2—C4F9-54- (50) 1304153 【化3 5】

C=N一Ο—S〇2—CF3(CF2&gt;6—Η C=NΟ—S〇2—C4F9 (CF2)6—Η

^〇-^rN-〇-S〇2-CP3

(CF2)6—Η

C*=N_O—S〇2—CF3 (CF2)s-H C-N—〇—S02—C4F9 (CF2)6-H —0—S02—CF3 (CF2)6~H

(CF2)6—Η ^ O—S02—CF3

(CF2)6—H - O—S02 - C4F9 (CF2)6—η

=N-O-S02 - CF3 (CF2)6-H

Among the above exemplified compounds, the following three compounds are more preferable. -55- (51)1304153 【化3 6】 C4H9 一〇2S—Ο—Ν·

C=N一〇一〇S〇2—C4H9 CN 【化3 7】CH3- C=N-〇S〇2&quot;(CH2)3CH3 CH3- C:M-OS〇2** (CH2 )3 CH 3

[化3 8]

C=N—0—S02~C4F9 i (cf2)6—h

In the positive resist composition of the present invention, the mass ratio (B 1 ) of the content of the component (B 1 ) : ( B 2 ) is preferably 1 0 : 9 0 : 2 5 : 7 5 to 7 5 · · 2 5 is better, with 4 0 : 6 0 : Best. (B 1 ) The composition of (B 1 ) is higher than the mass of (B2 ) by the above-mentioned vanishing pattern shape, EL shift, and dimensional fidelity, and the (B 1 ) component of each of the positive resist compositions of the present invention is (A) 100 parts by mass of the component may be obtained by containing 1 to 10 parts by mass, preferably 3 to 7 parts by mass, and more preferably 5 to 7 parts by mass, based on the lower limit of the above range. Further, when scum generation is suppressed and a good shape can be obtained, the upper limit of the circumference is preferably 値 or less. ••(b2~01) and (B 2 ) are g 90 : 1〇 When g 60 : 40 is inside, it can be characterized. The content is relatively good, and the content is optimal. (To a sufficient effect, the content of the (B2) component in the positive resist composition of the above invention is relative to -56-(52) 1304153 in the (A) component of 100 parts by mass to contain 1 to 1 part by mass. Preferably, it is more preferably 2 to 8 parts by mass, and most preferably 3 to 7 parts by mass. ( Β 2 ) The content of the component is more than or equal to the lower limit 上述 of the above range. Further, the present invention is positive. When the type of the photoresist composition is excellent in coating properties, it is preferably at most the upper limit of the above range.

In the present invention, the (Β) component may contain one or more kinds of the above ( Β 1 ) component and the acid generator component other than the component (Β2). The other acid generator component is not particularly limited, and a material which has been proposed so far as an acid generator for enhancing chemical resistance can be used. For example, a key salt acid generator such as an iodine salt or a phosphonium salt which is not contained in the above ( Β 1 ) component and (Β2 ) component, an oxime sulfonate acid generator, a dialkyl or a bisarylsulfonyl group Diazomethane acid generator such as diazomethane or poly(disulfonyl)diazomethane, nitrobenzyl sulfonate acid generator, and iminosulfonate acid generator A variety of known compounds such as diterpenoid acid generators. The total content of the (Β) component in the positive resist composition of the present invention is preferably from 2 to 20 parts by mass, based on 1 part by mass of the (Α) component, and is contained in an amount of from 5 to 15 parts by mass. More preferably, it is preferably from 8 to 14 parts by mass. When it is within the above range, the formation of the pattern can be sufficiently performed, and a good effect can be obtained. It is also possible to obtain a homogeneous solution, which is better with good preservation stability. (Β) In the total measurement of the components, the ratio of the (Β 1 ) component to the (Β 2 ) component is preferably 50% by mass or more, and more preferably 75% by mass or more by 100% by mass. optimal. -57- (53) 1304153 &lt;Nitrogen-containing organic compound (D) &gt; In the positive resist composition of the present invention, the shape of the resist pattern is improved, and the stability over time (p 〇ste) When X ρ 〇surestabi 1 ity 0 fthe • latent image formed by the pattern-wise exposure of the resist layer), a nitrogen-containing organic compound (D) of any composition may be further added. ^ This (D) component, there are proposals for various compounds, and it is also possible to use any of the known ingredients, generally using an aliphatic amine, particularly a secondary aliphatic amine or a tertiary aliphatic amine.

