JP6079360B2 - Acid diffusion controller, photoresist composition, resist pattern forming method, compound and method for producing compound - Google Patents

Description

  The present invention relates to an acid diffusion controller, a photoresist composition, a resist pattern forming method, a compound, and a method for producing the compound.

  A chemically amplified photoresist composition generates an acid from an acid generator in an exposed area by irradiation with exposure light such as far ultraviolet light such as ArF excimer laser light and KrF excimer laser light, and this acid is used as a catalyst. Thus, the dissolution rate of the exposed part and the unexposed part in the developer is changed to form a resist pattern on the substrate.

  Such a photoresist composition is required to have not only excellent resolution performance but also excellent line width roughness (LWR) performance indicating a variation in the line width of the resist pattern as the processing technology becomes finer. . In response to this demand, an acid diffusion control agent is contained in the photoresist composition for the purpose of appropriately controlling the diffusion of the acid generated from the acid generator. In order to improve the performance of such an acid diffusion controller, various structures have been studied, and a photoresist composition containing an acid diffusion controller having a hydroxy group and a morpholine structure has been studied (Japanese Patent Application Laid-Open (JP-A)). 2011-170315 gazette).

  Under such circumstances, in the present situation where the miniaturization of the resist pattern is progressing more and more, the focus margin (Exposure) is suppressed from the viewpoint of suppressing the deterioration of the pattern shape such as the top loss and the stability of the processing process. There is also a demand for excellent Latitudé (EL) performance. However, the above-mentioned conventional photoresist composition cannot satisfy these requirements.

JP 2011-170315 A

  This invention is made | formed based on the above situations, The objective is to provide the acid diffusion control agent which can form the photoresist composition excellent in LWR performance, EL performance, and pattern shape.

The invention made to solve the above problems is
Nitrogen-containing compound containing a group having —SO ₂ — or —SO ₃ — between carbon-carbon bonds of a monovalent hydrocarbon group having 2 to 30 carbon atoms (hereinafter also referred to as “nitrogen-containing compound (S)”) An acid diffusion controller (hereinafter also referred to as “acid diffusion controller (I)”).

  Since the acid diffusion controller of the present invention is composed of the compound having the specific structure, the photoresist composition containing the compound has excellent LWR performance, EL performance, and pattern shape. Although the reason why the acid diffusion control agent has the specific structure described above is not necessarily clear, for example, the nitrogen-containing compound (S) constituting the acid diffusion control agent interacts with an acid. By having a sulfonyl group or a sulfonate group in addition to the nitrogen-containing group, it is considered that the affinity between the nitrogen-containing compound (S) and the polymer constituting the resist film is increased. As a result, the nitrogen-containing compound ( For example, the diffusion and uneven distribution of S) in the resist film are moderately suppressed.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子又は炭素数１〜２０の１価の有機基である。但し、Ｒ^１とＲ^２とが互いに結合して、これらが結合している窒素原子と共に環構造を形成していてもよい。Ｘは、単結合、カルボニル基、エーテル基、イミノ基、炭素数１〜２０の２価の炭化水素基又はこれらを組み合わせた基である。Ｙは、炭素数２〜３０の１価の炭化水素基の炭素−炭素結合間に−ＳＯ_２−又は−ＳＯ_３−を有する基である。但し、この基が有する水素原子の一部又は全部は置換されていてもよい。） The nitrogen-containing compound (S) is preferably represented by the following formula (1) (hereinafter, the compound represented by the following formula (1) is also referred to as “compound (1)”).

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, provided that R ¹ and R ² are bonded to each other; A ring structure may be formed together with the nitrogen atom to which these are bonded, and X is a single bond, a carbonyl group, an ether group, an imino group, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a combination thereof. Y is a group having —SO ₂ — or —SO ₃ — between carbon-carbon bonds of a monovalent hydrocarbon group having 2 to 30 carbon atoms, provided that this group has a hydrogen atom Part or all of may be substituted.)

  The said compound (1) consists of a compound which has the said specific structure, and the photoresist composition containing this is excellent in LWR performance, EL performance, and pattern shape. The reason why the acid diffusion control agent has the specific structure and thus exerts the above effect is not necessarily clear. For example, the compound (1) constituting the acid diffusion control agent is an amino group that interacts with an acid. In addition to this, having a sulfonyl group or a sulfonate group is considered to increase the affinity between the compound (1) and the polymer constituting the resist film. As a result, in the resist film of the compound (1) And the like are moderately suppressed.

（式（２）中、Ｒ^３は、炭素数１〜２０の２価の鎖状炭化水素基又は炭素数３〜２０の２価の脂環式炭化水素基である。Ｚは、−ＳＯ_２−又は−ＳＯ_３−である。Ｒ^４は、炭素数１〜２０の１価の鎖状炭化水素基又は炭素数３〜２０の１価の脂環式炭化水素基である。但し、Ｒ^３及びＲ^４が有する水素原子の一部又は全部は置換されていてもよい。また、Ｒ^３とＲ^４とが互いに結合してこれらが結合しているＺと共に環構造を形成していてもよい。） Y in the above formula (1) is preferably represented by the following formula (2).

(In the formula (2), ^{R 3} is a divalent alicyclic hydrocarbon group having a divalent chain hydrocarbon group or a 3 to 20 carbon atoms having 1 to 20 carbon atoms .Z is -SO ₂ -Or -SO _3- R ⁴ is a monovalent chain hydrocarbon group having 1 to 20 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, provided that R ³ And a part or all of hydrogen atoms of R ⁴ may be substituted, or R ³ and R ⁴ may be bonded to each other to form a ring structure together with Z to which these are bonded. .)

  It is considered that the above compound has the above specific structure, so that the above-mentioned affinity is further enhanced. As a result, the LWR performance, EL performance and pattern shape of the photoresist composition containing the acid diffusion controller are further improved. .

（式（３）中、Ｒ^１’及びＲ^２’は、それぞれ独立して、炭素数１〜１０の１価の鎖状炭化水素基又は炭素数３〜２０の１価の脂環式炭化水素基である。但し、Ｒ^１’とＲ^２’とが互いに結合して、これらが結合している窒素原子と共に環構造を形成していてもよい。Ｒ^ａは、水素原子、カルボキシ基、シアノ基、炭素数１〜１５の１価の炭化水素基又は炭素数１〜１５の１価の複素環基である。この炭化水素基及び複素環基が有する水素原子の一部又は全部は置換されていてもよい。Ｒ^ｂ及びＲ^ｃは、それぞれ独立して、単結合、炭素数１〜１０の２価の鎖状炭化水素基又は炭素数３〜１５の２価の脂環式炭化水素基である。但し、この鎖状炭化水素基及び脂環式炭化水素基が有する水素原子の一部又は全部は置換されていてもよい。また、Ｒ^ｂとＲ^ｃとが互いに結合して、これらが結合する炭素原子と共に環構造を形成してもよい。Ｅは、−ＳＯ_２−又は−ＳＯ_３−である。Ｘは、上記式（１）と同義である。） The compound represented by the above formula (1) is preferably represented by the following formula (3).

(In Formula (3), R ^{1 ′} and R ^{2 ′} are each independently a monovalent chain hydrocarbon group having 1 to 10 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. Provided that R ^{1 ′} and R ^{2 ′} may be bonded to each other to form a ring structure together with the nitrogen atom to which R ^{1 ′} and R ^{2 ′} are bonded, and R ^a is a hydrogen atom, a carboxy group, or a cyano group. A monovalent hydrocarbon group having 1 to 15 carbon atoms or a monovalent heterocyclic group having 1 to 15 carbon atoms, wherein some or all of the hydrogen atoms of the hydrocarbon group and heterocyclic group are substituted. R ^b and R ^c are each independently a single bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 15 carbon atoms. However, part or all of the hydrogen atoms of the chain hydrocarbon group and alicyclic hydrocarbon group may be substituted. And a R ^b and ^{R c} are bonded to each other, may .E to form a ring structure together with the carbon atoms to which they are attached, -SO ₂ - or -SO ₃ - is .X, the above equation (1 Is synonymous with

  It is considered that the compound has a bulky cyclic sulfonyl structure or sultone structure, so that diffusion of the compound (1) in the resist film is more appropriately suppressed, and as a result, the compound contains the acid diffusion controller. The LWR performance, EL performance and pattern shape of the photoresist composition are further improved.

（式（４）中、Ｇは、−Ｏ−又は−ＣＨ_２−である。Ｒ^ｄは、ヒドロキシ基、シアノ基、ハロゲン原子又は炭素数１〜１０の１価の炭化水素基である。ｋは、０〜９の整数である。ｎは、１〜４の整数である。ｍは、１〜６の整数である。） The compound represented by the above formula (1) is preferably represented by the following formula (4).

(In Formula (4), G is —O— or —CH ₂ —. R ^d is a hydroxy group, a cyano group, a halogen atom, or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Is an integer from 0 to 9. n is an integer from 1 to 4. m is an integer from 1 to 6.)

  It is considered that the above compound has the above specific structure, whereby the diffusion in the resist film is further moderately suppressed by the bulk of the molecule, and the interaction with the acid generated from the acid generator is also moderately increased. . As a result, the LWR performance, EL performance, and pattern shape of the photoresist composition containing the acid diffusion controller are further improved.

The photoresist composition of the present invention comprises:
[A] a polymer having an acid dissociable group (hereinafter, also referred to as “[A] polymer”),
[B] acid generator, and [C] the acid diffusion controller (hereinafter also referred to as “[C] acid diffusion controller”)
Containing.

  Since the said photoresist composition contains the said acid diffusion control agent mentioned above, it is excellent in LWR performance, EL performance, and pattern shape.

The photoresist composition is
[D] Acid diffusion control agent other than [C] acid diffusion control agent (hereinafter also referred to as “[D] Other acid diffusion control agent”)
It is preferable to further contain.
In addition to the [C] acid diffusion control agent, the photoresist composition contains [D] another acid diffusion control agent, thereby improving LWR performance, EL performance, and pattern shape. The reason why the above effect is improved by the fact that the photoresist composition further contains [D] another acid diffusion control agent is not necessarily clear, but, for example, diffusion as a whole compound constituting the acid diffusion control agent It is conceivable that the degree can be adjusted.

The resist pattern forming method of the present invention comprises:
(1) A step of forming a resist film using the photoresist composition;
(2) a step of exposing the resist film; and (3) a step of developing the exposed resist film.
According to the resist pattern forming method, since the above-described photoresist composition is used, a resist pattern having a small LWR and an excellent pattern shape can be formed while ensuring a wide exposure margin.

（式（ｉ）中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子又は炭素数１〜２０の１価の有機基である。但し、Ｒ^１とＲ^２とが互いに結合して、これらが結合している窒素原子と共に環構造を形成していてもよい。Ｘは、単結合、カルボニル基、エーテル基、イミノ基、炭素数１〜２０の２価の炭化水素基又はこれらを組み合わせた基である。Ｙ’は、炭素数２〜３０の１価の炭化水素基の炭素−炭素結合間に−ＳＯ_３−を有する基である。但し、この基が有する水素原子の一部又は全部は置換されていてもよい。） The compound of the present invention is represented by the following formula (i).

