JP4940621B2 - Basic compound, radiation sensitive acid diffusion controller and positive radiation sensitive resin composition - Google Patents

Description

  The present invention relates to a basic compound, a radiation-sensitive acid diffusion controller, and a positive radiation-sensitive resin composition. More specifically, a novel basic compound suitable as a radiation-sensitive acid diffusion controller in a positive-type radiation-sensitive resin composition particularly useful for fine processing using various radiations such as deep ultraviolet rays, electron beams, and X-rays. The present invention also relates to a radiation-sensitive acid diffusion controller comprising the basic compound and a positive radiation-sensitive resin composition containing the radiation-sensitive acid diffusion controller.

In the field of microfabrication represented by the manufacture of semiconductor devices, further higher integration is progressing, and in recent years, a microfabrication technique capable of microfabrication at a level of less than 0.10 μm is required.
As a method for miniaturizing such a pattern, shortening of the wavelength of an exposure light source can be mentioned. Today, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength) are used from the g-line and i-line conventionally used. 193 nm), F ₂ excimer laser (wavelength 157 nm), or EUV (wavelength 13 nm, etc.).
On the other hand, with respect to photoresist materials corresponding to these processes, photoresists made of novolak resin and naphthoquinone diazide used for g-line and i-line are known. In this photoresist, the pattern becomes tapered due to strong absorption in the far ultraviolet region, and it is difficult to form a fine pattern. Further, since this photo resist has a low photosensitivity quantum yield of light reaction at the time of exposure of 1 or less, the life of the excimer laser oscillation gas is short, and it is used in a photo resist where the lens is easily damaged by the excimer laser. In this case, it becomes a problem from the viewpoint of the life of the lens.

Photoresists suitable for excimer lasers that solve these problems include a resin component that causes a chemical reaction with a change in solubility in a developer in the presence of an acid catalyst, and a radiation-sensitive acid generator that generates acid upon exposure. A number of chemically amplified photoresists containing benzene have been proposed.
Typical examples thereof include a resin component in which a phenolic hydroxyl group of polyhydroxystyrene is protected with an acid dissociable group such as an acetal group or a t-butoxycarbonyl group, and a triarylsulfonium salt typified by a triphenylsulfonium salt. A chemically amplified photoresist for a KrF excimer laser using a radiation-sensitive acid generator is widely known (for example, see Patent Document 1).

  On the other hand, as a chemically amplified photoresist for ArF excimer laser, a resin based on a polyhydroxystyrene skeleton used in KrF excimer laser is not suitable because of strong absorption at a wavelength of 193 nm. Therefore, resin components such as a (meth) acrylate resin having an alicyclic skeleton, a polymer of a norbornene derivative having an alicyclic skeleton in the main chain, and a copolymer of a norbornene derivative and maleic anhydride have been proposed (for example, , See Patent Document 2).

  On the other hand, Patent Document 3 discloses a cyclic sulfonium salt-type radiation-sensitive acid generator containing a substituted or unsubstituted naphthyl group and a radiation-sensitive resin composition using the same. It is clear that radiation-sensitive resin compositions using sulfonium salts having these structures show good performance in terms of transmittance at 220 nm and sensitivity, pattern shape and storage stability when used in ArF excimer lasers. Has been.

By the way, in the radiation sensitive resin composition using an acid generator, the acid generate | occur | produced by exposure spread | diffuses in a resist, and there exists a problem that a line edge roughness (henceforth "LER") characteristic falls. Therefore, attempts have been made to improve LER characteristics by adding 3-pyrrolidino (piperidino) -1,2-propanediol or the like to the radiation-sensitive resin composition.
However, the LER characteristic is not always sufficient, and further improvement of the LER characteristic has been desired.
JP 59-45439 A JP 2001-354669 A Japanese Patent Laid-Open No. 10-232490

  An object of the present invention is to provide a novel base suitable as a radiation-sensitive acid diffusion control agent in a positive radiation-sensitive resin composition useful for microfabrication using various radiations such as far ultraviolet rays, electron beams, and X-rays. A positive-type radiation-sensitive resin composition containing a radiation-sensitive compound, a radiation-sensitive acid diffusion control agent comprising the basic compound, and a radiation-sensitive acid diffusion control agent, and capable of expressing performance excellent in LER characteristics It is to provide.

〔一般式（Ｖ）において、Ｒは水素原子、メチル基、エチル基、フッ素原子又はトリフルオロメチル基を示す。Ｒｆはフッ素原子又はトリフルオロメチル基を示す。Ｒ ^１ 、Ｒ ^２ 、Ｒ ^３ 及びＲ ^４ は相互に独立に炭素数１〜４の直鎖状若しくは分岐状のアルキル基を示す。Ｒ ^５ はメチル基、エチル基又はプロピル基を示す。ｎは０〜３の整数である。Ｍ^＋はスルホニウムカチオン又はヨードニウムカチオンを示す。尚、Ｒ ^１ とＲ ^２ 、Ｒ ^２ とＲ ^３ 、Ｒ ^３ とＲ ^４ 、及び、Ｒ ^１ とＲ ^４ のうちの少なくとも１つの組合せが環を形成していてもよい。〕 As means for achieving the above object, the invention of claim 1
A basic compound comprising an onium salt represented by the following general formula (V) .

[In general formula (V) , R shows a hydrogen atom, a methyl group, an ethyl group, a fluorine atom, or a trifluoromethyl group. Rf represents a fluorine atom or a trifluoromethyl group. R ¹ , R ² , R ³ and R ⁴ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms. R ⁵ represents a methyl group, an ethyl group or a propyl group. n is an integer of 0-3. M ⁺ represents a sulfonium cation or an iodonium cation. Note that at least one combination of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , and R ¹ and R ⁴ may form a ring. ]

〔一般式（２）において、Ｒ^２、Ｒ^３及びＲ^４は相互に独立に置換若しくは非置換の炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、又は置換若しくは非置換の炭素数６〜１８のアリール基を示すか、或いは、Ｒ^２、Ｒ^３及びＲ^４のうちのいずれか２つ以上が相互に結合して式中のイオウ原子と共に環を形成している。尚、Ｒ^２、Ｒ^３及びＲ^４における置換基は、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基、ヒドロキシル基、カルボキシル基、オキソ基（即ち、＝Ｏ基）、炭素数１〜４のヒドロキシアルキル基、シアノ基、又は炭素数２〜５のシアノアルキル基である。〕 The invention of claim 2
The basic compound according to claim 1, wherein M ^{+ in the} general formula (V) is a sulfonium cation represented by the following general formula (2).

[In General Formula (2), R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon number. 6-18 aryl groups are shown, or any two or more of R ² , R ³ and R ⁴ are bonded to each other to form a ring together with the sulfur atom in the formula. ^{Incidentally,} the substituent in R 2, ^{R 3} and ^{R 4} are alkyl groups having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a hydroxyl group, a carboxyl group, an oxo group (i.e., = O group), carbon A hydroxyalkyl group having 1 to 4 carbon atoms, a cyano group, or a cyanoalkyl group having 2 to 5 carbon atoms. ]

〔一般式（３）において、Ｒ^５及びＲ^６は相互に独立に置換若しくは非置換の炭素数１〜１０の直鎖状若しくは分岐状のアルキル基、又は置換若しくは非置換の炭素数６〜１８のアリール基を示すか、或いは、Ｒ^５及びＲ^６が相互に結合して式中のヨウ素原子と共に環を形成している。尚、Ｒ^５及びＲ^６における置換基は、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基、ヒドロキシル基、カルボキシル基、オキソ基（即ち、＝Ｏ基）、炭素数１〜４のヒドロキシアルキル基、シアノ基、又は炭素数２〜５のシアノアルキル基である。〕 The invention of claim 3
The basic compound according to claim 1, wherein M ^{+ in the} general formula (V) is an iodonium cation represented by the following general formula (3).

[In General Formula (3), R ⁵ and R ⁶ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 18 carbon atoms. Or R ⁵ and R ⁶ are bonded to each other to form a ring together with the iodine atom in the formula. Incidentally, the substituent in ^{R 5} and ^{R 6} are alkyl groups having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a hydroxyl group, a carboxyl group, an oxo group (i.e., = O group), 1 carbon atoms 4 hydroxyalkyl group, cyano group, or cyanoalkyl group having 2 to 5 carbon atoms. ]

The invention of claim 4
A radiation-sensitive acid diffusion controller comprising the basic compound according to claim 1.

The invention of claim 5
(A) the radiation-sensitive acid diffusion controller according to claim 4;
(B) a radiation sensitive acid generator;
(C) an alkali-insoluble or hardly-alkali-soluble resin having an acid-dissociable group, which comprises an acid-dissociable group-containing resin that becomes alkali-soluble when the acid-dissociable group is dissociated. A positive-type radiation-sensitive resin composition.