An aliphatic amine such as an amine (alkylamine or alkanolamine) obtained by substituting at least one hydrogen atom of ammonia nh3 with an alkyl group having 1 or less carbon atoms or a hydroxyalkyl group. Specific examples thereof include monoalkylamines such as η-hexylamine, η-heptylamine, η-octylamine, η-decylamine, η-decylamine; diethylamine, di-n-propylamine, a dialkylamine such as di-η-heptylamine, di-η-octylamine or dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, di-n-butyl Amine, di-n-hexylamine, tri-n-pentylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-decylamine, tri-n-decylamine, three a trialkylamine such as η-dodecylamine; an alkanol such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-η-octanolamine or tri-n-octanolamine amine. Among them, an alkanolamine and a trialkylamine are preferred, and an alkanolamine is preferred. Among the alkanolamines, triethanolamine or triisopropanolamine is preferred. They may be used alone or in combination of two or more. (D) The component (A) component is 1 〇 〇 by mass, and is usually used in the range of 0.01 to 5.0 parts by mass. -58- (54) 1304153 &lt; (E) Component&gt; * Further, the positive-type positive-resistance composition of the present invention is used to prevent deterioration of sensitivity caused by the addition of the above-mentioned (D) component, or to enhance photoresist For the purpose of post exposure stability of the latent image formed by the pattern-wise exposure of the resist layer *, an optional organic carboxylic acid or phosphorus oxyacid or

φ Its derivative (E) (this specification is also referred to as (E) component). Further, the component (D) may be used in combination with the component (E), or any one of them may be used alone. An organic carboxylic acid such as malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid or the like is preferred. Phosphorus oxyacid or its derivative, such as phosphoric acid, di-n-butyl phosphate, diphenyl phosphate and other derivatives such as phosphoric acid or its ester, phosphonic acid (ph〇sph〇nic acid), dimethyl phosphonate , phosphonic acid-di-n-butyl ester, phenylphosphonic acid, phosphonyl 9 diphenyl ester, dibenzyl phosphonate and other derivatives such as phosphonic acid and its ester, phosphinic acid (

Phosphinic acid), phosphinic acid such as phenylphosphinic acid and phosphinic acid such as ester thereof. Derivatives, of which phosphonic acid is preferred. (E) The component is generally used in an amount of from 1 to 5.0 parts by mass per 100 parts by mass of the component (A). &lt;Organic solvent&gt; The positive resist composition of the present invention can be produced by dissolving a material in an organic solvent.

-59- (55) 1304153 An organic solvent is used as long as it can dissolve the components to be used. For example, a known solvent which is conventionally used as a reinforced chemical resist solvent can be used. Use two or more types. • the above solvents such as lactones such as r-butyrolactone, or ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoethyl Acid ester, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, or dipropylene glycol monoacetate monomethyl φ ether, monoethyl ether, monopropyl Polyols such as ether, monobutyl ether or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, acetic acid An ester such as ester, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate or ethyl ethoxypropionate. The organic solvent may be used singly or in combination of two or more kinds. . Further, a mixed solvent obtained from propylene glycol monomethyl ether acetate (PGMEA) and a polar φ solvent is preferably used, and the addition ratio (mass ratio) can be appropriately determined depending on the compatibility of PGMEA with a polar solvent. Yes, preferably • is from 1:9 to 9:1, more preferably from 2:8 to 8:2. More specifically, the polar solvent is ethyl lactate (EL) _, and the mass of PGMEA · EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2 〇, in an organic solvent Further, for example, it is preferred to use at least one mixed solvent of 7-butyrolactone selected from PGMEA and EL φ. At this time, the ratio of the former to the latter is 70:30 to 9.5:5.