(In formula (i), R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, provided that R ¹ and R ² are bonded to each other; A ring structure may be formed together with the nitrogen atom to which these are bonded, and X is a single bond, a carbonyl group, an ether group, an imino group, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a combination thereof. Y ′ is a group having —SO ₃ — between the carbon-carbon bonds of a monovalent hydrocarbon group having 2 to 30 carbon atoms, provided that a part of hydrogen atoms of this group or All may be substituted.)

  The compound is considered to have a high affinity with a polymer or the like constituting the resist film by having the specific structure. Therefore, as described above, it can be suitably used as an acid diffusion control agent, and as a result, a photoresist composition containing this is excellent in LWR performance, EL performance, and pattern shape.

（式（ａ）、式（ｂ）及び式（ｉ）中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子又は炭素数１〜２０の１価の有機基である。但し、Ｒ^１とＲ^２とが互いに結合して、これらが結合している窒素原子と共に環構造を形成していてもよい。Ｘは、単結合、カルボニル基、エーテル基、イミノ基、炭素数１〜２０の２価の炭化水素基又はこれらを組み合わせた基である。Ｙ’は、炭素数２〜３０の１価の炭化水素基の炭素−炭素結合間に−ＳＯ_３−を有する基である。但し、この基が有する水素原子の一部又は全部は置換されていてもよい。Ｌは、ハロゲン原子である。） The manufacturing method of the compound represented by the following formula (i) of the present invention is
A step of reacting an amine compound represented by the following formula (a) with an organic halide represented by the following formula (b);

(In Formula (a), Formula (b), and Formula (i), R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, provided that R ¹ And R ² may be bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded, X is a single bond, a carbonyl group, an ether group, an imino group, or a group having 1 to 20 carbon atoms. Y ′ is a group having —SO ₃ — between the carbon-carbon bonds of a monovalent hydrocarbon group having 2 to 30 carbon atoms, provided that it is a divalent hydrocarbon group or a combination thereof. (Part or all of the hydrogen atoms of this group may be substituted. L is a halogen atom.)

  According to the method for producing the compound, the compound represented by the formula (i) can be produced easily and in a high yield by reacting the specific amine compound with the specific organic halide. .

  As described above, according to the acid diffusion controller, the photoresist composition and the resist pattern forming method of the present invention, a resist pattern having a small LWR and an excellent pattern shape can be formed while ensuring a wide focus margin. Can do. The compound of the present invention can be suitably used as the acid diffusion controller, and according to the method for producing the compound of the present invention, this compound can be produced simply and with good yield. These can be suitably used in the microfabrication field where further miniaturization proceeds in the future.

<Acid diffusion controller (I)>
The acid diffusion controller (I) of the present invention comprises a nitrogen-containing compound (S). The acid diffusion controller (I) can form a photoresist composition having excellent LWR performance, EL performance, and pattern shape by having the specific structure. The reason why the nitrogen-containing compound (S) constituting the acid diffusion controller (I) has the above specific structure and thus exhibits the above effect is not necessarily clear. For example, the nitrogen-containing compound (S) is an acid and By having a sulfonyl group or a sulfonate group in addition to the interacting nitrogen-containing group, it is considered that the affinity between the nitrogen-containing compound (S) and the polymer constituting the resist film is increased. For example, diffusion and uneven distribution of the nitrogen-containing compound (S) in the resist film can be appropriately suppressed.

<Nitrogen-containing compound (S)>
The nitrogen-containing compound (S) includes a group having —SO ₂ — or —SO ₃ — between carbon-carbon bonds of a monovalent hydrocarbon group having 2 to 30 carbon atoms (hereinafter referred to as “group (x)”). A nitrogen-containing compound. The nitrogen-containing compound (S) is not particularly limited as long as it is a compound containing a group (x) and a nitrogen atom.

  Examples of the monovalent hydrocarbon group having 2 to 30 carbon atoms include a monovalent chain hydrocarbon group having 2 to 30 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, and carbon. Examples thereof include monovalent aromatic hydrocarbon groups of several 6 to 30.

Examples of the monovalent chain hydrocarbon group having 2 to 30 carbon atoms include:
Alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, hexyl group;
An alkenyl group such as a propenyl group, a butenyl group or a pentenyl group;
Examples thereof include alkynyl groups such as propynyl group, butynyl group and pentynyl group.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms include:
Monocyclic cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group;
Norbornyl group, adamantyl group, tricyclodecyl group, tetracyclododecyl group, tricyclo [2.2.1.0 ^3,5 ] heptan-2-yl group, tricyclo [2.2.1.1 ^3,5 ] heptane A polycyclic cycloalkyl group such as a 2-yl group;
A monocyclic cycloalkenyl group such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group;
Examples thereof include polycyclic cycloalkenyl groups such as norbornenyl group and tricyclodecenyl group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include:
Aryl groups such as phenyl, tolyl, xylyl, naphthyl and anthryl;
Examples thereof include aralkyl groups such as benzyl group, phenethyl group, and naphthylmethyl group.

  As the monovalent hydrocarbon group, from the viewpoint of improving the LWR performance, EL performance, and pattern shape of the acid diffusion controller (I), among these, a monovalent chain hydrocarbon group, monovalent fat Cyclic hydrocarbon groups are preferred, monovalent alicyclic hydrocarbon groups are more preferred, cycloalkyl groups are more preferred, and polycyclic cycloalkyl groups are particularly preferred.

-SO 2 in the hydrocarbon group _- and -SO 3 _- is not particularly restricted but includes carbon bond, a carbon - - carbon bearing between carbon single bond.

As the group (x), for example,
Examples of the group having —SO ₂ — include a group derived from sulfone, a group derived from cyclic sulfone, and the like.
Examples of the group having —SO ₃ — include a group derived from a sulfonate ester, a group derived from sultone, and the like.

  The nitrogen atom content in the nitrogen-containing compound (S) is not particularly limited. For example, amino group, substituted amino group, ammonium group, amide group, imide group, hydrazyl group, carbamate group, urea group, thiourea group, It is included as a nitrogen atom constituting a cyano group, a nitrogen-containing heterocyclic group or the like. Among these, an amino group, a substituted amino group, an amide group, an imide group, and a hydrazyl group are preferable, and an amino group and a substituted amino group are more preferable.

  As the nitrogen-containing compound (S), the compound (1) is preferable.

<Compound (1)>
The compound (1) is represented by the above formula (1).

In the above formula (1), ^{R 1} and ^{R 2} are each independently a monovalent organic group hydrogen atom or a C 1-20. However, R ¹ and R ² may be bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded. X is a single bond, a carbonyl group, an ether group, an imino group, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a group obtained by combining these. Y is a group having —SO ₂ — or —SO ₃ — between carbon-carbon bonds of a monovalent hydrocarbon group having 2 to 30 carbon atoms. However, one part or all part of the hydrogen atom which this group has may be substituted.
Hereinafter, with respect to the compound (1), the (R ¹ ) (R ² ) N— group, the X group, and the Y group will be described in order.

[(R ¹ ) (R ² ) N-group]
Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ¹ and R ² include a chain hydrocarbon group having 1 to 20 carbon atoms and an alicyclic hydrocarbon group having 3 to 20 carbon atoms. , An aromatic hydrocarbon group having 6 to 20 carbon atoms, a group having one or more groups containing a hetero atom between carbon-carbon bonds of these groups, and replacing some or all of the hydrogen atoms of these groups And a group substituted with a group.

  Examples of the chain hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an alkynyl group having 2 to 20 carbon atoms. As said alicyclic hydrocarbon group, a C3-C20 cycloalkyl group, a C3-C20 cycloalkenyl group, etc. are mentioned, for example. Examples of the aromatic hydrocarbon group include an aryl group having 6 to 20 carbon atoms and an aralkyl group having 7 to 20 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms include:
Examples include a methyl group, an ethyl group, a linear or branched propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a tetradecyl group, and an icosyl group.

Examples of the alkenyl group having 2 to 20 carbon atoms include:
Examples include an ethenyl group, a linear or branched propenyl group, a butenyl group, a hexenyl group, a decenyl group, and an icocenyl group.

Examples of the alkynyl group having 2 to 20 carbon atoms include
Examples include ethynyl group, propynyl group, linear or branched butynyl group, hexynyl group, decynyl group, icosinyl group and the like.

Examples of the cycloalkyl group having 3 to 20 carbon atoms include, for example,
Examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclodecyl group, a norbornyl group, an adamantyl group, a tricyclodecyl group, and a tetracyclododecyl group.

Examples of the C3-C20 cycloalkenyl group include:
Examples thereof include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, a cyclodecenyl group, and a norbonenyl group.

Examples of the aryl group having 6 to 20 carbon atoms include:
Examples include phenyl group, tolyl group, xylyl group, mesityl group, ethylphenyl group, t-butylphenyl group, naphthyl group, methylnaphthyl group, anthryl group and the like.

Examples of the aralkyl group having 7 to 20 carbon atoms include:
A benzyl group, a phenethyl group, a naphthylmethyl group, an anthrylmethyl group, etc. are mentioned.

Examples of the group containing a hetero atom that the above group may have between carbon-carbon bonds include:
—O—, —NR ″ — (R ″ is a monovalent hydrocarbon group), —S—, —CO—, —CS—, a group obtained by combining these, and the like.

Examples of the substituent that the above group may have include, for example:
Halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, amino group such as unsubstituted amino group, alkylamino group, dialkylamino group, hydroxy group, carboxy group, cyano group, nitro group, alkyl substituted Examples thereof include an aromatic heterocyclic group such as a furyl group, an imidazolyl group, and a pyrazolyl group, an acyl group, an acetoxy group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group.

Examples of the ring structure that R ¹ and R ² may be bonded to each other and formed together with the nitrogen atom to which they are bonded include:
Azacycloalkane structures such as azacyclopentane structure, azacyclohexane structure, azacycloheptane structure and azacyclooctane structure; diazacycloalkane structures such as piperazine structure and imidazolidine structure; azaoxacycloalkane structures such as morpholine structure Can be mentioned.

Examples of the group represented by (R ¹ ) (R ² ) N— include groups represented by the following formulas.

In said formula, R ( ^alpha) is respectively independently a C1-C6 alkyl group. X ′ is a halogen atom. n is an integer of 1 to 4. g is an integer of 1-4.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^α include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, Examples include t-butyl group. Among these, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

As the group represented by the above (R ¹ ) (R ² ) N—, a group represented by the following formula (A) is preferable. When the group represented by the above (R ¹ ) (R ² ) N— is a group represented by the following formula (A), the basicity of the amino group is appropriately increased, and [B] from the acid generator It is considered that the interaction with the acid to be generated increases more moderately. As a result, the LWR performance, EL performance, and pattern shape of the photoresist composition containing the acid diffusion controller (I) are improved.