〔一般式（４）において、Ｒ^７は水素原子又はメチル基を示す。各々のＲ^８は相互に独立に炭素数４〜２０の１価の脂環式炭化水素基若しくはその誘導体、又は炭素数１〜４の直鎖状若しくは分岐状のアルキル基を示し、且つ、Ｒ^８は以下の（１）又は（２）の条件を満たす。
（１）Ｒ^８のうちの少なくとも１つは炭素数４〜２０の１価の脂環式炭化水素基若しくはその誘導体である。
（２）いずれか２つのＲ^８が相互に結合して、それぞれが結合している炭素原子と共に炭素数４〜２０の２価の脂環式炭化水素基若しくはその誘導体を形成している。〕 The invention of claim 6
The positive radiation sensitive resin composition according to claim 5, wherein the (C) acid-dissociable group-containing resin contains a repeating unit represented by the following general formula (4).

In [general formula (4), R ⁷ represents a hydrogen atom or a methyl group. Each R ⁸ independently represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms, and R 8 ⁸ satisfies the following condition (1) or (2).
(1) At least one of R ⁸ is a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof.
(2) Any two of R ⁸ are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atom to which each R ⁸ is bonded. ]

〔式（ａ）、式（ｂ）、式（ｃ）において、各Ｒ^９は相互に独立に炭素数１〜４の直鎖状若しくは分岐状のアルキル基を示す。また、式（ｃ）において、ｍは０又は１である。〕 The invention of claim 7
The positive radiation sensitive resin composition according to claim 6, wherein —COOC (R ⁸ ) _{3 in the} general formula (4) is the following formula (a), (b), or (c).

[In Formula (a), Formula (b), and Formula (c), each R ⁹ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms. In the formula (c), m is 0 or 1. ]

〔一般式（５）において、Ｒ^１０は水素原子又はメチル基を示す。〕 The invention of claim 8
The positive radiation sensitive resin composition according to any one of claims 5 to 7, wherein the (C) acid dissociable group-containing resin further contains a repeating unit represented by the following general formula (5).

In [Formula ^{(5), R 10} represents a hydrogen atom or a methyl group. ]

  If a positive radiation-sensitive resin composition containing an acid diffusion controller composed of a basic compound of the present invention as an essential component is used, it is represented by actinic rays such as KrF excimer laser (wavelength 248 nm) or ArF excimer laser (wavelength 193 nm). As a chemically amplified resist sensitive to far ultraviolet rays, the resolution is high and the LER characteristics are also improved. Therefore, it can be used extremely favorably in the manufacture of integrated circuit elements that are expected to become increasingly finer in the future.

The present invention will be described in detail below.
[1] Basic compound The basic compound of the present invention comprises an onium salt represented by the above general formula (V) . This basic compound contains a nitrogen atom and generates a sulfonic acid group upon irradiation with radiation, resulting in a decrease in basicity or neutrality (hereinafter also referred to as “nitrogen-containing basic compound”).

In the general formula (V) , R represents a hydrogen atom, a methyl group, an ethyl group, a fluorine atom or a trifluoromethyl group. Rf represents a fluorine atom or a trifluoromethyl group. R ¹ , R ² , R ³ and R ⁴ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms. R ⁵ represents a methyl group, an ethyl group or a propyl group. n is an integer of 0-3. M ⁺ represents a sulfonium cation or an iodonium cation. Note that at least one combination of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , and R ¹ and R ⁴ may form a ring.

In the general formula (V) , M ⁺ is a sulfonium cation or an iodonium cation. Among these, from the viewpoint of improving the resolution of the resist, M ⁺ is preferably a sulfonium cation represented by the following general formula (2).

Here, R ² , R ³ and R ⁴ in the general formula (2) will be described. In the general formula (2), R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon number. 6-18 aryl groups are shown, or any two or more of R ² , R ³ and R ⁴ are bonded to each other to form a ring together with the sulfur atom in the formula.
Examples of the substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms as R ² , R ³ and R ⁴ include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and the like are preferable, and examples of the substituted or unsubstituted aryl group having 6 to 18 carbon atoms include a phenyl group, A naphthyl group, an anthranyl group, a phenanthryl group, a biphenyl group, and the like. These include an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a hydroxyl group, a carboxyl group, and an oxo group (that is, ═O group). ), A substituent such as a hydroxyalkyl group having 1 to 4 carbon atoms, a cyano group, and a cyanoalkyl group having 2 to 5 carbon atoms.
Further, when any two or more of R ² , R ³ and R ⁴ are bonded to each other to form a ring together with the sulfur atom in the formula, a 3 to 10-membered ring including the sulfur atom Is preferably formed, and in particular, a 5- to 7-membered ring is preferably formed.

M ⁺ is preferably an iodonium cation represented by the following general formula (3).

In the general formula (3), R ⁵ and R ⁶ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 6 carbon atoms. 18 aryl groups are shown, or R ⁵ and R ⁶ are bonded to each other to form a ring together with the iodine atom in the formula. Examples of the substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms as R ⁵ and R ⁶ include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group and the like are preferable, and examples of the substituted or unsubstituted aryl group having 6 to 18 carbon atoms include phenyl group, naphthyl group, Anthranyl group, phenanthryl group, biphenyl group and the like can be mentioned, and these include an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a hydroxyl group, a carboxyl group, an oxo group (that is, ═O group), carbon It may be substituted with a substituent such as a hydroxyalkyl group having 1 to 4 carbon atoms, a cyano group, or a cyanoalkyl group having 2 to 5 carbon atoms.
In addition, when R ⁵ and R ⁶ are bonded to each other to form a ring together with the iodine atom in the formula, it is preferable to form a 3- to 10-membered ring including the iodine atom, particularly 5 It is preferable to form a ˜7-membered ring.

  In the present invention, specific examples of preferable nitrogen-containing basic compounds include triphenylsulfonium 5- (N, N-diethyl) -4-hydroxy-1,1,2,2-tetrafluoropentanesulfonate, 1-naphthyldimethyl. Sulfonium 5- (N, N-diethyl) -4-hydroxy-1,1,2,2-tetrafluoropentanesulfonate, 1-naphthyldiethylsulfonium 5- (N, N-diethyl) -4-hydroxy-1,1 , 2,2-tetrafluoropentanesulfonate, 1- (4-hydroxynaphthyl) dimethylsulfonium 5- (N, N-diethyl) -4-hydroxy-1,1,2,2-tetrafluoropentanesulfonate, 1- ( 4-hydroxynaphthyl) diethylsulfonium 5- (N, N-diethyl) -4-hydroxy- 1,2,2,2-tetrafluoropentanesulfonate, 1- (4-cyanonaphthyl) dimethylsulfonium 5- (N, N-diethyl) -4-hydroxy-1,1,2,2-tetrafluoropentanesulfonate, -(4-Nitronaphthyl) dimethylsulfonium 5- (N, N-diethyl) -4-hydroxy-1,1,2,2-tetrafluoropentanesulfonate, 1- (4-nitronaphthyl) diethylsulfonium 5- (N , N-diethyl) -4-hydroxy-1,1,2,2-tetrafluoropentanesulfonate, 1- (4-methylnaphthyl) dimethylsulfonium 5- (N, N-diethyl) -4-hydroxy-1,1 , 2,2-Tetrafluoropentanesulfonate, 1- (4-methylnaphthyl) diethylsulfonium 5- (N N-diethyl) -4-hydroxy-1,1,2,2-tetrafluoropentanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 5- (N, N-diethyl)- 4-hydroxy-1,1,2,2-tetrafluoropentanesulfonate, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium 5- (N, N-diethyl) -4-hydroxy-1,1 , 2,2-Tetrafluoropentanesulfonate, 1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium 5- (N, N-diethyl) -4-hydroxy-1,1,2,2-tetrafluoro Pentanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 5- (N, N-diethyl) Examples include -4-hydroxy-1,1,2,2-tetrafluoropentane sulfonate.

The nitrogen-containing basic compound of the present invention has an action of suppressing the diffusion phenomenon of an acid generated from an acid generator (B), which will be described later by exposure, in a resist film and suppressing an undesirable chemical reaction in a non-exposed region ( It functions as a so-called acid diffusion control agent). By blending this nitrogen-containing basic compound into the radiation-sensitive resin composition, the storage stability of the radiation-sensitive resin composition is improved and the resolution as a resist is further improved. In addition, it is possible to suppress changes in the line width of the resist pattern due to fluctuations in the holding time (PED) from exposure to development processing. Therefore, a radiation-sensitive resin composition having excellent process stability can be obtained by blending the nitrogen-containing basic compound into the radiation-sensitive resin composition.
In addition, the basic compound of the present invention is used in a radiation-sensitive resin composition useful as a chemically amplified photoresist used in the field of microfabrication such as the manufacture of semiconductor devices, in active radiation (for example, KrF excimer laser, ArF excimer laser). , F ₂ excimer laser, (ultra-far ultraviolet rays typified by EUV, various kinds of radiation such as electron beam) and the like.