-60- (56) 1304153 The amount of the organic solvent to be used is not particularly limited, and may be appropriately selected in accordance with the concentration applied to the substrate, the thickness of the coating film, etc., and generally can be solid in the photoresist composition. The concentration of the component is from 2 to 20% by mass, preferably from 5 to 15% by mass. • Other optional components The positive-type positive-resistance composition of the present invention can be further compounded with φ plus a mixture of additives, for example, an additive resin which can improve the properties of the photoresist film. , dissolution inhibitors, plasticizers, stabilizers, colorants, halo inhibitors, dyes, and the like. &lt;Formation Method of Photoresist Pattern&gt; The method for forming the photoresist pattern of the present invention can be carried out, for example, by the following method. That is, the first positive-type photo-resistance composition of the present invention is coated on a substrate of a chopped wafer, using a spin coater or the like, and subjected to a temperature of 80 to 丨5 〇, for 40 to 12 seconds, preferably 6 〇 to 90 seconds pre-cooked to form a photoresist film. Subsequently, the ArF excimer laser is selectively exposed to the desired reticle pattern by using, for example, an ArF exposure apparatus or the like, and then subjected to a temperature of 80 to 150 ° C. 0 to 120 seconds, preferably 60 to 90 seconds of PEB (post-exposure heating). Next, it is subjected to development treatment using, for example, a tetramethylammonium hydroxide aqueous solution of a developing solution of, for example, 〇·1 to 10% by weight. It can be combined with the necessity of wet -61 - (57) 1304153 after development and then burned. After this processing step, the same photoresist pattern as the reticle pattern can be faithfully produced. Further, an organic or inorganic antireflection film may be provided between the substrate and the coating layer of the photoresist composition. The wavelength for exposure is not specific. For example, ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet) ^, VUV (vacuum ultraviolet), EB (electronic line) can be used. Radiation such as X-rays and soft X-rays. Further, the photoresist composition of the present invention is particularly effective for ArF excimer lasers. The EL offset and dimensional fidelity can be effectively improved by using the positive resist composition of the present invention. Moreover, the pattern is not easily collapsed, and the line edge unevenness (L E R ) of the side surface of the wiring pattern is also uneven. Although the reason is not determined, it is presumed that the (B 1 ) component has an acid generator produced by a sulfonium salt of triphenylphosphine φ because the cation moiety has a substituent derived from naphthalene. When the components are compared, it can suppress the light absorption in the exposure wavelength band, so that when the exposure amount is the same, the amount of acid generated per 1 mole of the acid generator component can be suppressed. In particular, in the wavelength region of the ArF excimer laser, it is possible to effectively suppress the absorption of light (especially, the transparency of the ArF excimer laser light). In the present invention, when the component (B1) is used in combination with the component of the sulfonate-based acid generator (B2), the above-mentioned plural characteristics can be simultaneously achieved by the synergistic effect of the two. -62- (58) 1304153 [Embodiment] [Examples] ^ (Synthesis Example 1) • 2-Ethyl-2-adamantyl methacrylate, raw spinane lactone methacrylate, and 3- O.lmol of a mixture of hydroxy-1 -adamantane methacrylate is dissolved in 150 ml of THF (tetrahydrofuran), and then AIBN (4 mol% relative to the aforementioned monomer 1 mol%) is made at 70 At °C, φ starts the radical polymerization, and the chain transfer agent for the polymerization uses the compound represented by the following chemical formula: [Chem. 3 9] CF3 ---- CFa

Further, a polymerization reaction was carried out by adding 3 mol% to the total amount of AIBN in an amount of 100 mol% with respect to the monomer to be fed. After the end of the polymerization, the reaction solution was poured into 2000 ml of η-heptane, and stirred at 25 ° C for 30 minutes, and the precipitated solid was collected by filtration. This solid was dissolved again in 20 ml of THF, poured into 2000 ml of n-heptane, and stirred at 25 ° C for 30 minutes, and the precipitated solid was collected by filtration, and dried to give the resin A shown in the following chemical formula. In the following chemical formula, 'n/m/l = 40/40/20 (mole ratio). Resin A has a mass average molecular weight of 6,000 Å dispersion (mass average molecular weight / number average molecular weight) of 1.5 ° • 63- (59) 1304153 [Chem. 4 0: CH.

C2H5

OH

[Example 1] 6.0 parts by mass of the compound of the above formula (bl-ΟΙ) of the resin A obtained in Synthesis Example 1 in 100 parts by mass of the component (B), and 6.0 parts by mass of the compound represented by the above formula (b2-01) , (D) component of triethanolamine 0.4:5 parts by mass, dissolved in 7-butyrolactone (GBL) 25 parts by mass, and a mixture with propylene glycol monomethyl ether acetate (PM) and methyl pentanone (MAK) (mass ratio 8:2) to prepare a positive resist composition having a solid concentration of about 9 mass%. Next, the organic anti-reflection film composition "AR-46" (trade name, manufactured by Siplai Co., Ltd.) was applied onto a 8-inch wafer by a spin coater and 225 ° on a hot plate. After baking for 60 seconds at C, and drying, an organic antireflection film having a film thickness of 29 nm was obtained. Thereafter, the positive-type photoresist composition obtained above was uniformly applied onto the anti-reflection film using a spin coater, and then pre-baked (PAB) at 105 ° C for 60 seconds on a hot plate to be dried. A photoresist layer having a film thickness of 200 nm was obtained. -64- (60) 1304153 Next, the ArF excimer laser (• 193 nm) was interposed using an ArF exposure apparatus NSR-S 3 06 (manufactured by Ricoh Co., Ltd., NA (number of openings) = 0.78, 2/3 wheel). 6% half-tone mask is selected; sexual illumination. Subsequently, PEB treatment was carried out under conditions of 10 ° C for 60 seconds, and development was carried out for 60 seconds using an aqueous solution of 23 ° C and 2.38 mass % tetramethylammonium hydroxide, followed by washing for 20 seconds, and Vibrate and dry. Further, φ is further heated at 1 〇〇 ° C for 60 seconds, and after drying, a line and space pattern is formed (hereinafter referred to as L/S pattern). The following characteristics are evaluated. &lt;Sensitivity&gt; The most appropriate exposure amount for forming an 85 nm line and space (pitch of 180 nm) was measured as the sensitivity (EOP) in units of mJ/cm 2 (energy), and the results are shown in Table 1 below.