In the above formula (A), R ^{1 ′} and R ^{2 ′} are each independently a monovalent chain hydrocarbon group having 1 to 10 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. It is a group. However, R ^{1 ′} and R ^{2 ′} may be bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded.

Examples of the monovalent chain hydrocarbon group having 1 to 10 carbon atoms represented by R ^{1 ′} and R ^{2 ′} include a chain hydrocarbon represented by R ¹ and R ² in the above formula (1). Among the groups exemplified as the group, those having 1 to 10 carbon atoms can be mentioned.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ^{1 ′} and R ^{2 ′} include, for example, alicyclic represented by R ¹ and R ² in the above formula (1). The group etc. which were illustrated as a hydrocarbon group are mentioned.

Examples of the ring structure that may be formed together with the nitrogen atom to which R ^{1 ′} and R ^{2 ′} are bonded to each other include, for example, R ¹ and R ^{2 in} the above formula (1) What was illustrated as a ring structure which may form by combining is mentioned.
It is.

  The group represented by the above formula (A) is preferably a 1-azacycloalkyl group, more preferably a 5- to 8-membered 1-azacycloalkyl group, and a 1-azacyclopentyl group or 1-azacyclohexyl group. More preferred is a 1-azacyclohexyl group.

[X group]
X is a single bond, a carbonyl group, an ether group, an imino group, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a group obtained by combining these.

  Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by X include, for example, a divalent chain hydrocarbon group having 1 to 20 carbon atoms and a divalent alicyclic group having 3 to 20 carbon atoms. Examples thereof include a hydrocarbon group and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Examples of the divalent chain hydrocarbon group include an alkanediyl group having 1 to 20 carbon atoms, an alkenediyl group having 2 to 20 carbon atoms, and an alkynediyl group having 2 to 20 carbon atoms. As said bivalent alicyclic hydrocarbon group, a C3-C20 cycloalkanediyl group, a C3-C20 cycloalkenediyl group, etc. are mentioned, for example. Examples of the divalent aromatic hydrocarbon group include an arenediyl group having 6 to 20 carbon atoms and an arenediylalkanediyl group having 7 to 20 carbon atoms.

Examples of the alkanediyl group having 1 to 20 carbon atoms include:
Examples include a methanediyl group, a linear or branched ethanediyl group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, an octanediyl group, a decandiyl group, a hexadecandiyl group, and an icosanediyl group.

Examples of the alkenediyl group having 2 to 20 carbon atoms include:
A linear or branched ethenediyl group, propenediyl group, butenediyl group, hexenediyl group, decenediyl group, icosendiyl group and the like can be mentioned.

Examples of the alkynediyl group having 2 to 20 carbon atoms include:
Examples include an ethynediyl group, a propynediyl group, a linear or branched butynediyl group, a hexynediyl group, a decynediyl group, and an icosindiyl group.

Examples of the C3-C20 cycloalkanediyl group include:
Cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cycloheptanediyl group, cyclooctanediyl group, cyclodecanediyl group, norbornanediyl group, adamantanediyl group, tricyclodecanediyl group, tetracyclododecane A diyl group etc. are mentioned.

Examples of the C3-C20 cycloalkenediyl group include:
Examples include a cyclopropenediyl group, a cyclobutenediyl group, a cyclopentenediyl group, a cyclohexenediyl group, a cyclooctenediyl group, a cyclodecenediyl group, and a norbornenediyl group.

Examples of the C6-20 arenediyl group include:
Examples thereof include a benzenediyl group, a methylbenzenediyl group, a dimethylbenzenediyl group, a naphthalenediyl group, and an anthracenediyl group.

Examples of the C7-20 arenediylalkanediyl group include:
Examples thereof include benzenediylmethanediyl group, benzenediylethanediyl group, naphthalenediylmethanediyl group, anthracenediylethanediyl group and the like.

  Among the groups represented by X, examples of the group obtained by combining groups other than the hydrocarbon group include an ester group, an amide group, a carbonate group, a carbamate group, and a urea group. Among these, an ester group and an amide group are preferable, and an ester group is more preferable.

Examples of the group obtained by combining the above groups represented by X above include:
_{- (CH 2) m-COO} -, - (CH 2) m-OCO -, - (CH 2) m-CONH -, - (CH 2) m-NHCO -, - (CH 2) m-O-, _{- (CH 2) m-NH} -, - (CH 2) m-OCOO -, - (CH 2) m-OCONH -, - (CH 2) m-NHCOO -, - (CH 2) m-NHCONH- ( As mentioned above, m is an integer of 1-6. Among these, from the viewpoint of easy production of the compound _{(1), - (CH 2} ) m-COO- is preferred. As m, 1-4 are preferable, 1 or 2 is more preferable, and 1 is further more preferable.

[Y group]
Y is a group having —SO ₂ — or —SO ₃ — between carbon-carbon bonds of a monovalent hydrocarbon group having 2 to 30 carbon atoms. However, one part or all part of the hydrogen atom which this group has may be substituted. Y is not particularly limited as long as it has the above structure, and may have one —SO ₂ — or —SO ₃ —, or two or more. Y may have both —SO ₂ — and —SO ₃ —.

  Examples of Y include a group represented by the following formula.

In the above formula, each ^Rβ is independently an alkyl group having 1 to 6 carbon atoms. Ar is a monovalent aromatic group or a monovalent aromatic heterocyclic group. h is an integer of 0-3. R ^d and k are synonymous with the above formula (4).

  Y is preferably a group represented by the above formula (2). When Y is a group represented by the above formula (2), it is considered that the affinity of the compound (1) with the polymer or the like constituting the resist film is further increased. As a result, the acid diffusion controller (I LWR performance, EL performance and pattern shape of a photoresist composition containing

In the above formula (2), R ³ is a single bond, a divalent alicyclic hydrocarbon group having a divalent chain hydrocarbon group or a 3 to 20 carbon atoms having 1 to 20 carbon atoms. Z is —SO ₂ — or —SO ₃ —. R ⁴ is a monovalent chain hydrocarbon group having 1 to 20 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. However, some or all of the hydrogen atoms R ³ and R ⁴ have may be substituted. Further, R ³ and R ⁴ may be bonded to each other to form a ring structure together with Z to which these are bonded.

As a C1-C20 bivalent chain hydrocarbon group represented by said R < ³ >, the same thing as the group illustrated as a bivalent chain hydrocarbon group in X of said Formula (1), etc., for example Is mentioned.

Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ³ are the same as those exemplified as the divalent alicyclic hydrocarbon group in X of the above formula (1). And the like.

Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴ include groups exemplified as the monovalent chain hydrocarbon group in R ¹ and R ² of the above formula (1). The same thing is mentioned.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ⁴ include a monovalent alicyclic hydrocarbon group in R ¹ and R ² of the above formula (1). And the same as those mentioned above.

Examples of the substituent that R ³ and R ⁴ may have include the groups exemplified as the substituent that the hydrocarbon group may have in R ¹ and R ² of the above formula (1), and The same thing is mentioned.

  As group represented by said Formula (2), group represented by a following formula (Ya) is preferable. When the group represented by the above formula (2) is represented by the following formula (Ya), the compound (1) has a bulky cyclic sulfonyl structure or sultone structure, so that in the resist film of the compound (1) As a result, the LWR performance, EL performance and pattern shape of the photoresist composition containing the acid diffusion controller (I) are further improved.

In formula (Ya), R ^a represents a hydrogen atom, a carboxy group, a cyano group, a monovalent hydrocarbon group having 1 to 15 carbon atoms, or a monovalent heterocyclic group having 1 to 15 carbon atoms. Some or all of the hydrogen atoms of this hydrocarbon group or heterocyclic group may be substituted. R ^b and R ^c are each independently a single bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 15 carbon atoms. However, some or all of the hydrogen atoms of the chain hydrocarbon group and alicyclic hydrocarbon group may be substituted. R ^b and R ^c may be bonded to each other to form a ring structure together with the carbon atom to which they are bonded. E is —SO ₂ — or —SO ₃ —.

Examples of the monovalent hydrocarbon group having 1 to 15 carbon atoms represented by ^Ra include, among the groups exemplified as the hydrocarbon group in R ¹ and R ² of the above formula (1), 15 and the like.
Among these, an alkyl group and an aryl group are preferable, and a methyl group, an ethyl group, a phenyl group, and a naphthyl group are more preferable.

Examples of the monovalent heterocyclic group having 1 to 15 carbon atoms represented by ^Ra above include:
As an aromatic heterocyclic group,
A nitrogen atom-containing group such as a pyrrolyl group or a pyridyl group; an oxygen atom-containing group such as a furyl group, a furfuryl group or a pyranyl group; a sulfur atom-containing group such as a thienyl group or a tenenyl group;
As an aliphatic heterocyclic group,
Nitrogen atom-containing groups such as pyrrolidyl group and piperidyl group; oxygen atom-containing groups such as tetrahydrofuranyl group and tetrahydropyranyl group; sulfur atom-containing groups such as tetrahydrothiophenyl group and tetrahydrothiophenylmethyl group; nitrogen oxygen such as morpholyl group An atom containing group etc. are mentioned.
Among these, an aromatic heterocyclic group is preferable, and a pyridyl group, a furyl group, and a thienyl group are more preferable.

Examples of the substituent that R ^a may have include those exemplified as the substituent that the hydrocarbon group may have in R ¹ and R ² of the above formula (1). Among these, an amino group is preferable and an unsubstituted amino group is more preferable.

R ^a is preferably a hydrogen atom, a carboxy group, a cyano group, an alkyl group, an aminoalkyl group, an aryl group or an aromatic heterocyclic group, more preferably a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group, More preferred is a hydrogen atom.

As the divalent chain hydrocarbon group having 1 to 10 carbon atoms represented by R ^b and R ^c , for example, for the divalent chain hydrocarbon group represented by X in the above formula (1), Examples thereof include those having 1 to 10 carbon atoms.

Examples of the divalent alicyclic hydrocarbon group having 3 to 15 carbon atoms represented by R ^b and R ^c, for example, a divalent alicyclic hydrocarbon group represented by X in the above formula (1) For example, those having 3 to 15 carbon atoms may be mentioned.

Examples of the substituent that the chain hydrocarbon group and the alicyclic hydrocarbon group may have include the same groups as those exemplified as the substituent that R ³ and R ⁴ may have, and the like. Is mentioned.

Examples of the ring structure that may be formed together with the carbon atom to which R ^b and R ^c are bonded to each other include, for example, a norbornane structure or an adamantane structure containing —SO ₂ — or —SO ₃ — in the structure. , Tricyclodecane structure, tetracyclododecane structure and the like.

[Compound (1)]
Examples of the compound (1) include compounds represented by the following formulas.