<Synthesis of nitrogen-containing basic compound>
The method for synthesizing the nitrogen-containing basic compound of the present invention is not particularly limited. For example, the following synthesis examples can be given.

In the above synthesis example, n is an integer of 0 to 3. R represents a hydrogen atom, a methyl group, an ethyl group, a fluorine atom or a trifluoromethyl group. Rf represents a fluorine atom or a trifluoromethyl group.
R ¹ , R ² , R ³ and R ⁴ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms. In this case, at least one combination of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , and R ¹ and R ⁴ may form a ring.
R ⁵ represents a methyl group, an ethyl group or a propyl group. M ⁺ represents a sulfonium ion or an iodonium ion.

Moreover, in the said synthesis example, the hydroxyl group derived from the allyl alcohol of compound (III) can be converted into carboxylic acid ester and sulfonic acid ester by making it react with carboxylic acid and sulfonic acid. It can also be converted to ether by reacting with an alkyl halide. Furthermore, it can also be halogenated by using a halogenating agent such as PX ₃ (X represents halogen). Moreover, an olefin can be produced | generated by making it react with a dehydrating agent, and it can hydrogenate by performing a reduction | restoration.

[2] Positive-type radiation-sensitive resin composition The positive-type radiation-sensitive resin composition of the present invention comprises (A) a radiation-sensitive acid diffusion controller composed of the nitrogen-containing basic compound, and (B) a radiation-sensitive property. An acid generator and (C) an alkali-insoluble or alkali-insoluble resin having an acid-dissociable group, and an acid-dissociable group-containing resin that becomes alkali-soluble when the acid-dissociable group is dissociated To do.

<(A) Radiation-sensitive acid diffusion controller>
The (A) radiation-sensitive acid diffusion controller (hereinafter referred to as “acid diffusion controller (A)”) contained in the radiation-sensitive resin composition of the present invention contains the nitrogen-containing basic compound. It suppresses the diffusion phenomenon in the resist film of the acid generated from the acid generator (B) described later by exposure and suppresses an undesirable chemical reaction in the non-exposed region.
The compounding amount of the acid diffusion controller (A) is preferably 15 parts by mass or less, more preferably 0.001 to 10 parts by mass, particularly preferably 100 parts by mass of the acid dissociable group-containing resin (C) described later. Is 0.005 to 5 parts by mass. In this case, by setting the blending amount of the acid diffusion control agent to 0.001 part by mass or more, it is possible to suppress a decrease in pattern shape and dimensional fidelity as a resist depending on process conditions, and to 15 parts by mass or less. Thereby, the sensitivity as a resist and the developability of the exposed portion can be further improved.

  The acid diffusion controller (A) is preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 3 to 10 parts by weight with respect to 100 parts by weight of the acid generator (B). Part. By setting the acid diffusion controller (A) within the above range, a positive radiation-sensitive resin composition having performance excellent in LER characteristics can be obtained.

<(B) Radiation sensitive acid generator containing fluorine atom>
The radiation-sensitive acid generator (B) (hereinafter referred to as “acid generator (B)”) contained in the radiation-sensitive resin composition of the present invention is visible light, ultraviolet light, far ultraviolet light, electron beam, X It is a substance that generates acid upon exposure to radiation such as rays.
The acid generator (B) dissociates acid-dissociable groups such as an alkyladamantyl group, t-butyl group, and tetrahydropyranyl group present in the resin by the action of an acid generated by exposure. As a result, the exposed portion of the resist film becomes soluble in an alkali developer, and a positive resist pattern is formed.
As an acid generator (B) in this invention, the compound (henceforth "acid generator (7)") represented by following General formula (7) can be mentioned, for example.

[In General Formula (7), R ¹¹ is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxyl group having 1 to 10 carbon atoms, or a carbon number. Represents a linear or branched alkoxycarbonyl group having 2 to 11; R ¹² represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms; and j is an integer of 0 to 3. And each R ¹³ independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or an optionally substituted naphthyl group, or two the R ¹³ are to form a divalent group having 2 to 10 carbon atoms bonded to each other, the divalent group may be substituted, k is an integer of 0 to 2, X ^- is It denotes an anion having a structure of ^{_{- C n F 2n + 1 SO}} 3 n is an integer from 1 to 10. ]

In the general formula (7), examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by R ¹¹ , R ^12, and R ¹³ include a methyl group, an ethyl group, an n-propyl group, and i-propyl. Group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl Group, n-nonyl group, n-decyl group and the like. Of these alkyl groups, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, and the like are preferable.

Examples of the linear or branched alkoxyl group having 1 to 10 carbon atoms of R ¹¹ include, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group. Group, 1-methylpropoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n- Nonyloxy group, n-decyloxy group, etc. can be mentioned. Of these alkoxyl groups, a methoxy group, an ethoxy group, an n-butoxy group, and the like are preferable.

Examples of the linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms of R ¹¹ include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, and an n-butoxycarbonyl group. Group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n -An octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group, etc. can be mentioned. Of these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and the like are preferable.

R ¹¹ in the general formula (7) is preferably a hydrogen atom, a hydroxyl group, a methoxy group, an ethoxy group, an n-butoxy group, or the like. Moreover, as R < ¹² > in General formula (7), a hydrogen atom, a methyl group, an ethyl group, t-butyl group, etc. are preferable. Moreover, as j in General formula (7), 0 or 1 is preferable.

In the general formula (7), examples of the optionally substituted phenyl group represented by R ¹³ include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl group, 2 , 4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl group, 4 A phenyl group such as an ethylphenyl group or a phenyl group substituted with a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms; the phenyl group or the alkyl-substituted phenyl group is converted into a hydroxyl group, a carboxyl group, One or more or one or more of cyano group, nitro group, alkoxyl group, alkoxyalkyl group, alkoxycarbonyl group, alkoxycarbonyloxy group, etc. And the like can be mentioned.

  Among the substituents for the phenyl group and the alkyl-substituted phenyl group, examples of the alkoxyl group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1- Examples thereof include a linear, branched or cyclic alkoxyl group having 1 to 20 carbon atoms such as a methylpropoxy group, a t-butoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

  Examples of the alkoxyalkyl group include those having 2 to 21 carbon atoms such as a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a 2-methoxyethyl group, a 1-ethoxyethyl group, and a 2-ethoxyethyl group. Examples include linear, branched or cyclic alkoxyalkyl groups.

  Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, and a 1-methylpropoxycarbonyl group. , T-butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl and the like, and a linear, branched or cyclic alkoxycarbonyl group having 2 to 21 carbon atoms.

  Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, Examples thereof include linear, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as cyclopentyloxycarbonyl group and cyclohexyloxycarbonyl.

As the optionally substituted phenyl group for R ¹³ in the general formula (7), a phenyl group, a 4-methoxyphenyl group, a 4-t-butoxyphenyl group, and the like are preferable.

Examples of the optionally substituted naphthyl group for R ¹³ include 1-naphthyl group, 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 2,3-dimethyl -1-naphthyl group, 2,4-dimethyl-1-naphthyl group, 2,5-dimethyl-1-naphthyl group, 2,6-dimethyl-1-naphthyl group, 2,7-dimethyl-1-naphthyl group, 2,8-dimethyl-1-naphthyl group, 3,4-dimethyl-1-naphthyl group, 3,5-dimethyl-1-naphthyl group, 3,6-dimethyl-1-naphthyl group, 3,7-dimethyl- 1-naphthyl group, 3,8-dimethyl-1-na Butyl group, 4,5-dimethyl-1-naphthyl group, 5,8-dimethyl-1-naphthyl group, 4-ethyl-1-naphthyl group 2-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl A naphthyl group substituted with a naphthyl group such as a 2-naphthyl group or 4-methyl-2-naphthyl group or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms; these naphthyl groups or alkyl substitutions Examples include a group in which a naphthyl group is substituted with one or more of hydroxyl group, carboxyl group, cyano group, nitro group, alkoxyl group, alkoxyalkyl group, alkoxycarbonyl group, alkoxycarbonyloxy group and the like. .

Examples of the alkoxyl group, alkoxyalkyl group, alkoxycarbonyl group and alkoxycarbonyloxy group which are substituents for the naphthyl group and the alkyl-substituted naphthyl group are the same as the corresponding groups exemplified for the phenyl group and the alkyl-substituted phenyl group, respectively. Things can be mentioned. As the naphthyl group which may be substituted for R ¹³ in the general formula (7), 1-naphthyl group, 1- (4-methoxynaphthyl) group, 1- (4-ethoxynaphthyl) group, 1- (4- n-butoxynaphthyl) group and the like are preferable.