&lt;EL Offset&gt; The L/S pattern was measured in the range of the exposure amount in the range of the pattern size of 85 nm ± 10%, and the change amount of the pattern size per 1 mJ of the exposure amount was measured (EL offset; unit) :nm/mj ). The results are shown in Table 1 below. <Mask pattern linearity (m a s k - 1 i n e a r i t y ) &gt; The L/S pattern is formed using the line mask pattern of llOnm and 130 nm, and the MEF (mask error factor) is obtained by the following equation. -65- (61) 1304153 MEF= I CDiso-CDuo I / | MD130-MDi10 | - In the above formula, 'CD130 and CD11() each represent an L&S diagram formed using a mask pattern of l3〇nm and llOnm Type of photoresist pattern width (nm). MD13〇 and MDiio each indicate the width (nm) of the reticle pattern, MD130 = • 1 3 Ο, MD i! ο = 1 1 〇. It is a reticle pattern with different line widths. When using the same exposure amount of φ, whether the parameters of the pattern can be faithfully reproduced, and the closer the ME of the MEF is to 1, the better the linearity of the reticle pattern. The results are shown in Table 1 below. &lt;Graphic Collapse&gt; In the selective exposure, the exposure time is increased, and while the width of the accompanying pattern is gradually narrowed, the extent to which the pattern is collapsed is observed by SEM. The results are shown in Table 1 below.

&lt;LER&gt; For the 85 nm L/S pattern (pitch 180 nm) obtained in the above EOP, uneven line edge irregularities (LER) were formed on the surface of the wiring pattern sidewall, and the 3σ of the LER scale was obtained. In addition, 3σ is measured by using the length measuring SEM (product name "S-9220" manufactured by Hitachi, Ltd.), and 32 points of the resist pattern width of the sample are measured, and the standard error (σ) calculated from the result is 3 times. (3 σ ). The smaller the number of σ is, the smaller the unevenness of the edge of the line is, and the light resistance of -66-(62) 1304153 is obtained. The results are shown in Table 1 below. '* (Comparative Example 1)' In the above Example 1, the component (B) was changed to 6.0 parts by mass of the compound represented by the above chemical formula (b2-01), and triphenylphosphine nonafluorobutane sulfonate 2 In the same manner as in the above-described Example 1, the L/S pattern was formed in the same manner as in the above-mentioned Example 1, and the same evaluation of φ was performed. The results are shown in Table 1 below. Table 1 Example 1 Comparative Example 1 Sensitivity (mJ/cm2) 30 26 EL Deviation (nm/mJ) 4.86 8.5 MEF 0.45 0.29 Pattern collapse (nm) 49.8 55.3 ELR (nm) 9.7 10.6 -67-

Claims (1)

1304153 X. Patent Application No. 94141161 Patent Application Revision of Chinese Patent Application Revision Amendment of June 27, 1997 of the Republic of China 1 · A positive-type photoresist composition containing (A) increasing alkali by the action of acid a soluble resin component and (B) a positive photoresist composition which generates an acid generator component of acid φ by exposure, wherein the component (B) contains a cation having the following formula (b-Ι) a key salt acid generator (B1) and an oxime sulfonate acid generator (B2) having a structure represented by the following formula (b-2). Wherein R1, is an alkyl group, an alkoxy group, a halogen atom, or a thiol group; r2,, R3, is an independently aryl group or alkyl group which may have a substituent 〇 or 1 to Integer of 3] 1304153 [Chemical 2] Cr=N-Ο-S〇2—R21 [wherein R21' is an organic group; R22' is a monovalent organic group or a cyano group] wherein the content of the (B1) component is relatively The content of the component (B2) is from 1 to 10 parts by mass based on 100 parts by mass of the component (A), and the content of the component (B2) is from 1 to 10 parts by mass based on 100 parts by mass of the component (A). 2. The positive resist composition according to claim 1, wherein the mass ratio of the content of the component (B1) to the content of the component (B2) (Bl): (B2) is 10: 90 to 90. : 10. 3. The positive-type photoresist composition according to claim 1, wherein the component (A) is contained, the terminal of the polymer has a hydroxyl group bonded to a carbon atom, and the carbon atom at the α position of the hydroxyl group has at least 1 electronic attraction • Resin based resin. 4. The positive-type resist composition of claim 1, which contains 0.01 to 5 parts by mass of the nitrogen-containing organic compound (D) per 100 parts by mass of the (Α) component. A method for forming a photoresist pattern, comprising the step of forming a photoresist film on a substrate by using the positive photoresist composition according to any one of claims 1 to 4 to make the photoresist The step of film exposure, the step of developing the aforementioned photoresist film to form a photoresist pattern.