In the above formula, G is —O— or —CH ₂ —. R ^d is a hydroxy group, a cyano group, a halogen atom, or a monovalent hydrocarbon group having 1 to 10 carbon atoms. k is an integer of 0-9. n is an integer of 1 to 4. m is an integer of 1-6. R ^γ is independently an alkyl group having 1 to 6 carbon atoms. E is an aminoalkyl group, a carboxy group, or a cyano group. X ″ is a halogen atom. Ar is a monovalent aromatic group or monovalent aromatic heterocyclic group. H is an integer of 0 to 3. f is an integer of 1 to 10. is there.

  Among these, the compound represented by the above formula (3) is preferable.

In the above formula (3), R ^{1 ′} and R ^{2 ′} are each independently a monovalent chain hydrocarbon group having 1 to 10 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. It is a group. However, R ^{1 ′} and R ^{2 ′} may be bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded. R ^a is a hydrogen atom, a carboxy group, a cyano group, a monovalent hydrocarbon group having 1 to 15 carbon atoms, or a monovalent heterocyclic group having 1 to 15 carbon atoms. Some or all of the hydrogen atoms of the hydrocarbon group and heterocyclic group may be substituted. R ^b and R ^c are each independently a single bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 15 carbon atoms. However, some or all of the hydrogen atoms of the chain hydrocarbon group and alicyclic hydrocarbon group may be substituted. R ^b and R ^c may be bonded to each other to form a ring structure together with the carbon atom to which they are bonded. E is —SO ₂ — or —SO ₃ —. X is synonymous with the above formula (1).

  Moreover, the compound represented by the said Formula (4) is more preferable among the compounds represented by the said Formula (3). The compound represented by the above formula (4) has the above specific structure, so that diffusion in the resist film is further moderately suppressed due to the bulk of the molecule, and [B] an acid generated from the acid generator It is considered that the interaction between the two increases moderately. As a result, the LWR performance, EL performance, and pattern shape of the photoresist composition containing the acid diffusion controller (I) are further improved.

In the formula (4), G is, -O- or -CH ₂ -. R ^d is a hydroxy group, a cyano group, a halogen atom, or a monovalent hydrocarbon group having 1 to 10 carbon atoms. k is an integer of 0-9. n is an integer of 1 to 4. m is an integer of 1-6.

[Production Method of Compound (1)]
The compound (1) can be produced, for example, by reacting an amine compound represented by the following formula (a) with an organic halide represented by the following formula (B) according to the following reaction scheme. .

In the above formula (a), formula (B) and formula (1), R ¹ , R ² , X and Y have the same meaning as in the above formula (1). L is a halogen atom.

  Examples of the halogen atom represented by L include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable.

  The compound represented by the above formula (1) is produced by reacting the amine compound represented by the above formula (a) with the organic halide represented by the above formula (B) in a solvent such as toluene. can do. Since this reaction can easily proceed, compound (1) can be obtained simply and with high yield by this production method.

  The organic halide represented by the above formula (B) is reacted, for example, from a dihalide containing an X group and a hydroxy compound containing a Y group in a solvent such as dichloromethane in the presence of a basic compound such as triethylamine. Can be obtained.

<Photoresist composition>
The photoresist composition of the present invention contains [A] a polymer, [B] an acid generator, and [C] the acid diffusion controller. In addition to these components, the photoresist composition may further contain [D] another acid diffusion controller and [E] solvent as suitable components, and the range not impairing the effects of the present invention. In addition, you may further contain another arbitrary component. Hereinafter, each component will be described.

<[A] polymer>
[A] The polymer is a polymer having an acid dissociable group. [A] The polymer is at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure, in addition to a structural unit containing an acid dissociable group (hereinafter also referred to as “structural unit (I)”). It is preferable to further include the structural unit (II) including the structure of, and may further include other structural units such as a structural unit having a polar group. [A] The polymer may have one or more of each structural unit. Hereinafter, each structural unit will be described.

[Structural unit (I)]
The structural unit (I) is a structural unit containing an acid dissociable group. Examples of the structural unit (I) include a structural unit (I-1) represented by the following formula (5).

In said formula (5), ^RA is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R ^p1 , R ^p2 and R ^p3 are each independently an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms. However, R ^p2 and R ^p3 may be bonded to each other to form a cycloalkanediyl group having 4 to 20 carbon atoms together with the carbon atom to which they are bonded.

  As the structural unit (I-1), structural units represented by the following formulas (5-1) to (5-4) are preferable.

In the above formulas (5-1) to (5-4), R ^A , R ^p1 , R ^p2 and R ^p3 have the same ^{meaning as} in the above formula (5). i and j are each independently an integer of 1 to 4.

  Examples of the structural unit represented by the above formulas (5-1) to (5-4) include a structural unit represented by the following formula.

In the above formula, R ^A has the same meaning as in the above formula (5).

  The structural unit (I) is preferably a structural unit represented by the above formula (5-1) or a structural unit represented by the formula (5-2), and is derived from 1-alkyl-1-cyclopentyl (meth) acrylate. The structural unit derived from 2-alkyl-2-adamantyl (meth) acrylate is more preferable.

  As a content rate of structural unit (I), 10 mol%-100 mol% are preferable with respect to all the structural units which comprise a [A] polymer, 20 mol%-80 mol% are more preferable, 30 mol% More preferred is ˜70 mol%. When the content ratio of the structural unit (I) is less than the lower limit, the pattern forming property of the photoresist composition may be deteriorated. Further, the solubility of the resist film in a developer can be increased.

[Structural unit (II)]
The structural unit (II) is a structural unit including at least one structure selected from the group consisting of a lactone structure, a cyclic carbonate structure, and a sultone structure. [A] By having the structural unit (II), the polymer can improve basic resist characteristics such as adhesion between a resist film formed from the photoresist composition and the substrate.

  Examples of the structural unit (II) include a structural unit represented by the following formula.

In the above formula, R ^L1 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

  Of these, the structural unit (II) is preferably a structural unit containing a lactone structure or a structural unit containing a sultone structure, more preferably a structural unit containing a norbornane lactone structure or a structural unit containing a norbornane sultone structure.

  As a content rate of structural unit (II), 30 mol%-80 mol% are preferable with respect to all the structural units which comprise a [A] polymer, 40 mol%-70 mol% are more preferable, 45 mol% More preferred is ~ 65 mol%. If the content ratio of the structural unit (II) is less than the lower limit, the adhesion of the resist pattern formed from the photoresist composition to the substrate may be lowered. Moreover, when the content rate of structural unit (II) exceeds the said upper limit, the pattern formation property of the said photoresist composition may fall.

[Other structural units]
[A] The polymer may have other structural units other than the structural units (I) and (II). As said other structural unit, the structural unit etc. which have a polar group are mentioned, for example. Examples of the polar group include a hydroxy group, a carboxy group, a cyano group, a nitro group, and a sulfonamide group. Among these, a hydroxy group and a carboxy group are preferable, and a hydroxy group is more preferable.
Examples of the structural unit having a polar group include a structural unit represented by the following formula.

In the above formula, R ^B is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ^C is a hydrogen atom or a methyl group.

  As a content rate of the said other structural unit, it is 30 mol% or less normally with respect to all the structural units which comprise a [A] polymer, and 20 mol% or less is preferable. If the content ratio of the other structural units exceeds the upper limit, the pattern forming property of the photoresist composition may be lowered.

  [A] The content of the polymer in the photoresist composition is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 85% by mass or more.

<[A] Polymer Synthesis Method>
[A] The polymer can be synthesized, for example, by polymerizing a monomer giving each structural unit in a suitable solvent using a radical polymerization initiator.

  Examples of the radical polymerization initiator include azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropylpropylene). Pionitrile), azo radical initiators such as 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate; benzoyl peroxide, t-butyl hydroperoxide, And peroxide radical initiators such as cumene hydroperoxide. Of these, AIBN and dimethyl 2,2'-azobisisobutyrate are preferred, and AIBN is more preferred. These radical initiators can be used alone or in combination of two or more.

Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane;
Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane;
Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene;
Halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene;
Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate;
Ketones such as acetone, methyl ethyl ketone, 4-methyl-2-pentanone, 2-heptanone;
Ethers such as tetrahydrofuran, dimethoxyethanes, diethoxyethanes;
Examples include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and 4-methyl-2-pentanol. The solvent used for these polymerizations may be used alone or in combination of two or more.

  As reaction temperature in the said superposition | polymerization, 40 to 150 degreeC and 50 to 120 degreeC are preferable normally. The reaction time is usually preferably 1 hour to 48 hours and 1 hour to 24 hours.

  [A] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is not particularly limited, but is preferably 1,000 or more and 50,000 or less, more preferably 2,000 or more and 30,000 or less. Preferably, it is 3,000 or more and 20,000 or less. [A] If the Mw of the polymer is less than the lower limit, the heat resistance of the resulting resist film may be reduced. Conversely, if the Mw of the [A] polymer exceeds 50,000, the developability of the resist film may be reduced.

  [A] The ratio (Mw / Mn) of Mw to the number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer is usually from 1 to 5, preferably from 1 to 3, more preferably from 1 to 2. .

Mw and Mn of the polymer in this specification are values measured using gel permeation chromatography (GPC) under the following conditions.
GPC column: 2 G2000HXL, 1 G3000HXL, 1 G4000HXL (above, manufactured by Tosoh)
Column temperature: 40 ° C
Elution solvent: Tetrahydrofuran (Wako Pure Chemical Industries)
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<[B] Acid generator>
[B] The acid generator generates an acid upon exposure, and the acid dissociates an acid-dissociable group in the [A] polymer to generate a polar group such as a carboxy group. As a result, the [A] polymer The solubility in the developer changes. As the content of the [B] acid generator in the photoresist composition, a low molecular compound form (hereinafter also referred to as “[B] acid generator” as appropriate) may be used as part of the polymer. Either in the form of an incorporated acid generating group or in both forms.

  [B] Examples of the acid generator include onium salt compounds, N-sulfonyloxyimide compounds, halogen-containing compounds, and diazoketone compounds.

  Examples of the onium salt compounds include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.

  Examples of the sulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept- 2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium camphorsulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexyl Phenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldipheny Sulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium camphorsulfonate, 4-methanesulfonylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2 -Yl-1,1,2,2-tetrafluoroethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium camphorsulfonate, trifer Ruhosuhoniumu 1,1,2,2-tetrafluoro-6- (1-adamantanecarbonyloxy) - hexane-1-sulfonate, and the like.

  Examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nona. Fluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophene Ni-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium camphorsulfonate , 1- (6-n-butoxynaphthalen-2-yl) Torahydrothiophenium trifluoromethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydro Thiophenium perfluoro-n-octanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2 , 2-tetrafluoroethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium camphorsulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate , 1- (3,5-dimethyl-4 Hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl- 4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxy Phenyl) tetrahydrothiophenium camphorsulfonate and the like.

  Examples of the iodonium salt include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl- 1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium camphorsulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, Bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2 1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t- butylphenyl) iodonium camphorsulfonate, and the like.

Examples of the sulfonimide compound include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene 2,3-dicarboximide, N- (2- (3- tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethane-sulfonyl Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide etc. can be mentioned.