In addition, the divalent group having 2 to 10 carbon atoms formed by bonding two R ¹³ to each other is preferably a 5-membered or 6-membered cyclic structure together with a sulfur atom in the formula, particularly preferably a 5-membered cyclic structure. A group that forms (that is, a tetrahydrothiophene ring structure) is desirable. Examples of the substituent for the divalent group include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxyl group, an alkoxyalkyl group, an alkoxy group exemplified as the substituent for the phenyl group and the alkyl-substituted phenyl group. Examples thereof include a carbonyl group and an alkoxycarbonyloxy group.

As R ¹³ in the general formula (7), a methyl group, an ethyl group, a phenyl group, a 4-methoxyphenyl group, a 1-naphthyl group, and two R ¹³ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom. A divalent group is preferred.

In the general formula (7), k is preferably 0 or 1. ^{_{Further, X - C n F 2n +}} 1 Medium ^{_{- - C n F 2n + 1}} SO 3 group is a perfluoroalkyl group with carbon number n, may be the substrate is linear or branched. X ^- is n in the preferred 4 or 8.

  Specific examples of the acid generator (7) include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, 1-naphthyldimethylsulfonium trifluoromethanesulfonate, 1-naphthyldimethylsulfonium nonafluoro-n-butanesulfonate, 1-naphthyldimethylsulfonium perfluoro-n-octanesulfonate, 1-naphthyldiethylsulfonium trifluoromethanesulfonate, 1-naphthyldiethylsulfonium nonafluoro-n-butanesulfonate, 1- Naphthyldiethylsulfonium perfluoro-n-octanesulfonate,

  1- (4-hydroxynaphthyl) dimethylsulfonium trifluoromethanesulfonate, 1- (4-hydroxynaphthyl) dimethylsulfonium nonafluoro-n-butanesulfonate, 1- (4-hydroxynaphthyl) dimethylsulfonium perfluoro-n-octanesulfonate, 1- (4-hydroxynaphthyl) diethylsulfonium trifluoromethanesulfonate, 1- (4-hydroxynaphthyl) diethylsulfonium nonafluoro-n-butanesulfonate, 1- (4-hydroxynaphthyl) diethylsulfonium perfluoro-n-octanesulfonate, 1- (4-cyanonaphthyl) dimethylsulfonium trifluoromethanesulfonate, 1- (4-cyanonaphthyl) dimethylsulfonium nonafluoro-n-buta Sulfonate, 1- (4-cyanonaphthyl) dimethylsulfonium perfluoro-n-octanesulfonate, 1- (4-cyanonaphthyl) diethylsulfonium trifluoromethanesulfonate, 1- (4-cyanonaphthyl) diethylsulfonium nonafluoro-n-butane Sulfonate, 1- (4-cyanonaphthyl) diethylsulfonium perfluoro-n-octane sulfonate,

  1- (4-nitronaphthyl) dimethylsulfonium trifluoromethanesulfonate, 1- (4-nitronaphthyl) dimethylsulfonium nonafluoro-n-butanesulfonate, 1- (4-nitronaphthyl) dimethylsulfonium perfluoro-n-octanesulfonate, 1- (4-nitronaphthyl) diethylsulfonium trifluoromethanesulfonate, 1- (4-nitronaphthyl) diethylsulfonium nonafluoro-n-butanesulfonate, 1- (4-nitronaphthyl) diethylsulfonium perfluoro-n-octanesulfonate, 1- (4-methylnaphthyl) dimethylsulfonium trifluoromethanesulfonate, 1- (4-methylnaphthyl) dimethylsulfonium nonafluoro-n-butanesulfonate, 1- (4 Methylnaphthyl) dimethylsulfonium perfluoro-n-octanesulfonate, 1- (4-methylnaphthyl) diethylsulfonium trifluoromethanesulfonate, 1- (4-methylnaphthyl) diethylsulfonium nonafluoro-n-butanesulfonate, 1- (4- Methylnaphthyl) diethylsulfonium perfluoro-n-octanesulfonate,

  1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octane sulfonate, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-methoxy Naphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-methoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-ethoxynaphthalene) -1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-ethoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-ethoxynaphthalen-1-yl) tetrahydro Thiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophene Examples thereof include nium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, and the like.

  Among these acid generators (7), triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophene Nimononafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydro Thiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiofe Nipar Ruoro -n- octanesulfonate and the like are preferable.

In the present invention, in addition to the acid generator (7), other acid generators such as the following onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, and sulfonic acid compounds may be used. it can.
Examples of the onium salt compound include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Specific examples of the onium salt compound include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, and bis (4-t-butylphenyl) iodonium nona. Fluoro-n-butanesulfonate, cyclohexyl, 2-oxocyclohexyl, methylsulfonium trifluoromethanesulfonate, dicyclohexyl, 2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, and the like.

Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound. Specific examples of halogen-containing compounds include (trichloromethyl such as phenylbis (trichloromethyl) -s-triazine, 4-methoxyphenylbis (trichloromethyl) -s-triazine, 1-naphthylbis (trichloromethyl) -s-triazine. ) -S-triazine derivatives and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane.
Examples of the diazo ketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, a diazonaphthoquinone compound, and the like. Specific examples of the diazo ketone include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2, naphthoquinonediazide of 2,3,4,4′-tetrahydroxybenzophenone. -4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-naphthoquinonediazide-4-sulfonic acid ester of 1,1,1-tris (4-hydroxyphenyl) ethane Examples include 2-naphthoquinonediazide-5-sulfonic acid ester.

Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds of these compounds. Specific examples of the sulfone compound include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and the like.
Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, alkyl sulfonic acid imides, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Specific examples of the sulfonic acid compounds include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept- 5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide nonafluoro-n-butanesulfonate, N-hydroxysuccinimide perfluoro-n -Octane sulfonate, 1 8-naphthalenedicarboxylic acid imide trifluoromethanesulfonate, 1,8-naphthalenedicarboxylic acid imide nonafluoro -n- butane sulfonate, can be exemplified 1,8-naphthalenedicarboxylic acid imide perfluoro -n- octanesulfonate like.

  Among these other acid generators, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium Nonafluoro-n-butanesulfonate, cyclohexyl, 2-oxocyclohexyl, methylsulfonium trifluoromethanesulfonate, dicyclohexyl, 2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate,

Trifluoromethanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide , Perfluoro-n-octanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide nonafluoro-n- Butane sulfonate, N-hydroxysuccinimide perfluoro-n-octane sulfonate, 1,8-naphthalenedicarboxylic acid imide trifluoromethane sulfonate and the like are preferable.
In this invention, an acid generator (B) can be used individually or in mixture of 2 or more types.

  The amount of the acid generator (B) in the radiation-sensitive resin composition of the present invention is usually 0.1 to 20 parts by mass with respect to 100 parts by mass of the acid dissociable group-containing resin (C) described later. Preferably, it is 0.1-15 mass parts, More preferably, it is 0.1-10 mass parts, More preferably, it is 0.5-10 mass parts. By setting it as such a compounding quantity, the sensitivity and developability as a resist are fully securable. Moreover, when the compounding amount of the acid generator (B) is less than 0.1 parts by mass, the sensitivity and developability tend to decrease. On the other hand, when it exceeds 20 parts by mass, the transparency to radiation decreases, A rectangular resist pattern tends to be difficult to obtain.

<(C) Acid-dissociable group-containing resin>
Component (C) in the positive radiation sensitive resin composition of the present invention is an alkali-insoluble or alkali-insoluble resin having an acid-dissociable group, and becomes alkali-soluble when the acid-dissociable group is dissociated. Resin (hereinafter referred to as “acid-dissociable group-containing resin (C)”).
The term “alkali-insoluble or alkali-insoluble” as used herein is employed when forming a resist pattern from a resist film formed using a radiation-sensitive resin composition containing an acid-dissociable group-containing resin (C). When developing a film using only the acid dissociable group-containing resin (C) instead of the resist film under alkaline development conditions, 50% or more of the initial film thickness of the film remains after development. means.

The acid dissociable group in the acid dissociable group-containing resin (C) is, for example, a group that substitutes a hydrogen atom in an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group, and in the presence of an acid. It means a group that dissociates.
Examples of such an acid dissociable group include a t-butoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a (thiotetrahydropyranylsulfanyl) methyl group, a (thiotetrahydrofuranylsulfanyl) methyl group, and an alkoxy-substituted methyl group. Groups, alkylsulfanyl-substituted methyl groups, groups represented by the following general formula (8) (hereinafter referred to as “acid-dissociable groups (8)”), and the like.