  [B] Among these, as the acid generator, onium salt compounds are preferable, sulfonium salts are more preferable, triphenylsulfonium salts are more preferable, and triphenylsulfonium adamantane-1-yloxycarbonyldifluoromethanesulfonate is particularly preferable.

  [B] As the content of the acid generator, when the [B] acid generator is a [B] acid generator, the [A] polymer 100 is used from the viewpoint of ensuring the sensitivity and developability of the photoresist composition. 0.1 parts by mass or more and 30 parts by mass or less are preferable, 0.5 parts by mass or more and 20 parts by mass or less are more preferable, and 1 part by mass or more and 15 parts by mass or less are more preferable. [B] When the content of the acid generator is less than 0.1 parts by mass, the sensitivity and developability of the photoresist composition tend to be lowered. On the other hand, when the content of the [B] acid generator exceeds 30 parts by mass, the transparency to the exposure light is lowered, and it is difficult to obtain a desired resist pattern. [B] 1 type (s) or 2 or more types can be used for an acid generator.

<[C] acid diffusion controller>
[C] The acid diffusion controller is the acid diffusion controller (I) of the present invention. The said photoresist composition is excellent in LWR performance, EL performance, and pattern shape by containing the acid diffusion control agent (I) in addition to the [A] polymer and the [B] acid generator. [C] The acid diffusion control agent is described in the above-mentioned section of acid diffusion control agent (I).

  From the viewpoint of improving the LWR performance, EL performance, and pattern shape of the photoresist composition, the lower limit of the content of the [C] acid diffusion controller is 0. 1 part by weight is preferred, 0.2 part by weight is more preferred, 0.3 part by weight is further preferred, 0.6 part by weight is particularly preferred, and 1.2 part by weight is even more particularly preferred. On the other hand, the upper limit of the content of the [C] acid diffusion controller is preferably 30 parts by mass, more preferably 20 parts by mass, and even more preferably 15 parts by mass. [C] When the content of the acid diffusion controller exceeds the above upper limit, the sensitivity of the photoresist composition may decrease.

<Optional component>
[[D] Other acid diffusion controllers]
The photoresist composition may contain [D] another acid diffusion controller as necessary. The photoresist composition can further improve LWR performance, EL performance, and pattern shape by further containing [D] another acid diffusion controller in addition to [C] acid diffusion controller. [D] The reason why the above effect can be further improved by further containing another acid diffusion controller is not necessarily clear, but, for example, the degree of diffusion of the entire compound constituting the acid diffusion controller is determined. It can be considered that it can be adjusted. [D] The content of the other acid diffusion controller in the photoresist composition includes an acid diffusion controller as a low molecular compound as described later (hereinafter referred to as “[D] Other acid diffusion controller” May be in the form of acid diffusion control groups incorporated as part of the polymer, or in both forms.

  [D] Other acid diffusion control agents include, for example, a compound represented by the following formula (6) (hereinafter also referred to as “nitrogen-containing compound (I)”), a compound having two nitrogen atoms in the same molecule (Hereinafter also referred to as “nitrogen-containing compound (II)”), compounds having three nitrogen atoms (hereinafter also referred to as “nitrogen-containing compound (III)”), amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds Etc.

In said formula (6), R < ⁵ > -R < ⁷ > is respectively independently a hydrogen atom, the linear, branched or cyclic alkyl group which may be substituted, an aryl group, or an aralkyl group.

  Examples of the nitrogen-containing compound (I) include monoalkylamines such as n-hexylamine; dialkylamines such as di-n-butylamine; trialkylamines such as triethylamine; aromatic amines such as aniline. Can be mentioned.

  Examples of the nitrogen-containing compound (II) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, and the like.

  Examples of the nitrogen-containing compound (III) include polyamine compounds such as polyethyleneimine and polyallylamine; and polymers such as dimethylaminoethylacrylamide.

  Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. Can be mentioned.

  Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea and the like. .

  Examples of the nitrogen-containing heterocyclic compound include pyridines such as pyridine and 2-methylpyridine; morpholines such as morpholine and N-undecylcarbonyloxyethylmorpholine; pyrazine, pyrazole and the like.

  Moreover, the compound which has an acid dissociable group can also be used as said nitrogen-containing organic compound. Examples of the nitrogen-containing organic compound having such an acid dissociable group include Nt-butoxycarbonylpiperidine, Nt-butoxycarbonylimidazole, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl- 2-phenylbenzimidazole, Nt-butoxycarbonyl-di-n-octylamine, Nt-butoxycarbonyl-diethanolamine, Nt-butoxycarbonyl-dicyclohexylamine, Nt-butoxycarbonyl-diphenylamine, N- Examples thereof include t-butoxycarbonyl-4-hydroxypiperidine, Nt-amyloxycarbonyl-4-hydroxypiperidine and the like.

  [D] As another acid diffusion controller, a photodegradable base which is exposed to light and generates a weak acid by exposure can also be used. Examples of the photodegradable base include an onium salt compound that decomposes upon exposure and loses acid diffusion controllability. Examples of the onium salt compound include a sulfonium salt compound represented by the following formula (D1), an iodonium salt compound represented by the following formula (D2), and the like.

In the above formula (D1) and formula (D2), R ^{8 to} R ¹² are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a halogen atom. Z ⁻ and Q ⁻ are each independently an anion represented by OH ⁻ , R ^δ —COO ⁻ , R ^δ —SO ₃ ^— or the following formula (D3). However, R ( ^delta) is an alkyl group, an aryl group, or an aralkyl group.

In said formula (D3), R < ¹³ > is a C1-C12 linear or branched alkyl group by which a part or all of a hydrogen atom may be substituted by the fluorine atom, or C1-C12 These are linear or branched alkoxyl groups. u is an integer of 0-2.

[D] The content of the other acid diffusion controller is [D] When the other acid diffusion controller is [D] another acid diffusion controller, [A] with respect to 100 parts by mass of the polymer, 0-20 mass parts is preferable, 0.1 mass part-15 mass parts is more preferable, 0.3 mass part-10 mass parts is still more preferable. [D] When the content of the other acid diffusion control agent exceeds the upper limit, the sensitivity of the photoresist composition may be lowered.
[D] The content of the other acid diffusion control agent is from the viewpoint of improving the LWR performance, EL performance, and pattern shape of the photoresist composition, with respect to 1 part by mass of [C] acid diffusion control agent. And preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.2 parts by mass or more and 5 parts by mass or less.

[[E] Fluoropolymer]
The photoresist composition may contain a [E] fluoropolymer (excluding the [A] polymer). When the photoresist composition contains the [E] fluorine-containing polymer, when the resist film is formed, the distribution is near the resist film surface due to the oil-repellent characteristics of the fluorine-containing polymer in the film. There is a tendency to be unevenly distributed, and it is possible to prevent the acid generator, the acid diffusion controller, and the like from being eluted into the immersion medium during immersion exposure. Further, due to the water-repellent characteristics of the [E] fluoropolymer, the advancing contact angle between the resist film and the immersion medium can be controlled within a desired range, and the occurrence of bubble defects can be suppressed. Furthermore, the receding contact angle between the resist film and the immersion medium is increased, and high-speed scanning exposure is possible without leaving water droplets. Thus, when the said photoresist composition contains a [E] fluoropolymer, the resist film suitable for an immersion exposure method can be formed.

  [E] The fluorine-containing polymer is not particularly limited as long as it is a polymer having fluorine atoms, but the fluorine atom content (% by mass) is higher than that of the [A] polymer in the photoresist composition. It is preferable. [A] When the fluorine atom content is higher than that of the polymer, the degree of uneven distribution described above becomes higher, and characteristics such as water repellency and elution suppression of the resulting resist film are improved.

[E] The fluorine atom content of the fluoropolymer is preferably 1% by mass or more, more preferably 2 to 60% by mass, further preferably 4 to 40% by mass, and particularly preferably 7 to 30% by mass. [E] If the fluorine atom content of the fluoropolymer is less than the above lower limit, the hydrophobicity of the resist film surface may be lowered. In addition, the fluorine atom content rate (mass%) of a polymer can obtain | require the structure of a polymer by < ¹³ > C-NMR spectrum measurement, and can calculate it from the structure.

  [E] The fluoropolymer preferably has at least one selected from the group consisting of the following structural unit (Ea) and structural unit (Eb). [E] The fluoropolymer may have one or more structural units (Ea) and structural units (Eb).

[Structural unit (Ea)]
The structural unit (Ea) is a structural unit represented by the following formula (7a). [E] A fluorine-containing polymer can adjust a fluorine atom content rate by having a structural unit (Ea).

(In the formula (7a), ^{R D} is a hydrogen atom, a methyl group or a trifluoromethyl group .G represents a single bond, an oxygen atom, a sulfur _{atom, -CO-O -, - SO} 2 -O-NH- , —CO—NH— or —O—CO—NH—, wherein R ^E is a monovalent chain hydrocarbon group having 1 to 6 carbon atoms having at least one fluorine atom or at least one fluorine atom. And a monovalent aliphatic cyclic hydrocarbon group having 4 to 20 carbon atoms.

Examples of the chain hydrocarbon group having 1 to 6 carbon atoms and having at least one fluorine atom represented by R ^E, for example, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, Perfluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,1,3,3,3-hexafluoropropyl group, perfluoro n-propyl group, perfluoro i-propyl group Perfluoro n-butyl group, perfluoro i-butyl group, perfluoro t-butyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, perfluorohexyl group and the like. It is done.

Specific examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms and having at least one fluorine atom represented by R ^E, for example, monofluoromethyl cyclopentyl group, difluorocyclopentyl groups, perfluorocyclopentyl group, mono Examples include fluorocyclohexyl group, difluorocyclopentyl group, perfluorocyclohexylmethyl group, fluoronorbornyl group, fluoroadamantyl group, fluorobornyl group, fluoroisobornyl group, fluorotricyclodecyl group, and fluorotetracyclodecyl group. .

  Examples of the monomer that gives the structural unit (Ea) include trifluoromethyl (meth) acrylic acid ester, 2,2,2-trifluoroethyl (meth) acrylic acid ester, and perfluoroethyl (meth) acrylic acid. Ester, perfluoro n-propyl (meth) acrylate, perfluoro i-propyl (meth) acrylate, perfluoro n-butyl (meth) acrylate, perfluoro i-butyl (meth) acrylate, Perfluoro t-butyl (meth) acrylic acid ester, 2- (1,1,1,3,3,3-hexafluoropropyl) (meth) acrylic acid ester, 1- (2,2,3,3,4 , 4,5,5-octafluoropentyl) (meth) acrylic acid ester, perfluorocyclohexylmethyl (meth) Acrylic acid ester, 1- (2,2,3,3,3-pentafluoropropyl) (meth) acrylic acid ester, monofluorocyclopentyl (meth) acrylic acid ester, difluorocyclopentyl (meth) acrylic acid ester, perfluorocyclopentyl (Meth) acrylic acid ester, monofluorocyclohexyl (meth) acrylic acid ester, difluorocyclopentyl (meth) acrylic acid ester, perfluorocyclohexylmethyl (meth) acrylic acid ester, fluoronorbornyl (meth) acrylic acid ester, fluoroadamantyl (Meth) acrylic acid ester, fluorobornyl (meth) acrylic acid ester, fluoroisobornyl (meth) acrylic acid ester, fluorotricyclodecyl (meth) acrylic acid ester, Le Oro tetracyclododecene decyl (meth) and acrylic acid esters.