  [In General Formula (8), each R is independently a linear or branched alkyl group having 1 to 14 carbon atoms, or a non-bridged or bridged monovalent fat having 3 to 20 carbon atoms. A cyclic hydrocarbon group, or any two R's bonded to each other, and together with the carbon atoms to which each is bonded, a non-bridged or bridged divalent having 3 to 20 carbon atoms An alicyclic hydrocarbon group is formed, and the remaining R is a linear or branched alkyl group having 1 to 14 carbon atoms, or a non-bridged or bridged monovalent alicyclic ring having 3 to 20 carbon atoms. And each of these groups may be substituted. ]

  Examples of the alkoxy-substituted methyl group include methoxymethyl group, ethoxymethyl group, methoxyethoxymethyl group, n-propoxymethyl group, n-butoxymethyl group, n-pentyloxymethyl group, n-hexyloxymethyl group, benzyl An oxymethyl group etc. can be mentioned.

  Examples of the alkylsulfanyl-substituted methyl group include a methylsulfanylmethyl group, an ethylsulfanylmethyl group, a methoxyethylsulfanylmethyl group, an n-propylsulfanylmethyl group, an n-butylsulfanylmethyl group, an n-pentylsulfanylmethyl group, Examples thereof include an n-hexylsulfanylmethyl group and a benzylsulfanylmethyl group.

  In the general formula (8), examples of the linear or branched alkyl group having 1 to 14 carbon atoms of R include, for example, a methyl group, an ethyl group, an n-propyl group, an I-propyl group, an n-butyl group, 2-methylpropyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group , N-tetradecyl group and the like.

  Examples of the substituent of the alkyl group include a hydroxyl group, a carboxyl group, an oxo group (═O), a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, etc.), a straight chain having 1 to 8 carbon atoms, Branched alkoxyl group (for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, etc.), carbon number 2-8 linear or branched alkoxyalkoxyl groups (for example, methoxymethoxy group, ethoxymethoxy group, t-butoxymethoxy group, etc.), C2-C8 linear or branched alkylcarbonyloxy group (For example, methylcarbonyloxy group, ethylcarbonyloxy group, t-butylcarbonyloxy group, etc.), straight chain having 2 to 8 carbon atoms Or branched alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group) can be exemplified one or more, or one or more such

Examples of the non-bridged or bridged monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms of R include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclo A cycloalkyl group such as an octyl group; a bicyclo [2.2.1] heptyl group, a bicyclo [2.2.2] octyl group, a tetracyclo [4.2.0.1 ^2,5 . 1 ^7,10 ] dodecyl group, adamantyl group and the like.

  Examples of the substituent of the monovalent alicyclic hydrocarbon group of R and the divalent alicyclic hydrocarbon group formed by bonding any two R to each other include, for example, a hydroxyl group, a carboxyl group, Oxo group (= O), cyano group, halogen atom (for example, fluorine atom, chlorine atom, etc.), linear or branched alkyl group having 1 to 14 carbon atoms (for example, methyl group, ethyl group, n-propyl) Group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, etc.), linear or branched alkoxyl group having 1 to 8 carbon atoms (for example, methoxy Group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, etc.), linear or branched having 2 to 8 carbon atoms Alkyki Alkyl groups (for example, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, etc.), C2-C8 linear or branched alkoxyalkoxyl groups (for example, methoxymethoxy group, ethoxymethoxy group, t- Butoxymethoxy group, etc.), a linear or branched alkylcarbonyloxy group having 2 to 8 carbon atoms (for example, methylcarbonyloxy group, ethylcarbonyloxy group, t-butylcarbonyloxy group, etc.), C2-8 A linear or branched alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, etc.), a linear or branched cyanoalkyl group having 2 to 14 carbon atoms (for example, cyanomethyl) Group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl group, etc.) Linear or branched fluoroalkyl group having 1 to 14 carbon atoms (e.g., fluoromethyl group, trifluoromethyl group, pentafluoroethyl group and the like) can be given one or more, or one or more such.

  Specific examples of the acid dissociable group (8) are t-butyl groups and the following formulas (8-1) to (8-20) (where each m is an integer of 0 to 2). Groups and the like.

  In the acid-dissociable group-containing resin (C), one or more acid-dissociable groups can be present. Introduction rate of acid-dissociable groups in acid-dissociable group-containing resin (C) [number of acid-dissociable groups relative to the total number of acid functional groups and acid-dissociable groups in acid-dissociable group-containing resin (C) The ratio] can be appropriately selected depending on the acid dissociable group and the type of resin into which the group is introduced, but is preferably 5 to 100%, more preferably 10 to 100%.

  Further, the structure of the acid-dissociable group-containing resin (C) is not particularly limited as long as it has the above-described properties, and various structures can be used. In particular, the phenolic hydroxyl group in poly (p-hydroxystyrene) Of a phenolic hydroxyl group in a resin obtained by substituting a part or all of hydrogen atoms with an acid-dissociable group, a copolymer of p-hydroxystyrene and / or p-hydroxy-α-methylstyrene and (meth) acrylic acid A resin in which part or all of the hydrogen atoms and / or carboxyl group hydrogen atoms are substituted with an acid-dissociable group can be preferably used.

Moreover, the structure of acid dissociable group containing resin (C) can be variously selected according to the kind of radiation to be used. For example, as an acid-dissociable group-containing resin (C) particularly suitable for a radiation-sensitive resin composition using a KrF excimer laser, for example, a repeating unit represented by the following general formula (9) (hereinafter referred to as “repeating unit ( 1) ") and a repeating unit in which the phenolic hydroxyl group in the repeating unit (1) is protected with an acid-dissociable group, an alkali-insoluble or alkali-insoluble resin (hereinafter referred to as" resin (C1) "). Is preferred. The resin (C1) is, ArF excimer laser, F ₂ excimer laser can also be suitably used in radiation-sensitive resin compositions using other radiation such as electron beams.

[In General Formula (9), R ¹⁴ represents a hydrogen atom or a monovalent organic group, and when a plurality of R ¹⁴ are present, they may be the same or different from each other, and a and b are each an integer of 1 to 3 It is. ]

  As the repeating unit (1), a unit in which a non-aromatic double bond of p-hydroxystyrene is cleaved is particularly preferable.

  The resin (C1) may further contain other repeating units. Examples of the other repeating unit include vinyl aromatic compounds such as styrene; (meth) acrylic acid such as t-butyl (meth) acrylate, adamantyl (meth) acrylate, and 2-methyladamantyl (meth) acrylate. Examples include units in which a polymerizable unsaturated bond such as esters is cleaved.

Examples of the acid-dissociable group-containing resin (C) particularly suitable for a radiation-sensitive resin composition using an ArF excimer laser include, for example, a repeating unit represented by the following general formula (10) (hereinafter referred to as “repeating unit ( 2) ") and / or an alkali-insoluble or hardly alkali-soluble resin (hereinafter referred to as" resin (")) having a repeating unit represented by the following general formula (4) (hereinafter referred to as" repeating unit (3) "). C2) ") is preferred. The resin (C2) may also be suitably used in KrF excimer laser, F ₂ excimer laser radiation-sensitive resin composition using other radiation such as electron beams.

[In the general formula (10), each B independently represents a hydrogen atom or a monovalent acid dissociable group, and at least one of B is a monovalent acid dissociable group, and each D represents Independently, it represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and k is an integer of 0 to 2. ]

In [general formula (4), R ⁷ represents a hydrogen atom or a methyl group. Each R ⁸ independently represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms, and R 8 ⁸ satisfies the following condition (1) or (2). (1) At least one of R ⁸ is a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof. (2) Any two of R ⁸ are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atom to which each R ⁸ is bonded. ]

In addition, —COOC (R ⁸ ) ₃ in the repeating unit (3) is preferably the following formula (a), (b), or (c).

[In Formula (a), Formula (b), and Formula (c), each R ⁹ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms. In the formula (c), m is 0 or 1. ]

  Moreover, as repeating unit (3), the unit derived from t-butyl (meth) acrylate, the repeating unit represented by following formula (3-1)-(3-18), etc. are preferable, for example.

[In the formulas (3-1) to (3-18), R ¹⁵ represents a hydrogen atom or a methyl group. ]

The resin (C2) can further have one or more other repeating units.
Examples of the other repeating unit include norbornene (bicyclo [2.2.1] hept-2-ene), 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2]. 2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-fluorobicyclo [2.2.1] hept-2-ene, tetracyclo [4.4 .0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-hydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] monomers having a norbornene skeleton such as dodec-3-ene; unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; the following formulas (4-1) to (4-8) And a unit (hereinafter referred to as “repeating unit (4)”) in which a polymerizable unsaturated bond such as (meth) acrylic acid ester is cleaved. Among these, the following formula (4-1) is preferable.

[In the formulas (4-1) to (4-8), each R ¹⁶ independently represents a hydrogen atom or a methyl group, and each R ¹⁷ independently represents a substituted or unsubstituted C 1-14. An alkyl group, a hydroxyl group, or a cyano group is shown, i is an integer of 0-3, T shows a methylene group or a C2-C8 alkylene group. ]

In the resin (C2) having the repeating unit (2), it is particularly preferable to further have a unit derived from maleic anhydride as the other repeating unit.
In addition, in the resin (C2) having the repeating unit (3) and the repeating unit (4), in particular, the repeating unit represented by the following formulas (5-1) to (5-4) is further used as another repeating unit. It is preferable to have one or more.

In [Formula (5-1) to (5-4), each ^{R 18} represents a hydrogen atom or a methyl group independently of each other. ]

When the acid-dissociable group-containing resin (C) is produced by polymerization of a polymerizable unsaturated monomer or through the polymerization, the resin is a polyfunctional monomer having two or more polymerizable unsaturated bonds. A branched structure can be introduced by a unit derived from the above and / or an acetal crosslinking group. By introducing such a branched structure, the heat resistance of the acid-dissociable group-containing resin (C) can be improved.
In this case, the introduction rate of the branched structure in the acid-dissociable group-containing resin (C) can be appropriately selected depending on the branched structure and the type of resin into which the branched structure is introduced. % Or less is preferable.

The molecular weight of the acid dissociable group-containing resin (C) is not particularly limited and may be appropriately selected. The polystyrene-reduced weight molecular weight (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC). Is usually 1,000 to 500,000, preferably 2,000 to 400,000, more preferably 3,000 to 300,000.
The Mw of the acid-dissociable group-containing resin (C) having no branched structure is preferably 1,000 to 150,000, more preferably 3,000 to 100,000, and the acid dissociable having a branched structure. Mw of the functional group-containing resin (C) is preferably 5,000 to 500,000, more preferably 8,000 to 300,000. By using the acid-dissociable group-containing resin (C) having Mw in such a range, the resulting resist has excellent development characteristics.

  The ratio (Mw / Mn) between the Mw of the acid-dissociable group-containing resin (C) and the polystyrene equivalent number molecular weight (hereinafter referred to as “Mn”) measured by GPC is not particularly limited, and can be appropriately selected. However, it is 1-10 normally, Preferably it is 1-8, More preferably, it is 1-5. By using the acid dissociable group-containing resin (C) having Mw / Mn in such a range, the resulting resist has excellent resolution performance.

Although there is no limitation in particular about the manufacturing method of acid dissociable group containing resin (C), For example, the method of introduce | transducing 1 or more types of acid dissociable groups into the acidic functional group in the alkali-soluble resin manufactured previously; A method of polymerizing one or more polymerizable unsaturated monomers having a group, optionally together with another polymerizable unsaturated monomer; one or more polycondensable components having an acid dissociable group, Can be produced by a polycondensation method together with other polycondensable components.
Polymerization of the polymerizable unsaturated monomer and the polymerization of one or more polymerizable unsaturated monomers having an acid dissociable group in the production of the alkali-soluble resin are carried out by using the polymerizable unsaturated monomer used Depending on the type of reaction medium, etc., a polymerization initiator such as a radical polymerization initiator, an anionic polymerization catalyst, a coordination anion polymerization catalyst, a cationic polymerization catalyst, or a polymerization catalyst is appropriately selected, bulk polymerization, solution polymerization, precipitation polymerization, It can implement by appropriate polymerization forms, such as emulsion polymerization, suspension polymerization, and block-suspension polymerization.
The polycondensation of one or more polycondensable components having an acid dissociable group can be preferably carried out in an aqueous medium or a mixed medium of water and a hydrophilic solvent in the presence of an acidic catalyst.

<Dissolution control agent>
The positive radiation sensitive resin composition of the present invention may be blended with a dissolution control agent having the property of increasing the solubility in an alkaline developer by the action of an acid.
As such a dissolution control agent, for example, a compound having an acidic functional group such as a phenolic hydroxyl group, a carboxyl group, or a sulfonic acid group, or a compound in which the hydrogen atom of the acidic functional group in the compound is substituted with an acid dissociable group Etc.
A dissolution control agent can be used individually or in mixture of 2 or more types. The compounding quantity of a dissolution control agent is 20 mass parts or less normally with respect to 100 mass parts of all the resin components in a radiation sensitive resin composition, Preferably it is 10 mass parts or less.

<Surfactant>
In the positive radiation sensitive resin composition of the present invention, a surfactant exhibiting an action of improving the coating property, striation, developability and the like of the radiation sensitive resin composition may be blended.
As such a surfactant, any of anionic, cationic, nonionic or amphoteric surfactants can be used, but nonionic surfactants are preferred. Examples of the nonionic surfactant include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, and the following trade names “KP” (Shin-Etsu Chemical Co., Ltd.). ), "Polyflow" (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), "F Top" (manufactured by Tokemu Products), "Megafuck" (manufactured by Dainippon Ink & Chemicals), "Fluorard" (manufactured by Sumitomo 3M), "Asahi Guard" ”And“ Surflon ”(manufactured by Asahi Glass) and the like.
Surfactant can be used individually or in mixture of 2 or more types.
The compounding amount of the surfactant is usually 2 parts by mass or less, preferably 1.5 parts by mass or less as an active ingredient of the surfactant with respect to 100 parts by mass of the total resin components in the radiation-sensitive resin composition. .

<Sensitizer>
The positive-type radiation-sensitive resin composition of the present invention has an action of absorbing radiation energy and transmitting the energy to the acid generator (B), thereby increasing the amount of acid generated, and sensitivity. A sensitizer capable of improving the viscosity can also be blended. Sensitivity can be further improved by the sensitizer.
Examples of such sensitizers include acetophenones, benzophenones, naphthalene, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like.
These sensitizers can be used alone or in admixture of two or more. The compounding quantity of a sensitizer is 50 mass parts or less normally with respect to 100 mass parts of all the resin components in a radiation sensitive resin composition, Preferably it is 30 mass parts or less.

<Other acid diffusion control agents>
The positive radiation sensitive resin composition of the present invention may contain an acid diffusion control agent other than the acid diffusion control agent (A) (hereinafter referred to as “other acid diffusion control agent”).
As other acid diffusion control agents, for example, a compound represented by the following general formula (11) [hereinafter referred to as “nitrogen-containing compound (i)”. ], A compound having two nitrogen atoms in the same molecule [hereinafter referred to as “nitrogen-containing compound (b)”. ], Polyamino compounds and polymers having three or more nitrogen atoms [hereinafter these are collectively referred to as “nitrogen-containing compounds (c)”. Amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.

In the general formula (11), each R ¹⁹ is independently a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl. Indicates a group. Here, examples of the substituted or unsubstituted linear, branched, or cyclic alkyl group include those having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. Group, cyclopentyl group, cyclohexyl group and the like.

  Specific examples of the nitrogen-containing compound (a) include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine and the like. Di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine Di (cyclo) alkylamines such as dicyclohexylamine; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri -N-octylamine, tri-n-nonylamine, tri-n-decylamine, Tri (cyclo) alkylamines such as cyclohexyldimethylamine, methyldicyclohexylamine, tricyclohexylamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline , Aromatic amines such as 4-nitroaniline, diphenylamine, triphenylamine and naphthylamine.

  Specific examples of the nitrogen-containing compound (b) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4, 4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-amino Phenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-Aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1- Chiruechiru] benzene, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether.

  Examples of the nitrogen-containing compound (c) include polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer, and the like.

  Specific examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, and Nt-butoxycarbonyldi-n-decylamine. Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-1 -Adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4'-diaminodiphenylmethane, N, N'-di-t-butoxycarbonyl Hexamethylenediamine, N, N, N′N′-tetra-t-butoxycarbonyl hex Methylenediamine, N, N′-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t- Butoxycarbonyl-1,9-diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N '-Di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenz Nt-butoxycarbonyl group-containing amino compounds such as imidazole, formamide, N-methylformamide N, N- dimethylformamide, acetamide, N- methylacetamide, N, N- dimethylacetamide, propionamide, benzamide, pyrrolidone, N- methylpyrrolidone and the like.

  Specific examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri -N-butylthiourea etc. are mentioned.

  Specific examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, and Nt-butoxycarbonyl-2-phenylbenzimidazole. Pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide , Pyridines such as quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine; piperazines such as piperazine, 1- (2-hydroxyethyl) piperazine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine , 3-pi Rijino-1,2-propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane.

  The blending amount of the other acid diffusion control agent is usually 15 parts by mass or less, preferably 10 parts by mass or less, with respect to 100 parts by mass of the total resin components in the radiation-sensitive resin composition.