  As a content rate of the said structural unit (Ea), 0-50 mol% is preferable with respect to all the structural units which comprise a [E] fluoropolymer, 0-40 mol% is more preferable, 5-35 mol is preferable. % Is more preferable. By using such a content ratio, a higher dynamic contact angle on the resist coating surface can be expressed during immersion exposure.

[Structural unit (Eb)]
The structural unit (Eb) is a structural unit represented by the following formula (7b). [E] Since the fluoropolymer increases the hydrophobicity by having the structural unit (Eb), the dynamic contact angle on the surface of the resist film formed from the photoresist composition can be further improved.

In said formula (7b), R <^F> is a hydrogen atom, a methyl group, or a trifluoromethyl group. R ¹⁴ is a (s + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom, —NR′—, a carbonyl group, —CO—O—, or a terminal at the R ¹⁵ side of R ¹⁴ Also includes a structure in which —CO—NH— is bonded. R ′ is a hydrogen atom or a monovalent organic group. R ¹⁵ is a single bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms, or a divalent aliphatic cyclic hydrocarbon group having 4 to 20 carbon atoms. X ² is a divalent chain hydrocarbon group having 1 to 20 carbon atoms and having at least one fluorine atom. A ¹ is an oxygen atom, —NR ″ —, —CO—O— * or —SO ₂ —O— *. R "is a hydrogen atom or a monovalent organic group. * ^{Is .R 16} indicating a binding site that binds to ^{R 16} is a hydrogen atom or a monovalent organic group .s is 1-3 Provided that when s is 2 or 3, a plurality of R ¹⁵ , X ² , A ¹ and R ¹⁶ may be the same or different.

When R ¹⁶ is a hydrogen atom, it is preferable in that the solubility of the [E] fluoropolymer in an alkaline developer can be improved.

Examples of the monovalent organic group represented by R ¹⁶ include an acid-dissociable group, an alkali-dissociable group, or a hydrocarbon group having 1 to 30 carbon atoms that may have a substituent. .

  Examples of the structural unit (Eb) include structural units represented by the following formulas (7b-1) to (7b-3).

In the above formulas (7b-1) to (7b-3), R ^{14 ′} is a divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. R ^F , X ² , R ¹⁶ and s are as defined in the above formula (7b). When s is 2 or 3, the plurality of X ² and R ¹⁶ may be the same or different.

  As a content rate of the said structural unit (7b), 0-90 mol% is preferable with respect to all the structural units which comprise a [E] fluoropolymer, 5-85 mol% is more preferable, 10-80 mol % Is particularly preferred. By setting it as such a content rate, the resist film surface formed from the said photoresist composition can improve the fall degree of a dynamic contact angle in alkali image development.

[Structural unit (Ec)]
[E] In addition to the structural units (Ea) and (Eb), the fluoropolymer may have a structural unit containing an acid dissociable group (hereinafter also referred to as “structural unit (Ec)”). Good. [E] When the fluoropolymer has the structural unit (Ec), the shape of the resulting resist pattern becomes better. Preferable examples of the structural unit (Ec) include the structural unit (I) in the above-described [A] polymer.

  As a content rate of the said structural unit (Ec), 0-80 mol% is preferable with respect to all the structural units which comprise a [E] fluoropolymer, 10-80 mol% is more preferable, 20-75 mol%. Is more preferable, and 30 to 75 mol% is particularly preferable. When the content ratio of the structural unit (Ec) exceeds the above upper limit, the hydrophobicity of the resulting resist film surface may be lowered.

[Other structural units]
[E] In addition to the above structural unit, the [E] fluoropolymer includes, for example, at least one structure selected from the group consisting of a structural unit containing an alkali-soluble group, a lactone structure, a cyclic carbonate structure, and a sultone structure. You may have other structural units, such as a structural unit and a structural unit containing an alicyclic group. As said alkali-soluble group, a carboxy group, a sulfonamide group, a sulfo group etc. are mentioned, for example. Preferable examples of the structural unit having at least one structure selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure include the structural unit (II) in the above-mentioned [A] polymer.

  As a content rate of said other structural unit, it is 30 mol% or less normally with respect to all the structural units which comprise a [E] fluoropolymer, and 20 mol% or less is preferable. When the content ratio of the other structural unit exceeds the upper limit, the pattern formability of the resist film may be lowered.

  As content of [E] fluoropolymer in the said photoresist composition, 0-20 mass parts is preferable with respect to 100 mass parts of [A] polymer, and 1 mass part-15 mass parts are more preferable. 2 mass parts-10 mass parts are further more preferable. [E] If the content of the fluoropolymer exceeds the above upper limit, the pattern forming property of the photoresist composition may be lowered.

<[F] solvent>
The photoresist composition usually contains a [F] solvent. [F] Solvent can dissolve or disperse at least [A] polymer, [B] acid generator and [C] acid diffusion controller, and [D] other acid diffusion controller contained as desired. If it is a solvent, it will not specifically limit.

  [F] Examples of the solvent include alcohol solvents, ether solvents, ketone organic solvents, amide solvents, ester organic solvents, hydrocarbon solvents, and the like.

As an alcohol solvent, for example,
Methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert- Pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n- Nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, furf Alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, mono-alcohol solvents such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 -Polyhydric alcohol solvents such as ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether.

  Examples of the ether solvent include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, methoxybenzene, anisole (methylphenyl ether) and the like.

  Examples of ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone (2-heptanone), ethyl-n-butyl ketone. , Ketones such as methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone And system solvents.

  Examples of the amide solvents include N, N′-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone and the like can be mentioned.

  Examples of the ester solvents include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec sec -Butyl, n-pentyl acetate, i-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-acetate -Nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoe Til ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl Ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate , N-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, etc. .

Examples of the hydrocarbon solvent include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, and cyclohexane. , Aliphatic hydrocarbon solvents such as methylcyclohexane;
Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene and n-amylnaphthalene Group hydrocarbon solvents and the like.

  Among these, ester solvents and ketone solvents are preferable, and propylene glycol monomethyl ether acetate, cyclohexanone, and γ-butyrolactone are more preferable. The photoresist composition may contain one or more [F] solvents.

[Other optional ingredients]
The photoresist composition may contain other optional components in addition to the above [A] to [F]. Examples of the other optional components include surfactants, alicyclic skeleton-containing compounds, and sensitizers. Each of these other optional components may be used alone or in combination of two or more.

(Surfactant)
Surfactants have the effect of improving coatability, striation, developability, and the like. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol diacrylate. Nonionic surfactants such as stearate; commercially available products include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173 (above, manufactured by DIC), Florard FC430, FC431 (above, Sumitomo 3M) Manufactured by Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (above, manufactured by Asahi Glass Industrial Co., Ltd.) Can be mentioned. As content of surfactant in the said photoresist composition, it is 2 mass parts or less normally with respect to 100 mass parts of [A] polymers.

(Alicyclic skeleton-containing compound)
The alicyclic skeleton-containing compound has an effect of improving dry etching resistance, pattern shape, adhesion to the substrate, and the like.

Examples of the alicyclic skeleton-containing compound include adamantane derivatives such as 1-adamantanecarboxylic acid, 2-adamantanone, and 1-adamantanecarboxylic acid t-butyl;
Deoxycholic acid esters such as t-butyl deoxycholate, t-butoxycarbonylmethyl deoxycholic acid, 2-ethoxyethyl deoxycholic acid;
Lithocholic acid esters such as t-butyl lithocholic acid, t-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid;
3- [2-Hydroxy-2,2-bis (trifluoromethyl) ethyl] tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, 2-hydroxy-9-methoxycarbonyl-5-oxo-4-oxa-tricyclo [4.2.1.0 ^3,7 ] nonane, and the like. The content of the alicyclic skeleton-containing compound in the photoresist composition is usually 5 parts by mass or less with respect to 100 parts by mass of the [A] polymer.

(Sensitizer)
The sensitizer exhibits an effect of increasing the amount of acid generated from the [B] acid generator and the like, and has an effect of improving the “apparent sensitivity” of the photoresist composition.

  Examples of the sensitizer include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like. These sensitizers may be used alone or in combination of two or more. As content of the sensitizer in the said photoresist composition, it is 2 mass parts or less normally with respect to 100 mass parts of [A] polymers.

<Method for preparing photoresist composition>
The photoresist composition includes, for example, a [A] polymer, a [B] acid generator, a [C] acid diffusion controller, an optional component contained as necessary, and a [F] solvent in a predetermined ratio. Can be prepared. The photoresist composition is preferably filtered, for example, with a filter having a pore size of about 0.2 μm after mixing. The total solid content concentration of the photoresist composition is usually 0.1% by mass to 50% by mass, preferably 0.5% by mass to 30% by mass, and more preferably 1% by mass to 20% by mass.

<Resist pattern formation method>
The method for forming a resist pattern according to the present invention includes:
(1) A step of forming a resist film using the photoresist composition;
(2) a step of exposing the resist film; and (3) a step of developing the exposed resist film.

  According to the resist pattern forming method, since the photoresist composition described above is used, it is possible to form a resist pattern having a small LWR and an excellent pattern shape while ensuring a wide exposure margin. Hereinafter, each step will be described.

[(1) Process]
In the step (1), a resist film is formed using the photoresist composition. A resist film is formed by applying on a substrate by an appropriate application means such as spin coating, cast coating, roll coating or the like. Examples of the substrate on which the resist film is formed include a silicon wafer, silicon dioxide, a wafer coated with an antireflection film, and the like. Examples of the coating method on the substrate include spin coating, cast coating, roll coating, and the like. Specifically, after applying the photoresist so that the resulting resist film has a predetermined film thickness, the solvent in the coating film is vaporized by, for example, soft baking (SB) to form the resist film. . As temperature of SB, it is 60 to 150 degreeC normally, and 80 to 130 degreeC is preferable. The SB time is usually 5 seconds to 600 seconds, and preferably 10 seconds to 300 seconds.

[(2) Process]
In the step (2), the resist film formed in the step (1) is exposed. This exposure is performed, for example, by irradiating exposure light through a photomask having a predetermined pattern (in some cases, through an immersion medium such as water). The exposure light is appropriately selected and irradiated from, for example, visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, etc. according to the line width of the target pattern. Among these, far ultraviolet rays such as ArF excimer laser light (wavelength 193 nm) and KrF excimer laser light (wavelength 248 nm) are preferable, and ArF excimer laser light is particularly preferable.