<Other additives>
Furthermore, in the positive radiation sensitive resin composition of the present invention, additives other than those described above, for example, dyes, pigments, adhesion assistants, and halation preventions, as long as the effects of the present invention are not impaired. An agent, a storage stabilizer, an antifoaming agent, a shape improving agent, etc., specifically, 4-hydroxy-4′-methylchalcone can be blended.
In this case, by blending a dye or pigment, the transmittance of the radiation-sensitive resin composition can be adjusted to reduce the influence of halation during exposure, and by adhering an adhesion aid, adhesion to the substrate can be achieved. Can improve sex.

<Preparation of composition solution>
The positive-type radiation-sensitive resin composition of the present invention is usually obtained by dissolving each component in a solvent at the time of use to form a uniform solution, and then filtering with a filter having a pore size of about 0.2 μm, for example, if necessary. Prepared as a composition solution.
Examples of the solvent include ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, lactones, (halogenated) hydrocarbons, and the like. More specifically, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, acetate esters , Hydroxyacetic acid esters, lactic acid esters, alkoxyacetic acid esters, (non) cyclic ketones, acetoacetic acid esters, pyruvate esters, propionate esters, N, N-di Le Kill formamides, N, N- dialkyl acetamides, N- alkylpyrrolidones, .gamma.-lactones, may be mentioned (halogenated) aliphatic hydrocarbons, and (halogenated) aromatic hydrocarbons, and the like.

  Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, Diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, isopropenyl acetate, isopropenyl pro Pionate, G Ene, xylene, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy- Methyl 3-methylbutyrate, methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion Methyl acid, 3- Tokishipuropion ethyl, N- methylpyrrolidone, N, N- dimethylformamide, N, may be mentioned N- dimethylacetamide.

  Among these solvents, propylene glycol monoalkyl ether acetates, 2-heptanone, lactic acid esters, 2-hydroxypropionic acid esters, 3-alkoxypropionic acid esters, etc. have good in-plane uniformity during coating. This is preferable. The said solvent can be used individually or in mixture of 2 or more types.

If necessary, other solvents such as benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1 Use high-boiling solvents such as octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, etc. be able to.
These other solvents can be used alone or in admixture of two or more. The proportion of other solvents used is usually 50% by mass or less, preferably 30% by mass or less, based on the total solvent.

  The total amount of the solvent used is such that the total solid concentration of the solution is usually 5 to 50% by mass, preferably 10 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 10 to 30% by mass, The amount is preferably 10 to 25% by mass. By setting the total solid content concentration of the solution within this range, it is preferable in that the in-film uniformity during coating is good.

<Formation of resist pattern>
When forming a resist pattern from the positive radiation sensitive resin composition of the present invention, the composition solution prepared as described above is applied by an appropriate application means such as spin coating, cast coating, roll coating or the like. For example, a resist film is formed by coating on a substrate such as a silicon wafer or a wafer coated with aluminum. Thereafter, a heat treatment (hereinafter referred to as “PB”) is performed in advance in some cases, and then the resist film is exposed through a predetermined mask pattern.

The radiation that can be used for exposure includes the emission line spectrum of a mercury lamp (wavelength 254 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength), depending on the type of acid generator (B) used. 193 nm), far ultraviolet rays such as F ₂ excimer laser (wavelength 157 nm), EUV (wavelength 13 nm, etc.), X-rays such as synchrotron radiation, charged particle beams such as electron beams, etc., preferably far ultraviolet rays And a charged particle beam, particularly preferably a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm) and an electron beam.
The exposure conditions such as the radiation dose are appropriately selected according to the composition of the positive radiation sensitive resin composition, the type of additive, and the like.
In forming a resist pattern, it is preferable to perform a heat treatment after exposure (hereinafter, this heat treatment is referred to as “PEB”) from the viewpoint of improving the apparent sensitivity of the resist.
The heating conditions for PEB are appropriately adjusted depending on the composition of the radiation-sensitive resin composition, the type of additive, and the like, but are usually 30 to 200 ° C, preferably 50 to 150 ° C.

Then, a predetermined resist pattern is formed by developing the exposed resist film with an alkaline developer.
Examples of the alkali developer include alkali metal hydroxides, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo [5.4. 0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene and the like, an alkaline aqueous solution in which at least one alkaline compound is dissolved is used. A particularly preferred alkaline developer is a tetraalkylammonium developer. It is an aqueous solution of hydroxides.
It is preferable that the density | concentration of alkaline aqueous solution is 10 mass% or less, More preferably, it is 1-10 mass%, More preferably, it is 2-5 mass%. When the concentration of the alkaline aqueous solution is 10% by mass or less, dissolution of the unexposed portion in the developer can be sufficiently suppressed.
Further, it is preferable to add an appropriate amount of a surfactant or the like to the alkaline developer, whereby the wettability of the developer with respect to the resist can be enhanced.
In addition, after developing with an alkaline developer, it is generally washed with water and dried.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Here, “part” and “%” are based on mass unless otherwise specified.

<Synthesis Example of Triphenylsulfonium 5- (N, N-diethyl) -4-hydroxy-1,1,2,2-tetrafluoropentanesulfonate [Compound (A-1)]>
1,1,2,2-Tetrafluoro-2-bromo-1-iodoethane (100 g) and allyl alcohol (22.7 g) were dissolved in ethyl acetate (500 ml), and azoisobutyronitrile (2.6 g) was added to the solution. Thereafter, the temperature was raised to 60 ° C. and the reaction was allowed to stir for 3 hours, and then the reaction solution was poured into 100 ml of water. Thereafter, extraction was performed 3 times with 50 ml of ethyl acetate, and the obtained organic layer was washed 3 times with 50 ml of 10% aqueous sodium carbonate solution, then 3 times with 50 ml of 5% aqueous oxalic acid solution, and the pH of the separated aqueous layer was further adjusted. Washing was repeated with distilled water until 7. Next, the organic layer was dried over 30 g of magnesium sulfate, and after magnesium sulfate was filtered off, the solvent was distilled off with a rotary evaporator to obtain 91.5 g of compound (i) [see the following reaction formula (I) ].

Reaction formula (I)

  Next, 10.5 g of sodium hydroxide was added to a solution of 91.5 g of this compound (i) in 500 ml of ethanol, and the mixture was stirred in an ice water bath at 0 ° C. Thereafter, the reaction solution was put into 1 L of ice water. Next, extraction was performed with 500 ml of ethyl acetate, and the ethyl acetate layer was washed twice with 70 ml of 10% aqueous sodium hydrogen carbonate solution, then washed 3 times with 5% aqueous oxalic acid solution, and further distilled until the pH of the separated aqueous layer reached 7. Repeated washing with water. Thereafter, the organic layer was dried with 30 g of magnesium sulfate, the magnesium sulfate was filtered off, and then the solvent was distilled off with a rotary evaporator to obtain 52.1 g of compound (ii) [see the following reaction formula (B). ].

Reaction formula (b)

  Next, 52.1 g of this compound (ii) was dissolved in 300 ml of diethylamine and stirred at 50 ° C. for 5 hours to be reacted. Then, 62.0 g of compound (iii) was obtained by distilling off the solvent with a rotary evaporator [see the following reaction formula (c)].

Reaction formula (c)

  A solution prepared by dissolving 35.4 g of sodium dithionite and 27.3 g of sodium carbonate in 225 ml of water was placed in a 2 L three-necked flask sufficiently purged with nitrogen, and 225 ml of a solution of 30 g of the above compound (iii) in acetonitrile was added. In addition, the mixture was reacted at 80 ° C. for 5 hours. After cooling, the acetonitrile layer separated into two layers was separated, and the acetonitrile layer was distilled off under reduced pressure to remove acetonitrile. Next, 168 ml of water and 126 mg of sodium tungstate dihydrate were added to the residue, and 10.5 g of hydrogen peroxide (concentration: 30%) was added dropwise at room temperature, followed by stirring at 60 ° C. for 1 hour. Thereafter, water was removed under reduced pressure to obtain 18.0 g of compound (iv) [see the following reaction formula (d)].

Reaction formula (d)

To a solution obtained by dissolving 17.5 g of triphenylsulfonium bromide in 75 ml of water, a solution obtained by dissolving 13.6 g of the above compound (iv) in CHCl ₃ was added. After stirring at room temperature for 1 hour, the organic layer was separated, washed twice with 50 ml of water and then distilled off under reduced pressure to give colorless and highly viscous oily triphenylsulfonium 5- (N, N-diethyl) -4- 12.7 g of hydroxy-1,1,2,2-tetrafluoropentanesulfonate [compound (A-1)] was obtained [see the following reaction formula (e)].

Reaction formula (e)

As a result of analyzing ¹ H-NMR (trade name: JNM-EX270, manufactured by JEOL Ltd.) using this compound as deuterated chloroform, the obtained chemical shift was ¹ HNMR [σ ppm ( _{CD 3 Cl): 1.53 (6H} , t), 3.12-3.21 (4H, m), 3.48-3.50 (2H, m), 3.55-3.62 (2H, m), 3.78-3.82 (1H, m), 7.26-7.78 (15H, m, Ph)], confirming that it was the target compound.

Moreover, as a result of analyzing using the mass spectrometer (Brand name: JMS-AX505W, JEOL Co., Ltd.) on condition of the following, the parent ion peak of 310 was detected and it was confirmed that it was a target compound.
The mass analysis of the compound (A-1) was performed under the following conditions.
Apparatus: JMS-AX505W type mass spectrometer manufactured by JEOL Ltd. Emitter current: 5 mA (used gas: Xe)
Acceleration voltage: 3.0 kV
ION MULTI: 1.3
Ionization method: Fast atom bombardment method (FAB)
Detection ion: Anion (-)
Measurement mass range: 20-1500 m / z
Scan: 30 sec
Resolution: 1500
Matrix: 3-nitrobenzyl alcohol

<Performance evaluation of positive radiation sensitive resin composition>
Each component shown in Table 1 (where parts are based on mass) was mixed to obtain a uniform solution, and then filtered through a membrane filter having a pore size of 0.2 μm to prepare each composition solution.

In addition, each component in Table 1 is as follows.
<Acid diffusion control agent>
a-1;
3-Pyrrolidino (piperidino) -1,2-propanediol

<Acid generator>
B-1;
Triphenylsulfonium bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate B-2;
4-n-butoxy-1-naphthyltetrahydrothiophenium bicyclo [2.2.1] hept-2-yl) -1,1,2,2-tetrafluoroethanesulfonate B-3;
Triphenylsulfonium trifluoromethanesulfonate B-4;
4-n-Butoxy-1-naphthyltetrahydrothiophenium nonafluorobutanesulfonate

<Acid-dissociable group-containing resin>
C-1: a repeating unit represented by the formula (3-15) (provided that R ¹⁵ is a methyl group; the same shall apply hereinafter) and a repeating unit represented by the formula (4-1) (provided that R ¹⁶ is a methyl group. The same applies hereinafter.) A copolymer having a molar ratio of 40:60 (Mw = 9,000).
C-2: a repeating unit represented by the formula (3-15), a repeating unit represented by the formula (4-1), and a repeating unit represented by the formula (5-1) (provided that R ¹⁸ Is a methyl group. The same applies hereinafter.) A copolymer having a molar ratio of 45:30:25 (Mw = 9,000).
C-3: molar ratio of the repeating unit represented by the above formula (3-17) (provided that R ¹⁵ is a methyl group; the same shall apply hereinafter) and the repeating unit represented by the above formula (4-1). Is a 40:60 copolymer (Mw = 6,000).
C-4: The molar ratio of the repeating unit represented by the formula (3-17), the repeating unit represented by the formula (4-1), and the repeating unit represented by the formula (5-1) is 45. : 30:25 copolymer (Mw = 7,000).

<Additive (Solution Control Agent)>
D-1; the following formula (D-1)

<Solvent>
E-1; propylene glycol monomethyl ether acetate E-2; cyclohexanone E-3; γ-butyrolactone

  Next, each composition solution is applied onto a silicon wafer coated with an antireflection film (ARC) as a lower layer film by spin coating so that a resist film having a thickness of 0.20 μm is obtained, and then a hot plate is used. PB was performed at 90 ° C. for 90 seconds. Thereafter, exposure was performed using an ArF excimer laser exposure apparatus (manufactured by Nikon Corporation, numerical aperture 0.55) while changing the exposure amount, and then PEB was performed at 110 ° C. for 90 seconds, and 2.38 mass% tetramethylammonium hydroxy The resist pattern was formed by developing with an aqueous solution for 1 minute, washing with water and drying.

The performance evaluation was performed according to the following procedure. The evaluation results are shown in Table 2.
sensitivity;
An exposure amount for forming a line-and-space pattern (1L1S) having a line width of 0.10 μm in a one-to-one line width was defined as an optimum exposure amount, and this optimum exposure amount was defined as sensitivity.
resolution;
The minimum line width of the line-and-space pattern (1L1S) resolved with the optimum exposure amount was taken as the resolution.
Pattern shape;
A square cross section of a line and space pattern (1L1S) having a line width of 0.10 μm was observed and evaluated using a scanning electron microscope (length measurement SEM: S9220, manufactured by Hitachi, Ltd.).
The size of the lower side (La) and the size of the upper side (Lb) in the rectangular cross section of the line-and-space pattern (1L1S) with a line width of 0.10 μm are measured with a scanning electron microscope (Hitachi, length measurement SEM: S9920). And measured according to the following criteria.
○ (good): satisfying the condition of 0.85 ≦ Lb / La ≦ 1 x (defect): not satisfying the condition of 0.85 ≦ Lb / La ≦ 1 LER;
Scanning electron microscope (Hitachi length measurement SEM: S9220) with respect to the resist pattern formed by the exposure amount reproducing the line and space (1L1S) mask pattern dimension with the line width of 0.10 μm (by the optimum exposure amount) Was used, and the dispersion (3σ) of variation in the direction perpendicular to the line direction of the pattern was calculated and evaluated by observing one side surface of the pattern edge at a plurality of positions.

  As is clear from Table 2, the positive radiation sensitive resin composition using the basic compound (A-1) of the present invention as an acid diffusion controller is that of Comparative Example 1 in which the acid diffusion controller is not used. LER was found to be better than

Claims (8)

A basic compound comprising an onium salt represented by the following general formula (V) .

[In general formula (V) , R shows a hydrogen atom, a methyl group, an ethyl group, a fluorine atom, or a trifluoromethyl group. Rf represents a fluorine atom or a trifluoromethyl group. R ¹ , R ² , R ³ and R ⁴ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms. R ⁵ represents a methyl group, an ethyl group or a propyl group. n is an integer of 0-3. M ⁺ represents a sulfonium cation or an iodonium cation. Note that at least one combination of R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , and R ¹ and R ⁴ may form a ring. ] The basic compound according to claim 1, wherein M ^{+ in the} general formula (V) is a sulfonium cation represented by the following general formula (2).

[In General Formula (2), R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon number. 6-18 aryl groups are shown, or any two or more of R ² , R ³ and R ⁴ are bonded to each other to form a ring together with the sulfur atom in the formula. ^{Incidentally,} the substituent in R 2, ^{R 3} and ^{R 4} are alkyl groups having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a hydroxyl group, a carboxyl group, an oxo group (i.e., = O group), carbon A hydroxyalkyl group having 1 to 4 carbon atoms, a cyano group, or a cyanoalkyl group having 2 to 5 carbon atoms. ] The basic compound according to claim 1, wherein M ^{+ in the} general formula (V) is an iodonium cation represented by the following general formula (3).

[In General Formula (3), R ⁵ and R ⁶ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 18 carbon atoms. Or R ⁵ and R ⁶ are bonded to each other to form a ring together with the iodine atom in the formula. Incidentally, the substituent in ^{R 5} and ^{R 6} are alkyl groups having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a hydroxyl group, a carboxyl group, an oxo group (i.e., = O group), 1 carbon atoms 4 hydroxyalkyl group, cyano group, or cyanoalkyl group having 2 to 5 carbon atoms. ]   A radiation-sensitive acid diffusion controller comprising the basic compound according to claim 1. (A) the radiation-sensitive acid diffusion controller according to claim 4;
(B) a radiation sensitive acid generator;
(C) an alkali-insoluble or hardly-alkali-soluble resin having an acid-dissociable group, which comprises an acid-dissociable group-containing resin that becomes alkali-soluble when the acid-dissociable group is dissociated. A positive-type radiation-sensitive resin composition. The positive radiation sensitive resin composition according to claim 5, wherein the (C) acid-dissociable group-containing resin contains a repeating unit represented by the following general formula (4).

In [general formula (4), R ⁷ represents a hydrogen atom or a methyl group. Each R ⁸ independently represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms, and R 8 ⁸ satisfies the following condition (1) or (2).
(1) At least one of R ⁸ is a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof.
(2) Any two of R ⁸ are bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof together with the carbon atom to which each R ⁸ is bonded. ] The positive radiation sensitive resin composition according to claim 6, wherein —COOC (R ⁸ ) _{3 in the} general formula (4) is the following formula (a), (b), or (c).

[In Formula (a), Formula (b), and Formula (c), each R ⁹ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms. In the formula (c), m is 0 or 1. ] The positive radiation sensitive resin composition according to any one of claims 5 to 7, wherein the (C) acid dissociable group-containing resin further contains a repeating unit represented by the following general formula (5).

In [Formula ^{(5), R 10} represents a hydrogen atom or a methyl group. ]