  After the exposure, post-exposure baking (PEB) is preferably performed to promote dissociation of the acid-dissociable group of the [A] polymer by the acid generated by the exposure in the exposed portion of the resist film. This PEB causes a difference in solubility in an alkaline developer between an exposed portion (exposed portion) and an unexposed portion (unexposed portion). As temperature of PEB, it is 50 to 180 degreeC normally, and 80 to 130 degreeC is preferable. The PEB time is usually 5 to 600 seconds, preferably 10 to 300 seconds.

[(3) Process]
In step (3), the exposed resist film is developed with a developer to form a predetermined resist pattern. After development, it is common to wash with water and dry. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, Ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4. 3.0] An aqueous alkali solution in which at least one of alkaline compounds such as 5-nonene is dissolved is preferable. In addition, as a developer, an organic solvent such as a hydrocarbon solvent, an ether solvent, an ester solvent, a ketone solvent, an alcohol solvent, or a solvent containing an organic solvent can be used.

  In addition, when performing immersion exposure, before the step (2), in order to protect the direct contact between the immersion liquid and the resist film, an immersion protective film insoluble in the immersion liquid is formed on the resist film. May be provided. Examples of the immersion protective film include a solvent peeling type protective film that peels off with a solvent before the step (3) (see, for example, JP-A-2006-227632), and a developer peeling type that peels off simultaneously with the development in the step (3). Any of the protective films (see, for example, WO2005-069076 and WO2006-035790) may be used. However, from the viewpoint of throughput, it is preferable to use a developer peeling type immersion protective film.

<Compound>
The compound of the present invention is represented by the above formula (i). The compound is considered to have a high affinity with a polymer or the like constituting the resist film by having the specific structure. Therefore, as described above, it can be suitably used as an acid diffusion control agent, and as a result, a photoresist composition containing this is excellent in LWR performance, EL performance, and pattern shape.

In the above formula (i), ^{R 1} and ^{R 2} are each independently a monovalent organic group hydrogen atom or a C 1-20. However, R ¹ and R ² may be bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded. X is a single bond, a carbonyl group, an ether group, an imino group, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a group obtained by combining these. Y ′ is a group having —SO ₃ — between carbon-carbon bonds of a monovalent hydrocarbon group having 2 to 30 carbon atoms. However, one part or all part of the hydrogen atom which this group has may be substituted.

<Method for producing compound>
The method for producing the compound represented by the above formula (i) of the present invention includes:
And a step of reacting the amine compound represented by the above formula (a) with the organic halide represented by the above formula (b). According to the method for producing the compound, the compound represented by the formula (i) can be produced easily and in a high yield by reacting the specific amine compound with the specific organic halide. .

In the above formula (a), formula (b) and formula (i), R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. However, R ¹ and R ² may be bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded. X is a single bond, a carbonyl group, an ether group, an imino group, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a group obtained by combining these. Y ′ is a group having —SO ₃ — between carbon-carbon bonds of a monovalent hydrocarbon group having 2 to 30 carbon atoms. However, one part or all part of the hydrogen atom which this group has may be substituted. L is a halogen atom.

The preparation method of the compound and the compound, carbon monovalent hydrocarbon group represented by Y is 2 to 30 carbon atoms in the manufacturing method of the above-mentioned compounds (1) and compound (1) - -SO ₃ between carbon bond This is the case where the group has-and is described above, and thus the description thereof is omitted here.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. Each physical property value in the following Examples and Comparative Examples was measured by the following method.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)]
Using Tosoh GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL), flow rate: 1.0 ml / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C., with monodisperse polystyrene as standard Measured by gel permeation chromatography (GPC).

[ ¹³ C-NMR analysis]
The ¹³ C-NMR analysis for determining the content of the structural unit of the polymer and the fluorine atom content was performed using a nuclear magnetic resonance apparatus (“JNM-ECP500” manufactured by JEOL Ltd.).

[Mass Spectrometry Analysis]
Mass spectrometric analysis of the compounds was performed using GC-MS (Agilent Technology, 7890A GC, 240MS system).

<Production of Compound (i)>
[Example 1]
(1) Synthesis of 5,5-dioxo-4-oxa-5λ ⁶ -thiatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl-chloroacetate Reaction in which the inside was sufficiently dried by vacuum heating After replacing the vessel with dry nitrogen, 9.51 g of 2-hydroxy-4-oxa-5λ ⁶ -thiatricyclo [4.2.1.0 ^3,7 ] nonane-5,5-dione (manufactured by Kuraray) was added to 50 mL of dichloromethane. The solution dissolved in was charged and cooled to 0 ° C. Thereto, 6.07 g of triethylamine was added so that the temperature of the reaction solution did not rise, and then 5.93 g of chloroacetyl chloride was added so that the reaction temperature would not rise. The mixture was stirred for 1 hour while maintaining 0 ° C., 100 mL of ultrapure water and 20 mL of a saturated aqueous sodium hydrogen carbonate solution were added, and the organic layer was recovered by a liquid separation operation. The organic layer was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure using an evaporator. 10.00 g of 5,5-dioxo-4-oxa-5λ ⁶ -thiatricyclo [4.2.1.0 ^{3 , 7} ] nonan-2-yl-chloroacetate (compound represented by the following formula (sa)) (purity 90%) was obtained.

GC-MS (MeOH-CI) m / z (rel. Intensity): 269 ([M ⁺ +1], 2), 267 ([M ⁺ +1], 8), 173 (100).

(2) Synthesis of 5,5-dioxo-4-oxa-5λ ⁶ -thiatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl-2- (piperidin-1-yl) acetate The reactor, which had been sufficiently dried inside, was replaced with dry nitrogen, and then 5,5-dioxo-4-oxa-5λ ⁶ -thiatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl-chloro. After 11.2 g of acetate and 100 mL of dry toluene were charged and dissolved, 4.54 g of piperidine was added dropwise while maintaining the temperature of the reaction solution at 23 ° C. After the dropwise addition, the mixture was stirred for 2 hours. After completion of the reaction, 100 mL of 1N HCl was added. The organic layer was recovered by a liquid separation operation, 100 mL of ultrapure water and 10 mL of a saturated aqueous sodium hydrogen carbonate solution were added thereto, and the organic layer was recovered by a liquid separation operation. The collected organic layer was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by an evaporator. The residue after concentration was purified by silica gel chromatography (developing solvent: ethyl acetate / n-hexane = 2/1 (volume ratio)), and 5,5-dioxo-4-oxa-5λ ⁶ -thiatricyclo [4.2.1]. .0 ^3,7] nonan-2-yl - was obtained (piperidin-1-yl) acetate (compound represented by the following formula (S-1)) 9.9 g (98% pure).

GC-MS (MeOH-CI) m / z (rel. Intensity): 316 ([M ⁺ +1], 7), 231 (2), 173 (100), 126 (44).

<Synthesis of polymer>
[[A] Synthesis of polymer]
[Synthesis Example 1]
The following compound (M-1) 11.92 g (20 mol%), compound (M-2) 41.07 g (30 mol%), compound (M-3) 15.75 g (15 mol%), compound (M- 4) 11.16 g (10 mol%), 20.10 g (25 mol%) of the compound (M-5) and 3.88 g of dimethyl 2,2′-azobis (2-isobutyronitrile) in 200 g of 2-butanone A monomer solution was prepared by dissolution. After charging 100 g of 2-butanone into a 1,000 mL three-necked flask and purging with nitrogen for 30 minutes, the reaction kettle was heated to 80 ° C. with stirring. Thereto, the monomer solution prepared above was dropped over 4 hours, and further aged at 80 ° C. for 2 hours after the completion of dropping. After completion of the polymerization, the polymerization reaction liquid was cooled to 30 ° C. or lower by water cooling. The polymerization reaction solution was concentrated under reduced pressure using an evaporator until the mass of the polymerization reaction solution reached 200 g. Thereafter, this concentrated polymerization reaction solution was put into 1,000 g of methanol, and reprecipitation operation was performed. The obtained slurry was filtered by suction filtration, and the solid content was washed with methanol three times. The obtained powder was vacuum-dried at 60 ° C. for 15 hours to obtain 88.0 g (yield 88%) of polymer (A-1) as a white powder. Mw of the polymer (A-1) was 9,300, and Mw / Mn was 1.60. As a result of ¹³ C-NMR analysis, the content ratio of the structural units derived from the compounds (M-1), (M-2), (M-3), (M-4) and (M-5) was 16 mol, respectively. %, 26 mol%, 19 mol%, 11 mol% and 28 mol%. The fluorine atom content rate of the polymer (A-1) was 0 mass%.

[[E] Synthesis of fluoropolymer]
[Synthesis Example 2]
In a 100 mL three-necked flask, 3.8 g (70 mol%) of the following compound (M-6), 1.2 g (30 mol%) of compound (M-7) and 10 g of 2-butanone were charged and dissolved. 0.09 g of 2′-azobis (2-isobutyronitrile) was added. After purging with nitrogen for 30 minutes, the reaction kettle was heated to 80 ° C. with stirring, and the polymerization reaction was carried out for 6 hours with the start of heating as the polymerization start time. After completion of the polymerization, the polymerization reaction liquid was cooled to 30 ° C. or less by water cooling, and concentrated under reduced pressure with an evaporator until the mass of the polymerization reaction liquid became 12.5 g. The concentrated polymerization reaction solution was slowly added to 75 g of n-hexane cooled to 0 ° C. to precipitate a solid content. The obtained slurry was filtered, the solid content was washed with n-hexane, and the obtained powder was vacuum dried at 40 ° C. for 15 hours to obtain 3.75 g of a polymer (E-1) as a white powder. (Yield 75%). Mw of the polymer (E-1) was 9,400, and Mw / Mn was 1.50. As a result of ¹³ C-NMR analysis, the content ratios of structural units derived from the compounds (M-6) and (M-7) were 68.5 mol% and 31.5 mol%, respectively. The fluorine atom content rate of the polymer (E-1) was 21.4 mass%.

[Synthesis Example 3]
In a 100 mL three-necked flask, 4.06 g (70 mol%) of the following compound (M-8), 0.94 g (30 mol%) of the above compound (M-7) and 10 g of 2-butanone were dissolved and further dissolved. , 2'-azobis (2-isobutyronitrile) 0.07g was added. After purging with nitrogen for 30 minutes, the reaction kettle was heated to 80 ° C. with stirring, and the polymerization reaction was carried out for 6 hours with the start of heating as the polymerization start time. After completion of the polymerization, the polymerization reaction liquid was cooled to 30 ° C. or less by water cooling, and concentrated under reduced pressure with an evaporator until the mass of the polymerization reaction liquid became 12.5 g. The concentrated polymerization reaction solution was slowly added to 75 g of n-hexane cooled to 0 ° C. to precipitate a solid content. The obtained slurry was filtered, the solid content was washed with n-hexane, and the obtained powder was vacuum-dried at 40 ° C. for 15 hours to obtain 3.5 g of a white powder polymer (E-2). (Yield 70%). Mw of the polymer (E-2) was 11,400, and Mw / Mn was 1.50. As a result of ¹³ C-NMR analysis, the content ratios of structural units derived from the compounds (M-8) and (M-7) were 70.9 mol% and 29.1%, respectively. The fluorine atom content rate of the polymer (E-2) was 19.4 mass%.

[Synthesis Example 4]
In a 100 mL three-necked flask, 1.42 g (30 mol%) of the following compound (M-9), 3.58 g (70 mol%) of compound (M-10) and 10 g of 2-butanone were dissolved and further dissolved. 0.14 g of 2′-azobis (2-isobutyronitrile) was added. After purging with nitrogen for 30 minutes, the reaction kettle was heated to 80 ° C. with stirring, and the polymerization reaction was carried out for 6 hours with the start of heating as the polymerization start time. After completion of the polymerization, the polymerization reaction liquid was cooled to 30 ° C. or less by water cooling, and concentrated under reduced pressure with an evaporator until the mass of the polymerization reaction liquid became 12.5 g. The concentrated polymerization reaction solution was slowly added to 75 g of n-hexane cooled to 0 ° C. to precipitate a solid content. The obtained slurry was filtered, the solid content was washed with n-hexane, and the obtained powder was vacuum dried at 40 ° C. for 15 hours to obtain 3.85 g of a polymer (E-3) as a white powder. (Yield 77%). Mw of the polymer (E-3) was 7,400, and Mw / Mn was 1.50. As a result of ¹³ C-NMR analysis, the content ratios of structural units derived from the compounds (M-9) and (M-10) were 30.5 mol% and 69.5 mol%, respectively. The fluorine atom content rate of the polymer (E-3) was 10.3% by mass.

<Preparation of photoresist composition>
The [B] acid generator, [C] acid diffusion controller, [D] other acid diffusion controller and [F] solvent used for the preparation of the photoresist composition are shown below.

[[B] acid generator]
B-1: Triphenylsulfonium adamantane-1-yloxycarbonyldifluoromethanesulfonate (compound represented by the following formula (B-1))

[[C] acid diffusion controller]
S-1: Compound represented by the above formula (S-1)

[[D] Other acid diffusion control agents]
D-1: N-undecylcarbonyloxyethylmorpholine (compound represented by the following formula (D-1))
D-2: Nt-amyloxycarbonyl-4-hydroxypiperidine (compound represented by the following formula (D-2))
D-3: Triphenylsulfonium 10-camphorsulfonate (compound represented by the following formula (D-3))

[[F] solvent]
F-1: Propylene glycol monomethyl ether acetate F-2: Cyclohexanone F-3: γ-Butyrolactone

[Example 2]
[A] 100 parts by mass of (A-1) as a polymer, [B] 9.9 parts by mass of (B-1) as an acid generator, [C] (S-1) 1 as an acid diffusion controller .91 parts by mass, (E-1) 5 parts by mass as [E] fluoropolymer, and (F-1) 1,981 parts by mass as [F] solvent, (F-2) 849 parts by mass and ( F-3) 100 parts by mass was mixed to prepare a photoresist composition (J-1).

[Examples 3 and 4 and Comparative Example 1]
In Example 2, the photoresist compositions (J-2) and (J-3) and the photoresist composition were used in the same manner as in Example 2 except that the components of the types and blending amounts shown in Table 2 below were used. (CJ-1) was prepared. In Table 2, “-” indicates that the corresponding component was not used.

<Evaluation>
A resist pattern was formed using the prepared photoresist composition according to the following method. Each evaluation about a photoresist composition was performed by performing the following measurement about the obtained resist pattern. The evaluation results are shown in Table 3 below.

[Formation of resist pattern]
Each photoresist composition shown in Table 3 was spin-coated on a 12-inch diameter silicon wafer, and then subjected to SB at 120 ° C. for 60 seconds to form a resist film having a thickness of 75 nm. Next, a mask pattern for forming a pattern of 50 nm Line 100 nm Pitch is formed on this resist film using an ArF excimer laser immersion exposure apparatus (NSR-S610C, manufactured by NIKON) under the conditions of NA = 1.3, ratio = 0.800, Annular. Exposed through. Next, the exposed resist film was subjected to PEB at 90 ° C. for 60 seconds. Thereafter, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, washed with water, and dried to form a positive resist pattern. At this time, an exposure amount at which a portion exposed through a mask pattern for forming a pattern of 50 nm Line 100 nm Pitch forms a Line having a line width of 50 nm was defined as an optimum exposure amount (Eop). This optimum exposure amount was defined as sensitivity (mJ / cm ² ).

[LWR performance]
A resist pattern having a line width of 50 nm Line 100 nm Pitch formed at the optimal exposure amount was observed from above the pattern using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG4000), and the line width was measured at arbitrary 10 points. The 3 sigma value (variation) representing the distribution of the measured line width was defined as the LWR performance (nm).

[EL performance]
A positive resist pattern was formed by the same method as described above by changing the exposure amount in 1.0 mJ / cm ² steps within the range of ± 10 mJ / cm ² of the optimum exposure amount. The exposure value was plotted on the horizontal axis and the size of the obtained line pattern was plotted on the vertical axis, and the slope of the obtained straight line was defined as EL performance (nm / (mJ / cm ² )).

[Pattern shape]
The cross-sectional shape of the positive resist pattern obtained by the above method is observed with an electron microscope (S-4800, manufactured by Hitachi High-Technologies), and the line width Lb in the middle of the height direction of the resist pattern and the pattern The line width La at the top was measured, and the value of (La / Lb) was calculated. The pattern shape is “good” when 0.9 ≦ (La / Lb) ≦ 1.1, and “bad” when (La / Lb) <0.9 or 1.1 <(La / Lb). ".

  As can be seen from the results in Table 3, it can be seen that the photoresist compositions of Examples using the acid diffusion controller of the present invention are excellent in LWR performance and EL performance. In addition, the pattern shape of the resist pattern formed by the photoresist composition of the example was good, whereas in the photoresist composition of the comparative example, the pattern shape was a top rounding and was poor.

  ADVANTAGE OF THE INVENTION According to this invention, the acid diffusion control agent and photoresist composition which can form the photoresist composition excellent in LWR performance, EL performance, and pattern shape are provided. In addition, a compound suitable for the acid diffusion controller and a method for producing the compound are provided. Therefore, the present invention can be suitably used in the field of microfabrication where further miniaturization will proceed in the future.

Claims (7)

An acid diffusion controller comprising a compound represented by the following formula (3) .

(In Formula (3), R ^{1 ′} and R ^{2 ′} are each independently a monovalent chain hydrocarbon group having 1 to 10 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. Provided that R ^{1 ′} and R ^{2 ′} may be bonded to each other to form a ring structure together with the nitrogen atom to which R ^{1 ′} and R ^{2 ′} are bonded, and R ^a is a hydrogen atom, a carboxy group, or a cyano group. A monovalent hydrocarbon group having 1 to 15 carbon atoms or a monovalent heterocyclic group having 1 to 15 carbon atoms, wherein some or all of the hydrogen atoms of the hydrocarbon group and heterocyclic group are substituted. R ^b and R ^c are each independently a single bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 15 carbon atoms. However, part or all of the hydrogen atoms of the chain hydrocarbon group and alicyclic hydrocarbon group may be substituted. And a R ^b and ^{R c} are bonded to each other, may .E to form a ring structure together with the carbon atoms to which they are attached, -SO ₂ - or -SO ₃ - is .X represents a single bond, a carbonyl Group, ether group, imino group, divalent hydrocarbon group having 1 to 20 carbon atoms, or a combination of these. The acid diffusion controller according to claim 1 , wherein the compound represented by the formula (3) is represented by the following formula (4).

(In Formula (4), G is —O— or —CH ₂ —. R ^d is a hydroxy group, a cyano group, a halogen atom, or a monovalent hydrocarbon group having 1 to 10 carbon atoms. Is an integer from 0 to 9. n is an integer from 1 to 4. m is an integer from 1 to 6.) [A] a polymer having an acid dissociable group,
A photoresist composition comprising [B] an acid generator, and [C] the acid diffusion controller according to claim 1 or 2 . [D] [C] The photoresist composition according to claim 3 , further comprising an acid diffusion controller other than the acid diffusion controller. (1) A step of forming a resist film using the photoresist composition according to claim 3 or claim 4 ,
(2) A resist pattern forming method comprising: exposing the resist film; and (3) developing the exposed resist film. A compound represented by the following formula (i).

(In Formula (i), R ¹ and R ² are each independently a monovalent chain hydrocarbon group having 1 to 10 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. there. However, it linked with R ¹ and R ² together may .X also form a ring structure with the nitrogen atom which they are attached represents a single bond, carbonyl group, ether group, imino group, A divalent hydrocarbon group having 1 to 20 carbon atoms or a combination thereof, Y ′ is a group represented by the following formula (Ya).

(In the formula (Ya), R ^a is a hydrogen atom, a carboxy group, a cyano group, a monovalent hydrocarbon group having 1 to 15 carbon atoms, or a monovalent heterocyclic group having 1 to 15 carbon atoms. Some or all of the hydrogen atoms of the hydrogen group or heterocyclic group may be substituted, and R ^b and R ^c are each independently a single bond or a divalent chain carbon atom having 1 to 10 carbon atoms. A hydrogen group or a divalent alicyclic hydrocarbon group having 3 to 15 carbon atoms, provided that part or all of the hydrogen atoms of the chain hydrocarbon group and the alicyclic hydrocarbon group are substituted. And R ^b and R ^c may be bonded to each other to form a ring structure together with the carbon atom to which they are bonded, and E is —SO ₃ —.) The manufacturing method of the compound represented by the following formula (i) which has the process with which the amine compound represented by the following formula (a) and the organic halide represented by the following formula (b) are made to react.

(In formula (a), formula (b) and formula (i), R ¹ and R ² are each independently a monovalent chain hydrocarbon group having 1 to 10 carbon atoms or 3 to 20 carbon atoms. It is a monovalent alicyclic hydrocarbon group, provided that R ¹ and R ² may be bonded to each other to form a ring structure together with the nitrogen atom to which these are bonded, X being a single bond , A carbonyl group, an ether group, an imino group, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a combination thereof, Y ′ is a group represented by the following formula (Ya). , A halogen atom.)

(In the formula (Ya), R ^a is a hydrogen atom, a carboxy group, a cyano group, a monovalent hydrocarbon group having 1 to 15 carbon atoms, or a monovalent heterocyclic group having 1 to 15 carbon atoms. Some or all of the hydrogen atoms of the hydrogen group or heterocyclic group may be substituted, and R ^b and R ^c are each independently a single bond or a divalent chain carbon atom having 1 to 10 carbon atoms. A hydrogen group or a divalent alicyclic hydrocarbon group having 3 to 15 carbon atoms, provided that part or all of the hydrogen atoms of the chain hydrocarbon group and the alicyclic hydrocarbon group are substituted. And R ^b and R ^c may be bonded to each other to form a ring structure together with the carbon atom to which they are bonded, and E is —SO ₃ —.)